Studies in Surface Science and Catalysis 46

ZEOLITES AS CATALYSTS, SORBENTS AND DETERGENT

BUILDERS
Applications and Innovations
This Page Intentionally Left Blank
Studies in Surface Science and Catalysis

Advisory Editors:B. Delmon and J.T. Yates

Vol. 46

ZEOLITES AS CATALYSTS.
SORBENTS AND
DETERGENT BUILDERS
Applications and Innovations
Proceedings of an International Symposium, Wurzburg, F.R.G.,
September 4-8,1988

Editors

H.G. Karge
Fritz-Haber-lnstitut der Max-Planck-Gesellscha ft, Faradayweg 4-6, D- 1000
Berlin 33 (West)

J. Weitkamp
University of Stuttgart, Institute of Chemical Technology I, Pfaffenwaldring,
D- 7000 Stuttgart 80, F. R. G.

ELSEVIER Amsterdam - Oxford - New York -Tokyo 1989

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Zeolites a s c a t a l y s t s . s o r b e n t s . and d e r e r g e n r b u l l d e r r applications

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I n c l u d e s indexes.
Blbliography p.
ISBN 0-444-87383-x
1. ZeoIites--Congrcsrsr. 2 . Sorbents--Congresres. 3 . D8Tmrponts.
Synthetlc--Conprssses. I . Kargm. H. 0 . t n e l l m u r 0 . ) 11. W8ltkamp.
J. ( J e n s ) 111. I n r s r n a t l o n a l Symposium on "Zeolltss as C a t i l y s t s .
S o r b a n t s . ana D e t e r g e n t B u l l d 8 r S ' (1988 H u r z b u r g . Germany)
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 V

CONTENTS

Preface .......................... XI11

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . XIV
International Scientific Committee . . . . . . . . . . . . . . . . . . .X I V
Executive Committee ........................... XV

Financial Support ........................... xv

I . CATALYSIS AND CATALYSIS-RELATED PROPERTIES

Skeletal Rearrangement Reactions of Olefins, Paraffins and

Aromatics over Aluminophosphate based Molecular Sieve Catalysts
J.A. Rabo, R.J. Pellet, P.K. Coughlin, E.S. Shamshoum .........1
Catalytic and Physical Properties of Silicon-Substituted
AlP04-5 Molecular Sieves
K.J. Chao, L.J. Leu ........................... 19

On the Nature of the Catalytic Activity of SAPO-5

Ch. Minchev, V. Kanazirev, V. Mavrodinova. V. Penchev, H. Lechert . . . . 29
Molecular Orbital Calculations on the Structural and Acidic
Characteristics of Aluminophosphates (AlPO). Si 1 icoaluminophosphates
(SAPO) and Metaluminophosphate (MeAPO) Based Molecular Sieves
R. Carson, E.M. Cooke, J. Dwyer, A. Hinchliffe, P.J. O'Malley . . . . . . 39
Relation between Paraffin Isomerisation Capability and
Pore Architecture of Large-Pore Bifunctional Zeolites
J.A. Martens, M. Tielen, P.A. Jacobs. .................. 49

Respective Influences of the Geometric and Chemical Factors

in the Conversion o f Aromatics over Acidic Zeolites
F. Fajula, M. Lambret, F. Figueras . . . . . . . . . . . . . . . . . . . 61
Para-Selectivity of Pentasil Zeolites
3.-H. Kim. S. Namba, T. Yashima ..................... 71
v1

Hydrogen Spillover in the Conversion of n-Alkanes on Zeolites

K.-H. Steinberg, U. Mroczek, F. Roeher . . . . . . . . . . . . . . . . 81
Intermediates in the Formation of Aromatics from Propene
and 2-Propanol on H-ZSM-5 Zeol i tes
H. Lechert, C. Bezouhanova, C. Oimitrov, V. Nenova . . . . . . . . . . . 91
Zeolite and Matrix Structures and their Role in Catalytic Cracking
C.J. Groenenboom ........................... 99

Evaluation of Non-Commercial Modified Large Pore Zeolites in FCC

E. Jacquinot, F. Raatz, A. Macedo. Ch. Marcilly . . . . . . . . . . . . 115
Surface-Metals Interactions in Fluid Cracking Catalysts During the
Upgrading of Vanadium Contaminated Gas Oils
M.L. Occelli, J.M. Stencel ....................... 127

Highly Dispersed Pt and Pt-Cr Clusters in Pentasils and their

Activity in Transformations of Lower Alkanes
E.S. Shpiro, G.J. Tuleuova, V.I. Zaikovskii, O.P. Tkachenko,
T.V. Vasina, O.V. Bragin, Kh.M. Minachev . . . . . . . . . . . . . . . . 143
Conversion of Light Alkanes into Aromatic Hydrocarbons.
3. Arornatization of Propane and Propene on Mixtures of HZSM5 and of Ga2O3
N.S. Gnep, J.Y. Doyemet, M. Guisnet . . . . . . . . . . . . . . . . . . 153
Shape-Selective Catalysis in Zeolites with Organic Substrates
Containing Oxygen
R.F. Parton, J.M. Jacobs, O.R. Huybrechts and P.A. Jacobs. . . . . . . . 163
lhe Use of Zeolite Catalysts for the Synthesis of Nitrogen-Containing
Organic Intermediates
W.F. Hoelderich ............................ 193

Comparison of the Alkylation of Anisole and Phenol wifh Methanol

on Pentasil and Ultrastable Zeolites
R.F. Parton. J.M. Jacobs. H.v. Ooteghem, P.A. Jacobs . . . . . . . . . . 211
Acidity Effect o f ZSM 5 Zeolites on Phenol Methylation Reaction
N.S. Chang, C.C. Chen, S.J. Chu, P.Y. Chen, T.K. Chuang . . . . . . . . 223
 VII

A new Catalyst for MIBK Synthesis - Palladium on ZSM-5 Zeolites

P.Y. Chen, S.J. Chu, N.S. Chang, T.K. Chuang, L.Y. Chen. . . . . . . . . 231
Acetylene Hydration on Zeolite Catalysts: An I.R. Spectroscopic Study
of the Surface Species
Gy. Onyestyak, J. Papp Jr.. 0. Kallo . . . . . . . . . . . . . . . . .241
Preparation and Characterization of Mo-HY Zeolites
A. Meszaros-Kis, J. Valyon ...................... 251

Propylene Metathesis Reaction over Mo/Y-Zeolites

M. Caniecki .............................. 259

Molybdenum-Oxide-Modif ied Pentasil Zeolites

I.M. Harris, J. Dwyer, A.A. Garforth, C.H. McAteer, W.J. Ball . . . . . 271
Surface and Catalytic Properties of the New Zeolite Type LZ 132
Z. TvaruZkova, M. Tupa, P. Jiru. A. Nastro. 6. Giordano, F. Trifiro . . 281
PtRh-Doped Zeolites as Three-Way-Catalysts: SIMS Analysis as a Tool
for the Selection of Suitable Zeolite Types
C. Plog, J. Haas, J. Steinwandel . . . . . . . . . . . . . . . . . . . 295
Transformation o f Ethanethiol over Zeolites
M. Ziol’ek, P. Decyk, M. Derewinski, J. Haber . . . . . . . . . . . . . 305
Study o f the Structure and the Redox Reactivity of NaX Encapsulated
Co( 1 I)-Phthalocyanine
G. Schulz-Ekloff, 0. Wohrle, V. Iliev, E. Ignatzek, A. Andreev . . . . 315
Selective Reduction o f Nitric Oxide over Zeolite-Supported
Iridium Catalyst
R. Myrdal, St. Kolboe ........................ 327

Metal-Doped Zeolites for Selective Catalytic Reduction of Nitrogen

Oxides in Combustion Gases
J.Haas, J.Steinwande1, C. Plog . . . . . . . . . . . . . . . . . . . 337
Vlll

Preparation of NiHZSM-5 Catalyst for Isomerization o f c8 Aromatics.

Solid-state Incorporation of Nickel
B. Wichterlova. S. Beran, L. Kubelkova, J. Novakova, A. SmieSkova,
R. Sebik ............................... 347

Formation of Carbocations from c6 Compounds in Zeolites

I. Kiricsi, H. Forster, G. Tasi .................... 355

An Infrared and Catalytic Study o f Isomorphous Substitution in

Pentasil Zeolites
M.F.M. Post, T. Huizinga, C.A. Emeis, J.M. Nanne, W.H.J. Stork . . . . 365
Calorimetric lnvestigation o f the Acidity of Dealuminated Y-Type
Zeolites Using Various Basic Probes
A. Auroux. Z.C. Shi, N. Echoufi, Y . Ben Taarit . . . . . . . . . . . . 377
The Acidity of a Modified Faujasite Structure, Zeolite CSZ-1
S. Cartlidge. R.L. Cotterman, M.L. Howes . . . . . . . . . . . . . . . 389
Control of Catalytic Properties of ZSM-5 made by Fast and
Template-free Synthesis
A. TiAler, P. Polanek, U. Girrbach, U. Muller, K.K. Unger . . . . . . . 399
Theoretical Studies of BrBnsted Acidity in Zeolites
R. Vetrivel. C.R.A. Catlow. E.A. Colbourn. M. Leslie . . . . . . . . . 409
N M R and I R Studies of Zeolites of the Erionite Type
F. Roefiner, K.-H. Steinberg, 0. Freude, M. Hunger, H. Pfeifer . . . . 421
Specific Platinum Particles Properties in Basic Zeolites
A. de Mallmann, D. Barthomeuf .................... 429

11. SORPTION

Fundamental Research and Modeling for a Technical Process of Selective

Adsorption of Normal Paraffins ("Parex"-Process of DDR) by Zeolite A
W. Schirmer, K. Fiedler, H. Stach, M.Suckow . . . . . . . . . . . . . 439
Sorbex Technology for Industrial Scale Separation
J.A. Johnson, A.R. Oroskar ...................... 451
 IX
Gas Oil Dearomatization by Adsorption
A. Laktic, J. Muhl. I. Beck. M. Beer . . . . . . . . . . . . . . . . . 469
Modeling Diffusion Pathways in MFI Materials by Time-Resolved
Powder Diffraction Techniques
B.F. Mentzen ............................. 477

Measurement of Intracrystalline Diffusivities of HZSM-5 Zeolite at

Higher Temperatures and Predictions of Shape Selectivity
K. Hashimoto, T. Masuda, M. Kawase . . . . . . . . . . . . . . . . . . 485
Measurement of Hydrocarbon Diffusion Coefficient in a Non-Isobaric
Chromatographic Column of Zeolite Crystal Powder
E. Aust, W. Hilgert, G. Emig ..................... 495

Molecular Mobility of Benzene and p-Xylene in M F I Type Zeolites

M. Bulow, J. Caro, B. Rohl-Kuhn, B. Zibrowlus . . . . . . . . . . . . 505
Diffusion of n-Hexane and 3-Methylpentane in H-ZSM-5 Crystals of
Various Sizes
P. Voogd, H. van Bekkum ........................ 519

k Comparative Study by Deuteron Solid State NMR Spectroscopy of the

Dynamics o f Benzene and Olefins in Faujasite- and Mordenite-Type Zeolites
B. Boddenberg. R. Burmeister, G. Spaeth . . . . . . . . . . . . . . . 533
Probing the Hydrogen Sorption States in Zeolites A by Infrared
Spectroscopy and Low-Temperature Gas Chromatography Supplemented by
Theoretical Calculations
H. Forster, W. Frede, G. Peters . . . . . . . . . . . . . . . . . . . 545
Fourier-Transform Infra-Red Photoacoustic Spectroscopy, A Useful Technique
for the Study of Strongly Physisorbed Molecules
J. Philippaerts, E.F. Vansant, Y.A. Yan . . . . . . . . . . . . . . . 555
Adsorption Properties of Large Crystals of ZSM-5 Zeolite as a Function
of the Degree of Dealumination
J. Kornatowski, M. Rozwadowski, A. Gutsze, K.E. Wisniewski . . . . . . 567
X

Self-Consistent-Charge Xu Calculations of Sorption Complexes of

Nitrous Oxide Attached to Transition Metal Occupied Zeolite Clusters
0. Zakharieva-Pencheva, M. Grodzicki, H. Forster . . . . . . . . . . . 575
IR Study o f the Adsorption of Benzene on HZSM5
A. Jentys, J.A. Lercher ...................... 565

Adsorption Separation o f Methylnaphthalene Isomers on X and Y Zeolites

V. Solinas. R. Monaci, E. Rombi, M.Morbidelli . . . . . . . . . . . . 595
Oxygen Enrichment of Air with Molecular Sieve Zeolites Using the
PSA/VSA Technique
G. ReiR .............................. 607

Adsorption and Diffusion o f Different Hydrocarbons in MFI Zeolite

of Varying Crystallite Size
D.H. Lin, V. Ducarme, 6. Coudurier, J.C. Vedrine . . . . . . . . . . . 615
High Resolution Sorption Studies of Argon and Nitrogen on Large Crystals
of Aluminophosphate A1 Po4-5 and Zeolite ZSM-5
U. Muller, K.K. Unger, 0. Pan, A. Mersmann, Y. Grillet,
F. Rouquerol. J. Rouquerol ...................... 625

A new Potential Large-Scale Application o f Zeolites as

Fire-Retardant Material
H.K. Beyer, G. Borbely, P. Miasnikov, P. Rozsa . . . . . . . . . . . . 635
111. ION EXCHANGE AND DETERGENT BUILDING

Industrial Production of Zeolites

E. Roland ............................. 645

Calcium and Magnesium Exchange in Na-A, Ma-X and their Precursor Gels
L.V.C. Rees ............................. 661

Fundamentals of Phosphate Substitution in Detergents by Zeolites -

Cobuilders and Optical Brighteners
M.J. Schwuger, M. Liphard ..................... 673
 XI

Zeolite A - A Builder for Liquid Detergents?

W. Leonhardt, B.-M. Sax ....................... 691

Development and Performance of Zeol ite-A-Bui It Non-Phosphate Detergents

H. Upadek, P. Krings ........................ 701

Simultaneous Separation of Suspended Sol ids, Ammonium and Phosphate Ions

from Waste Water by Modified Clinoptilolite
J. Olah. J. Papp, A. Meszaros-Kis, Gy. Mucsi, 0. Kallo . . . . . . . . 711
IV. MODIFICATION AND CHARACTERIZATION

Framework and Non-Framework A1 Species in Dealuminated Zeolite Y

P.J. Grobet, H. Geerts, M. Tielen, J.A. Martens and P.A. Jacobs . . . 721
Characterization of Calcined FAPO-5
S. Schubert, H.M. Ziethen, A.X. Trautwein, F. Schmidt, H.-X. Li,
J.A. Martens, P.A. Jacobs ...................... 735

Control of Pore-Opening Size of Zeolites

Y.F. Chu, C.F. Keweshan, E.F. Vansant . . . . . . . . . . . . . . . . . 749
I\ new Structural-Modification Technique for Zeolites:
Chemisorption o f Si2H6
Y. Yan, J . Verbiest, J. Philippaerts, E.F. Vansant. P. De Hulsters . . . 759
Dealumination of the Zeolites Offretite and Erionite Studied by
Sol id-State 29Si- and 27A1-MAS NMR Spectroscopy
K.P. Lillerud, M.Stocker ....................... 769

Gal liation and 180-exchange Reactivities of ZSM-5 and ZSM-11

A. Endoh, K. Nishimiya, K. Tsutsumi, T. Takaishi ........... 779

Thermal Decomposition of Ironpentacarbonyl in Zeolites of Faujasite Type.

A Study of the Influence of Argon, HE, H2/CO Gas Mixture and Various
Si/Al Ratios Using Mossbauer, ESR and Mass Spectroscopy
H.M. Ziethen. A.X. Trautwein .................... 709
Investigation of Ultra Stable Y by Differential Thermal Analysis
after Injection of Water Vapour
A. Yoshida, K. Inoue . . . . . . . . . . . . . . . . . . . . . . . . . 801
Properties of Hydrothermal Low-Damaged 5A and 1OX Zeolites
R. Schollner, H. Siege1 . . . . . . . . . . . . . . . . . . . . . . . . 811
Phase Transformations and Changes in Lattice Parameters of ZSM-5
as a Function of A1 Content and Temperature
G.T. Kokotailo, L. Riekert, A. TiRler . . . . . . . . . . . . . . . . . 821
The Effect of Sorbates and Elevated Temperatures on the Structures
of Some Zeolite Catalysts
C.A. Fyfe, G.T. Kokotailo, H. Strobl, H. Gies, G.J. Kennedy,
C.T. Pasztor, G.E. Barlow . . . . . . . . . . . . . . . . . . . . . . 827
The Effect of Temperature and Sorption of p-Xylene and Benzene
on the Structure of ZSM-5
G.T. Kokotailo, L. Riekert, A. TiSler. . . . . . . . . . . . . . . . . . 843
The Characterization of Modified ZSM-5 Catalysts prepared via a Sol id-state
Reaction for Propane Aromatization
Y. Yang, X. Guo, M. Oeng, L. Wang, Z. Fu . . . . . . . . . . . . . . . . 849

Author Index ......,.....,.. ............ .... 859

Subject Index . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . 863

Studies in Surface Science and Catalysis (other volumes in the series). . . 869
 XI11

PREFACE

This symposium was one of the smaller zeolite meetings held in between the big Inter-
national Zeolite Conferences. It is the latest in the series of meetings which started in
1978 in Szeged, Hungary, and continued in 1980 in Villeurbanne (Lyon), France; 1982 in
Bremen, FRG; 1984 in Prague, Czechoslovakia; 1985 in Si6fok, Hungary; and 1987 in
Nieuwpoort, Belgium. These conferences are intended t o cover selected fields from the
broad area of zeolite research and application. For the Wurzburg Symposium emphasis
was placed on zeolite catalysis, sorption and detergent builders. With respect t o
catalysis, particular attention was paid to the synthesis of fine chemicals with the help
of zeolite catalysts. An overview of this important field was given in two invited lectures
which were complemented by a number of related oral and poster contributions.
Special efforts were made to bring together experts from industry and academia. This
endeavour was successful, as was reflected both in the invited lectures, oral and poster
presentations and in the composition of the audience. An expected trend was the ever
increasing interest in the so-called new generation molecular sieves both for research
and application. A remarkable number of the presented studies were devoted t o these
materials. Innovations, however, were mostly visible in developing and refining
methods and techniques of investigation either in experiment or theory. Obviously,
successful application of highly sophisticated tools of solid state and surface science t o
problems of zeolite research now becomes possible. This seems t o promise a growth in
our knowledge of and deeper insight into the subtle details of zeolite properties and
behaviour.

Hellmut G. Karge Jens Weitkamp

Fritz Haber institute institute of Chemical Technology I
Max Planck Society, Berlin University of Stuttgart

January, 1989
XIV

ACKNOWLEDGMENTS
The organizers of the international Symposium on "ZEOLITES AS CATALYSTS,
SORBENTS AND DETERGENT BUILDERS", held at Wurzburg, Federal Republic of
Germany, September 4-8, 1988 express their appreciation to the members of the
International Scientific Committee who carried out the difficult and important task of
paper selection.
They also wish t o thank the members of the Executive Staff for their great efforts made
during preparation and running of the symposium. Particular thanks are due to Mrs. R.
Stottko for the coordination and execution of the finances, to Dr. St. Ernst for his active
participation in the organizational work and to Mrs. M. Rahimi, Mrs. E. Stankewitz and
Mrs. J. Reiffel for their most valuable assistance in preparing the proceedings.
Furthermore, the organizers thank the authors for submitting their manuscripts for
publication in these proceedingsand the referees for spending time and effort in order
to ensure the high scientific standard of the contributions.
Last but not least, the help and generous financial support of collaborating organiza-
tions and sponsors from the industry is gratefully acknowledged.

Hellmut G. Karge Jens Weitkamp.

INTERNATIONAL SCIENTIFIC COMMlllEE

H. BEYER, HungarianAcademy of Sciences, Budapest, Hungary.

5. CARTLIDGE, Grace GmbH, Worms, FRG.

P. CHRISTOPHLIEMK, Henkel KGaA, Dusseldorf, FRG.

J. DWYER, The University of Manchester, England.
F. FAJULA, Ecole Nationale Supkrieure de Chimie, Montpellier, France.

F. FETTING, Technische Hochschule Darmstadt, FRG.

W. H6LDERICH. BASF AG, Ludwigshafen, FRG.

W. KEIM, RWTH Aachen, FRG, and DMGK, Hamburg, FRG.
A. KISS, Degussa AG, Hanau, FRG.

H. KRAL, Dechema, FrankfurVM., FRG.

 xv

E.4. LEUPOLD, Hoechst AG, FrankfuWM., FRG.

R. MAUREL, lnstitut de Recherches sur la Catalyse, Villeurbanne, France.

I.E. MAXWELL, Koninklijke/Shell, Amsterdam, The Netherlands.

L. MOSCOU, Akzo Chemie BV, Amsterdam, The Netherlands.

G. OHLMANN, Academy of Sciences of the GDR, Berlin-Adlershof, GDR.

L. PUPPE, Bayer AG, Leverkusen, FRG.

M.S. SPENCER, ICI, Billingham, England.

J.B. UYlTERHOEVEN, Katholieke Universiteit Leuven, Belgium.

EXECUTIVE COMMllTEE

R. AMBERG, Berlin (West).

C.H.BERKE, Stuttgart, FRG.

A. BREHM, Oldenburg, FRG.

C.-Y. CHEN, Oldenburg, FRG.

H. DARMSTADT, Berlin (West).

St. ERNST, Oldenburg, FRG.

TH. KROMMINGA, Stuttgart, FRG.

D. LINDNER, Oldenburg, FRG.

G.W. MULLER, Stuttgart, FRG.
M. NEUBER, Karlsruhe, FRG.

W. NIESSEN, Berlin (West).

E. PERNKLAU, Stuttgart, FRG.

E. STANKEWITZ, Berlin (West).

R. STOTTKO, Berlin (West).

W. WACHSMANN, Berlin (West).

FINANCIAL SUPPORT

Akzo Chemie, Ketjen Catalysts, Amsterdam, The Netherlands.

BASF AG, Ludwigshafen, FRG.

BP International Limited, Sunbury-on-Thames, England.

Bayer AG, Leverkusen, FRG.
XVI

Degussa AG, Frankfurt, FRG.

Deutsche Forschungsgemeinschaft(DFG), Bonn, FRG.
Deutscher Akademischer Austauschdienst (DAAD), Bonn, FRG.
DGMK German Society for Petroleum Sciences and Coal Chemistry,
Processing and Application Division, Hamburg, FRG.
Exxon Chemical Holland B.V., Rotterdam, The Netherlands.
Grace GmbH, Worms, FRG.
Henkel KGaA, Dussseldorf, FRG.
Hoechst AG, Frankfurt, FRG.
lnstitut Frangais du Petrole, Rueil Malmaison, France.
International Zeolite Association (IZA).
Kali-Chemie AG, Hannover, FRG.
Max-Planck-Gesellschaft, Munchen, FRG.
Perkin Elmer GmbH, Uberlingen, FRG.
Rutgerswerke AG, Frankfurt, FRG.
SKW Trostberg AG, Trostberg, FRG.

Sud-Chemie AC, Miinchen, FRG.

I. CATALYSIS AND CATALYSIS-RELATED PROPERTIES
This Page Intentionally Left Blank
H.G. Karge, J . Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

SKELETAL REARRANGEMENT REACTIONS OF OLEFINS, PARAFFINS AND AROMATICS OVER

ALUMINOPHOSPHATE BASED MOLECULAR S I E V E CATALYSTS

J u l e A. Rabo, Regis J . P e l l e t , P e t e r K. C o u g h l i n and Edwar S. Shamshoum

Union Carbide C o r p o r a t i o n , O l d Saw M i l l R i v e r Road, Tarrytown, NY 10591, U.S.A.

ABSTRACT
Medium pore aluminophosphate based m o l e c u l a r s i e v e s w i t h t h e -11, -31 and
-41 c r y s t a l s t r u c t u r e s a r e a c t i v e and s e l e c t i v e c a t a l y s t s f o r 1-hexene
i s o m e r i z a t i o n , hexane d e h y d r o c y c l i z a t i o n and c 8 a r o m a t i c r e a c t i o n s . With
o l e f i n feeds, t h e y promote i s o m e r i z a t i o n w i t h l i t t l e loss t o competing
hydride transfer and c r a c k i n g r e a c t i o n s . With C8 aromatics, they
e f f e c t i v e l y c a t a l y z e xylene i s o m e r i z a t i o n and ethylbenzene d i s p r o p o r t i o n a t i o n
a t v e r y low xylene loss. As a c i d components i n b i f u n c t i o n a l c a t a l y s t s , t h e y
a r e s e l e c t i v e f o r p a r a f f i n and c y c l o p a r a f f i n i s o m e r i z a t i o n w i t h low c r a c k i n g
activity. I n these r e a c t i o n s t h e medium p o r e aluminophosphate based s i e v e s
a r e g e n e r a l l y l e s s a c t i v e b u t s i g n i f i c a n t l y more s e l e c t i v e t h a n t h e medium
pore z e o l i t e s . S i m i l a r i t y w i t h medium p o r e z e o l i t e s i s d i s p l a y e d b y an
o u t s t a n d i n g r e s i s t a n c e t o coke induced d e a c t i v a t i o n and b y a v a r i e t y o f shape
s e l e c t i v e actions i n catalysis. The e x c e l l e n t s e l e c t i v i t i e s observed w i t h
medium pore aluminophosphate based s i e v e s i s a t t r i b u t e d t o a unique combina-
t i o n o f m i l d a c i d i t y and shape s e l e c t i v i t y . S e l e c t i v i t y i s a l s o enhanced by
t h e presence o f t r a n s i t i o n metal framework c o n s t i t u e n t s such as c o b a l t and
manganese which may e x e r t a chemical i n f l u e n c e on r e a c t i o n i n t e r m e d i a t e s .

INTRODUCTION
According t o recent reports, t h e aluminophosphate based m o l e c u l a r s i e v e s
have a c i d i c c a t a l y t i c a c t i v i t y f o r a broad a r r a y o f p e t r o l e u m r e f i n i n g and
petrochemical reactions. In early studies (ref. 2) n-butane cracking
activities were reported for a number of silicoaluminophosphate (SAPO)
molecular sieves. These SAPO molecular sieves showed weak acidity by
comparison w i t h z e o l i t e s . Subsequently, i t was found t h a t t r a n s i t i o n m e t a l
substitution into certain aluminophosphate crystals resulted i n enhanced
a c i d i t y as i n d i c a t e d b y enhanced butane c r a c k i n g a c t i v i t y ( r e f . 3). With
medium pore species t h e g e n e r a l l y m i l d a c i d i t y combined w i t h u n i q u e shape
selectivity has resulted in improved catalytic selectivity in several
reactions. Thus, a r e v i e w of t h e p a t e n t l i t e r a t u r e r e v e a l s t h a t alumino-
phosphate based m o l e c u l a r s i e v e s have shown c a t a l y t i c activity in fluid
catalytic cracking (ref. 4), hydrocracking (ref. 5), dewaxing ( r e f . 6),
reforming (ref. 7), aromatic alkylations (ref. 8 ) , methanol t o o l e f i n
conversion (refs. 9,lO) and i n o l e f i n oligomerization (refs. 8.11). In
s e v e r a l cases o l e f i n s p l a y an i m p o r t a n t r o l e , e i t h e r as f e e d c o n s t i t u e n t s o r
as r e a c t i o n i n t e r m e d i a t e s . The enhanced s e l e c t i v i t y o f c e r t a i n SAPO's f o r
o l e f i n r e a c t i o n s has a l r e a d y been noted. Thus, s m a l l p o r e SAPO's, such as
SAPO-34, were found v e r y e f f e c t i v e a t i n t e r c o n v e r t i n g l i g h t o l e f i n s such as
ethylene, propylene and butylenes with little loss to paraffinic or
oligomeric products ( r e f , 12). The medium p o r e SAPO's were a l s o a c t i v e and
very selective for oligomerization of p r o p y l e n e and butenes t o o l e f i n i c
gasoline ( r e f . 11) o r t o d i s t i l l a t e s w i t h o u t the production o f p a r a f f i n s o r
aromatics.
The present paper reports on the catalytic properties of selected
aluminophosphate molecular sieves in model hydrocarbon reactions. The
m o l e c u l a r s i e v e s were s e l e c t e d t o r e p r e s e n t l a r g e and medium p o r e s i z e s w i t h
a v a r i e t y o f framework elements i n c l u d i n g t r a n s i t i o n m e t a l s , i n a d d i t i o n t o
aluminum and phosphorus. Model r e a c t i o n s were chosen t o e x p l o r e c a t a l y t i c
performance i n p a r a f f i n , o l e f i n and a r o m a t i c rearrangement r e a c t i o n s t o probe
molecular sieve character, shape selectivity and catalytic activity,
p a r t i c u l a r l y for reactions i n v o l v i n g o l e f i n s or o l e f i n r e a c t i o n intermediates.

EXPERIMENTAL
M o l e c u l a r Sieve C a t a l y s t P r e p a r a t i o n
The aluminophosphate based m o l e c u l a r s i e v e s used i n t h e p r e s e n t s t u d y were
prepared a c c o r d i n g t o procedures d e s c r i b e d i n US P a t e n t ( r e f s . 2, 13, 14).
The p r e p a r a t i o n o f medium p o r e r e f e r e n c e m o l e c u l a r sieves, LZ-105 z e o l i t e and
s i l i c a l i t e , have a l s o been d e s c r i b e d elsewhere ( r e f s . 15, 16).
For 1-hexene i s o m e r i z a t i o n and f o r a c i d c a t a l y z e d C8 a r o m a t i c r e a c t i o n s
a l l m o l e c u l a r s i e v e s were e v a l u a t e d i n t h e i r c a l c i n e d , powdered s t a t e . For
the study o f C8 aromatics, selected SAPO m o l e c u l a r s i e v e s were aluminum
exchanged o r steam t r e a t e d as n o t e d i n T a b l e I V . For b i f u n c t i o n a l c a t a l y s t s
used in paraffin cyclizationlisomerization and ethylbenzene-xylene
interconversions, the calcined molecular sieve powder was mixed with
platinum-loaded c h l o r i d e d gamma alumina powder. These m i x t u r e s were t h e n
bound u s i n g s i l i c a s o l and e x t r u d e d t o f o r m 1/16" e x t r u d a t e s which were d r i e d
and c a l c i n e d a t 500°C. The b i f u n c t i o n a l c a t a l y s t s were p r e p a r e d t o c o n t a i n
about 0.5% p l a t i n u m and about 40 t o 50% SAPO m o l e c u l a r s i e v e i n t h e f i n i s h e d
catalysts.

Cata 1ys t Eva1u a t ion

The powdered m o l e c u l a r sieves were e v a l u a t e d f o l l o w i n g t h e t r e a t m e n t
d e s c r i b e d above, w i t h o u t f u r t h e r a c t i v a t i o n . The 1-hexene i s o m e r i z a t i o n and
C8 aromatic isomerization tests were conducted in tubular, fixed bed,
continuous f l o w microreactors. The c a t a l y s t bed c o n t a i n e d one gram m o l e c u l a r
 3

s i e v e powder and one t o t h r e e grams o f s i m i l a r l y s i z e d q u a r t z c h i p s used as

diluent. The r e a c t o r was heated t o t h e chosen r e a c t i o n temperatures i n a
fluidized sand bath, and the r e a c t i o n t e m p e r a t u r e was monitored b y a
thermocouple .located i n t h e c a t a l y s t bed. Typical runs l a s t e d 3 t o 5 hours
d u r i n g which samples were c o l l e c t e d e v e r y 30 minutes.
P a r a f f i n c y c l i z a t i o n and i s o m e r i z a t i o n s t u d i e s were a l s o conducted i n t h e
m i c r o r e a c t o r system. The f e e d used i n t h i s s t u d y was t e c h n i c a l grade
n-hexane c o n t a i n i n g 87% n-hexane, 9% methylcyclopentane and 4% isopentanes.
T y p i c a l l y about 0.35 g o f ground e x t r u d a t e s (20/80 mesh) were mixed w i t h
quartz c h i p s and loaded t o t h e r e a c t o r . The r e a c t o r was heated t o t h e
r e a c t i o n temperature i n f l o w i n g hydrogen, p r i o r t o hexane f e e d i n t r o d u c t i o n .
Runs l a s t e d f o r 24 hours and samples were c o l l e c t e d o n l y a f t e r 20 h o u r s on
feed t o p e r m i t c a t a l y s t l i n e - o u t . L i q u i d and gaseous p r o d u c t s were c o l l e c t e d
and analyzed as d e s c r i b e d above.
The bifunctional platinum - SAP0 catalysts were evaluated for C8
a r o m a t i c r e a c t i o n s i n t h e presence o f hydrogen i n bench s c a l e r e a c t o r s .
T y p i c a l l y , 25 t o 50 cc c a t a l y s t e x t r u d a t e s were d i l u t e d w i t h about f o u r
volumes of s i m i l a r l y s i z e d q u a r t z chips, and p l a c e d i n a 1 1/4" ID r e a c t o r
w i t n q u a r t z c h i p s placed i n b o t h end zones. Feed which c o n s i s t e d o f e i t h e r
17% ethylbenzene + 83% m-xylene o r 40% ethylbenzene + 60% m-xylene was t h e n
pumped over t h e c a t a l y s t bed. Bench s c a l e r u n s l a s t e d s e v e r a l days and
p r o d u c t s were c o l l e c t e d d a i l y . Both gas and l i q u i d p r o d u c t s were q u a n t i f i e d
and analyzed and m a t e r i a l balances were determined. T y p i c a l l y t h e s e balances
were w i t h i n 2% o f c l o s u r e .
The r e a c t i o n c o n d i t i o n s f o r a l l c a t a l y s t t e s t s a r e g i v e n a l o n g w i t h t h e
t e s t r e s u l t s i n Tables I t o V.

RESULTS A N D DISCUSSION
Reactions o f O l e f i n s
Olefins p l a y a key r o l e as intermediates i n a number o f petroleum
r e f i n i n g and petrochemical r e a c t i o n s . Therefore, t o b e t t e r understand t h e
f u n c t i o n and u t i l i t y o f aluminophosphate-based c a t a l y s t s , i t i s d e s i r a b l e t o
examine t h e i r c a t a l y t i c c h e m i s t r y w i t h model o l e f i n s . As mentioned above,
t h e s i l icoaluminophosphate m o l e c u l a r s i e v e s have a l r e a d y been r e p o r t e d t o be
a c t i v e f o r o l i g o m e r i z a t i o n o f l i g h t o l e f i n s t o g a s o l i n e range p r o d u c t s ( r e f .
11). The r e s u l t s o f t h a t s t u d y a r e reproduced i n T a b l e I which p r e s e n t s
conversion and s e l e c t i v i t y d a t a f o r p r o p y l e n e o l i g o m e r i z a t i o n t o l i q u i d
products. These d a t a were o b t a i n e d u s i n g l a r g e , medium and s m a l l - p o r e SAPO's
and medium pore r e f e r e n c e LZ-105 z e o l i t e .
4

TABLE I
Vapor Phase P r o p y l e n e 01 i g o m e r i z a t i o n

M o l e c u l a r Sieve SAPO-5 SAPO- 11 SAPO-3 1 SAPO-34 LZ- 105

P o r e Size, A 8 6 1 4.3 6
Run Temperature, "F 700 700 700 700 703
Pressure, p s i g 25 25 50 25 25
P r o p y l ene WHSV 0.98 0.94 1.04 0.53 0.90
Time on Stream,hr. 4.3 4.2 5.5 2.33 3.5
p r o p y l e n e Conversion, % 0 86.3 76.2 41.6 81.6
C5+ S e l e c t i v i t y a 77.0 82.7 19.5 37.2

a) C5+ S e l e c t i v i t y = (C5+ y i e l d , wt%)/(C3= c o n v e r s i o n , wt%)x100.

The data show that the l a r g e pore SAPO-5 with a undirectional non
i n t e r s e c t i n g channel system ( r e f . 17) was i n a c t i v e f o r o l i g o m e r i z a t i o n b y t h e
t i m e t h e f i r s t sample had been taken. Since SAPO-5 e x h i b i t e d s i g n i f i c a n t
a c t i v i t y f o r butane c r a c k i n g ( r e f . 2), t h e lack o f oligomerization a c t i v i t y
was a t t r i b u t e d t o r a p i d c a t a l y s t coking, r e s u l t i n g i n d e a c t i v a t i o n .
The s m a l l p o r e SAPO-34 h a v i n g a c r y s t a l s t r u c t u r e analogous t o c h a b a z i t e
was also ineffective for propylene oligomerization. While 40% p r o p y l e n e
c o n v e r s i o n was observed, most o f the products consisted o f ethylene and
butenes, w i t h o n l y 20% s e l e c t i v i t y t o l i q u i d p r o d u c t s . L a r g e r o l i g o m e r s were
c o n c e i v a b l y formed i n t h e cages o f t h e -34 c r y s t a l s t r u c t u r e b u t c o u l d n o t
escape through t h e m o l e c u l a r s i e v e ' s s m a l l p o r e openings. The l i g h t o l e f i n
products observed, were presumably formed by the cracking of trapped
p r o p y l e n e oligomers. T h i s s c r a m b l i n g o f l i g h t o l e f i n s b y SAPO-34 was a l s o
observed by K a i s e r ( r e f . 12).
I n c o n t r a s t t o SAPO-5 and SAPO-34, t h e medium p o r e SAPO-11 and SAPO-31
exhibited significant oligomerization activity and s e l e c t i v i t y t o liquid
products. While the structure of the SAPO-31 is as yet unknown, the
s t r u c t u r e o f SAPO-11 has been r e p o r t e d . I t comprises u n i d i r e c t i o n a l , non
i n t e r s e c t i n g channels formed by 10 member oxygen r i n g s ( r e f . 17). Conversions
as h i g h as 86%, with C5+ p r o d u c t s e l e c t i v i t i e s as h i g h as 83%, were r e p o r t e d
under t h e s c r e e n i n g c o n d i t i o n s . The performance o f t h e medium p o r e SAPO's
a l s o d i f f e r e d s i g n i f i c a n t l y from t h a t o f t h e medium p o r e z e o l i t e r e f e r e n c e ,
LZ-105, which a l s o achieved h i g h p r o p y l e n e conversion, b u t a t o n l y 37% C5+
selectivity. The LZ-105 i s s t r u c t u r a l l y r e l a t e d t o ZSM-5 b u t i s p r e p a r e d
w i t h o u t an o r g a n i c template. The l i q u i d p r o d u c t s formed over LZ-105 were
h i g h l y aromatic, i n c o n t r a s t t o t h e SAPO p r o d u c t s which were p r e d o m i n a n t l y
o l e f i n i c . Furthermore, t h e major gas p r o d u c t formed over LZ-105 c o n s i s t e d o f
l i g h t paraffins. The LZ-105 p r o d u c t d i s t r i b u t i o n was attributed t o the
preponderance of hydrogen transfer reactions in which olefin feed and
o l i g o m e r i z a t e underwent secondary reactions, presumably o v e r strong acid
 5

s i t e s , t o produce l i g h t p a r a f f i n s and aromatics. It was concluded t h a t , t h e

medium p o r e SAPO'S l a c k e d t h e a c i d s t r e n g t h r e q u i r e d t o c a t a l y z e h y d r i d e s h i f t
r e a c t i o n s , and p o s s i b l y l a c k e d s p a t i a l r e q u i r e m e n t s t o f o r m t h e b u l k y t r a n s i -
t i o n s t a t e s e n v i s i o n e d f o r t h e s e h y d r i d e s h i f t r e a c t i o n s ( r e f . 11). This lack
of h y d r i d e s h i f t a c t i v i t y r e s u l t e d i n h i g h s e l e c t i v i t y t o o l e f i n i c g a s o l i n e .
In t h e p r e s e n t study, t h e r e a c t i o n s o f 1-hexene as c a t a l y z e d b y a number
of t h e s e m o l e c u l a r s i e v e s a r e summarized i n T a b l e 11. As b e f o r e , d a t a a r e
presented for large, medium and small pore SAPO's. The influence of
t r a n s i t i o n metal framework elements i s a l s o e x p l o r e d w i t h s e l e c t e d MeAPO and
MeAPSO m o l e c u l a r s i e v e s . In a d d i t i o n t o o l i g o m e r i z a t i o n and h y d r i d e t r a n s f e r
reactions observed with propylene feed, double bond and skeletal
i s o m e r i z a t i o n s , c y c l i z a t i o n and c r a c k i n g a r e a l s o p o s s i b l e u s i n g 1-hexene as
model r e a c t a n t ,

TABLE I 1
Reactions o f I-Hexene over A1 uminophosphate-Based M o l e c u l a r Sieves

Run C o n d i t i o n s :
Run Temperature 650°F
Pressure 40 p s i g
WHSV 5.5 l / h r

M o l e c u l a r Sieve SAPO SAPO FAPO MnAPO SAPO FAPO MnAPSO LZ-105

-5 -11 -11 -11 -31 -31 -31
Pore Size, A 8 6 6 6 7 7 7 6
T o t a l Conversion,% 85.1 84 .5 90.1 89.6 86.0 89.1 94.5 93.7
Selectivities:
Double Bond
Isomerization, % 79.1 46.2 22.1 28.0 82.2 42.5 43.2 2.4
Skel e t a 1
Isomerization, % 10.9 41.9 70.6 63.6 14.3 52.8 44.6 12.2
Oligomerization, % 5.6 4.3 2.4 0.9 1.7 0.9 4.1 55.1
Cracking, % 3.2 3.3 1.5 1.9 0.9 1.3 2.6 25.6

As w i t h propylene, t h e medium p o r e SAPO's a r e again q u i t e a c t i v e and a l s o

quite selective. Thus, SAPO-11 gave over 90% 1-hexene conversion w i t h over
90% s e l e c t i v i t y t o isomerized products, h a l f o f which were s k e l e t a l isomers.
It i s important t o note t h a t medium p o r e SAPO-11 i s s e v e r a l o r d e r s of
magnitude more coke r e s i s t a n t than t h e l a r g e p o r e SAPO-5. A f t e r o n l y 30
minutes on hexene feed, the SAPO-5 was catalytically i n a c t i v e whereas
i s o m e r i z a t i o n a c t i v i t y w i t h SAPO-11 remained unchanged t h r o u g h o u t t h e t h r e e
hour l o n g m i c r o - s c r e e n i n g t e s t . It i s envisioned t h a t t h e enhanced coke
r e s i s t a n c e o f t h e medium pore SAPO-11 i s due t o a p r o d u c t shape s e l e c t i v i t y .
Due t o s p a t i a l c o n s t r a i n t s w i t h i n t h e SUPO-11 s t r u c t u r e , b u l k y coke p r e c u r s o r s
a r e formed a t a g r e a t l y reduced r a t e r e l a t i v e t o t h e i r r a t e o f f o r m a t i o n i n
6

SAPO-5. U n t i l now t h i s r e s i s t a n c e t o coke formation has o n l y been observed

w i t h t h e medium pore ZSM type molecular sieves ( r e f . 18). Under t h e m i l d e r
c o n d i t i o n s o f t h i s screening s t u d y w i t h SAPO-11, l i t t l e o l i g o m e r i z a t i o n
activity was observed, but importantly, almost no cracking of hexene
occurred. I n c o n t r a s t , under i d e n t i c a l t e s t c o n d i t i o n s , t h e z e o l i t e r e f e r e n c e
LZ-105 had v e r y h i g h a c t i v i t y f o r both o l i g o m e r i z a t i o n and cracking, f o r m i n g
over 30% l i g h t products. Most o f t h e isomerized hexene o l e f i n s were consumed
i n these secondary r e a c t i o n s . The h i g h i s o m e r i z a t i o n s e l e c t i v i t y observed
w i t h t h e medium pore SAPO's i s probably a t t r i b u t a b l e t o s i g n i f i c a n t l y m i l d e r
a c i d s t r e n g t h than t h a t possessed b y the r e f e r e n c e z e o l i t e c a t a l y s t .
The i n c o r p o r a t i o n o f t r a n s i t i o n elements i n t o the c r y s t a l s t r u c t u r e o f
medium pore aluminophosphate molecular sieves enhances s k e l e t a l i s o m e r i z a t i o n
selectivity even beyond that observed with the SAPO's. Thus, the
s i l icoaluminophosphate SAPO-11 gives 42% conversion t o s k e l e t a l isomers w i t h
3% cracked product w h i l e t h e same aluminophosphate c r y s t a l phase c o n t a i n i n g
manganese as a framework constituent, MnAPO-11, gives 64% skeletal
i s o m e r i z a t i o n w i t h o n l y 2% cracked product. The i r o n c o n t a i n i n g FAPO-11 was
even more a c t i v e and s e l e c t i v e w i t h 71% and 1.5% i s o m e r i z a t i o n and c r a c k i n g
a c t i v i t i e s , respectively. S i m i l a r trends can be seen f o r t h e manganese and
i r o n s u b s t i t u t e d aluminophosphates w i t h t h e -31 s t r u c t u r e .

P a r a f f i n Reactions
The dehydrocycl i z a t i o n o f p a r a f f i n s r e p r e s e n t s a v e r y i m p o r t a n t c l a s s o f
reactions occurring in the gasoline reforming process. Through
dehydrocyclization low octane paraffins are converted to high octane
aromatics. P a r a f f i n i s o m e r i z a t i o n a l s o boosts g a s o l i n e octane i n r e f o r m i n g
s i n c e branched isomers t y p i c a l l y have v e r y s i g n i f i c a n t l y enhanced octane
numbers r e l a t i v e t o normal p a r a f f i n s . D e h y d r o c y c l i z a t i o n and i s o m e r i z a t i o n
are very often accompanied by undesirable cracking reactions enhancing
product octane a t t h e expense o f g a s o l i n e y i e l d . Shape s e l e c t i v e c r a c k i n g can
enhance octane by c r a c k i n g away t h e low octane p a r a f f i n s t o form gas. The
intermediacy o f o l e f i n s i n these r e a c t i o n s has been p r e v i o u s l y demonstrated
( r e f . 19). A simp1 i f i e d mechanism f o r t h e dehydrocycl i z a t i o n , i s o m e r i z a t i o n
and c r a c k i n g o f n hexane i s summarized below:
Pt

nG - nG-- CYCLO ~e

LIGHT OLEFINS
-
- BENZENE

LIGHT PARAFFINS
 7

Here, f i r s t o l e f i n i c i n t e r m e d i a t e s a r e generated over p l a t i n u m . These

i n t e r m e d i a t e s a r e e i t h e r cracked t o f o r m l i g h t e r o l e f i n s o r c y c l i z e d and
isomerized over t h e a c i d i c c h l o r i d e d alumina. The o l e f i n s and naphthenes
thus formed a r e f i n a l l y dehydrogenated over t h e p l a t i n u m t o f o r m p a r a f f i n s
and aromatics. Z e o l i t i c a c i d s such as m o r d e n i t e ( r e f . 20) and ZSM-5 ( r e f . 21)
have been s u b s t i t u t e d f o r t h e c h l o r i d e d alumina as a c i d c a t a l y s t components.
I n t h e p r e s e n t study, m i x t u r e s o f supported p l a t i n u m and aluminophosphate
based m o l e c u l a r s i e v e s have been t e s t e d f o r n-hexane rearrangement r e a c t i o n s
under reforming conditions (900°F, 200 psig). Results are summarized
g r a p h i c a l l y i n F i g u r e s 1 and 2, where s e l e c t i v i t i e s a r e p l o t t e d as f u n c t i o n s
Of n-hexane conversion. Data a r e presented f o r t h e l a r g e , medium and s m a l l
pore SAPO m o l e c u l a r s i e v e s mixed w i t h a Pt-alumina catalyst. Data f o r
p l a t i n u m mixed w i t h c h l o r i d e d alumina o r mixed w i t h s i l i c a l i t e a r e p r e s e n t e d
f o r reference. I n F i g u r e 1, t h e r a t i o o f iso-hexanes t o cracked p r o d u c t s i s
p l o t t e d a g a i n s t conversion. The c a t a l y s t c o n s i s t i n g o f p l a t i n u m and l a r g e
pore SAPO-5 is less active than reference platinum-chlorided alumina;
however, i t appears s i m i l a r i n selectivity, i n t h a t i t produces a s i m i l a r
distribution of isomerized and cracked p r o d u c t s . Mixed p l a t i n u m and s m a l l
pore SAPO-34 i s quite active f o r hexane conversions but selectivity for
isomerized hexanes i s s i g n i f i c a n t l y lower than observed w i t h t h e r e f e r e n c e ,
and a significant increase in the amount o f l i g h t cracked products is
observed. These r e s u l t s a r e t o be expected. SAPO-34 w i t h t h e c h a b a z i t e - t y p e
s t r u c t u r e possesses cages i n which t h e l a r g e hexene isomers can form; however,
due t o t h e small pore opening o f t h e -34 s t r u c t u r e , t h e isomers once formed
can n o t escape w i t h o u t c r a c k i n g t o l i g h t e r p r o d u c t s . The n o b l e m e t a l - l o a d e d
medium pore SAPO's -11 and -41 exhibit excellent hexane isomerization
s e l e c t i v i t i e s when a p p l i e d t o g e t h e r w i t h p l a t i n u m , p r o d u c i n g 2 t o 4 t i m e s t h e
amount o f isomers compared t o r e f e r e n c e p l a t i n u m - c h l o r i d e d alumina c a t a l y s t .
I n contrast, t h e medium pore s i l i c a l i t e and supported p l a t i n u m c a t a l y s t
mixture, w h i l e a c h i e v i n g s i g n i f i c a n t l y h i g h e r n-hexane conversion, i s far
l e s s s e l e c t i v e than t h e medium p o r e SAPO c a t a l y s t m i x t u r e and t h e c h l o r i d e d
alumina-platinum reference, p r o d u c i n g a l a r g e amount o f cracked p r o d u c t s .
S i m i l a r s e l e c t i v i t y t r e n d s a r e observed f o r t h e dehydrocycl i z a t i o n r e a c t i o n s
of n-hexane. Thus i n F i g u r e 2 t h e benzene t o l i g h t p r o d u c t s r a t i o i s p l o t t e d
a g a i n s t conversion f o r t h e same s e t o f c a t a l y s t s , and again t h e medium p o r e
SAPO's e x h i b i t s u p e r i o r s e l e c t i v i t y t o b o t h r e f e r e n c e m a t e r i a l s and t o b o t h
l a r g e and small pore SAPO c a t a l y s t systems. These r e s u l t s a r e i n complete
agreement w i t h t h e hexene i s o m e r i z a t i o n d a t a d e s c r i b e d above, wherein t h e
medium pore SAPO's show s i g n i f i c a n t l y reduced a c t i v i t y f o r c r a c k i n g r e a c t i o n s
while maintaining h i g h skeletal isomerization a c t i v i t y .
8

12r

11 - A

A
10.
0 A

!i 9-
5 *-
9
c 7-

x
I

'i
2

1-
+n +

Q o
A
1 . 1 1 1 ,

Fig. 1 . I s o m e r i z a t i o n / C r a c k i n g S e l e c t i v i t y R a t i o p l o t t e d as a f u n c t i o n o f
n-hexane conversion: ASAPO- 11 , X SAPO-41, +SAPO-5, OSAPO-34,
A S i l i c a l i t e and O P t / c h l o r i d e d - a l u m i n a r e f e r e n c e .

+ .75- A x
I A x
2
I A
I .50-

s
z
W
.25- ++
W
m 0
. A

I I 1 1 , I
0 10 20 30 40 50 60 7 0 80 90
n - HEXANE CONVERSION, WT%

F i g . 2. D e h y d r o c y c l i z a t i o n / C r a c k i n g S e l e c t i v i t y R a t i o p l o t t e d as a f u n c t i o n
of n-hexane conversion: ASAPO-11, XSAPO-41, +SAPO-5, OSAPO-34,
A S i l i c a l i t e and O P t / c h l o r i d e d - a l u m i n a r e f e r e n c e .
 9

Aromatic Reactions
I n a d d i t i o n t o reforming, t h e i s o m e r i z a t i o n o f C8 a r o m a t i c s t o produce
para-xylene i s another area where o l e f i n i c i n t e r m e d i a t e s may p l a y a s i g n i f i -
c a n t m e c h a n i s t i c r o l e . The p r o d u c t i o n o f p a r a - x y l e n e i s o f i n t e r e s t t o t h e
petrochemical i n d u s t r y because o f i t s use as monomer i n p o l y e s t e r p r o d u c t i o n .
I n a d d i t i o n t o C a r o m a t i c i s o m e r i z a t i o n , t h e r e a r e a number o f i m p o r t a n t
8
r o u t e s t o para-xylene i n c l u d i n g t h e a l k y l a t i o n o f t o l u e n e w i t h methanol and
the disproportionation o f toluene. The c a t a l y t i c p r o p e r t i e s o f t h e SAP0
m o l e c u l a r s i e v e s f o r t o l u e n e m e t h y l a t i o n r e a c t i o n s have been d e s c r i b e d ( r e f .
11). While b o t h l a r g e and medium pore SAPO's were a c t i v e f o r t h e a l k y l a t i o n
reaction, t h e medium pore m a t e r i a l s were d i s t i n g u i s h e d b y r e m a r k a b l y h i g h
s e l e c t i v i t y f o r methylation reactions, with disproportionation o f the toluene
feed r e p r e s e n t i n g l e s s than 2% o f t h e t o t a l conversion. By comparison, l a r g e
pore SAPO-5 had n e a r l y 60% d i s p r o p o r t i o n a t i o n s e l e c t i v i t y and t h e z e o l i t e
r e f e r e n c e LZ-105 had n e a r l y 80% d i s p r o p o r t i o n a t i o n s e l e c t i v i t y . The v e r y low
d i s p r o p o r t i o n a t i o n a c t i v i t y o f t h e medium p o r e SAPO's, attributed t o their
m i l d acid character, r e s u l t e d i n reduced l o s s e s o f t o l u e n e t o benzene and
increased xylene y i e l d s r e l a t i v e t o LZ-105 and SAPO-5.
In the present study, silicon and transition metal substituted
aluminophosphate m o l e c u l a r s i e v e s have a l s o been e v a l u a t e d f o r a c t i v i t y and
selectivity for para-xylene p r o d u c t i o n v i a C8 aromatic isomerization. In
commercial p r a c t i c e , C8 aromatic c u t s a r e o b t a i n e d f r o m r e f o r m a t e g a s o l i n e
and from pyrolysis naphtha streams. Both feeds contain a significant
fraction o f ethylbenzene which i s d i f f i c u l t t o s e p a r a t e f r o m xylenes by
p h y s i c a l techniques, and must be c a t a l y t i c a l l y c o n v e r t e d t o o t h e r p r o d u c t s .
T h i s c a t a l y t i c conversion can b e accomplished b y one o f two c o m n e r c i a l l y
a v a i l a b l e approaches. I n one approach, m o n o - f u n c t i o n a l a c i d c a t a l y s t s such
as ZSM-5 (ref. 22) isomerize xylenes and a l s o c o n v e r t ethylbenzene t o non
aromatics by selective ethyl group disproportionation.
'8
D i s p r o p o r t i o n a t i o n o f xylenes t o non C8 a r o m a t i c s i s a competing s i d e
r e a c t i o n l o w e r i n g t h e u l t i m a t e para-xylene y i e l d . A c i d c a t a l y s i s a l o n e can
not convert the ethyl-benzene to xylenes. To this end, bifunctional
catalysts c o n t a i n i n g b o t h a hydrogenation-dehydrogenation f u n c t i o n such as
p l a t i n u m as w e l l as an a c i d i c f u n c t i o n such as mordenite (ref. 2 3 ) , have
typically been employed. In the latter approach, ethylbenzene is
hydrogenated over Pt to ethylcyclohexene which is then isomerized to
dimethylcyclohexene o v e r t h e a c i d c a t a l y s t f u n c t i o n , and f i n a l l y c o n v e r t e d t o
xylenes b y dehydrogenation over t h e platinum.
10

2Hzf

CRACKED PRODUCTS

Conceptually, this route offers the possibility of enhanced xylene

yields, b u t since naphthenic intermediates are present, s i g n i f i c a n t acid
c a t a l y z e d r i n g opening and y i e l d l o s s o f a r o m a t i c s a r e a l s o p o s s i b l e . A
review o f a v a i l a b l e patent l i t e r a t u r e data (refs. 22, 23b) suggests that
because o f these u n d e s i r a b l e s i d e r e a c t i o n s , t h e b i f u n c t i o n a l approach t o
isomerization yields about the same amount of xylene as does the
monofunctional route.

C, Aromatic Reactions Witnout Hydrogen

-
v
I n t h e p r e s e n t study, t h e alumino-phosphate m o l e c u l a r s i e v e s have been
used a l o n e and w i t h added p l a t i n u m and hydrogen t o i s o m e r i z e C aromatic
8
feeds. In an i n i t i a l s c r e e n i n g s t u d y , a s e r i e s o f l a r g e t o medium p o r e s i z e
molecular sieves were evaluated for catalytic activity for m-xylene
rearrangements a t 1000°F without added metal and hydrogen. Under these
conditions all molecular sieves evaluated give essentially complete
isomerization o f m-xylene f e e d t o a thermodynamic e q u i l i b r i u m m i x t u r e of
xylene isomers, while the disproportionation activity to toluene and
trimethylbenzenes varies significantly. The results of this study are
summarized i n T a b l e 111 and i n F i g u r e 3, where x y l e n e d i s p r o p o r t i o n a t i o n
a c t i v i t y i s p l o t t e d as a f u n c t i o n o f m o l e c u l a r s i e v e p o r e s i z e . I n general,
a rough t r e n d can be seen i n which t h e m o l e c u l a r s i e v e s with l a r g e r p o r e
s i z e s a r e more a c t i v e f o r t h i s u n d e s i r a b l e s i d e r e a c t i o n . Thus under t h e
chosen screening conditions, SAPO-5, MAPO-5 and MAPO-36, all l a r g e pore
m o l e c u l a r s i e v e s w i t h a p p r o x i m a t e l y 8 angstrom p o r e s i z e s , c a t a l y z e f r o m 12
to 22 % disproportionation while SAPO-11, MAPO-11 and SAPO-41 with
a p p r o x i m a t e l y 6 angstrom pores s u f f e r o n l y 2 t o 7 % x y l e n e l o s s e s . These
r e s u l t s a r e c o n s i s t e n t w i t h t h e concept o f t r a n s i t i o n s t a t e shape s e l e c t i v i t y
where a b u l k y , bimolecular i n t e r a c t i o n o f two xylenes t o f o r m t o l u e n e and
t r i m e t h y l b e n z e n e i s d i f f i c u l t t o a c h i e v e i n t h e a p p r o x i m a t e l y 6 angstrom s i z e
channels.
 11

TABLE 111
m-Xylene Reactions Catalyzed by A1 uminophosphate-Based Molecular Sieves

Run Conditions:
Run Temperature 1000°F
Pressure 100 p s i g
WHSV 5.6 l / h r .

m-Xyl ene
a b Dispropor t ionat ion,
Molecular Sieve Pore Size Pore Volume % Conversion
SAPO-5 0.8 20.7
MAPO-5 0.8 22.4
MAPO-36 0.8 0.31 12.6
SAPO-3 1 0.65 0.17 15.1
SAPO-4 1 0.6 0.22 7.1
SAPO- 11 0.6 0.16 3.2
MAPO- 1 1 0.6 0.16 1.8

I: Determined by McBain Bakr g r a v i m e t r i c adsorption s t u d i e s ( r e f . 3).

Determined by water adsorption a t s a t u r a t i o n ( r e f . 3).

3oL

z
0
2 -
0 24
1
0

E
g18-
*
z
0
v)
212-
>
z
8w
z
2
X
6-

01 I
0.8 0.7 0.8 0.9
PORE SIZE, NM

Fig. 3. Xylene losses due t o d i s p r o p o r t i o n a t i o n are a f u n c t i o n o f the

molecular sieve c a t a l y s t ' s pore s i z e .

I n t h e next phase o f t h e present study, several medium pore molecular

sieves were evaluated f o r c a t a l y t i c performance with an ethylbenzene and
m-xylene feed. Again, t h e molecular sieves were t e s t e d with no added metal
12

o r hydrogen. Several of t h e s e aluminophosphate based m o l e c u l a r s i e v e s d i d

c o n t a i n t r a n s i t i o n m e t a l s as framework elements. The r e s u l t s o f t h i s s t u d y
are summarized i n Table I V and F i g u r e 4. From t h e Table i t can be seen t h a t
a l l m o l e c u l d r s i e v e s y i e l d p a r a - x y l e n e i n amounts e q u i v a l e n t t o thermodynamic
equilibrium. Surprisingly, the cobalt and manganese-containing molecular
s i e v e s w i t h t h e -31 t y p e s t r u c t u r e d i d n o t promote t h e e q u i l i b r a t i o n o f meta
t o ortho-xylene, so t h a t v e r y h i g h p a r a / o r t h o s e l e c t i v i t i e s were observed.
Since SAPO-31 w i t h i d e n t i c a l framework s t r u c t u r e does n o t e x h i b i t t h e h i g h
para and low o r t h o - x y l e n e s e l e c t i v i t y observed w i t h t h e MeAPSO-31 m o l e c u l a r
s i e v e s , t h e i r h i g h s e l e c t i v i t y m i g h t p o s s i b l y be i n t e r p r e t e d as p r o d u c t shape
selectivity due to restricted pore size. Obviously the Mn+2 framework
c a t i o n s a r e l a r g e r than t h e s i l i c o n and aluminum c a t i o n s t h e y a r e r e p l a c i n g ,
and t h i s c o u l d c o n c e i v a b l y r e s u l t i n r e s t r i c t i o n s i n t h e m o l e c u l a r sieve
channels. However, McBain-Bakr g r a v i m e t r i c adsorption studies with "plug
gauge-sized" molecules suggest t h a t MeAPSO-31 I s have p o r e s i z e s and volumes
s i m i l a r t o those o f t h e m e t a l - f r e e SAPO-31, which does n o t appear t o b e p a r a
s e l e c t i v e ( r e f . 3 ) . Furthermore, SAPO-11 w i t h s l i g h t l y s m a l l e r p o r e s i z e t h a n
CoAPSO-31 and MnAPSO-31 does n o t show n e a r l y t h e p a r a s e l e c t i v i t y observed
w i t h the t r a n s i t i o n metal-containing m o l e c u l a r s i e v e s w i t h t h e -31 crystal
structure. An a l t e r n a t e e x p l a n a t i o n i s needed. I t may b e t h a t t h e framework
t r a n s i t i o n metal i o n s i n t h e s e m o l e c u l a r s i e v e s e x e r t a chemical i n f l u e n c e on
the intermediates in isomerization, favoring the formation of the
para-isomer. Alternately, a c i d s i t e s may be u n i q u e l y l o c a t e d i n t h e MeAPSO
m o l e c u l a r s i e v e s such t h a t access o f r e a c t a n t s and r e a c t i o n i n t e r m e d i a t e s t o
these acid s i t e s i s s p a t i a l l y constrained, f a v o r i n g p a r a - s e l e c t i v i t y .

TABLE I V
m-XylenelEthylbenzene Reactions w i t h Medium Pore S i z e Aluminophosphate
Based M o l e c u l a r Sieves

Run C o n d i t i o n s :
Run Temperature 800°F
Pressure 100 p s i g
WHSV 5.6 l / h r .
P ar a/Or t h o %Para-Xyl ene % D i s p r o p o r t io n a t ion
M o l e c u l a r Sieve Xylene R a t i o Equilibration Xylenes Ethylbenzene
SAPO- 11 96 9.9 23.2
SAPO-11 (Al'3 exchanged)
SAPO-11 (Steam t r e a t e d )
:1.52
; 102
63
6.6
0.2
20.1
6 .O
SAPO-31 0.78 100 31.6 56.3
SAPO-31 (Steam t r e a t e d ) 1.56 102 1.7 10.4
MnAPSO- 11 0.88 104 5 .O 23.3
COAPSO-11 1.81 91 0.0 7.7
MnAPSO-31 3.59 120 0.0 17.7
COAPSO-31 3.06 111 1.7 23.0
LZ-105 0.99 100 23.6 58.5
 13

Figure 4 plots ethylbenzene vs xylene disproportionation activity for the

same series of catalysts. Data were obtained at a range of conversions by
varying reaction temperature. Again a1 1 catalysts were tested without added
metal or hydrogen. Data obtained with medium pore zeolite reference LZ-105
are also presented for comparison. The MeAPSO-31 molecular sieves are again
distinguished by superior selectivity. Thus at comparable ethylbenzene
conversions, the CoAPSO and MnAPSO-31 molecular sieves exhibit the lowest
activity for the undesirable xylene disproportionation while SAPO-11 and
SAPO-31 are considerably less selective. Data obtained with LZ-105 is
intermediate in selectivity. Again the enhanced selectivity observed with
the MeAPSO-31 molecular sieves may be due to a transition metal specific
influence on the reaction intermediates. Shape selective effects by
themselves cannot explain differences between these materials and the
transition metal-free SAPO's.

./
rn
J
6 13 20 27
% XYLENE LOSS

Fig. 4. Selectivity for ethylbenzene conversion plotted against xylene losses

for A MeAPSO's, 0 LZ-105 and SAPO's.
14

-
C Aromatic R e a c t i o n s w i t h Hydrogen
-
I n a final phase o f t h e c u r r e n t s t u d y , c a t a l y s t s c o n s i s t i n g o f s e l e c t e d
SAPO's and s u p p o r t e d p l a t i n u m have been e v a l u a t e d i n t h e presence o f hydrogen
for bifunctional C8 a r o m a t i c i s o m e r i z a t i o n . Two c a t a l y s t s were prepared,
one c o n t a i n i n g 40% o f t h e i n t e r m e d i a t e p o r e SAPO-11 and t h e o t h e r c o n t a i n i n g
40% o f l a r g e pore SAPO-5. Both c a t a l y s t s were prepared t o c o n t a i n about 0.6%
p l a t i n u m supported on alumina. The c a t a l y s t s were e v a l u a t e d a t 8OO0F, 185
p s i g and a t a space v e l o c i t y o f 1 and a hydrogen t o hydrocarbon r a t i o o f 14.
The f e e d used f o r t h e s e t e s t s c o n t a i n e d 17% e t h y l b e n z e n e and 83% m-xylene,
simulating a C8 aromatic cut obtained from reformate gasoline. Each
c a t a l y s t was e v a l u a t e d f o r s e v e r a l days on stream, and a t t h e h i g h hydrogen/
hydrocarbon r a t i o employed, l i t t l e or n o d e a c t i v a t i o n was observed. In
addition, the SAPO-11-containing catalyst was evaluated with a 40%
ethylbenzene + 60% m-xylene feed in order to better evaluate its
effectiveness i n c o n v e r t i n g ethylbenzene t o xylenes, and t o model a feed
s i m i l a r t o a p y r o l y s i s naphtha C8 cut. Typical performance d a t a f o r each
c a t a l y s t a f t e r s e v e r a l h o u r s on t h e 17% e t h y l b e n z e n e f e e d a r e summarized i n
Table V . Performance i n d i c a t o r s were c a l c u l a t e d assuming t h a t t h e naphthenes
formed during processing would in commercial practice be recycled, and
t h e r e f o r e t h e i r f o r m a t i o n would c o n t r i b u t e t o n e i t h e r e t h y l b e n z e n e c o n v e r s i o n
nor t o xylene losses. A c c o r d i n g t o t h e t e s t s b o t h c a t a l y s t s promote
near-complete xylene equilibration, and the catalyst containing SAPO-5
achieves h i g h e r ethylbenzene c o n v e r s i o n t h a n t h e SAPO-11 c a t a l y s t , 68% and
44% r e s p e c t i v e l y . However, t h e l a r g e p o r e m o l e c u l a r s i e v e i n c u r s n e a r l y 22%
x y l e n e l o s s e s w h i l e t h e SAPO-11 based c a t a l y s t a c t u a l l y produces 2.1% more
xylenes than were p r e s e n t i n i t i a l l y i n t h e feed. With SAPO-5 these l o s s e s
a r e due t o d i s p r o p o r t i o n a t i o n r e a c t i o n s p r o d u c i n g benzene, t o l u e n e and C9+
aromatics, and a l s o t o non c y c l i c p r o d u c t f o r m a t i o n , suggesting s i g n i f i c a n t
r i n g opening and c r a c k i n g . With t h e SAPO-11 c a t a l y s t t h e r e i s much l e s s
disproportionation activity, and almost n o ring-opened p a r a f f i n i c products
a r e observed.
While t h e p r e s e n t s t u d y has n o t examined t h e performance o f z e o l i t e based
catalysts, Table V summarizes patent literature data (ref. 23b) for a
m o r a e n i t e and p l a t i n u m / a l u m i n a m i x t u r e . Data f o r t h e P t and SAPO-11 m i x t u r e
obtained under similar conditions are presented for comparison. The
m o r d e n i t e c a t a l y s t i s s i g n i f i c a n t l y l e s s s e l e c t i v e t h a n SAPO-11, g i v i n g 25.6%
ethylbenzene c o n v e r s i o n w i t h o n l y 0.5% n e t x y l e n e p r o d u c t i o n .
The data obtained with high ethylbenzene feed shows even more
d r a m a t i c a l l y t h e e f f i c i e n t c o n v e r s i o n o f e t h y l b e n z e n e t o xylenes o v e r t h e
SAPO-11-containing c a t a l y s t . Thus a t 23.6% ethylbenzene conversion, a nearly
 15

13% i n c r e a s e i n x y l e n e y i e l d i s observed. T h i s i n d i c a t e s t h a t ethylbenzene

has been c o n v e r t e d w i t h 75% s e l e c t i v i t y t o xylene isomers. The r e m a i n i n g
conversion was t o d i s p r o p o r t i o n a t i o n products w i t h a g a i n almost n o r i n g
opening.

TABLE V
Cg Aromatic I s o m e r i z a t i o n With B i f u n c t i o n a l C a t a l y s t s
~~

b
Molecular Sieve Component SAPO-5 SAPO-11 SAPO-11 SAPO-11 Mordenite

a
M o l e c u l a r Sieve Content, % 40 40 40 40 50
Run Pressure, p s i g 800 800 840 800 800
Run Temperature,"C 185 185 250 165 175
H2/HC R a t i o 14 14 8.3 14 8
WHSV 1 1 2.9 1 3.6
Ethylbenzene i n Feed, % 17 17 17 40 15.5
Approach t o p-xylene
Equilibrium, % 94.9 97.3 94.5 96.2 99.3
Ethylbenzene Conversion, % 67.9 44.6 28.2 23.6 25.6
Net Xylene P r o d u c t i o n , % -21.6 2.1 1.5 12.8 0.5

a) I n a d d i t i o n t o the q u a n t i t y o f molecular sieve l i s t e d , a l l c a t a l y s t s

c o n t a i n e d 0.4-0.6% p l atinum.
b) Data o b t a i n e d f r o m U.S. P a t e n t 4,255,606, Example 1.

CONCLUSIONS
The medium p o r e aluminophosphate based m o l e c u l a r s i e v e s a r e a c t i v e and
selective catalysts f o r a variety of i m p o r t a n t hydrocarbon rearrangement
reactions. As acid catalysts, they promote olefin isomerization and
o l i g o m e r i z a t i o n w h i l e t h e y a r e s i g n i f i c a n t l y l e s s e f f e c t i v e a t t h e competing
h y d r i d e t r a n s f e r and c r a c k i n g r e a c t i o n s . I n t h e r e a c t i o n s o f a r o m a t i c s , t h e
medium pore aluminophosphates a r e again e f f e c t i v e f o r s k e l e t a l i s o m e r i z a t i o n
b u t show low e t h y l group d i s p r o p o r t i o n a t i o n a c t i v i t y . As a c i d components i n
bifunctional catalysts, t h e y a r e s e l e c t i v e f o r p a r a f f i n and c y c l o p a r a f f i n
i s o m e r i z a t i o n w i t h low c r a c k i n g a c t i v i t y .
These c a t a l y t i c p r o p e r t i e s c o n t r a s t s h a r p l y w i t h t h o s e o f medium p o r e
z e o l i t e s such as LZ-105 and w i t h s i l i c a l i t e . Thus, medium p o r e SAPO's a r e
considerably less active than LZ-105 for olefin, paraffin and a r o m a t i c
conversions when compared a t t h e same temperature. However, t h e y a r e more
s e l e c t i v e f o r o l e f i n and p a r a f f i n i s o m e r i z a t i o n s when e v a l u a t e d a t comparable
conversions .
Not s u r p r i s i n g l y , t h e c a t a l y t i c p r o p e r t i e s o f medium p o r e aluminophos-
phates a l s o c o n t r a s t w i t h l a r g e pore aluminophosphate-based m o l e c u l a r s i e v e s
of similar framework composition. With olefinic feeds, the l a r g e pore
molecular sieves d e a c t i v a t e v e r y r a p i d l y , presumably due t o p o r e p l u g g i n g b y
16

higher molecular weight products. The medium p o r e SAPO's a r e d r a m a t i c a l l y

more coke r e s i s t a n t . Under c o n d i t i o n s t h a t f u l l y d e a c t i v a t e SAPO-5 i n less
than 30 minutes, SAPO-11 I s a c t i v i t y remains unchanged f o r several hours.
With a r o m a t i c feeds, b o t h l a r g e and medium p o r e m o l e c u l a r s i e v e s a r e a c t i v e
for a l k y l a t i o n and i s o m e r i z a t i o n . However, t h e l a r g e pore molecular sieves
a r e s i g n i f i c a n t l y more a c t i v e f o r t h e d i s p r o p o r t i o n a t i o n o f d i a l k y l a r o m a t i c s ,
i m p l y i n g t r a n s i t i o n s t a t e shape s e l e c t i v i t y f o r t h e medium p o r e m o l e c u l a r
sieves. I n bifunctional catalysis i n v o l v i n g o l e f i n i c intermediates, large
pore m o l e c u l a r s i e v e s a r e more a c t i v e f o r c r a c k i n g and l e s s s e l e c t i v e f o r
skeletal isomerization reactions.
The c a t a l y t i c p r o p e r t i e s o f t h e aluminophosphate molecular sieves are
also influenced by chemical composition. The introduction o f transition
m e t a l s i n t o framework p o s i t i o n s enhances t h e a c t i v i t y and s e l e c t i v i t y f o r
o l e f i n i s o m e r i z a t i o n r e l a t i v e t o t h e silicoaluminophosphates. The t r a n s i t i o n
metal c o n t a i n i n g alurninophosphates a r e a l s o s u r p r i s i n g l y more s e l e c t i v e f o r
C8 a r o m a t i c rearrangements t h a n t h e c o r r e s p o n d i n g SAP0 m o l e c u l a r s i e v e s , an
e f f e c t which can n o t b e a t t r i b u t e d s o l e l y t o improved shape s e l e c t i v i t y .
The enhanced selectivities observed with medium pore silico- and
metalloaluminophosphates may, t o a l a r g e e x t e n t b e a t t r i b u t e d t o a u n i q u e
combination o f m i l d a c i d i t y and shape s e l e c t i v i t y . The l a c k o f h y d r i d e s h i f t
and c r a c k i n g a c t i v i t y i n o l e f i n - m e d i a t e d r e a c t i o n s i s suggestive o f m i l d
acidity. The observed r e s i s t a n c e to coke deactivation and t h e enhanced
selectivity t o para-xylene i n m e t h y l a t i o n and isomerization reactions is
evidence o f shape-sel e c t ive c a t a l y s i s .
In addition to these factors, however, transition metal framework
constituents appear to exert a special chemical effect on catalytic
performance which appears t o be independent o f m o l e c u l a r s i e v e a c i d s t r e n g t h
and spatial constraints. This effect is evidenced by cobalt and
manganese-containing molecular sieves as enhanced selectivity for
ethylbenzene d i s p r o p o r t i o n a t i o n i n t h e presence o f xylenes, and b y enhanced
para-selectivity i n xylene i s o m e r i z a t i o n . Thus, MnAPSO-31 has a l a r g e r p o r e
size than SAPO-11 as judged b y "plug gauge" molecules but i s f a r more
s e l e c t i v e f o r para-xylene and f o r ethylbenzene d i s p r o p o r t i o n a t i o n than t h e
SAPO-11 under comparable t e s t c o n d i t i o n s . T h i s enhanced s e l e c t i v i t y may b e
due to a uniquely 'located acid site in the transition metal-containing
molecular sieve with special and unexpected spatial requirements.
Alternately, i t may b e due t o a l i g a n d o r e l e c t r o n i c e f f e c t o f t h e t r a n s i t i o n
metal, affecting the transition states in aromatic isomerization and
disproportionation reactions.
 17

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H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

CATALYTIC AND PHYSICAL PROPERTIES OF SILICON-SUBSTITUTED A1P04-5 MOLECULAR

SIEVES

K.J. CHAO and L.J. LEU

Department o f Chemistry, Tsinghua U n i v e r s i t y , Hsinchu, Taiwan

ABSTRACT
The i n c o r p o r a t i o n o f S i i n t o AlP04-5 framework m o d i f i e s t h e a c i d i t y and
c a t a l y t i c p r o p e r t i e s o f t h e h o s t w i t h o u t d i s r u p t i n g i t s microporous s t r u c t u r e .
Bransted a c i d s i t e s w i t h medium s t r e n g t h were generated b y S i s u b s t i t u t i o n ,
w h i l e o n l y v e r y weak a c i d i t y was found on t h e o r i g i n a l A1P04-5. B o t h A1P04-5
and SAPO-5 were found t o be a c t i v e i n n o n - o x i d a t i v e dehydrogenation o f
ethylbenzene t o s t y r e n e ; t h e a c t i v i t y o f e t h y l benzene c r a c k i n g t o benzene
depends on t h e S i c o n t e n t o r B r d n s t e d a c i d i t y on SAPO-5.

INTRODUCTION
C r y s t a l l i n e aluminophosphate m o l e c u l a r s i e v e s c o n s i s t o f a l t e r n a t i n g alumina
and phosphate t e t r a h e d r a and so a r e e l e c t r o v a l e n t l y n e u t r a l w i t h no e x t r a -
framework c a t i o n s and no ion-exchange c a p a c i t y ( r e f . 1,2). The phosphorus atom
(E.N.=2.2) o f h i g h e l e c t r o n e g a t i v i t y may produce a s h i f t i n e l e c t r o n d e n s i t y
away from t h e aluminum atom (E.N.=1.6) r e s u l t i n g i n a d i p o l a r nature o f t h e
Alp04 s u r f a c e . U s i n g t h e s e m i e m p i r i c a l CND0/2 quantum c a l c u l a t i o n on a c l u s t e r
model o f Alp04 , M o f f a t e t a l . ( r e f . 3) found t h a t t h e oxygen atoms possess
n e g a t i v e charge and f u n c t i o n as Lewis base s i t e s , phosphorus atoms w i t h h i g h e r
p o s i t i v e charge compared w i t h aluminum atoms a c t as Lewis a c i d s i t e s ; and
Brdnsted a c i d s i t e s a r e t h e p r o t o n s a t t a c h e d t o t e r m i n a l oxygen atoms on t h e
s u r f a c e o f aluminophosphate. Therefore, t h e r e a r e v e r y few B r d n s t e d a c i d s i t e s
and t h e m a j o r i t y o f a c i d s i t e s i s Lewis a c i d s i t e s i n Alp04 m o l e c u l a r s i e v e s .
The s p e c t r o s c o p i c r e s u l t s ( r e f . 4) show t h a t t h e a c i d s i t e s a r e m o d e r a t e l y
s t r o n g and t h e base s i t e s a r e v e r y weak on A1P04-5 m o l e c u l a r s i e v e which has an
u n i d i m e n s i o n a l p o r e system c o n s i s t i n g o f c y l i n d r i c a l channels bounded by 12
membered r i n g s ( r e f . 5). The i n c o r p o r a t i o n o f s i l i c o n i n t o t h e aluminophosphate
framework leads t o s i l i c o a l u m i n o D h o s p h a t e m o l e c u l a r s i e v e s (SAPO) ( r e f . 6 ) . The
s i l i c o n atoms can m a i n l y s u b s t i t u t e i n t o t h e aluminophosphate framework v i a ( 1 )
s i l i c o n s u b s t i t u t i o n f o r phosphorus, ( 2 ) s u b s t i t u t i o n o f two s i l i c o n s f o r one
aluminum p l u s one phosphorus. The s i l i c o n s u b s t i t u t i o n f o r phosphorus r e s u l t s
i n a n e g a t i v e l y charged framework which can be coupled w i t h exchangeable
20

c a t i o n s and Brdnsted a c i d s i t e s . The amount o f Brdnsted a c i d s i t e s can be

increased by s i l i c o n s u b s t i t u t i o n f o r phosphorus i n t h e aluminophosphate
framework.
I n t h i s paper, we r e p o r t t h a t t h e i n c o r p o r a t i o n o f S i i n t o t h e n e u t r a l
A1P04-5 framework m o d i f i e s i t s p h y s i c a l and c a t a l y t i c p r o p e r t i e s w i t h o u t
disrupting its microporous s t r u c t u r e . The framework s i t t i n g o f S i was
confirmed by powder XRD, 2 9 S i MASNMR and EPMA ( e l e c t r o n microprobe a n a l y s i s ) .
The temperature programmed d e s o r p t i o n (TPD) o f ammonia from ammonia adsorbed
o r ammonium exchanged samples was used f o r c h a r a c t e r i z i n g t h e a c i d i t y and i o n -
exchange c a p a c i t y o f SAPO-5 and AlP04-5. The few Brfinsted a c i d s i t e s on AlP04-5
were found t o be a c t i v e i n xylene i s o m e r i z a t i o n and cumene c r a c k i n g ( r e f s . 7 - 9 ) .
L i t t l e a t t e n t i o n has been p a i d t o t h e importance o f b a s i c s i t e s on phosphates.
As a c a t a l y s t having s u i t a b l e acid-base p a i r s i t e s sometimes shows pronounced
a c t i v i t y even i f i t s a c i d o r base s t r e n g t h i s v e r y weak i n t h e form o f simple
a c i d o r base. I n t h i s work, t h e c a t a l y t i c a c t i v i t i e s o f A1P04-5 and SAPO-5
were t e s t e d on ethylbenzene conversion. Ethylbenzene was found t o be converted
t o benzene by a c i d i c c r a c k i n g on Brfinsted a c i d s i t e s and t o s t y r e n e by non-
o x i d a t i v e dehydrogenation on dual Lewis acid-base s i t e s .

EXPERIMENT
PreDaration and C h a r a c t e r i z a t i o n
The precusors o f AlP04-5 based molecular s i e v e s (AlP04-5, SAPO-5, BAPO-5
and MgAPO-5) were prepared by r e a c t i n g orthophosphoric a c i d (Verck) ,
pseudoboehmite (Verse1 250)/ and c a t i o n source o f Ludox HS-40 (Du P o n t ) , HgBOg,
o r MgC12 (Merck) w i t h t r i p r o p y l a m i n e i n t h e hydrothermal c o n d i t i o n o u t l i n e d by
Wilson e t a l . ( r e f . 1 ) . The c r y s t a l l i n e phase was i d e n t i f i e d by XRD on a
SCINTAG PADV powder d i f f r a c t o m e t e r and examined by scanning e l e c t r o n microscopy
w i t h EPMA on a Jeol Superprobe 733 i n s t r u m e n t and b y MASNMR spectroscopy on a
Bruker MSL-200 instrument. The elemental compositions o f products were a l s o
analyzed by I C P ( i n d u c t i v e l y - c o u p l e d plasma atomic emission spectrometry).
M o d i f i c a t i o n o f A1P04-5 and SAPO-5 samples, which had been c a l c i n e d a t 5OO0C,
was made by impregnation w i t h aqueous s o l u t i o n o f 2-5 w t % Mg(CHgC00)2 or F.3803
and MgC12 .
The NH4 form o f t h e molecular sieves was obtained by five-times-repeated
ion-exchange o f t h e s y n t h e t i c samples w i t h 1N NH4C1 s o l u t i o n ; t h e samples were
p r e t r e a t e d i n d r y n i t r o g e n and a i r f l o w a t 50OoC. A f t e r c a l c i n a t i o n a t 5OO0C,
samples o f A1P04-5 and SAPO-5 were a l s o cooled t o room temperature i n f l o w
n i t r o g e n and t r e a t e d w i t h ammonia f l o w a t 100 o r 200OC. Excess ammonia t h e n was
swept o u t from t h e sample a t 100 o r 2DD°C by f l o w i n g d r y N2. The a c i d i t y and
c a t i o n exchange c a p a c i t y o f molecular s i e v e products were determined by TPD o f
 21

o f ammonia from NH4SAPO-5 o r NHqMgAPO-5 and ammonia adsorbed AlP04-5 o r SAPO-5.

The evolved ammonia was trapped i n a s o l u t i o n o f b o r i c a c i d and t i t r a t e d b y
s u l f a m i c a c i d ( r e f . 1 0 ) . A h e a t i n g r a t e o f 5oC min-1 and a sweep gas f l o w r a t e
o f 30 cm3min-1 were used. The number o f m i l l i e q u i v a l e n t o f ammonia evolved p e r
gram sample was c a l c u l a t e d from t h e volume o f t i t r a n t used p e r two minut es vs.
temperature o r f o r t h e whole range o f d e s o r p t i o n temperature f rom 100 t o 50OoC.

C a t a l y t i c R eac t io n
The c a t a l y t i c a c t i v i t i e s on ethylbenzene conversion were determined i n a
fixe d -b ed m i c r o r e a c t o r system. A sample o f 0.25 g c a t a l y s t and 1.0 g q u a r t z
powder was sandwiched w i t h q u a r t z wool i n a s t a i n l e s s s t e e l tube o f 0.7 cm i n n e r
diamet e r. A l l experiments were performed a t atmospheric pressure. P r i o r t o
t e s t i n g , each sample was heated f r o m room temperature t o 6OO0C (5'C/min) and
c a l c i n e d a t 6OO0C f o r 2h i n a n a i r stream, purged by a h e l i u m stream f o r 30 m i n
and t h en c o oled t o t h e r e a c t i o n temperature. Ethylbenzene was f e d v i a a h e l i u m
stream which was s a t u r a t e d w i t h ethylbenzene vapor by passage t hrough a b u b b l e r .
Reactor f e ed stream and e x i s t stream were analyzed b y FID gas chromatography. A
5% SP-1200/1.75% Bentone on 100/120 S u p e l c o p o r t column was used f o r analyses.
As t h e vapor p re s s u r e o f t o l u e n e i s h i g h e r t h an t h a t o f ethylbenzene, t h e
c o n t e n t o f t o luene i m p u r i t y was found t o be i n creased t o 2.5 mole% o f t h e f eed.

RESULTS AND D I S C U S S I O N
A1 1 t he c r y s t a l 1 i n e p r o d u c t s have t h e s i m i l a r XRO p a t t e r n and framework
s t r u c t u r e as AlP04-5 ( r e f . 5 ) . The amount o f s i l i c o n i n c o r p o r a t i o n i n SAPO-5
i s low, as shown i n t h e c o m p o s i t i o n o f Al:P:Si=1:1:0.04-0.07 by EPMA and I C P .
The s i m i l a r S i c o n t e n t was found i n b o t h c r y s t a l and b u l k SAPO-5 samples. The
absence o f a octahedra 27Al MASNMR s i g n a l t o -0 ppm and t h e presence o f o n l y
one 31P MASNMR s i g n a l a t -31 ppm show t h a t t h e r e i s no amorphous m a t e r i a l
p r e s e n t i n t h e s y n t h e s i z e d SAPO-5 samples. Two s i l i c a species generat ed i n
SAPO-5 have been i d e n t i f i e d by *9Si MASNMR as shown i n F i g . 1. The s i g n a l s
w i t h chemical s h i f t s o f -92 and -111 ppm a r e p r o b a b l y c h a r a c t e r i s t i c of S i 4 '
s u b s t i t u t i o n f o r P5+ and t h e c l u s t e r o f s i l i c a i n SAPO-5 ( r e f . 11). The d i s s o -
c i a t i o n o f ammonia f r o m ammonium exchanged m o l e c u l a r sieves has been e s t a b l i s h e d
as t h e mechanism f o r g e n e r a t i n g Bransted a c i d s i t e s . The s t r e n g t h o f t h e s i t e s
generated i s r e f l e c t e d on t h e ammonia decomposition temperature. The amount ( i n
m i l l i e q u i v a l e n t ) and t h e temperature o f ammonia evolved from NH4SAPO-5 a r e i n
agreement w i t h t h a t from NH3 adsorbed on SAPO-5 a t 200°C as shown i n F i g . 2a
and Table 1. The a c i d values o f NH4' f o r m o f SAPO-5 a r e 0.7 and 0.5 f r a c t i o n s
o f t h e t o t a l s i l i c o n c o n t e n t s i n SAPO-5(A) and SAPO(6) r e s p e c t i v e l y , i n which
t h e S i c ont e nt s a r e 0.7 w t % of SAPO-5(A) and 1.2 w t % o f SAPO(6) r e s p e c t i v e l y .
22

T h i s i n d i c a t e s t h a t t h e r e l a t i v e c o n t r i b u t i o n o f S i s u b s t i t u t i n g P decreased
w i t h i n c r e a s i n g S i c o n t e n t i n samples.
AlP04-5 based m o l e c u l a r s i e v e s were a l s o s y n t h e s i z e d i n t h e presence o f
H3BO3 o r MgC12. The p r o d u c t s c o n t a i n e d ~ 0 . 1w t % o f B b y I C P o r -1.0 w t % o f
Hg by I C P and EPMA and were termed BAPO-5 o r MgAPO-5. The a n a l y t i c a l r e s u l t s
s u p p o r t t h e o c c u r r e n c e o f a r e a s o n a b l e a d d i t i o n o f B o r Mg t o A1P04-5
c o m p o s i t i o n . The TPD p r o f i l e s o f NH3 on AlP04-5, SAPO-5, BAPO-5 and MgAPO-5
a r e g i v e n i n F i g . 2. The AlP04-5 and BAPO-5 c o n t a i n v e r y few s t r o n g a c i d
s i t e s , and t h e m a j o r i t y o f s i t e s i s weak. There e x i s t s a abroad s i t e
d i s t r i b u t i o n on SAPO-5 which c o n t a i n s weak a c i d s i t e s as A1P04-5 (Td=200°C)
and s t r o n g B r d n s t e d a c i d s i t e s (Td=300°C). The s t r e n g t h o f t h e s e a c i d s i t e s
on AlP04-5 and SAPO-5 m o l e c u l a r s i e v e s i s weaker t h a n t h a t on z e o l i t e ZSM-5
(Td=400°C) ( r e f . 10). S u b s t i t u t i o n o f boron i n t o aluminophosphate l a t t i c e does
n o t appear t o p r o v i d e s t r o n g a c i d s i t e s , w h i l e t h e magnesium s u b s t i t u t i o n f o r
aluminum r e s u l t s i n a a n i o n i c framework and s m a l l member o f s t r o n g B r e n s t e d
a c i d s i t e s (Td=4J0°C). B u t extraneous o x i d e s and h y d r o x i d e s i n g e n e r a l do n o t
enhance B r d n s t e d a c i d i t y . A f t e r h e a t t r e a t m e n t a t 7OO0C, MgAPO-5 showed
p a r t i a l s t r u c t u r a l d e g r a d a t i o n as d e t e c t e d b y X-ray powder d i f f r a c t i o n . The
thermal s t a b i l i t y o f MgAPO-5 i s t h e r e f o r e l e s s t h a n t h a t o f A1PO4-5 and
SAPO-5 whose decomposition t e m p e r a t u r e >lOOO°C.

- 60 -100 -140
ppm vs. TMS

F i g . 1 . 29Si MASNMR spectrum o f SAPO-5(B)

 23

10

0
C

2.5 I
,---\

0 200 400 600

Temperature ("C)

F i g . 2. TPD o f NH3 f r o m m o l e c u l a r s i e v e s ( a ) SAPO-5, ammonia i n i t i a l l y sorbed

a t 100°C (-.-) o r 2OO0C (----) and NH4SAPO-5 (-); (b) A1P04-5, ammonia
i n i t i a l l y sorbed a t 100°C (-) or 2OO0C (----); ( c ) NH4BAPO-5 (---) and
NHqMgAPO-5 (-) (The TPD p r o f i l e s a r e o b t a i n e d by a l e a s t - s q u a r e s f i t t i n g o f
t i t r a t i o n data.)
24

TABLE 1
Composition and a c i d i t y o f m o l e c u l a r s i e v e s

SAPO-5( A) SAPO-5( B) A1P04-5

S u r f a c e S i :A1 :P b y EPMA 0.04:l.l:l.O 0.07:l.O:l.O -0:l.O:l.O

B u l k SI% ( w t ) b I C P - 1.2 0.1
S u r f a c e S i % (wtf b y EPMA 0.7 1.2 -
A c i d amount (m mole/g) 0.17 0.22 0.03
by TPD o f NH3 adsorbed
sample ( ZOOOC)
A c i d amount (T mole/g) - 0.22
by TPD o f NH4 exchanged
sample

Ethylbenzene c o n v e r s i o n
The c a t a l y t i c dehydrogenation o f e t h y l b e n z e n e i s o f i n d u s t r i a l i m p o r t a n c e
i n t h e manufacture o f s t y r e n e ( r e f s . 1 2 - 1 8 ) . I n o x i d a t i v e dehydrogenation,
an acid-promoted mechanism was proposed b y s t u d y i n g t h e r e a c t i o n on
Na.Si02.Al203 ( r e f . 12) and SnO.P205 ( r e f . 13) c a t a l y s t s . The c a t a l y t i c
a c t i v i t y o f o x i d e s on t h e n o n o x i d a t i v e d e h y d r o g e n a t i o n was c o n s i d e r e d t o be
r e l a t e d t o e i t h e r t h e semiconductor p r o p e r t i e s o f m e t a l i o n s i n m e t a l o x i d e s
such as C r i n Cr203.Al203 ( r e f . 14) and Fe i n FeO ( r e f . 151, o r t h e a c i d -
base p a i r s i t e s on t h e mixed o x i d e s as Ti02eZr02 ( r e f . 1 6 ) .
R e s u l t s from a c o n t i n u o u s - f l o w f i x e d - b e d m i c r o r e a c t o r a r e g i v e n i n Table 2 .
N o n - o x i d a t i v e dehydrogenation t o s t y r e n e and d e a l k y l a t i o n t o benzene were t h e
main r e a c t i o n s i n t h e c o n v e r s i o n o f e t h y l b e n z e n e on A1P04-5 based m o l e c u l a r
s i e v e s a t 5OO0C, w h i l e t h e amorphous aluminophosphates e x h i b i t e d v e r y low
a c t i v i t y on b o t h r e a c t i o n s . W i t h styrene:benzene mole r a t i o > 5 , AlP04-5 i s
more a c t i v e i n n o n - o x i d a t i v e dehydrogenation t h a n i n d e a l k y l a t i o n . Due t o t h e
presence o f B r d n s t e d a c i d s i t e s , t h e y i e l d o f s t y r e n e was suppressed and t h e
p r o d u c t i o n o f benzene was enhanced on SAPO-5. However, e t h y l b e n z e n e was f o u n d
t o have no s i g n i f i c a n t dehydrogenation on a l u m i n o s i l i c a t e m o l e c u l a r s i e v e
ZSM-5; d i s p r o p o r t i o n a t i o n o r d e a l k y l a t i o n p r o d u c t s o f d i e t h y l b e n z e n e , x y l e n e ,
t o l u e n e and benzene were o b t a i n e d on t h i s a c i d c a t a l y s t a t 320-500°C.
A1P04-5 and SAPO-5 c a t a l y s t s were a l s o m o d i f i e d b y i m p r e g n a t i o n w i t h aqueous
s o l u t i o n o f Mg(CH3C00)2~rH3B03 and MgC12 r e s p e c t i v e l y . The i n f o r m a t i o n
o b t a i n e d i n MgO and B2O3 m o d i f i c a t i o n concerns t h e r o l e s o f t h e a c i d and base
c e n t e r s o f c a t a l y s t s i n ethylbenzene c o n v e r s i o n . Table 2 shows t h a t t h e t o t a l
c o n v e r s i o n of e t h y l b e v e n e and t h e y i e l d o f s t y r e n e decrease w i t h t h e a d d i t i o n
o f HgBOg and change s l i g h t l y b y t r e a t i n g AlP04-5 w i t h Mg(CH$00)2. This
 25

i n d i c a t e s t h a t t h e b a s i c i t y of t h e c a t a l y s t may p l a y an i m p o r t a n t r o l e i n
dehydrogenation r e a c t i o n . The i n c o r p o r a t i o n o f boron i n t o A1P04-5 leads t o
BAPO-5 which has a c i d i t y and a c t i v i t y s i m i l a r t o A1P04-5. The s u b s t i t u t i o n
magnesium f o r a aluminum i n MgAPO-5 p r o v i d e s s t r o n g Brdnsted a c i d s i t e s and
gives h i g h preference f o r benzene p r o d u c t i o n on ethylbenzene conversion. When
the Brdnsted protons a r e p a r t i a l l y exchanged by magnesium c a t i o n s , t h e a c t i v i t y
o f d e a l k y l a t i o n i s reduced and t h e s e l e c t i v i t y o f dehydrogenation i s s l i g h t l y
increased on SAPO-5 (5,Mg). The i n c o r p o r a t i o n o f S i and Mg i n aluminophosphate
framework leads t o an increase i n t h e t o t a l number o f Brdnsted a c i d s i t e s ,
w h i l e Lewis a c i d and base s i t e s , which a r e most l i k e l y l o c a t e d on P and 0 atoms
r e s p e c t i v e l y , a r e o n l y s l i g h t l y changed. As t h e y i e l d o f s t y r e n e was n o t
increased by i n c o r p o r a t i n g S i o r Mg i n A1P04-5, t h e Brbnsted a c i d s i t e s seem
n o t t o p a r t i c i p a t e i n dehydrogenation r e a c t i o n .

TABLE 2
A c t i v i t i e s o f molecular sieves i n ethylbenzene conversion.a

Ethyl- Product d i s t r i b u t i o n ( % b y mole)

Catalystb benzene E thy1 - S t rene
conv. % Benzene Toluene benzene Styrene &
A1 Po4-5 5.8 1 .o 2.0 91.7 5.3 5.4
A1P04-5 (5,Mg) 6.1 0.5 2.1 91.4 6.0 11
A1P04-5 (2,B) 3.5 0.9 1.9 94.0 3.2 3.5
A1P04-5 (5,B) 0.3 0.3 2.5 97.2 0.1 0.4
SAPO-5 ( A ) 7.5 2.6 2.4 90.5 4.5 1.7
SAPO-5 12.9 10.8 1.9 84.6 2.6 0.3
SAP@-5 (5,Mg) 6.3 3.1 1.6 91.2 4.0 1.3
BAPO-5 7.3 1.7 1.9 90.2 6.2 3.7
MgAPO-5 26.2 23.1 2.3 71.7 2.9 0.1
ZSM-5 (5,Mg) 91.5 94.7 2.2 1.6 (1 . 5 I e -
ZSM-5 (5,Mg)' 31.2 22.9 4.8 66.3 (6.1)

aReaction temperature=500°C, atmospheric pressure; WHSV=O.Ol , time on

stream=lhr, feed=97.5 mole% ethylbenzene and 2.5 mole% toluene.
b w i t h 5 Wt9: Mg(CH3C00)2 and 2 o r 5 w t % H3BO-j impregnated A1P04-5 samples were
denoted as AlP04-5 (5,Mg) and AlP04-5 ( 2 , B ) o r AlP04-5 (5,B); w i t h 5 w t % MgC12
impregnated SAPO-5 and ZSM-5 were denoted as SAPO-5 (5,Mg) and ZSM-5 (5,Mg).
The Bransted a c i d values o f SAPO-5, SAPO-5 (A) and SAPO-5 (5,Mg) a r e 0.21,
0.17 and 0.15 m mole/g, r e s p e c t i v e l y .
C320OC.
dXy1 ene .
eDiethylbenzene.

The non-oxidative dehydrogenation over CrO3 c a t a l y s t i s based on t h e

chemisorption o f hydrogen on surface oxygen w i t h a cleavaqe o f t h e C-H bond
and the a l k y l group bounded t o a C r atom ( r e f . 1 4 ) . I n t h e p r e s e n t work,
26

c r y s t a l l i n e microporous A1P04-5 was found t o be a c t i v e i n ethylbenzene

dehydrogenation i n the absence o f oxygen. The r e s u l t s o f H3803 doping i n d i c a t e
t h a t t h e weak base s i t e s o f t h e c a t a l y s t may p l a y an i m p o r t a n t r o l e i n
dehydrogenation. However, t h e b a s i c i t y l o c a t e d on oxygen atoms i s n o t s t r o n g
enough, and t h e c o o p e r a t i o n w i t h a d j a c e n t a c i d i c s i t e s i s e s s e n t i a l t o c a t a l y z e
t h e r e a c t i o n . A concerted H2 e l i m i n a t i o n mechanism was proposed t o proceed on
A1P04-5 and SAPO-5. I n which, two hydrogens o f a- and B- carbons o f
ethylbenzene simultaneously a t t a c k t h e a c i d and base s i t e s o f t h e c a t a l y s t .
The average bond d i s t a n c e o f P-0 (1.52 A) i s very c l o s e t o t h e C-C bond
d i s t a n c e and s h o r t e r than t h e A1-0 (1.72 A) d i s t a n c e ( r e f . 5 ) , and t h i s may
p r o v i d e a proper environment f o r acid-base c a t a l y z e d r e a c t i o n . However, t h e
Lewis a c i d and base s i t e p a i r s a r e n o t s t r o n g as few Brdnsted a c i d s i t e s on
AlP04-5. The y i e l d o f s t y r e n e was n o t increased by r a i s i n g t h e r e a c t i o n
temperature above 5OO0C, a t t h i s temperature r e g i o n where Brdnsted a c i d
c r a c k i n g became s i g n i f i c a n t . As SAPO-5 and MgAPO-5 e x h i b i t b o t h Brdnsted a c i d
s i t e s and Lewis acid-base s i t e s , the adsorbed ethylbenzene on p r o t o n i c species
may b l o c k t h e f o r m a t i o n o f dehydrogenation i n t e r m e d i a t e s and i n t u r n reduce
the y i e l d o f styrene.

CONCLUSION
The present r e s u l t s show t h e importance o f b o t h t h e a c i d i t y and b a s i c i t y
o f AlPO4 and SAP0 molecular sieves on c a t a l y t i c r e a c t i o n s . I n t r o d u c t i o n o f
b i v a l e n t ( i .e. Mg) and t e t r a v a l e n t ( i .e. S i ) c a t i o n s i n t o t h e aluminophosphate
framework r e s u l t s i n t h e f o r m a t i o n o f Brdnsted a c i d s i t e s and enhances the
acidic catalytic a c t i v i t y .

REFERENCES
1 S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan and E.M. Flanigen, J . Am.
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H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

ON THE NATURE OF THE CATALYTIC ACTIVITY OF SAPO-5

CH.MINCHEV1, V.KANAZIREV1, V . H A V R O D I N O V A 1 , V.PENCHEV1 a n d H. LECHERT2

t l n s t i t u t e o f O r g a n i c C h e m i s t r y , S o f i a 1040 Bulgaria)
2 1 n s t i t u t e o f P h y s i c a l C h e m i s t r y , Hamburg Un v e r s i t y , 2 Hamburg 3 (FRG)

ABSTRACT
An a t t e m p t t o e s t i m a t e t h e n a t u r e o f t h e c a t a l y t i c a c t i v i t y o f SAPO-5
was made by means o f t h e " i n n e r s t a n d a r d " a p p r o a c h . SAPO-5 m a t e r i a l s
were compared w i t h model m i x t u r e s o f HY i n t r o d u c e d i n t o a n AIPO-5 m a t r i x
as w e l l as w i t h HZSM-5 and h i g h l y d e a l u m i n a t e d HY. The s e l e c t i v i t y
p a t t e r n s i n m-xylene c o n v e r s i o n s u p p o r t t h e a s s u m p t i o n o f a r e l a t i v e l y
homogeneous S i - i n c o r p o r a t i o n , The g e n e r a t e d a c t i v e c e n t e r s a r e s i t u a t e d
f a r f r o m each o t h e r as i n t h e c a s e o f t h e h i g h l y d e a l u m i n a t e d f a u J a s i t e .

I NTRODUCTI ON
The new g e n e r a t i o n o f a l u m i n o p h o s p h a t e - b a s e d m i c r o p o r o u s o x i d e s ( A I P 0 4 - n ,
SAPO-n, etc.) ( r e f . 1 ) r e v e a l s new p o s s i b i l i t i e s o f c a t a l y s i s by m o l e c u l a r
s i e v e s . The i n c o r p o r a t i o n o f S i i n t h e n o n - a c i d i c a l u m i n o - p h o s p h a t e frame-
work e l i c i t s i n many cases a s i g n i f i c a n t c a r b o n i o g e n i c c a t a l y t i c a c t i v i t y .
Recently, remarkable c a t a l y t i c a c t i v i t y o f SAPO-5 i n n - b u t a n e ( r e f . 2)
and cumene ( r e f . 3) c r a c k i n g , o - x y l e n e isomerization (ref.3), alkylation
o f t o l u e n e w i t h methanol ( r e f . 4 ) , o l i g o m e r i z a t i o n o f p r o p e n e ( r e f . 4 ) ,
c o n v e r s i o n o f decane ( r e f . 5) a n d methanol ( r e f . 6) was r e p o r t e d . The
c a t a l y t i c a c t i v i t y o f t h e aluminophosphate-type m a t e r i a l s ranges w i t h i n
a l m o s t two o r d e r s o f m a g n i t u d e a c c o r d i n g t o t h e c o m p o s i t i o n and p r e p a r a -
t i o n c o n d i t i o n s ( r e f . 2 ) . Adsorption and I R data suggest t h e e x i s t e n c e o f
a c i d i c c e n t e r s i n t h e SAPO-5 s t r u c t u r e ( r e f . 3, 5 - 7).
The n a t u r e o f t h e c a t a l y t i c a c t i v i t y o f t h e SAPO-5 m a t e r i a l s i s s t i l l
n o t f u l l y understood ( r e f . 7 ) . O b v i o u s l y , t h e mechanism o f S i i n c o r p o r a t i o n
i n t o t h e l a t t i c e i s o f g r e a t i m p o r t a n c e f o r t h e appearance o f c a t a l y t i c a l -
l y a c t i v e c e n t e r s . A t t e m p t s were made t o a p p l y some c u r r e n t c o n c e p t s i n t h e
z e o l i t e c a t a l y s i s t o t h e s e new o b j e c t s ( r e f . 7 ) . The g e n e r a t i o n o f non-com-
p e n s a t e d charges i n t h e a l u m i n o - p h o s p h a t e framework a n d t h e p o s s i b l e c o n t r o l
o f t h i s p r o c e s s a r e t h e most i m p o r t a n t d i s c u s s i o n t o p i c s i n t h e r e c e n t l i t e -
r a t u r e ( r e f . 5-8).
I n t h e p r e s e n t work, a n " i n n e r s t a n d a r d " a p p r o a c h has been a p p l i e d f o r
30

e s t i m a t i o n o f t h e p r o p e r t i e s o f SAPO-5 as a c i d c a t a l y s t . The HY z e o l i t e ,
m e c h a n i c a l l y d i s p e r s e d i n a m a t r i x o f AIP04-5, was used as an i n n e r
s t a n d a r d . The physico-chemical and c a t a l y t i c p r o p e r t i e s o f t h e so p r e p a r e d
model samples were compared t o those o f SAPO-5, as w e l l as t o ZSH-5 and
dealuminated HY w i t h low d e n s l t y o f t h e a c i d c e n t e r s .

EXPERIMENT
Samples and c h a r a c t e r i z a t i o n
SAPO-5 and A1P04-5 were s y n t h e s i z e d a c c o r d i n g t o ( r e f . 9,lO) by
u s i n g Pr3N (Herck) and a g e l whose c o m p o s i t i o n i s p r e s e n t e d i n T a b l e 1.

TABLE 1
Composition o f t h e r e a c t i o n m i x t u r e , mol

Sample Type Pr3N Si02 A1203 p2°5 H20

AP AIPO-5 1.5 - 1 .O 1 .o 40
SPI SAPO-5 2.0 0.4 1 .o 1 .o 50
SPII SAPO-5 2.0 0.9 1 .o 1 .o 50

Pseudoboehmite f r o m Condea, 85% o r t h o p h o s p h o r i c a c i d and amorphous s i l i c a

(Herck) were used as sources f o r Al2O3, P2O5 and SiO2 r e s p e c t i v e l y . The
c r y s t a l l i z a t i o n was c a r r i e d o u t under 423-453K i n T e f l o n tubes i n an a u t o -
c l a v e f o r 6 t o 24 hours. The f i n a l thermal t r e a t m e n t was performed i n a i r
a t 823-873K f o r 6 hours i n a m u f f l e oven.
The samples used f o r comparison were: HY(Si02/A1203-5.1) and HZSM-5
(Si02/A1203 -200) o b t a i n e d by t h e u s u a l d e c o m p o s i t i o n o f t h e NHq+-form
(ref.lO,as w e l l as a dealuminated HY, d e s i g n a t e d as US-Ex (Si02/A1203=200)
prepared a c c o r d i n g t o ( r e f . 1 2 ) . The model samples 0.95AP-0.05HY and
0.9AP-O.1HY were p r e p a r e d by thorough m i x i n g o f t h e A1P04-5 m a t e r i a l w i t h
5 and 10 w t % o f t h e inner s t a n d a r d HY, The p h i s i c o - c h e m i c a l characteri-
z a t i o n o f t h e samples was made by t h e f o l l o w i n g t e c h n i q u e s : X-ray powder
diffraction,CuKkby a DRON a p p a r a t u s , I R spectroscopy in the region o f
1400-400 cm-l u s i n g KBr d i s k s , by a Specord 75 I R s p e c t r o p h o t o m e t e r ,
e l e c t r o n microscopy by JSH-200 and simultaneous t h e r m a l a n a l y s i s
(TG-DTA- DTG) up t o 1 2 7 3 ~w~i t h 100/min i n a i r i n MOM a p p a r a t u s .
A d s o r p t i o n and c a t a l y t i c measurements
The adsorption-thermodesorption measurements were c a r r i e d o u t i n f l o w a t
e l e v a t e d temperature. The a d s o r p t i o n o f NH3(30 kPa, i n a He s t r e a m a t 423K
and TPD up t o 87310 was measured a 8 a l r e a d y descr i b e d ( r e f . 13).
The a d s o r p t i o n and c a t a l y t i c experiments w i t h m-xylene were p e r f o r m e d i n
one and t h e same f l o w - t y p e a p p a r a t u s c o u p l e d "on l i n e n w i t h a GC.
The c a t a l y s t ' s w e i g h t was 0.49. The m-xylene was i n t r o d u c e d b y means
 31

o f a s a t u r a t o r . H i g h - p u r i t y N2 was used as a c a r r i e r gas.

The p r e l i m i n a r y t r e a t m e n t o f t h e c a t a l y s t s was c a r r i e d o u t f o r 5 h o u r s
i n n i t r o g e n a t 773K, f o l l o w e d b y e s t a b l i s h i n g t h e temperature a t 453K and
then i n t r o d u c i n g m-xylene from t h e s a t u r a t o r . The a d s o r p t i o n was t r a c e d
by t h e f r o n t a l method and chromatographical m o n i t o r i n g o f t h e m-xylene con-
centration a t the reactor outlet. The c a t a l y t i c experiments f o r t h e m-xylene
c o n v e r s i o n were performed immediately a f t e r t h e a d s o r p t i o n as f o l l o w s :
r a i s i n g up t h e temperature t o 673K; p a s s i n g t h e r e a g e n t t h r o u g h t h e c a t a l y s t
u n t i l c o n s t a n t a c t i v i t y was reached and v a r y i n g t h e c o n t a c t t i m e i n t h e
range 0 . 3 - 42h by changing t h e f l o w r a t e o f t h e c a r r i e r gas. The a n a l y -
s i s o f t h e r e a g e n t m i x t u r e and t h e r e a c t o r e f f l u e n t was accomplished by GC.
The t o l u e n e d i s p r o p o r t i o n a t i o n was c a r r i e d o u t i n a c o n t i n u o u s f l o w reac-
tor (ref. 14) a t 723 and 753K. The WHSV was l . I h - l , Ptoluene=27.5kPa and t h e
Hg/toluene molar ratio.2.5.

RESULTS
Physico-chemical c h a r a c t e r i z a t i o n o f t h e i n i t i a l and model samples
I n accordance w i t h t h e l i t e r a t u r e , t h e r e s u l t s Obtained show t h a t t h e
phase p u r i t y o f AIP04-5
( r e f . 1,6) and SAPO-5 ( r e f . 5 ) is
s t r o n g l y dependent on t h e c o n d i -
‘1 t i o n s o f p r e p a r a t i o n . Combined
thermal a n a l y s i s proved t o be Very
u s e f u l i n p u r i t y c o n t r o l ( r e f . 15),
t o g e t h e r w i t h X-ray and I R s p e c t r o -
scopy. I n F i g . 1 t h e DTG curves o f
*‘pure** AIPO-5 and SAPO-5, as w e l l
as those o f samples w i t h i n c r e a s i n g
amounts o f phase i m p u r i t y ( c u r v e s
b-d) a r e presented. nlmpuren samp-
les were p r e p a r e d u s i n g t h e same
I 373. . 573. . .773 . .973 . .1173 I s t a r t i n g g e l by d i f f e r e n t d u r a t i o n s
TEMPERATUK,K
o f c r y s t a l l i z a t i o n ( c u r v e s b-c) or
b y a d i f f e r e n t way o f homogenizing
Fig.l. DTG o f as-synthesized: a,AIPO-5; o f t h e r e a c t i o n mixture (curve d ) .
b,c,d, AlPO-5 w i t h i m p u r i t y ; , e, SAPO-5. They were s u b j e c t e d t o thermal ana-
l y s i s a f t e r d r y i n g a t 333K and r e -
h y d r a t a t i o n . The minimum o f t h e DTG curves a t 453K a r e an i n d i c a t i o n o f t h e
presence o f an u n i d e n t i f i e d s e p a r a t e phase which i s n o t s t a b l e a t 823K.
I t i s t o be p o i n t e d o u t t h a t X-ray and I R spectroscopy, which a r e t h e
32

usual c o n t r o l techniques, are ineffective for establishing i m p u r i t y con-

c e n t r a t i o n s such as t h a t p r e s e n t i n t h e sample c o r r e s p o n d i n g t o c u r v e b,
Fig.l.Taking i n t o c o n s i d e r a t i o n t h a t t h e p r e p a r a t i o n o f monophase a l u m i n i u m
o r t h o p h o s p h a t e s i s q u i t e d i f f i c u l t a n d c a n be a c h i e v e d by a v e r y p r e c i s e
m a i n t e n a n c e o f t h e r e s p e c t i v e optimum c o n d i t i o n s f o r each p r o d u c t ( r e f . 161,
we recommend a d d i t i o n a l c o n t r o l by t h e r m a l a n a l y s i s ( r e f . 15).
The p u r i t y o f samples c o n t a i n i n g h i g h e r amounts o f u n d e s i r e d p r o d u c t
(Fig.l, c u r v e s c,d) may be c h e c k e d by I R s p e c t r o s c o p y ( F i g . 2 ) . The in-
crease o f t h e i m p u r i t y y i e l d can
be c l e a r l y i n d e n t i f i e d i n t h e
r e g i o n 950-400 a n d 1200-1050 cm-l.
The d i f f e r e n c e between t h e I R s p e c t -
r u m o f t h e p u r e AIP04-5 a n d SAPO-5
i n t h i s range i s n e g l i g i b l e .
The complex p h y s i c o - c h e m i c a l
c h a r a c t e r i z a t i o n showed t h a t p r a c t i -
c a l l y p h a s e - p u r e AIPO-5 a n d SAPO-5
w e r e s y n t h e s i z e d , whose d i f f r a c t i o n
p a t t e r n s a r e i n v e r y good agreement
w i t h t h e l i t e r a t u r e data ( r e f . 9,lO).
The s c a n n i n g e l e c t r o n m i c r o g r a p h s
c o n f i r m t h e good c r y s t a l l i n i t y o f
t h e m a t e r i a l s used i n t h e a d s o r p t i o n
and c a t a l y t i c experiments. The c r y s -
t a s have a h e x a g o n a l c r o s s - s e c t i o n

1200 800 1 O f a b o u t 10-22y.m.

W A V E N U ~ R cm-1
.
The same methods w e r e a p p l i e d
Fig.2. I R spectrum o f as-synthesized: in he c o m p a r a t i v e s t u d y o f t h e mo-
a, AIPO-5; c,d, AIPO-5 w i t h i m p u r i t y ; de I samples 0 . 9 5 AP-0.05HY and
e, SAPO-5; 0 . 9 AP-O.1HY. The X-ray a n d I R spec-
t r o s c o p y d a t a show t h a t c l e a r i n d i c a -
t i o n s f o r t h e presence o f a z e o l i t i c
m a t e r i a l (HY i n t h i s case) c a n be d i s t n g u i s h e d when i t s c o n c e n t r a t i o n i n
t h e AIP04-5 i s about 5wt% (Fig.3) o r h gher (Fig.4) I

TPD o f NH3 a n d m - x y l e n e a d s o r p t i o n
A r e l a t i v e l y w i d e t e m p e r a t u r e r a n g e o f NH3 d e s o r p t i o n , F i g . 5 , i s character-
i s t i c f o r a l l samples. The f o l l o w i n g r e g u l a r i t i e s c a n be o b s e r v e d f r o m t h e
data presented:
-The c o n c e n t r a t i o n o f t h e c e n t e r s r e a c t i n g w i t h ammonia i s h i g h e s t i n
HY. The model m i x t u r e s 0 . 9 5 AP-0.05HY and 0 . 9 AP-O.1HY d e s o r b ammonia i n
 33

1OOo 600
Fig.3. X-ray d i f f r a c t i o n p a t t e r n WAVENUM)ER , crn"

o f c a l c i n e d AIPO-5 ( a ) , and 0 . 9 5
AIPO-5 - 0.05HY (b); t h e arrows F i g . 4 I R spectrum o f c a l c i n e d
n o t e l i n e s c h a r a c t e r i s t i c o f HY. 0 . 9 AIPO-5 - O.1HY ( a ) , 0.95
AIPO-5-0.05HY ( b ) , AIPO-5 (C).

HY(0.4 g 1-
SPll ---I

.-
HZSM-5
I-

SP I
a- SPII

F i g . 5 . TPD chromatograms o f NH3 F i g . 6 . C o n v e r s i o n o f m-xylene

HY(O.4g)-pure HY; HY(0.04g)-HY as a f u n c t i o n o f t h e m o d i -
d i l u t e d w i t h i n e r t rnater i a l . f i e d c o n t a c t time.
34

t h e same temperature range b u t i t s quant t y i s much s m a l l e r compared t o t h e

'non-di l u t e d " HY.
-SPI, 0.95 AP-0.05HY and 0 , 9 AP-O.1HY have v e r y s i m i l a r TPD c u r v e s . The
TPD maximum of' t h e above-mentioned mater a l s i s s h i f t e d t o lower temperatu-
r e s , w h i l e t h a t o f S P I I i s s h i f t e d t o h i g h e r ones,
-The TPD chromatograms o f HZSM-5 and US-Ex used f o r comparison are typi-
c a l f o r z e o l i t e s o f t h i s k i n d . They i n d i c a t e a h i g h e r r e l a t i v e c o n t r i b u t i o n
o f t h e s t r o n g a c i d c e n t e r s . T h e number o f t h e s i t e s i n t e r a c t i n g w i t h NH3 i s
v e r y low because o f t h e h i g h S i / A l o f t h e s e samples.
Comparison o f t h e q u a n t i t i e s o f NH3 desorbed ( T a b l e 2) f o r AIP04-5
and SAPO-5 shows, i n agreement w i t h ( r e f . 1,3,6 and 71, t h a t t h e former have
lower a c i d i t y . The s h i f t o f t h e maximum r a t e o f ammonia d e s o r p t i o n t o h i g h e r
temperatures f o r S P I I compared t o t h e o t h e r aluminophosphate samples i n d i -
cates a s p e c i f i c e f f e c t o f t h e increased
TABLE 2 S i c o n t e n t on t h e a c i d i t y , The d a t a f o r
Thermodesorption o f ammonia, t h e mixed samples r e v e a l t h e s i g n i f i -
adsor bed a t 420K, P~%=30kPa c a n t r o l e o f t h e aluminophosphate
m a t r i x , which o b v i o u s l y has a c o n s i d e r -
Samples mmol NH3/g a b l e number o f c e n t e r s i n t e r a c t i n g
AP 0.12 w i t h ammonia ( r e f . 17).
HY 0.96 The m-xylene a d s o r p t i o n r e s u l t s
0.95AP-0.05HY 0.14 recorded i n t h e p r e - c a t a l y t i c region
0.9AP-0. 1OHY 0.16 showed t h a t HY adsorbed 0 . 8 6 mmol/g
SP I 0.22 m-xylene, w h i l e a d s o r p t i o n values f o r
SPI I 0.24 a l l o t h e r samples amounted t o 0 . 0 3 -
HZSM-5 0.08 0 . 1 6 mmol/g. The above r e s u l t s i n d i -
US-E x 0.04 cate t h a t the differences i n the
acide centers' concentration i n the
samples under e x a m i n a t i o n m a n i f e s t themselves i n a l i k e manner w i t h
r e s p e c t t o t h e model m-xylene substance, which i s used f o r t h e c a t a l y t i c
characterization.

C a t a l y t i c studies
M-xylene c o n v e r s i o n was s t u d i e d a t 673K. The f l o w r a t e o f t h e m-xylene
and t h e w e i g h t o f t h e c a t a l y s t s were v a r i e d i n o r d e r t o o b t a i n c l o s e values
f o r t h e o v e r a l l r a t e o f c o n v e r s i o n a t d i f f e r e n t c o n t a c t t i m e s . Under t h e
e x p e r i m e n t a l c o n d i t i o n s used, b o t h i s o m e r i z a t i o n and d i s p r o p o r t i o n a t i o n o f
t h e m-xylene proceed. Table 3 r e v e a l s t h e c o n s i d e r a b l e d i f f e r e n c e s i n t h e
c a t a l y t i c a c t i v i t y o f t h e samples.Contact t i m e s d i f f e r i n g by about one o r d e r
o f magnitude a r e necessary t o o b t a i n c l o s e degrees o f c o n v e r s i o n u s i n g HY
 35

TABLE 3

Conversion o f m-xylene, T ~ 6 7 3 K

Samples Contact Total r a t e Products o f Disprop. , %

time, h o f convers ion, % i somer i z a t ion, X S= Isom. , X

APW 41.5 10.0 7.7 0.30

0.95AP- 0.3 25.6 12.1 0.95

0.05HY 0.4 28.1 13.9 1.01
0.5 37.7 17.3 1-10

0.9AP- 0.6 34.4 19.5 0.72

O.1OHY 0.7 37.5 20.8 0.80
1. O 48.5 23.6 0.97

0.3 23.9 11.8 0.96

0.02gHY 0.4 28.1 13.9 1.01
1 .o 44.3 19.3 1.32

0.40gHY 5.9 63.7 29.5 1.13

SPI Iw 5.9 37.2 30.6 0.21

7.0 43.9 34.7 0.26

SP I w 5.9 42.4 37.3 0.14

10.4 24.6 20.2 0.20

US-Ex 19.8 40.2 29.4 0.36
41.5 48.0 30.2 0.59

HZSM-5 5.9 37.7 37.4 0.01

10.4 43.2 41.9 0.03

wThese samples showed a tendency towards d e a c t i v a t i o n

on one s i d e , and S P I , S P I I and US-Ex on t h e o t h e r . T h i s i s i n good agreement

w i t h t h e above-established differences i n the adsorption center density o f
t h e samples. The AP sample e x h i b i t s v e r y low a c t i v i t y . T h e degree o f conver-
s i o n o b t a i n e d even f o r 42h c o n t a c t t i m e i s o n l y 1O.OX.The a c t i v i t y o f t h e
m i x t u r e s 0 . 9 5 AP-0.05HY and 0 . 9 AP-O.1HY i s m a i n l y due t o t h e HY component.
B y v a r y i n g t h e c o n t a c t times necessary t o o b t a i n c l o s e degrees o f conver-
s i o n , t h e f o l l o w i n g range o f a c t i v i t y i s observed:
Alp04 < US-Ex < HZSM-5 6 SAPO-5 < < HY
Most e s s e n t i a l i n f o r m a t i o n about t h e p r o p e r t i e s o f t h e i n v e s t i g a t e d sam-
p l e s can be d e r i v e d f r o m t h e s e l e c t i v i t y d a t a . On t h e b a s i s o f t h e r a t i o
between t h e d i s p r o p o r t i o n a t i o n and i s o m e r i t a t i o n p r o d u c t s , S, one can con-
clude t h a t :
- As expected, d i s p r o p o r t i o n a t i o n proceeds t o a very low degree on ZSM-5
- HY e x h i b i t s t h o h i g h e s t s e l e c t i v i t y f o r d i s p r o p o r t i o n a t i o n . T h e s i m i l a r
performances o f 0.95 AP-O.05HY and 0 . 9 AP-O.1HY r e v e a l t h e predominant
r o l e o f t h e HY component i n t h e m i x t u r e s .
- d i s p r o p o r t i o n a t i o n proceeds t o a much lower degree on SAPO-5 and US-Ex
samples, compared t o HY.
The t h u s e s t a b l i s h e d d i f f e r e n c e s i n t h e d i s p r o p o r t i o n a t i o n a c t i v i t y o f
t h e samples under c o n s i d e r a t i o n were c o n f i r m e d i n t h e t o l u e n e c o n v e r s i o n .
The observed degrees o f t o l u e n e d i s p r o p o r t i o n a t i o n on HZSM-5 and S P I a t
753K a r e 9.5 and 24% r e s p e c t i v e l y . For HY, even a t a 3OoC lower r e a c -
t i o n temperature, t h i s q u a n t i t y was found t o be 49%.

DISCUSSION
One o f t h e i m p o r t a n t q u e s t i o n s i n t h e s t u d y o f t h e new s i l i c o - a l u m i n o -
phosphate molecular s i e v e s today concerns t h e i r a c i d c e n t e r c o n c e n t r a t i o n s .
I n p r i n c i p l e , d e v i a t i o n from the e l e c t r o n e u t r a l i t y o f t h e c r y s t a l l a t t i c e
and t h e g e n e r a t i o n o f a c t i v e a c i d c e n t e r s may be expected when a d e f i n i t e
mechanism o f S i i n c o r p o r a t i o n ( S i f o r P) t a k e s p l a c e . However, t h e prepara-
t i o n o f s u f f i c i e n t l y "pure" SAPO as w e l l as i t s a c c u r a t e c h a r a c t e r i z a t i o n i s
a d i f f i c u l t and s t i l l i n a d e q u a t e l y a s c e r t a i n e d problem. D i s t u r b a n c e o f t h e
balance o f t h e T-elements i n t h e s t r u c t u r e may be accompanied by f o r m a t i o n
o f Si-0-Si " i s l a n d s " o r s i l i c a patches ( r e f . 5,7) and appearance o f e x t r a -
neous A 1 or P ( r e f . 7 ) . The p o s s i b l e f o r m a t i o n o f p o c k e t s w i t h a z e o l i t e
c h a r a c t e r (no phosphorus) has a l s o been c o n s i d e r e d ( r e f . 1 8 ) . I n the present
investigation, t h e use o f HY as an inner s t a n d a r d shows t h a t t h e presence o f
a few p e r c e n t s o f " f o r e i g n " phases i n AlPO-5 as a model f o r pockets, a c i d
fragments o r o t h e r m i c r o h e t e r o g e n e i t i e s can have a g r e a t e f f e c t as a source
o f a d s o r p t i o n and c a t a l y t i c c e n t e r s , e s p e c i a l l y i f t h o s e m i c r o h e t e r o g e -
n e i t i e s possess a h i g h d e n s i t y o f a c t i v e s i t e s . The s t a r t i n g AlPO-5 sample
s t u d i e d e x h i b i t e d a c o n s i d e r a b l e number o f c e n t e r s i n t e r a c t i n g w i t h NH3 and
m-xylene b u t a low c a t a l y t i c a c t i v i t y , i n agreement w i t h ( r e f . c,3,6). ~ d -
m i x i n g o f o n l y 5wt% HY t o t h i s sample i n c r e a s e d t h e a d s o r p t i o n c a p a c i t y f o r
ammonia by 17% and caused a c a t a l y t i c a c t i v i t y g r o w t h by s e v e r a l o r d e r s . A
rough e s t i m a t i o n on t h e b a s i s o f t h e a d s o r p t i o n d a t a shows a 4-5 t i m e s lower
center-density i n t h e SAPO-5 samples used, as compared t o t h e HY z e o l i t e .
I n SAPO-5 t h e number o f t h e a d s o r p t i o n s i t e s was 5-6 and 2-3 t i m e s g r e a t e r
than t h o s e f o r US-Ex and ZSM-5 r e s p e c t i v e l y .
The c a t a l y t i c s t u d i e s c o n f i r m t h e d e c i s i v e importance o f t h e c e n t e r d e n s i -
t i e s o f t h e i n v e s t i g a t e d Samples f o r t h e i r c a t a l y t i c behaviour. A good c o r r e -
l a t i o n between t h e c a t a l y t i c a c t i v i t y i n m-xylene c o n v e r s i o n and ammonia ad-
s o r p t i o n was observed when t h e c o n t r i b u t i o n o f t h e aluminophosphate m a t r i x
was t a k e n i n t o account ( t h e ammount o f ammonia adsorbed on AIPO-5 was sub-
t r a c t e d f r o m t h a t f o u n d f o r t h e SAPO samples). I n F i g . 6 t h e m-xylene con-
 37

v e r s i o n I S p r e s e n t e d as a f u n c t i o n o f t h e m o d i f i e d c o n t a c t t i m e 2 ' Z g . a /F,
where g i s t h e c a t a l y s t ' s w e i g h t , a, i s t h e amount o f ammonia desorbed,
mmol/g, and F i s t h e m-xylene f l o w , mmol/g.h.This approach i s s i m i l a r t o
t h a t a p p l i e d i n t h e i n v e s t i g a t i o n o f HZSM-5 z e o l i t e s w i t h d i f f e r e n t Al con-
t e n t ( r e f . 1 1 ) . A s one can see f r o m t h e f i g u r e , t h e values o b t a i n e d f o r a l -
most a l l samples f i t w e l l t o one and t h e same k i n e t i c c u r v e . On t h e b a s i s o f
t h e s e d a t a one can s p e c u l a t e on t h e s i m i l a r p e r f o r m a n c e s o f t h e a c t i v e cen-
t e r s i n t h e p r e s e n t e d s e r i e s o f q u i t e d i f f e r e n t z e o l i t e s o n one s i d e , a n d
SAPO-5 on t h e o t h e r . A t t h e p r e s e n t s t a g e o f i n v e s t i g a t i o n we c a n n o t o b t a i n
s u f f i c i e n t p r o o f o f such a h y p o t h e s i s , T h e r e i s no doubt,however, that the
a c t i v i t y p a t t e r n s o f SAPO-5 i n m-xylene c o n v e r s i o n show a c l o s e r e s e m b l a n c e
t o t h o s e o f A I P O - 5 samples c o n t a i n i n g a f e w p e r c e n t s o f HY z e o l i t e . I t seems
t h a t a r e l a t i v e l y broad range o f a c i d centers a r e e f f e c t i v e i n t h i s r e a c t i o n .
Important a d d i t i o n a l i n f o r m a t i o n about t h e c a t a l y t i c p r o p e r t i e s o f
t h e samples can be drawn f r o m t h e s e l e c t i v i t y d a t a . W h i l e c l o s e r a t e s o f
b o t h d i s p r o p o r t i o n a t i o n and i s o m e r i z a t i o n o f m-xylene a r e t y p i c a l f o r HY
and i t s m i x t u r e s w i t h AIPO-5,in t h e c a s e o f SAPO-5, US-Ex and ZSM-5 samples
t h e i s o m e r i z a t i o n p r e v a i l s . The low e x t e n t o f d i s p r o p o r t i o n a t i o n on t h e
shape s e l e c t i v e HZSM-5 r e f l e c t s t h e i n f l u e n c e o f t h e s t r u c t u r a l f a c t o r s
when a b i m o l e c u l a r r e a c t i o n p r o c e e d s . Compared t o ZSH-5, US-Ex a n d SAPO-5
e x h i b i t a much more open c r y s t a l s t r u c t u r e , c o n t a i n i n g 12-membered oxygen
r i n g s . Therefore, t h e r e l a t i v e l y low s e l e c t i v i t y f o r d i s p r o p o r t i o n a t i o n o f
SAPO-5 and US-Ex c a t a l y s t s i s d e t e r m i n e d by f a c t o r s o t h e r t h a n t h e t r a n s i -
t i o n - s t a t e s e l e c t i v i t y . T h e geometry o f t h e a c t i v e c e n t e r d i s t r i b u t i o n (num-
ber o f c l o s e s t n e i g h b o u r i n g a c i d s i t e s a n d t h e d i s t a n c e s between them) as
w e l l as t h e l o c a l e n v i r o n m e n t a l e f f e c t s , may p l a y a p r e v a i l i n g r o l e compared
t o t h e o v e r a l l chemical composition e f f e c t ( r e f . 1 9 ) . The o b s e r v e d S u b t l e
i n f l u e n c e o f t h e a l u m i n o p h o s p h a t e m a t r i x i t s e l f on t h e c a t a l y t i c p r o p e r t i e s
o f t h e model m i x t u r e s i s h a r d t o e x p l a i n on t h e b a s i s o f t h e r e s u l t s
p r e s e n t l y o b t a i n e d . More i m p o r t a n t f r o m o u r p o i n t o f v i e w i s t h a t t h e se-
l e c t iv i t P a t t e r n s o f t h e chosen model r e a c t i o n a r e v e r y s e n s i t i v e i n d i s -
t i n g u i s h ng some i n t r i n s i c f e a t u r e s o f t h e SAPO-5 on t h e one hand and s u c h
common 1 y used z e o l i t e s as HY and ZSM-5 on t h e o t h e r .
F i n a l y , we assume t h a t w i t h t h e p r o c e d u r e u s e d f o r o u r SAPO-5 p r e p a r a -
t i o n , no c o n s i d e r a b l e f o r m a t i o n o f f o r e i g n phases o r a c i d f r a g m e n t s w i t h
i s o l a t e d h e a p i n g o f a c t i v e s i t e s i s t a k i n g p l a c e . The a c i d s t r e n g t h d i s t r i -
b u t i o n i n these m a t e r i a l s i s c l o s e t o t h a t in t h e H Y - f a u j a s i t e b u t t h e
d e n s i t y i s many t i m e s l o w e r . T h e s i m i l a r i t y between c a t a l y t i c p r o p e r t i e s a n d
e s p e c i a l l y t h e s e l e c t i v i t y o f SAPO-5 a n d US-Ex l e a d s us t o t h e c o n c l u s i o n
t h a t t h e S i i n c o r p o r a t i o n i s r e l a t i v e l y homogeneous. The a c i d c e n t e r s gene-
r a t e d a r e s e t a t a distance, s i m i l a r l y t o t h e case o f t h e h i g h l y dealumi-
38

nated f a u j a s i t e , which i s p r o b a b l y t h e reason f o r t h e low d i s p r o p o r t i o n a -

t i o n c a p a b i l i t y o f SAPO-5.

ACKNOWLEDGEMENTS
The a u t h o r s a c k n o w l e d g e t h e B u l g a r i a n Academy o f S c i e n c e s , M i n i s t r y o f c u l -
t u r e , science and education and t h e Deutsche Forschungsgemeinschaft f o r
s u p p o r t of t h i s w o r k . They t h a n k t o D r . U . L o h s e f o r p r o v i d i n g t h e US-Ex
sample a n d Mrs.N.Micheva a n d Mr.V.Minkov f o r helpful assistance.

REFERENCES

1 E . M . F l a n i g e n , B.M. Lok, R . L . P a t t o n a n d S.T. W i l s o n , i n Y. Murakami

A . I i j i m a a n d J. Ward ( E d s . ) , New Developments i n Z e o l i t e S c i e n c e Tech-
n o l o g y , E l s e v i e r , NY, 1986, pp.103-112
2 B.M. Lok, C.M. Messina, R . L . P a t t o n , R.T. G a j e k , T.R. Cannon a n d
E . M . Flanigen,J.Am.Chem.Soc., 106, (19841, 6092
3 Xu Qinhua, Y . A i z h e n , B. S h u l i n a n d Xu K a i j u n , i n Y. Murakami, A . I i j i m a
and J.Ward (Eds.),New Developments i n Z e o l i t e S c i e n c e T e c h n o l o g y , E l s e v i e r
NY, 1986, pp.835-842
4 R.J. P e l l e t , G.N. Long a n d J.A. Rabo, i b i d , pp.843-849
5 J . A . M a r t e n s , M. M e r t e n s , P . J . G r o b e t , P.A. J a c o b s , i n P. G r o b e t , W, Mor-
t i e r and G. S c h u l z - E k l o f f ( E d s . ) , l n n o v a t i o n s i n Z e o l i t e M a t e r i a l s S c i e n c e ,
E l s e v i e r , Amsterdam, 1988, pp.97-106
6 N . J . Tapp, N.B. M i l e s t o n e , D.M. B i b b y , i b i d , pp.393-402
7 E . M . F l a n i g e n , R . L . P a t t o n , S . T . W i l s o n , i b i d , pp.13-28
8 R.Khouzami, G. C o u d u r i e r , B.F.Mentzen, J . C . V e d r i n e , i b i d , pp.355-364
9 EP 103117
10 EP 43562
l t V. K a n a z i r e v , T - T s o n c h e v a , C h r . Minchev, Z. Phys.Neue F o l g e , 149, ( 1 9 8 6 ) ,
237
12 U . Lohse, E . A l s d o r f , H.Stach, Z . a n o r g . a l l g . C h e m . , 447, ( 1 9 7 8 ) , 64
13 V. K a n a z i r e v , N. B o r i s o v a , Z e o l i t e s , 2, ( 1 9 8 2 ) , 23
14 V . Mavrodinova, Ch. Minchev, V. Penchev, H. L e c h e r t , Z e o l i t e s , 5 , ( 1 9 8 5 ) ,
217
15 Ch. Minchev, V . Minkov, V. Penchev, i n p r e p a r a t i o n
16 A . K n i e p , Angew.Chem., 9 8 , (19861, 520
17 V.R. Choudhary, D . B . A k o l e k a r , J . C a t a l . , l O J , (19871, 115
18 L.S. de S a l d a r r i a g a , C. S a l d a r r i a g a , M . E . D a v i s , J.Am.Chem.Soc., 109,
( 1 9 8 7 ) , 2686
19 D. B a r t h o m e u f , i n F . R i b i e r o , A. R o d r i g u e s , L. R o l l m a n , C. Naccache(Eds.)
Z e o l i t e s : S c i e n c e and T e c h n o l o g y , M a r t i n u s N i j h o f f P u b l . The Hague, p p .
31 7-346
H.G. Karge,J. Weitkamp (Editors),Zeolites 0s Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

MOLECULAR ORBITAL CALCULATIONS ON THE STRUCTURAL AND ACIDIC CHARACTERISTICS

OF ALUMINOPHOSPHATES (AlPO) , SILICOALUMINOPHOSPHATES (SAPO) AND
METALUMINOPHOSPHATE (MeAPO) BASED MOLECULAR SIEVES

R.CARSON, E.M.COOKE, J.DWYER*, A. HINCHLIFFE and P.J.O'MALLEY*,

Department of Chemistry
UMIST
Manchester M60 1QD
England.

ABSTRACT
STO-3G molecular orbital calculations on aluminophosphate units show
that the optimised AlOP angle is smaller than that predicted for silicate
or aluminosilicate units. The variation in the energy of the AlOP linkage
over a range of angles from 100" to 180" suggests that smaller TOT angles
are energetically favoured for AlPO structures. Acidity calculations using
a 3-21G basis set predict that the ffronsted acid site strength of MgAPO
is large compared with bridged zeolite forms. CND0/2 studies of single four
ring (S4R) and double four ring (D4R) units suggests a more hydrophobic
nature for aluminophosphate based systems compared with silica based
systems. An average acid site strength for SAPOs, less than HY and HZSM5.
is predicted.

INTRODUCTION
A large family of novel aluminophosphate molecular sieves has recently
been described in the literature 111. These microporous solids not only
exhibit properties characteristic of zeolites but also show unusual
physicochemical properties ascribable to their unique chemical composition.
These new classes of materials were sought for in order to explore new
framework compositions of oxides outside of the already known
aluminosilicate zeolites and silica molecular sieves.

Based on the crystal chemistry of framework oxides and crystal

chemical principles, the first elements explored as tetrahedral framework
cations were aluminium and phosphorous giving rise to the A1P04-n(A1PO)
designation where n denotes a specific structure type. Later substitution
of Si to give SAPO, other elements to give MeAPO, silica and other elements
(MeAPSO) has given rise to a whole range of new materials consisting of
tetrahedral oxide frameworks. More than two dozen structure types have
40

HO ,OH HO ,OH n H

7; 7;
la1
HO

I i
Fig 1 Units used for ab-initio calculations
c
H H
I
Fig 2 S - 4 R unit used in CNDOl2 calculations

D-4R unit H, Sila..,Ab, 0-2ITERln

H, are charge compensating protons
)not shown
ITERI are terminating atoms
0 0
= oxygen I T ' atom Si I Al
Fig 3 0-4R unit used in CNDO/Z calculations
- U , 0 6
E
1Ti -
-lrnt

loo 120 140 160 180

bond angleldegrees fi10X ,fX=Sia All
Fig. 4 . Potential energy curves k r l a l S i O S i . ~ l e
(OSiOHAI and IdIAIOP units ISTO 3G MSISl

I11 In1

S I P Al 4
- Al

\
,OHIO3561 f03MZIHd )MfO31021

51- SI
\A-l SI
Irnl frnl

-AI
fP1
Fq 5 CMnpoutKn of S-1R unlts Charges m Lmdglng
?y&gPnS alven in parenthesis
 41

been reported and this includes framework topologies analogous to zeolites,

e.g. chabazite (-34. -44, -47). erionite (-17). gismodine (-431, levynite
(-35). linde Type A (-42), faujasite (-37) and sodalite (-20) plus a large
number of novel structures such as -5, -11, -31 [ 2 ] etc. Pore sizes range
from 0.3 nm to 0.8 nm encompassing small, intermediate and large pore
structures. Surface selectivity varies from weakly to mildly hydrophilic
and depends upon the nature of the incorporated element and the structure
type. Incorporation of many of the framework elements generates negatively
charged frameworks and acid sites.

The use of molecular orbital calculations, both at the ab-initio and

semi-empirical level has proven fruitful in obtaining a more thorough
understanding of those bonding forces governing structural stability and
acidity in zeolites [3,4,51. It is of interest therefore to examine the
materials described above via such methods. In this report the stability
2+
and acidic characteristics of AlPO, SAP0 and MeAPO (Me = Mg ) forms are
investigated via non-empirical and semi-empirical methods. The models and
methods used are similar to thosedescribed previously [5,8]. The units used
for the calculations are illustrated in Figs 1,2, and 3.

RESULTS AND DISCUSSION

Ab-initio Studies
Stability of AlOP as a function of /AlOP and Acidity Determination for

SCF-MO calculations employing the STO-3G basis set were used along
with the unit of Fig.la for the lAlOP study. First the bridging bond
lengths (A10 and PO) and the /AlOP were optimised. The optimised values
obtained are given in Table 1 together with the optimised values obtained
previously 1121 for ZSiOSiZ , SSiOAlE and ~SiOHAElinkages.In Fig.4(d)
the variation in the energy of the unit of Fig.la is illustrated as a
function of the/AlOP. In this study the PO(br) and AlO(br) were held
constant at their optimum values of Table 1. From Table 1 it can be seen
that the optimised TOT angle for the aluminophosphate unit is lower than
the corresponding silicate and aluminosilicate units. Fig.4 also shows that
the flexibility of the TOT angle over a range of values from 140" - 180" is
also less for the AlPO unit compared with SSiOSiS and [ZSiOAlE 1
-1
.
The
42

TABLE 1
Optimal bond lengths and Angles calculated using the STO-3G Basis Set

(OH)3SiOSi(OH); 143.7 1.59 1.59

[ (OH)3SiOAl(OH)3]a-' 139 . O 1.57 1.69

(OH)3SiOHA1(OH); 132.0 1.67 1.80

(OH)3 ~ i OH)
~ ~ ( 125.0 1.77 1.58

a
Values taken from references (12,131
b See also ref. [22].

TABLE 2

Average TOT angle for aluminophosphate based molecular sieves and dense
phases.

Reference
System Angle/"

AlPO-5 150"

AlPO-21 141.9 ~191

Low-Quartz A1P04 142.5 [201
Low-Cristoballite A1P04 145.0 [201
Low-Tridymite A1P04 150.0 [201
 43

flexibility is however greater than that observed for the ZSiOHAlZ unit.
The low optimum TOT angle value of 125" for the aluminophosphate unit
indicates that this angle should give rise to the most stable AlPO
structures. A selection of A10P angles found for the new molecular sieves
and for some dense A1P04 phases is outlined in Table 2. In general the
experimental values are larger than the theoretically predicted optimum
value. Inspection of Pig.4 shows however that a certain flexibility in the
AlOP angle is to be expected between 120" - 180" so that the experimental
angles are within an acceptable range. TOT angle values as low as 121.8'
have been reported for AlPO-11 confirming that such small angle values are
stable for these materials. A charge density analysis of the A1P04 quartz
2
analogue indicated that the hybridisation of the bridging 0 atom was sp
indicating an AlOP angle of 120" [141. It was suggested that the
experimentally measured internuclear angle of 182.3" was due principally to
the presence of bent bonds. It would be of interest to see if such a
situation also exists for the other frameworks of Table 2. The low optimum
angle for AlOP linkages suggests that small ring systems such as 3 rings
and 4 rings should be stabilised for aluminophosphate based systems 1151.
Strict alternation of A1 and P prohibits odd-numbered ring systems however.
The 3-21G basis set has been used along with the unit of Fig.lb to
calculate the acidic characteristics of MgAPO molecular sieves. The
calculated partial charge on the bridging proton (qH = 0.5093) and the
calculated hydroxyl stretching frequency (COH = 3901 cm -1) can be compared
with the corresponding value of qH = 0.4727 and iOH
= 3931 cm-l obtained
for the H3SiOHA1H unit [8]. The greater proton partial charge plus the
3
decreased vibrational frequency for the MgAPO unit suggests that strong
acidity should be exhibited by MgAPO molecular sieves. The high rate of
cracking of n-butane observed over MgAPO is in agreement with this
prediction [ 2 ] . For MgAPSO a hydroxyl stretching band at 3595 cm-l is
observed in addition to a band at 3621 cm-l 111. The 3621 cm-l band is
observed for SAP0 as well and hence can be assigned to 3SiOHA13 type
hydroxyls. The 3595 cm-l band is therefore likely to rise due to ZMgOHPi
sites. The experimental difference in frequency observed of 26 cm-l is in
excellent agreement with the calculated difference of 30 cm-l above.
44

CNDO/2 studies of S4R's and D4R's containing Si. A1 and P.

As described in the previous sections ab-initio molecular orbital

calculations are successful in predicting local forces governing the
stability and electronic properties of molecular sieve frameworks. It is of
course to be expected that long range forces can also play a large part in
determining molecular sieve properties. For this reason, therefore, it
would be useful to examine larger units of molecular sieves via molecular
orbital methods. Ab-initio calculations are of limited use for large units
because the cost in terms of computer time, even for highly advanced
supercomputers, becomes unreasonable. It is necessary to resort to the less
accurate semi-empirical methods. Of these semi-empirical calculations
CND0/2 has been used for some time to study larger zeolite secondary
building units such as single four rings (S4R) and single six rings (S6R)
[4,91. In this section CNDO/2 studies are performed on S4R and D4R units
containing the T atoms, Si, A1 and P. The geometry of the units is shown
in Figs 2 and 3 . In Tables 3 and 4 the electronic charges on the various T
atoms are given for the silicate and aluminophosphate S4R and D4R units
respectively. In general the polarity of the SiO and A 1 0 are comparable
for both the S4R and D 4 R systems. The PO bonds are however predicted to be
less polar suggesting that hydrophobic adsorption behaviour should be
favoured for A l P O systems. A similar conclusion has been arrived at in
reference (22) via use of ab initio SCF calculations at the STO-3G basis
set level.
The larger units of Figs 2 and 3 also permit us to investigate the
correlation between overall chemical composition and the average acid site
strengths. Recent experimental studies have compared the acidic
characteristics of SAPO materials with zeolites such as HY and HZSM5
[1,161. In general the concentration and strength of the Bronsted acid
sites has been found to be lower for the SAPO forms. As outlined
previously hypothetical replacement of P by Si gives rise to a bridged
.
hydroxyl group of the form SSiOHA13 Substitution of two silicon atoms
for an A1 and a P atom should give rise to a neutral framework charge.
Both types of substitutions have been shown to occur 111. The low
concentration of acid sites can be ascribed to the low Si content of SAPOs
so far investigated. The acid site strength and its composition dependence
can be studied using the S4R compositions of Fig.5 Taking the charge on the
bridging proton as a measure of Bronsted acid strength it can be seen from
Fig.5 that the acid site strength of the SAPO S4R unit is predicted to
 45

TABLE 3 : Electronic charges calculated for atomic positions in silicate

and aluminophosphate S4Rs. Numbering scheme is as given in Fig 2 . (CNDO/2).

Si
I
- SiI A1
I
-P
Si- Si P - A1i

T1 0.4853 0.5851

T2
0.4853 0.0573

T3 0.4853 0.5851

T4 0.4853 0.0573

-0.2186 -0.1411
O5
-0.2186 -0.1411
6'
O7 -0.2186 -0.1411
-0.2186 -0.1411
a'
H9 -0.1333 -0.0044

H1 0 -0.1333 -0.0044

H1 1 -0.1333 -0.1757

H1 2 -0.1333 -0.1757
-0.1333 -0.0044
*13
-0.1333 -0.0044
H14
-0.1333 -0.1757
H15
-0.1333 -0.1757
H1 6
46

TABLE 4
Electronic charges calculated for atomic positions in silicate and
aluminophosphate D4Rs. Numbering scheme is as given in Fig.3.

Si - Si P - A1
A<+€’’ 1
I ,A4
P -A1
;P

Atom T1 .4626 0.2518

Atom T2 .4626 0.4114
Atom T3 .4626 0.2518
Atom T4 .4626 0.4114
Atom T5 .4626 0.4114
Atom T6 .4626 0.2518
Atom T7 .4626 0.4114
Atom T8 .4626 0.2518
Atom 01 -.2892 -0.2503
Atom 02 -.2526 -0.2065
Atom 03 -.2892 -0.2503
Atom 04 -.2526 -0.2065
Atom 05 -.2892 -0.2503
Atom 06 -.2526 -0.2065
Atom 07 -.2892 -0.2503
Atom oa -.2526 -0.2065
Atom 09 -.2560 -0.2085
Atom 010 -.2560 -0.2085
Atom 011 -.2560 -0.2085
Atom 012 -.2560 -0.2085
Atom H1 -.0637 -0.1975
Atom H2 -.0637 0.1996
Atom H3 -.0637 -0.1975
Atom H4 -.0637 0.1996
Atom H5 -.0637 -0.1996
Atom H6 -.0637 0.1975
Atom H7 -.0637 -0.1996
Atom H8 -.0637 -0.1975
be less than that of the aluminosilicate unit with Si/Al = 3 but greater
than that calculated for the unit with Si/A1 = 1. Thus the CNDO/Z
calculations suggest that, the average acid site strength should be less
than HY and HZSM5. The experimental determination of acid site strengths in
SAPO-5 and SAPO-11 are in agreement with this finding
[MI.

CONCLUSIONS
Molecular orbital calculations both at the non-empirical and
semi-empirical level have been shown to provide some valuable insights into
the nature of the forces governing structural stability and acidity within
AlPO, SAP0 and MeAPO frameworks, Combined with previous studies on
aluminosilicate systems they show the value of such calculations in
attempts to rationalise molecular sieve properties.

ACKNOWLEDGEMENTS

P J O'M and J D would like to thank BP International plc, Research Centre,

Sunbury-on-Thamesfor an EMRA. PJO'M also wishes to acknowledge receipt of
a Sir Eric Rideal Bursary from the Society of Chemical Industry.

REFERENCES
1 E.M. Flanigen, R.Lyle Patton and S.T. Wilson, in P.J.Grobet et al.
(Editors), Innovations in Zeolite Materials Science, Elsevier.
Amsterdam, 1988, p.13.
2 E.M. Flanigen in Y. Murakami et al. (Editors), New Developments in
Zeolite Science and Technology, Elsevier, Amsterdam 1988, p.103.
3 G.V. Gibbs, E.P. Meagher, M.D. Newton and D.K. Swanson. in M O'Keefe,
.et al. (Editors),Structure amd Bonding in Crystals, Academic Press
New York, 1981, p.195.
4 G.M. Zhidomirov and V.B. Kazansky, Advances in Catalysis, 34, 1986,
131.
5 P.J. O'Malley and J. Dwyer. Chem.Phys.Letts., 143, 1988, 97.
6 W.J.Hehre, L. Radom, P.V.R. Schleyer and J.A. Pople, Ab-Initio
Molecular Orbital Theory, John Wiley & Sons, New York, 1986.
7 W.J. Mortier. J.Sauer, J.A. Lercher and H. Noller, J.Phys.Chem., 88,
1984, 905.
8 P.J. O'Malley and J. Dwyer, J.C.S. Chem.Commun., 1987, 72.
9 S . Beran and J. Dubsky, J.Phys.Chem., 83, 1979, 2538.
10 J.A. Pople and D.L. Beveridge, Approximate Molecular Orbital Theory,
McGraw-Hill, New York. 1970.
11 M.F. Guest and J. Kendrick, An Introductory Guide to GAMESS,
University of Manchester Regional Computer Centre, Manchester.
12 G.L. Geisinger, G.V. Gibbs and A. Navrotsky, Phys.Chem.Minera1, 11,
1985, 266.
48

13 P.J. O'Malley and J. Dwyer, Zeolites, in press.

14 N. Though, D. Schwarzenbach. Acta Cryst., A35 (1979) 658.
15 W.M. Meier, in Y.Murakinani et al. (Editors), New Developments in
Zeolite Science and Technology, Elsevier, Amsterdam, 1986, p.3.
16 N.J.Tapp, N.B. Mileston and D. M. Bibby in P.J. Grobet et al.
(Editors), Innovations in Zeolite Materials Science, Elsevier,
Amsterdam, 1988, p.393
17 D. Freude, M. Hunger and H. Pfeifer, Chem.Phys.Letts., 128, 1986, 62.
18 J.M. Bennett, J.P. Cohen, E.M. Flanigen, J.J. Pluth and J.V. Smith,
Amer.Chem.Soc.Symp.Ser.. 218, 1983, 109.
19 J.M. Bennett, J.P. Cohen. G. Artioli, J.J. Pluth and J.V. Smith,
Inorg. Chem., 24, 1985, 188.
20 D. Muller, E. Jahn and G. Ladwig, Chem.Phys.Letts.,volume 1984, 109.
21 P.J. O'Malley, J. Dwyer and A. Hinchliffe, to be submitted to
J.Molec. Struct.
22 J. Sauer, H. Haberlandt and W. Schirmer in P.A. Jacobs et a1 (Editors)
structure and Bonding in modified Zeolotes, Elsevier, Amsterdam, 1984
p. 313.
H.G. Karge, J. Weitkamp (Editors),Zeolites 0s Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

RELATION BETWEEN PARAFFIN ISOMERISATION CAPABILITY AND PORE ARCHITECTURE OF

LARGE- PORE BIFUNCTIONAL ZEOLITES

J.A. MARTENS, M. TIELEN and P.A. JACOBS

Laboratorium voor Oppervlaktechemie, K.U. Leuven, Kardinaal Mercierlaan 92,

8-3030 Leuven, Belgium

ABSTRACT
I n t h i s study long-chain n - p a r a f f i n s i n t h e range from nonane t o
heptadecane were converted over b i f u n c t i o n a l z e o l i t e Y, USY, ZSM-3, ZSM-20 and
BETA c a t a l y s t s i n t h e presence of hydrogen. n - P a r a f f i n s can be s e l e c t i v e l y
converted i n t o branched isomers, provided t h e hydrogenation-dehydrogenation
f u n c t i o n i s i n balance w i t h the a c i d f u n c t i o n o f t h e c a t a l y s t . The
e q u i l i b r a t i o n o f the two c a t a l y t i c functions depends on t h e c a t a l y s t as w e l l as
on the carbon number o f the feed. For each z e o l i t e t h e r e e x i s t s an optimum
loading w i t h noble metal which depends on the chain l e n g t h o f the n - p a r a f f i n
feed. I f the geometry and dimensions o f t h e z e o l i t e pores are such t h a t
hydrocracking i s suppressed by molecular s h a p e - s e l e c t i v i t y , t h e y i e l d o f
isomerisation i s improved s u b s t a n t i a l l y . The presence o f mesopores i n z e o l i t e Y
c r y s t a l s i s r e f l e c t e d i n the isomerisation y i e l d .

INTRODUCTION
Branching o f n - p a r a f f i n s , contained i n petroleum f r a c t i o n s , i s desirable
from several p o i n t s o f view and needs no f u r t h e r elaboration. Noble-metal-
containing f a u j a s i t e s are e x c e l l e n t c a t a l y s t s f o r such isomerisation r e a c t i o n s
[l]. A p r e r e q u i s i t e f o r o b t a i n i n g high isomerisation y i e l d s i s that the
hydrogenation-dehydrogenation a c t i v i t y and the Br0nsted a c i d i t y o f the c a t a l y s t
are i n balance [2,3]. Such a c a t a l y s t , according t o Weitkamp, exhibits 'ideal
b i f u n c t i o n a l behaviour' [ 4 ] . The c l a s s i c a l b i f u n c t i o n a l mechanism, advanced by
Weisz [ 5 ] and by Coonradt and Garwood [6] provides a useful d e s c r i p t i o n o f the
events during the conversion o f n - p a r a f f i n s over i d e a l b i f u n c t i o n a l c a t a l y s t s
[ 7 ] . According t o t h e c l a s s i c a l r e a c t i o n scheme, the metal phase establishes an
e q u i l i b r i u m between p a r a f f i n s and o l e f i n s . The o l e f i n s d i f f u s e towards the
Brensted acid s i t e s and are protonated t o g i v e alkylcarbenium ions. The r a t e -
determining step i s the rearrangement and/or s c i s s i o n o f a1 kylcarbenium ions.
Although i n such a c a t a l y s t i t i s considered t h a t both functions are i n
balance, it should be realised that no upper bound exists for the
hydrogenati on-dehydrogenat i o n a c t i v i t y [8].
I n t h i s work i t w i l l be shown t h a t the balance between t h e two f u n c t i o n s i s
catalyst- as well as feedstock-depending. Moreover, in w e l l -balanced
50

bifunctional zeolites t h e shape and dimensions of the zeolite pores are

a d d i t i o n a l parameters which i n f l u e n c e t h e y i e l d o f isomerisation. This w i l l be
demonstrated w i t h n - p a r a f f i n s ranging from nonane (n-C,) t o heptadecane (n-Cl7)
using z e o l i t e s Y, USY, ZSM-PO, ZSM-3 and BETA, which are among t h e most open
a l u m i n o s i l i c a t e s t r u c t u r e s a c t u a l l y known. ZSM-3 i s a twelve-membered ring
zeolite with cages, comparable t o faujasite supercages [9]. The crystal
s t r u c t u r e o f ZSM-3 i s r e l a t e d t o f a u j a s i t e , b u t t h e topology remains unknown
[lo]. ZSM-20 i s a twelve-membered r i n g z e o l i t e w i t h unknown s t r u c t u r e and which
seems a l s o t o be r e l a t e d t o f a u j a s i t e [ll].
Z e o l i t e BETA i s an i n t e r g r o w t h o f
two z e o l i t e frameworks [12]. The c r y s t a l s are permeated by a tridimensional
network of twelve-membered ring channels A t the channel
[7,12-141.
i n t e r s e c t i o n s there i s l e s s f r e e space than i n a f a u j a s i t e supercage [13,141.
Z e o l i t e Y and USY d i f f e r by t h e presence o f s o - c a l l e d mesopores and appreciable
q u a n t i t i e s o f extra-framework A1 i n t h e l a t t e r m a t e r i a l [15-171.

EXPERIMENT
ZSM-3 was the ZSM-3(2) m a t e r i a l o f r e f . 9 . The s i z e o f t h e c r y s t a l s was
around 1 pm and the S i / A l r a t i o was 1.9. ZSM-20 was synthesized according t o
the standard method o f Ernst e t a l . [18]. The S i / A l r a t i o was 5.0 and the
c r y s t a l s i z e around 0.5 pm. ZSM-20 was c a l c i n e d a t 673 K i n f l o w i n g oxygen.
BETA was synthesized according t o a p r e v i o u s l y reported r e c i p e (B1 i n ref.19)
using a K - f r e e g e l . The S i / A l r a t i o o f BETA was 8.0 and t h e c r y s t a l s i z e around
0.2 pm. 1 was a Na-Y z e o l i t e w i t h a S i / A l r a t i o o f 2.45, purchased from
Ventron. Usy z e o l i t e was prepared by teaming NH4-Y [20]. The S i / A l r a t i o o f
the framework o f USY determined with 2 6 S i M$S NMR was 4.4.
The ze l i t e s were converted t o the NH4 -form by c o n t a c t i n g 5 g o f z e o l i t e
5
w i t h 0.5 dm o f a 0.5 M NH4C1 s o l u t i o n under r e f l u x conditions. Subsequently,
platinum tetrammine complex was exchanged a t r om temperature i n the z e o l i t e s
by c o n t a c t i n g 2 g o f z e o l i t e w i t h 0.1 dm' o f an aqueous s o l u t i o n o f
Pt(NH3) C12. The uptake o f platinum complex was assumed t o be q u a n t i t a t i v e .
The z e o l i t e powder was shaped i n t o p e l l e t s w i t h a diameter o f 0.3-0.5 mm by
compression, crushing and sieving. 0.2 g o f t h e p e l l e t s were charged i n a
r e a c t o r tube w i t h an i n t e r n a l d i a t e r o f 1 cm. The c a t a l y s t bed was heated
w i t h a t e m era ure r i s e o f 0.1 K s' from 300 t o 673 K under a stream o f oxygen
o f 0.33 c a s-' and a pressure o f 0.15 MPa. The temperature was kept a t 673 K
f o r one hour. Subsequently, t h e bed was flushed w i t h nitrogen, and hydrogen was
admitted f o r one hour, using the same f l o w as f o r oxygen. The a c t i v a t i o n o f
Pt/ZSM-3 was performed a t 573 K, i n order t o avoid a l o s s o f c r y s t a l l i n i t y [ 9 ] .
The c a t a l y t i c experiments consisted o f converting s i n g l e n - p a r a f f i n
feedstocks i n a fixed-bed, continuous-flow microreactor, described e a r l i e r [8].
The Hp/hydrocarbon molar r a t i o i n the feed was 100. The experiments were
performed a t v a r i a b l e W/Fo values, i n which W stands f o r t h e amount o f c a t a l y s t
and Fo f o r t h e molar f l o w r a t e o f n - p a r a f f i n a t t h e r e a c t o r i n l e t . D e t a i l e d
analysis o f t h e r e a c t i o n products was c a r r i e d o u t w i t h GLC using c a p i l l a r y
columns coated w i t h Cp-Sil-5. The b i f u n c t i o n a l z e o l i t e c a t a l y s t s w i l l be
denoted by t h e z e o l i t e type, preceded by t h e amount o f noble metal ( i n w t - % )
contained i n i t .
RESULTS
Catal v t i c a c t i v i t y
In Fig.1 the degree of conversion of decane and heptadecane over
0.75Pt/ZSM-3 i s p l o t t e d against W/Fo. As the slopes i n Fig.1 are i n i t i a l
 51

r e a c t i o n rates, an e i g h t f o l d increase o f the i n i t i a l r e a c t i o n r a t e i s observed

when decane is rep1 aced w i t h heptadecane.
The degree o f conversion o f heptadecane over d i f f e r e n t c a t a l y s t s i s p l o t t e d
versus the r e a c t i o n temperature i n Fig.2. Catalysts 0.3Pt/Y and 0.5Pt/Y show
the same a c t i v i t y . The a c t i v i t y o f 0.75Pt/ZSM-3 i s lower than t h a t o f the
z e o l i t e Y c a t a l y s t s . lPt/USY, lPt/ZSM-20 and lPt/BETA are s u b s t a n t i a l l y more
active.

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 lo

WIF, (kg 8 mmol-') 320 360 4 0 0 440 480 520 560

temperature( K )

Fig.1. Degree o f conversion o f decane and Fig.2. Degree o f conversion o f

heptadecane against W/Fo over 0.75Pt/ZSM- heptadecane over lPt/USY, lPt/BETA,
3 a t 508 K and 0.35 MPa. lPt/ZSM-20, 0.75Pt/ZSM-3, 0.3 and
0.5Pt/Y against r e a c t i o n temper-
a t u r e a t 0.7 MPa w i t h W/Fo=l.l kg s
mmol -1.
Hvdrocrac k ino Patterns
The cracked product d i s t r i b u t i o n s o f n-Cg t o n-C17 over 0.75Pt/ZSM-3 shown
i n Fig.3 are s l i g h t l y asymmetric. For complementary fragments w i t h carbon
number x and n-x, the l i g h t e s t product i s always t h e most abundant. Central
scission o f the hydrocarbon chain i s the major cracking event w i t h nonane and
decane, yielding C4tC5 and C5 products, respectively. With undecane, the
formation o f c5tc6 i s s l i g h t l y lower than o f c4tC7. Central cracking o f
dodecane i n c6 fragments i s suppressed w i t h respect t o t h e formation o f C4tcs
or C5tC7 alkanes. With tridecane and l a r g e r n - p a r a f f i n s , the d i s t r i b u t i o n
curves e x h i b i t d i s t i n c t minima f o r c6 and Cn-6 products. Fig.3 a l s o shows t h a t
the formation o f methane, ethane and t h e i r complementary fragments w i t h carbon
number n - 1 and n-2, respectively, decreases w i t h increasing chain length, n, o f
the feed.
The hydrocracking p a t t e r n of heptadecane over d i f f e r e n t c a t a l y s t s i s shown
i n Fig.4. A common feature for a l l c a t a l y s t s i s t h a t t h e formation o f C 6 t c l l
alkanes i s somewhat suppressed w i t h respect t o other fragments. This e f f e c t
52

P
Q)
Y
0
z
0

carbon number
Fig.3. Hydrocracked carbon number f r a c t i o n s from n - p a r a f f i n s over 0.75Pt/ZSM-3
a t 0.7 MPa. The f u l l curves comprise a l l products with a given carbon number;
t h e dashed curves rep esent t h e branched products.
W/Fo = 0.5 kg s mmol-I f o r n- , n-C n-C 1 and n-C14, 0.f kg s mmol-l f o r n-
C12 and n-C 0.7 kg s ~ n m o l - ~ ~ nf!6;o r ana 1.1 kg s mmol- f o r n-C * T=602 K
f o r n-Cg, 5b$ K f o r n-ClO, 574 K f o r n - C l l , 564 K f o r n-C 563 K 1 h n-Ci3,
560 K f o r n-C14, 558 K f o r n-C15, 558 K f o r n-C16 and 539 K1& n-Ci7.
 53

i s l e s s pronounced w i t h l P t / U S Y and l P t / Z S M - Z O and i s very s i g n i f i c a n t over

lPt/BETA. I n order t o q u a n t i f y t h i s , t h e molar r a t i o c5/c6 has been p l o t t e d i n
Fig.5 against t h e y i e l d o f hydrocracking over t h e d i f f e r e n t c a t a l y s t s .
Irrespective o f t h e hydrocracking y i e l d , t h e c5/c6 r a t i o i s highest f o r
lPt/BETA and decreases according t o the f o l l o w i n g c a t a l y s t sequence:
lPt/BETA > 0.75Pt/ZSM-3 > 0.3Pt/Y, O,SPt/Y, 1Pt/ZSM-20 > lPt/USY.
The composition o f the c6 f r a c t i o n , obtained from heptadecane over l P t / U S Y
i n Fig.6 i s shown t o be independent o f the hydrocracking y i e l d from 20 t i l l 80%
hydrocracking. The same behaviour was found w i t h t h e other c a t a l y s t s . I n Table
1, the amount o f 2,3-dimethylbutane i n the c6 f r a c t i o n , obtained a t medium
hydrocracking y i e l d s , i s given f o r d i f f e r e n t feeds and c a t a l y s t s . For each
c a t a l y s t , i t tends t o increase w i t h increasing carbon number o f t h e feed. From
heptadecane i t decreases i n the f o l l o w i n g c a t a l y s t sequence:
lPt/BETA > l P t / Z S M - L O > 0.75Pt/ZSM-3 > 0.3Pt/Y, 0.5Pt/Y > lPt/USY.

carbon number

Fig.4. Hydrocracked carbon number f r a c t i o n s from heptadecane lover 0.3Pt/Y,

O.SPt/Y, lPt/USY, lPt/BETA and lPt/ZSM-20 a t W/Fo-l.l kg s mnol- and 0.7 MPa;
T 4 2 3 K f o r O.JPt/Y, 521 K f o r 0.5Pt/Y, 456 K f o r lPt/BETA, 458 K f o r lPt/ZSM-
20 and 452 K f o r lPt/USY.
54

so
0.75PtlZSM-3
~ 0 1.10 40

30

20

0.95 I PtIUSY 10
0.90 . * . I . ' . " 0 7
0 20 40 60 80 100 0 20 40 60 80 100

Y,, (96) Y,, (%)

Fig.5. Molar r a t i o o f c5/c6 products versus Fig.6. Hexane (A) ,2-methylpentane
hydrocracking y i e l d from heptadecane over (o), 3-methylpentane (+), 2,Z-di-
0.3 and 0.5Pt/Y, l P t / U S Y , lPt/BETA and 1 P t / methylbutane (0) and 2,3-dimethyl
ZSM-20. Reaction c o n d i t i o n s o f Fig.2. butane (A) i n t h e c6 cracked
product f r a c t i o n against t h e
hydrocracking y i e l d from hepta-
decane over l P t / U S Y . The r e a c t i o n
c o n d i t i o n s a r e those o f Fig.2.

Fig.7. Isomerisation and hydro-

cracking y i e l d against degree o f
conversion o f heptadecane over
0.75Pt/ZSM-3. The r e a c t i o n
c o n d i t i o n s are those o f Fig.2.
0 20 40 60 80 100
conversion (%I
TABLE 1
Amount o f 2,3-dimethylbutane i n C6 f r a c t i o n (%) a t medium hydrocracking y i e l d

catalyst feed
n-Cln n-CI1 n-C17 n-CIF, n-C16 n-C17

1Pt/USY 2.0 - 3.5 3.7

0.3Pt/Y 2.0 - 3.8
0.5Pt/Y - 3.8
0.75Pt/ZSM-3 2.4 2.7 3.1 4.0 4.0 4.4
lPt/ZSM-LO 2.3 - 5.0
lPt/BETA 5.8 - 7.5 - 9.7 9.3

Maximum isomerisation y i e l d
The y i e l d o f i s o m e r i s a t i o n and hydrocracking from heptadecane over
0.75Pt/ZSM-3 i s p l o t t e d i n Fig.7 against t h e degree o f conversion. The former
e x h i b i t s a maximum, t h e values o f which are given i n Table 2 f o r t h e d i f f e r e n t
n - p a r a f f i n s and c a t a l y s t s . Over lPt/USY, lPt/ZSM-20 and lPt/BETA t h e maximum
isomerisation y i e l d decreases w i t h i n c r e a s i n g carbon number o f t h e feed. Over
0.75Pt/ZSM-3 t h e maximum y i e l d o f isomerisation increases w i t h increasing
carbon number o f the feed.
 55

TABLE 2
Maximum isomerisation yield (%) from n-paraffins
catalyst feed
n-CQ n-Cln n-CI1 n-C1, n-Clr; n-CI6 n-C17

1 Pt/USY - 52 - 50 47
0.5Pt/Y 61
0.3Pt/Y - 56 - 57
0.75Pt/ZSM-3 59 62 62 66 67 69 72
lPt/ZSM-20 - 52 - 50
lPt/BETA - 63 - 51

DISCUSSION
Catalvtic activitv. balance between functions and chain lenqth of feed
The reactivity of n-paraffins over bifunctional catalysts increases with
increasing chain length. For n-C6 to n-C11 alkanes Weitkamp has shown that the
initial reaction rate over Pt/CaY increases when the carbon number of the feed
is increased [21]. In Fig.1 it is shown that over a 0.75Pt/ZSM-3 zeolite an
eightfold increase in activity occurs when n-C17 is used as feed instead of n-
C10. According to the classical bifunctional mechanism, this increase in
reactivity with increasing carbon number can, for obvious thermodynamic
reasons, result from an increased partial pressure of olefins formed by
dehydrogenation on the noble metal and/or from an enhanced reactivity of these
olefins over the acid sites of the catalyst when their chain length increases.
The presence of methane and ethane in the hydrocracked products indicates
that hydrogenolysis is superimposed on the bifunctional conversion [2]. This C-
C bond cleavage on the noble metal surface is significant in the conversion of
hexane and heptane over Pt/CaY, whereas it is virtually absent when octane or
larger n-paraffinic feeds are converted [21]. From the data of Fig.3 it can be
seen that over 0.75Pt/ZSM-3 the formation of methane and ethane is highest from
nonane, decreases with increasing carbon number of the feed and is negligible
for tetradecane and larger n-alkanes. Provided the reactivity of the olefins on
the Brensted acid sites increases faster with increasing chain length than does
the monofunctional conversion of the corresponding n-a1 kane over the metal
particles, then the decreasing contribution of monofunctional metal catalysis
with increasing carbon number is explained.
For a given bifunctional catalyst, the equilibration of the two catalytic
functions clearly depends on the carbon number of the feed. With the
0.75Pt/ZSM-3 catalyst this balance exists for n-CI4 to n-C17 feeds. The present
results suggest that for shorter n-paraffins, the amount of noble metal on the
catalyst required to obtain a bifunctional conversion must be lower.
56

Isomerisation maximum and chain lenqth of feed

The isomerisation yield from decane and dodecane over Pt/USY and Pt/DBY is
not dependent on such experimental conditions as partial pressure of He and n-
paraffin and reaction temperature and consequently the isomerisation yield is a
unique function of conversion [7,20]. Therefore, the experimental conditions
under which the maximum isomerisation yield is determined are irrelevant, as
the isomerisation yield is only conversion dependent.
Over 0.75Pt/ZSM-3 the maximum isomerisation yield increases when the carbon
number of the feed is increased (Table 2 ) . The contribution of hydrogenolysis
decreases in a parallel manner (Fig.3). Therefore, the loss of isomerisation
yield can be the result of a loss of feedstock through hydrogenolysis. When
heptadecane is converted over lPt/USY, lPt/BETA and lPt/ZSM-20, hydrogenolysi s
is absent (Fig.4), while these catalysts are much more active than 0.75Pt/ZSM-3
(Fig.2). This can be explained by the enhanced acid strength per Brfinsted site
o f twelve-membered ring zeolites with decreasing aluminium content [22,23].
Over lPt/USY, 1PtIZSM-20 and lPt/BETA, the isomerisation maximum is higher with
decane than with heptadecane (Table 2). This, again, is a manifestation of the
dependence o f the equilibration of the functions on the carbon number of the
feed. If for a given metal function and a given feed the acid function is too
strong, higher isomerisation yields may be expected for shorter n-paraffins.
In conclusion, for a given catalyst the maximum isomerisation yield seems
to depend on the carbon number of the feed in the way qualitatively pictured in
Fig.8. It shows a maximum for a given chain length of the feed. For shorter n-
paraffins, the yield of isomerisation decreases due to a loss of feedstock by
hydrogenolysis. For larger feedstocks, the isomerisation yield is decreased by
hydrocracking as the acid function becomes too strong, resulting again in an
unbalanced catalyst.

0Q) , ' balance

.- Fig.8. Evolution of the maximum
t 00 too i someri sati on yield with
C
0 increasing carbon number of the
*z
m
strong strong feed.
.-
In metal function acid function

:
carbon number of feed

Over 0.3Pt/Y and 0.5Pt/Y the maximum isomerisation yield from heptadecane
is 57 and 61%, respectively (Table 2). Some hydrogenolysis occurs over 0.5Pt/Y
 57

(Fig.4), i n d i c a t i n g t h a t a loading o f 0.5% platinum i s i n excess o f the

optimum. For the conversion o f heptadecane over Pt/Y t h e optimum platinum
loading must t h e r e f o r e be between 0.3 and 0.5%.

I f i t i s observed for a given c a t a l y s t t h a t i n t h e homologous s e r i e s o f

long-chain n - p a r a f f i n s ( s t a r t i n g from octane [24]) t h e i s o m e r i s a t i o n maximum
continuously decreases, i t f o l l o w s t h a t t h e two f u n c t i o n s are n o t w e l l
e q u i l i b r a t e d and t h a t the hydrogenation-dehydrogenation f u n c t i o n i s too weak.
This seems t o be t h e case f o r Pt/CaY (SK-200) [21].
Isomerisation maximum and hvdrocrackina oat t e r n
The y i e l d o f isomers from a long-chain p a r a f f i n i s l i m i t e d , even over w e l l -
balanced b i f u n c t i o n a l c a t a l y s t s . Hydrocracking reactions, which are consecutive
t o isomerisation reactions, consume p r e f e r e n t i a l l y t h e d i - and tribranched feed
isomers [24]. The isomerisation-hydrocracking network o f n-C8 and l a r g e r n-
p a r a f f i n s over lPt/USY c a t a l y s t i s depicted i n Scheme 1 [24].

n-paraffin --t monobranched --t dibranched -+ tribranched

isomers isomers isomers
/
a,a-
branched branched

1.2
cracked products

Scheme 1. Isomerisation-hydrocracking reaction network of long-chain n-

p a r a f f i n s over lPt/USY [24].

When decane i s converted over Pt/USY, 69% o f the cracked products o r i g i n a t e

from type A hydrocracking [25]. Type A hydrocracking involves j-scission of
a, y , v - t r i b r a n c h e d alkylcarbenium ions. The remaining cracked products are
formed by B1, B2 and C hydrocracking. Over Pt/USY and Pt/CaY t h e formation o f
propane and complementary fragments v i a hydrocracking o f feed isomers from n-C8
t o n-CI6 n - p a r a f f i n s does not occur f r e q u e n t l y [26,27]. I n these cases the
s c i s s i o n p r o b a b i l i t y o f a C-C bond increases when i t s l o c a t i o n i s c l o s e r t o the
center o f the hydrocarbon chain [26,27]. The data o f Fig.4 i n d i c a t e t h a t there
are deviations from t h i s p a t t e r n w i t h heptadecane over Pt/Y: c6 alkanes are
l e s s abundantly formed than C5 products. There i s no mechanistic reason why
w i t h heptadecane t h e formation o f C5 fragments should be more abundant than o f
c6 [24]. The anomaly i n the d i s t r i b u t i o n o f t h e cracked products a t c6 and cn-6
should o r i g i n a t e from molecular s h a p e - s e l e c t i v i t y imposed by the pore geometry
on t h e rearrangements and/or p - s c i s s i o n o f t h e intermediate alkylcarbenium
ions. I n any case, t h i s phenomenon i s l e s s pronounced w i t h USY than w i t h Y. I t
i s s t r i k i n g t h a t t h e former z e o l i t e contains a secondary large-pore system
58

(mesopores) . The C5/Cs r a t i o o f the hydrocracked products from heptadecane over

0.75Pt/ZSM-3, 1Pt/ZSM-20, 0.3 and 0.5Pt/Y and l P t / U S Y i s d i f f e r e n t (Figs.5) and
decreases i n t h e f o l l o w i n g order:
BETA > ZSM-3 > Y > ZSM-20 > USY.
Thus t h e suppression o f c e r t a i n hydrocracking routes r e s u l t i n g i n c6 fragments
by s t e r i c c o n s t r a i n t s exerted by t h e i n t r a c r y s t a l l i n e v o i d volume o f these
z e o l i t e s must increase i n t h e opposite order. Weitkamp e t a l . found t h a t the
product d i s t r i b u t i o n s from undecane and tetradecane over 0.27Pd/ZSM-20 and
0.5Pt/CaY are very s i m i l a r [28]. The present data show t h a t d i f f e r e n c e s i n the
s t r u c t u r e o f t h e void volume o f ZSM-20, Y and USY appear w i t h heptadecane. With
BETA [14] and ZSM-3 (Fig.3) t h e d e v i a t i o n from t h e r e g u l a r hydrocracking
p a t t e r n sets i n a t undecane. The exact n a t u r e o f t h i s shape-selective
suppression o f c6 formation i s n o t y e t c l e a r .
Type A hydrocracking takes place i f i n t h e parent feed isomer the side
chains are a t a , a ,y - p o s i t i o n s . Hydrocracking mechanisms B1, B2 and C are
operative i f s p e c i f i c requirements concerning the c o n f i g u r a t i o n o f the side
chains are met (Scheme 1). 2,3-dimethylbutane, e.g., is formed by B1
hydrocracking o f 2,3,3-trimethylbranched and by B2 hydrocracking o f 2,3,5-
trimethylbranched o r 2,3-dimethyl-5-ethylbranched isomers o f the feed [24]. The
content o f 2,3-dimethylbutane i n the c6 f r a c t i o n i s t h e r e f o r e a measure f o r the
c o n t r i b u t i o n o f B1 and B2 hydrocracking. The Cs fraction of the cracked
products from n-C10 to n-C17 n - p a r a f f i n s over lPt/BETA i s r i c h i n 2,3-
dimethylbutane (Table 1). T h i s i n d i c a t e s t h a t over t h i s z e o l i t e a s u b s t a n t i a l
number o f the tribranched isomers are converted v i a 61 and B2 hydrocracking
instead o f v i a A hydrocracking. Mechanistically, t h i s means t h a t e i t h e r type A
p - s c i s s i o n o f a , y , y -tribranched alkylcarbenium ions i s suppressed, o r t h e i r
formation i s hindered.
ZSM-3, ZSM-20 and Y e x h i b i t behaviour intermediate
between BETA and USY, r e f l e c t i n g again the existence o f s p e c i f i c d i f f e r e n c e s i n
the s t r u c t u r e o f the v o i d volume o f these z e o l i t e s .
The c a t a l y s t s 0.75Pt/ZSM-3 and 0.3-0.5Pt/Y are p e r f e c t l y balanced f o r the
conversion o f heptadecane. The maximum i s o m e r i s a t i o n y i e l d i s ,
however, 10%
higher over ZSM-3 (Table 2 ) . This d i f f e r e n c e should be ascribed t o t h e shape-
s e l e c t i v e suppression o f some o f the hydrocracking routes i n t h i s z e o l i t e . The
higher c5/c6 r a t i o and t h e higher amount o f 2,3-dimethylbutane i n t h e c6
f r a c t i o n are manifestations o f this effect. lPt/ZSM-PO and lPt/BETA have
adequate pore geometries f o r o b t a i n i n g h i g h isomerisation y i e l d s . Because o f
the h i @ a c i d strength o f these z e o l i t e s , t h e isomerisation y i e l d i s lower than
over 0.75Pt/ZSM-3.
 59

CONCLUSIONS
The e q u i l i b r a t i o n o f the c a t a l y t i c f u n c t i o n s i n a b i f u n c t i o n a l z e o l i t e
c a t a l y s t depends on the chain l e n g t h o f t h e n - p a r a f f i n t o be converted. The
required amount o f noble metal increases w i t h increasing chain l e n g t h o f the n-
p a r a f f i n feed. F o r the conversion o f each n - p a r a f f i n t h e r e e x i s t s an optimum
noble metal loading. A given metal loading i s adequate o n l y f o r t h e conversion
o f a r e s t r i c t e d range o f n - p a r a f f i n s . According t o the c l a s s i c a l b i f u n c t i o n a l
mechanism no upper bound e x i s t s f o r t h e hydrogenation-dehydrogenation a c t i v t Y
o f the c a t a l y s t . I n p r a c t i c e the hydrogenation-dehydrogenation a c t i v i t y has t o
be enhanced by increasing the amount o f noble metal on t h e c a t a l y s t . AS
platinum e x h i b i t s hydrogenolysis, there i s an upper bound o f t h e metal load ng
above which hydrogenolysis i s superimposed on the b i f u n c t i o n a l convers on
pathway. With an optimized combination o f c a t a l y s t and feed the highest
isomerisation y i e l d i s obtained. 0.75Pt/ZSM-3 presents an i d e a l c a t a l y s t f o r
the b i f u n c t i o n a l conversion o f C14-C17 n - p a r a f f i n s . For the conversion o f
heptadecane over z e o l i t e Y, the optimum platinum loading i s 0.3-0.5%.
Certain hydrocracking routes leading t o t h e formation o f c6 fragments are
suppressed i n large-pore z e o l i t e s due t o s t e r i c c o n s t r a i n t s exerted by the
i n t r a c r y s t a l l i n e v o i d volume. The enrichment o f 2,3-dimethylbutane i n the c6
cracked products i n d i c a t e s t h a t type A hydrocracking i s s t e r i c a l l y suppressed.
The s t e r i c c o n s t r a i n t s exerted by the i n t r a c r y s t a l l i n e v o i d volume increase i n
order: BETA > ZSM-3 > Y > ZSM-20 > USY. With well-balanced c a t a l y s t s the
maximum isomerisation y i e l d t h a t can be obtained from a long-chain n - p a r a f f i n
should decrease i n the same order. BETA has t h e adequate pore geometry f o r
obtaining high isomerisation yield. A loading with 1% o f platinum is
i n s u f f i c i e n t t o counterbalance t h e strong a c i d i t y o f t h i s z e o l i t e . The shape-
s e l e c t i v e suppression o f c e r t a i n hydrocracking routes i s l e s s pronounced w i t h
USY than w i t h Y due t o the presence o f mesopores i n the former z e o l i t e .

ACKNOWLEDGMENTS

J.A.M. and P.A.J. acknowledge t h e Belgian Fund f o r S c i e n t i f i c Research f o r a

grant (Research Associate) and a research p o s i t i o n (Research D i r e c t o r ) ,
r e s p e c t i v e l y . This work has been sponsored by t h e Belgian Government (Diensten
Wetenschapsbeleid) i n the frame o f a concerted a c t i o n on c a t a l y s i s .
60

REFERENCES

M. S t e i j n s , G.F. Froment, P.A. Jacobs, J.B. Uytterhoeven and J. Weitkamp,

Erdol, Kohle, Erdgas, Petrochem. 31 (1978) 581.
J. Weitkamp, W. Gerhardt and P.A. Jacobs, Acta Phys. Chem. 31 (1985) 261.
G.E. Giannetto, 6. Perot and M. Guisnet, Ind. Eng. Chem. Prod. Res. Dev. 25
(1986) 481.
J. Weitkamp, Erdol, Kohle, Erdgas, Petrochem. 31 (1978) 13.
P.B. Weisz, Adv. Catal. 13 (1962) 137.
M.L. Coonradt and W.E. Garwood, Ind. Eng. Chem. Prod. Res. Dev. 3 (1964) 38.
J.A. Martens and P.A. Jacobs, Z e o l i t e s 6 (1986) 334.
P.A. Jacobs, J.B. Uytterhoeven, M. S t e i j n s , G.F. Froment and J. Weitkamp,
Proceed. f i f t h I n t . Conf. Z e o l i t e s , L.V.C. Rees, Ed., Heyden, London 1980,
607.
J. Perez-Pariente, V. Fornes, J.A. Martens and P.A. Jacobs, Stud. Surf. Sci.
Catal. 37 (1988) 123.
10 G.T. K o k o t a i l o and J. C i r i c , Adv. Chem. Ser. 101 (1971) 109.
11 J. C i r i c , US Pat. 3,972,893 (1976).
12 M.M.J. Treacy and J.M. Newsam, Nature 332 (1988) 249.
13 J.A. Martens, M. Tielen, P.A. Jacobs and J. Weitkamp, Z e o l i t e s 4 (1984) 98.
14 J.A. Martens, J. Perez-Pariente and P.A. Jacobs, Acta Phys. Chem. 31 (1985)
487.
15 W. Schirmer and H. Thamm, I z v . Akad. Nauk. Gruz. SSR Ser. Khim. 5 (1979)
217.
16 U. Lohse and M. Mildebrath, 2 . Anorg. A l l g . Chem. 476 (1981) 126.
17 G. Engelhardt, U. Lohse, V. Patzelova, M. Magi, M. Tarmak and E. Lippmaa,
Z e o l i t e s 3 (1983) 233.
18 S. Ernst, G.T. K o k o t a i l o and J. Weitkamp, Stud. Surf. Sci. Catal. 37 (1988)
25.
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20 M. S t e i j n s , G.F. Froment, P.A. Jacobs, J.B. Uytterhoeven and J. Weitkamp,
Ind. Eng. Chem. Prod. Res. Dev. 20 (1981) 654.
21 J. Weitkamp, ACS Symp. Ser. 20 (1975) 1.
22 P.A. Jacobs, Catal. Rev. Sci. Eng. 24 (1982) 415.
23 E. Dempsey, J. Catal. 33 (1974) 497; 39 (1975) 155.
24 J.A. Martens, P.A. Jacobs and J. Weitkamp, Appl. Catal. 20 (1986) 239.
25 J.A. Martens, P.A. Jacobs and J. Weitkamp, Appl. Catal. 20 (1986) 282.
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28 J. Weitkamp, S. Ernst, V. Cortes Corberiin and G.T. Kokotailo, 7 t h I n t e r n .
Z e o l i t e Conf., Tokyo, Japan, 1986, P r e p r i n t s o f p o s t e r papers, Japan
Association o f Zeolites, Tokyo, 1986, 239.
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V.,Amsterdam - Printed in The Netherlands

R E S P E C T I V E INFLUENCES OF THE GEOMETRIC AND CHEMICAL FACTORS I N THE CON-

VERSION OF AROMATICS OVER ACIDIC ZEOLITES

F. FAJULA,M. LAMBRET and F .FIGUERAS

L a b o r a t o i r e de Chimie Organique Physique e t C i n e t i q u e Chimique Appliquees UA
418 CNRS. ENSCM, 8 Rue de 1 ' E c o l e Normale - 34075 M o n t p e l l i e r Cedex France.

ABSTRACT
The c a t a l y t i c behaviour o f a s e r i e s o f mordenites and o f f r e t i t e s w i t h
v a r y i n g aluminium c o n t e n t and o r i g i n has been analyzed f o r t h e a l k y l a t i o n o f
benzene and t o l u e n e by e t h a n o l and t h e d i s p r o p o r t i o n a t i o n o f t o l u e n e as a
f u n c t i o n o f t h e i r A1 m o l a r f r a c t i o n ( m = A l / A l + S i ) . F o r b o t h r e a c t i o n s , t h e
a c t i v i t y , expressed on a p e r - w e i g h t b a s i s , passes t h r o u g h a maximum w i t h
m=0.1 f o r m o r d e n i t e and m=0.12 f o r o f f r e t i t e . As m decreases, t h e amount o f
coke d e p o s i t e d d u r i n g t h e d i s p r o p o r t i o n a t i o n r e a c t i o n decreases, b u t t h e
d e a c t i v a t i o n r a t e i n c r e a s e s . A l k y l a t i o n r e a c t i o n s u s i n g e t h a n o l as r e a g e n t
a r e c h a r a c t e r i z e d by l o n g s t a b l e l i f e t i m e s o f t h e c a t a l y s t s . The main
i n f l u e n c e o f t h e aluminium c o n t e n t was f o u n d t o be on t h e ethylbenzene
s e l e c t i v i t y , which reached 70-90% f o r m < 0.12.

INTROOUCT I ON
Because o f t h e i r g r e a t i n d u s t r i a l importance, t h e reactions o f aromatic
hydrocarbons on a c i d i c forms o f z e o l i t e c a t a l y s t s have been t h e s u b j e c t o f
e x t e n s i v e s t u d i e s . On t h e o t h e r hand, t h e r e a c t i o n mechanisms a r e now w e l l
known and t h e p r o d u c t d i s t r i b u t i o n s s i m p l e enough t h a t a r o m a t i c s u b s t r a t e s
may be used as model molecules f o r c a t a l y s t c h a r a c t e r i z a t i o n . The c o n v e r s i o n
o f aromatic hydrocarbons has been m o s t l y s t u d i e d e i t h e r on a l u m i n i u m - r i c h ,
l a r g e - p o r e s t r u c t u r e s (X,Y,MOR r e f s . 1 - 3 ) o r on s i l i c o n - r i c h , shape-selective
m a t e r i a l s (ZSM-5, refs.4-10). Z e o l i t e s o f t h e f i r s t f a m i l y a r e h i g h l y ac-
t i v e , even a t r e l a t i v e l y l o w temperatures (20O-30O0C), b u t c a t a l y s t aging
due t o c o k i n g i s severe, l e a d i n g t o d e a c t i v a t i o n i n a few hours. ZSM-5 based
catalysts a r e used a t h i g h e r temperatures (400-600°C). They show l i t t l e
d e a c t i v a t i o n w i t h t i m e on stream and t h e i r a c t i v i t y and s e l e c t i v i t y a r e
e s s e n t i a l l y c o r r e l a t e d t o s t r u c t u r a l and m o r p h o l o g i c a l f e a t u r e s . Because o f
t h e s e l i m i t a t i o n s and d i f f e r e n t e x p e r i m e n t a l c o n d i t i o n s , it i s difficult to
e v a l u a t e t h e e f f e c t o f t h e chemical c o m p o s i t i o n ( a c i d s i t e d e n s i t y and
s t r e n g t h ) o f t h e z e o l i t e s on t h e i r c a t a l y t i c behaviour.
I n t h i s work we have used benzene and t o l u e n e a l k y l a t i o n b y e t h a n o l and
toluene disproportionation t o test the activity of large-pore zeolite
c a t a l y s t s w i t h widely varying aluminium c o n t e n t , p r e p a r e d b y d e a l u m i n a t i o n
62

o f mordenites and o f f r e t i t e s . Three aspects o f t h e i r c a t a l y t i c behaviour,

namely t h e i r s t a b i l i t y , t h e i r a c t i v i t y and t h e i r selectivity, have been
p a r t i c u l a r l y analyzed as a f u n c t i o n o f t h e i r aluminium c o n t e n t .

METHODS
Catalysts
Two s e r i e s o f z e o l i t e s were used : i ) Mordenites w i t h aluminium molar
f r a c t i o n s ( m = A l / A l t S i ) r a n g i n g from 0.167 t o 0.025 ( o r S i / A 1 r a n g i n g from 5
t o 40). Samples w i t h m values o f 0.167, 0.129 and 0.099 (Si/A1=5,6.9 and
9.2) were obtained from t h e S o c i 6 t 6 Chimique de l a Grande Paroisse ( A l i t e
1801, Norton (Zeolon 100H) and Union Carbide, respectively. Three
dealuminated s o l i d s w i t h m=0.062, 0.035 and 0.025 were s u p p l i e d by t h e
I n s t i t u t FranCais du P e t r o l e . ii1 O f f r e t i t e s w i t h aluminium molar f r a c t i o n s
ranging from 0.284 t o 0.059 ( S i / A l from 2.52 t o 1 6 ) . Two p a r e n t z e o l i t e s
w i t h m=0.284 and 0.211 ( S i / A l = 2.52 and 3.73 r e s p e c t i v e l y ) were synthesized
according t o r e f . 11. Successive hydrothermal and a c i d treatments (ref.12)
o f t h e ammonium forms o f t h e l a t t e r y i e l d e d dealuminated o f f r e t i t e s w i t h
m=0.133, 0.103, 0.083 and 0.059.
Before t h e t e s t , a l l samples were exchanged t w i c e w i t h ammonium n i t r a t e
s o l u t i o n s a t r e f l u x temperature, washed, oven-dried, and f i n a l l y c a l c i n e d i n
a shallow bed a t 500°C f o r 5h i n f l o w i n g a i r . The r e s u l t i n g c a t a l y s t s were
c h a r a c t e r i z e d by XRD, SEM, v o l umetry and elemental a n a l y s i s , as d e s c r i b e d
p r e v i o u s l y ( r e f s . 13,141.

Procedures
C a t a l y t i c r e a c t i o n s were c a r r i e d o u t i n a f i x e d bed, down-flow dif-
f e r e n t i a l r e a c t o r o p e r a t i n g a t atmospheric pressure ( n i t r o g e n f l o w ) on lOOmg
o f c a t a l y s t ( i n t h e form o f powder). Products were analyzed by o n - l i n e gas
chromatography.
The e t h y l a t i o n r e a c t i o n s were i n v e s t i g a t e d i n t h e temperature range
220-275°C. The aromatic hydrocarbon (benzene and toluene, purity > 99.8%)
was i n t r o d u c e d f i r s t i n t o t h e system. A f t e r f i v e minutes t h e ethanol ( p u r i t y
> 99.8%) was added using an independent s a t u r a t o r .
Toluene d i s p r o p o r t i o n a t i o n r e a c t i o n s were s t u d i e d i n t h e temperature
range 300-400°C.

RESULTS AND DISCUSSION

Physicochemical p r o p e r t i e s o f t h e a c t i v a t e d z e o l i t e s
The dealumination o f z e o l i t e s by combined steam and a c i d t r e a t m e n t s i n -
duces n o t o n l y a decrease o f t h e i r aluminium and c a t i o n c o n t e n t (Table 1 )
 63

CI
r
I

-D
Y
E
U A
0

g
0
0.1 -
A
r.
0

m
c
C A 0
a
8
4 0 I 1

S t a b i l i t y o f the c a t a l y t i c a c t i v i t y . 1 .Benzene a l k y l a t i o n w i t h e t h a n o l .
The advantages o f u s i n g e t h a n o l i n s t e a d o f e t h y l e n e as t h e a l k y l a t i n g agent
have been a l r e a d y p o i n t e d o u t by Chandawar et al. (ref.10) for ZSM-5
z e o l i t e s . The most s i g n i f i c a n t f e a t u r e r e p o r t e d by t h e a u t h o r s was t h e l o n g
s t a b l e l i f e t i m e o f t h e c a t a l y s t s . Their r e s u l t s support t h e hypothesis o f
Anderson e t a l . (ref.18) t h a t t h e e t h y l group i n e t h y l b e n z e n e was formed
f r o m ethanol w i t h o u t t h e i n t e r m e d i a t e f o r m a t i o n o f e t h y l e n e . T h i s would
reduce t h e f o r m a t i o n o f r e s i d u e s t h r o u g h t h e p o l y c o n d e n s a t i o n o f t h e o l e f i n ,
which i s known t o be t h e main cause o f c a t a l y s t d e a c t i v a t i o n ( r e f s . l , 2 ) .
Low d e a c t i v a t i o n r a t e s o f t h e c a t a l y s t s were a l s o observed here, as
shown by F i g u r e 2 f o r t h e a l k y l a t i o n o f benzene a t 250°C o v e r t h e m o r d e n i t e
sample having an A 1 m o l a r f r a c t i o n o f 0.127.
Among t h e v a r i o u s f a c t o r s which were analyzed ( t y p e o f z e o l i t e , v a l u e o f
m, experimental c o n d i t i o n s ) t h e one h a v i n g t h e most pronounced e f f e c t on
64

c a t a l y t i c s t a b i l i t y was found t o be t h e h y d r o c a r b o n / a l c o h o l r a t i o . P r o v i d e d
t h i s r a t i o be h i g h e r t h a n 7, a l l c a t a l y s t s p r e s e r v e d more t h a n 90% o f t h e i r
i n i t i a l a c t i v i t y under o u r t e s t c o n d i t i o n s .

1
100 200
t i me (min.)
Fig.2. Rate o f benzene e t h y l a t i o n a t 250°C versus t i m e on m o r d e n i t e ( m =

0.127). I n f l u e n c e o f t h e benzene : e t h a n o l r a t i o . ( A ) 3.85, ( m ) 7, ( 0 ) 9.

2. To1 uene disproportionation. At a1 1 temperatures studied, the

c a t a l y s t s d e a c t i v a t e d w i t h t i m e on stream. The e x p e r i m e n t a l d a t a were con-
s i s t e n t w i t h a f i r s t - o r d e r r e a c t i o n and f i r s t - o r d e r catalyst deactivation.
The deactivation rate constants (kd) were obtained from t h e equation
- t
r=roe k d where ro and r a r e t h e r e a c t i o n r a t e s a t t = o and t ( r e f s . 1 9 , 2 0 ) .
The values o f k d o b t a i n e d on two o f f r e t i t e s and f o u r m o r d e n i t e s a t 300°C and
400°C and t h e amounts o f carbon measured on t h e spent c a t a l y s t s ( a f t e r 3
hours on stream) a r e g i v e n i n Table 2.
The r a t e s o f d e a c t i v a t i o n were found o f t h e same o r d e r o f magnitude f o r
both s t r u c t u r e s .
On o f f r e t i t e , t h e amounts o f carbonaceous d e p o s i t s formed a t t h e end o f
t h e t e s t appeared independent o f t h e aluminium c o n t e n t and t e m p e r a t u r e wher-
eas, on mordenite, t h e y decreased s t e a d i l y w i t h m. The d e t e r m i n a t i o n o f t h e
porous volumes, a c c e s s i b l e t o hydrocarbons (n-hexane and c y c l o h e x a n e ) , o f
t h e used c a t a l y s t s r e v e a l e d t h a t d u r i n g t h e t e s t , t h e samples had l o s t o n l y
20 t o 30% o f t h e i r o r i g i n a l s o r p t i o n c a p a c i t y . D e a c t i v a t i o n was t h e r e f o r e
due t o t h e coverage o f t h e a c i d s i t e s by s t r o n g l y adsorbed r e s i d u e s r a t h e r
than t o a pore p l u g g i n g . The d e a c t i v a t i o n r a t e s a r e hence expected to
i n c r e a s e when m decreases, as i t i s observed f o r b o t h z e o l i t e s .
 65

I n f l u e n c e o f aluminium c o n t e n t on a c t i v i t y
F i g u r e s 3 and 4 p r e s e n t t h e e v o l u t i o n s o f t h e r e a c t i o n r a t e s , expressed
on a p e r gram b a s i s , as a f u n c t i o n o f t h e aluminium m o l a r f r a c t i o n f o r t h e
a l k y l a t i o n o f benzene a t 250°C and t h e d i s p r o p o r t i o n a t i o n o f t o l u e n e a t
300°C on b o t h z e o l i t e s . F o r t h e l a t t e r r e a c t i o n t h e v a l u e s t a k e n i n t o ac-
count a r e t h e i n i t i a l r e a c t i o n r a t e s determined f r o m t h e l n r v e r s u s t p l o t s .
I n a l l cases volcano c u r v e s were o b t a i n e d w i t h t h e i r maxima around
m=0.1-0.12. A t f i r s t glance, such b e h a v i o u r corresponds t o t h a t expected
a c c o r d i n g t o B a r t h o m e u f ' s p r e d i c t i o n s ( r e f .21) r e g a r d i n g t h e c o r r e l a t i o n s
between a c i d i t y and c a t a l y t i c a c t i v i t y i n z e o l i t e s . The r a t e o f a r e a c t i o n
depends on t h e e f f e c t i v e number of sites and on t h e i r e f f i c i e n c y and
strength. A t h i g h A1 c o n t e n t , the interactions between A l O i t e t r a h e d r a
decrease b o t h t h e e f f i c i e n c y and t h e s t r e n g t h o f t h e s i t e s . When t h e a l -
uminium c o n t e n t decreases, t h e decrease o f t h e number o f s i t e s i s over
balanced by t h e i n c r e a s e o f t h e i r e f f i c i e n c y and s t r e n g t h up t o a l i m i t i n g
A1 molar fraction below which none of the A104 tetrahedra is in a
n e x t - n e a r e s t - n e i g h b o u r s i t u a t i o n . Below t h i s t h r e s h o l d , which was c a l c u l a t e d
at m=0.096 for mordenite and m=0.12 for offretite, activities on a
p e r - w e i g h t b a s i s a r e expected t o decrease, whereas t h e a c t i v i t y p e r s i t e
(and t u r n - over numbers) should remain constant. Although the former
c o n d i t i o n i s w e l l f u l f i l l e d h e r e and t h e values o f t h e o p t i m a c l o s e l y agree
w i t h theory, t h e turn-over numbers a r e d e f i n i t e l y n o t c o n s t a n t below t h e
v a l u e o f m=0.1, as shown i n f i g u r e s 5 and 6. T h i s means t h a t t h e c a t a l y t i c
a c t i v i t y i s n o t determined s o l e l y by t h e a c i d i t y o f t h e samples. We have
seen e a r l i e r t h a t , upon d e a l u m i n a t i o n , t h e porous volume o f t h e z e o l i t e s was
significantly increased. Moreover, the actual amount of tetrahedrally
c o o r d i n a t e d aluminium i n t h e h i g h l y dealuminated m o r d e n i t e s and o f f r e t i t e s
i s d i f f i c u l t t o e s t i m a t e b y s o l i d s t a t e n.m.r. spectroscopy due t o t h e
presence o f s i 1 anol groups ( r e f .22 1. There a r e indeed s e v e r a l reasons which
could be p u t f o r w a r d t o e x p l a i n why t h e behaviour o f actual zeolite
c a t a l y s t s deviates from theory. It s h o u l d be p o i n t e d o u t , however, t h a t on
t h e same s e r i e s o f mordenites, below t h e v a l u e o f m=0.1, t u r n - o v e r numbers
were found t o i n c r e a s e i n t h e e t h y l a t i o n o f benzene (Fig.51, and t o decrease
i n the disproportionation o f toluene (Fig.6) whereas t h e y remained c o n s t a n t
i n t h e isomerization o f orthodichlorobenzene (ref.23). From t h i s i t can be
s p e c u l a t e d t h a t t h e changes i n A1 c o n t e n t n o t o n l y a f f e c t t h e a c i d i t y , b u t
also strongly influence the specific interactions between the reagent
molecules and t h e a c i d c e n t e r s . At present t h e exact nature o f these
i n t e r a c t i o n s and t h e way i n which t h e y a r e m o d i f i e d a r e s t i l l obscure.
 m
m

TABLE 1 : Chemical composition and c r y s t a l l i n i t y o f t h e samples a f t e r exchange-with ammonium n i t r a t e and

calcination

Leo1 it e OFF MOR

Si/Ala 2.52 3.7 6.5 8.7 12 16 5 6.9 9.2 15 27 39

m 0.284 0.211 0.133 0.103 0.083 0.059 0.167 0.127 0.098 0.062 0.035 0.025
At/Alb 0.62 0.7, 0.85 0.80 0.91 0.90 0.85 0.98 0.99 0.98 0.98 0.92
%Crystc 90 100 80 90 110 80 80 90 100 80 70 60

a : Determined from t h e chemical analyses a f t e r d i s s o l u t i o n o f t h e samples (SCA CN RS S o l a i z e )

b : A = K f o r o f f r e t i t e and Na f o r m o r d e n i t e
c : p e r c e n t o f c r y s t a l l i n i t y e v a l u a t e d by XRO. * = r e f e r e n c e sample

TABLE 2 : Rate constants ( k i n min-') f o r d e a c t i v a t i o n , and amounts o f carbonaceous

deposits i n the dfsproportionation o f toluene

Zeolite OFF MOR

m = Al/Al+Si 0.103 0.059 0.127 0.098 0.062 0.035

a t 300°C
l o 3 kd 3.8 6 4.7 8.9 4.6 7.7
wt%C 2.33 2.34 4.5 3.28 1.88 1.75
a t 3400 "C
10 kd 2.9 5.5 3.3 - 5.1
wt%C 1.93 2.1 5.22 - 1.9
 67

I n a l l f i g u r e s ( A )M o r d e n i t e ( ) Offretite

0.1 0.2 0.1 0.2

m m
Fig.3. I n f l u e n c e o f t h e A1 f r a c t i o n Fig.4. I n f l u e n c e o f t h e A1 f r a c t i o n
on t h e a c t i v i t y f o r benzene e t h y l a t i o n on t h e a c t i v i t y f o r t o l u e n e d i s p r o -
a t 250°C. p o r t i o n a t i o n a t 300°C.

A A
n
F A n 10.
v
& 5 z
I

i A

:. .:
W

0 i
b-- 0 5 .

.
0 I . 1 F
0.1 0.2
m
A
I

0.1
A I.
0.2
Fig.5. Turn-over numbers as a f u n c t i o n m
o f m f o r t h e a l k y l a t i o n o f benzene
Fig.6. Turn-over numbers as a f u n c t i o n
o f m f o r the disproportionation o f
toluene

v)
N
50t F i g . 7 . S e l e c t i v i t y f o r e t h y l benzene
a t 250°C as a f u n c t i o n o f m.
; 01 I
0.1 0.2
0 .

m
68

From a p r a c t i c a l p o i n t o f view, t h e d a t a o f F i g u r e s 3 and 4 i n d i c a t e

n e v e r t h e l e s s c l e a r l y t h a t t h e range o f aluminium content i n which the
z e o l i t e s develop t h e i r maximum a c t i v i t y i s narrow and does n o t depend on t h e
type o f r e a c t i o n considered.

I n f l u e n c e o f aluminium c o n t e n t on s e l e c t i v i t i e s
Benzene a l k y l a t i o n . A t 250°C e t h y l e n e and mono and d i e t h y l b e n z e n e s were
t h e o n l y p r o d u c t s formed ( w i t h a molar r a t i o monoldiethylbenzene=7-8).
Traces o f d i e t h y l e t h e r were formed on t h e aluminium r i c h o f f r e t i t e s a t
220°C. As i t has been r e p o r t e d by Chandawar e t a l . ( r e f . 1 0 ) t h e s e l e c t i v i t y
f o r ethylbenzene i n c r e a s e d w i t h i n c r e a s i n g t h e benzene : e t h a n o l r a t i o and
d e c r e a s i n g c o n t a c t t i m e . Under our optimum c o n d i t i o n s and w i t h a benzene :
e t h a n o l r a t i o o f 7 , t h e aluminium c o n t e n t had a l s o an i n f l u e n c e ( F i g u r e 7).
The s e l e c t i v i t y f o r ethylbenzenes i n c r e a s e d as m decreased f r o m 0.28 t o 0.12
and t h e n reached a n e a r l y c o n s t a n t v a l u e ( 8 0 2 10%) f o r b o t h z e o l i t e s . T h i s
e v o l u t i o n c o r r e l a t e s w i t h an i n c r e a s e o f t h e a c i d s t r e n g t h o f t h e s o l i d s
(ref.21).
The d e h y d r a t i o n o f a l c o h o l r e q u i r e s o n l y a weak a c i d i t y and i s c a t a l y z e d
by a l l t h e s i t e s present i n t h e zeolite. Benzene alkylation requires
s t r o n g e r a c i d s i t e s ( r e f . 2 4 ) . When m decreases, t h e p r o p o r t i o n o f t h e l a t t e r
increases, and below m=0.12 a l l t h e s i t e s a r e s t r o n g enough t o c a t a l y z e t h e
reaction.
Toluene a l k y l a t i o n . A t 275"C, w i t h a t o l u e n e / e t h a n o l r a t i o o f 2, the
e t h y l a t i o n r e a c t i o n was accompanied by d i s p r o p o r t i o n a t i o n o f t o l u e n e i n t o
xylenes and benzene. Three t y p e s o f s e l e c t i v i t i e s c o u l d be d i s t i n g u i s h e d , i
t h e alkylation/disproportionation ratio, ii ) a p a r a x y l e n e s e l e c t i v i t y and
iii) a p a r a e t h y l t o l u e n e s e l e c t i v i t y .
The i n i t i a l s e l e c t i v i t i e s were l i t t l e a f f e c t e d by m o d i f y i n g t h e a l u m i n i -
um c o n t e n t . T h i s can be e a s i l y understood s i n c e b o t h t h e a l k y l a t i o n and d i s -
proportionation activities exhibit parallel evolutions (Figs.3 and 4).
Noreover i n i t i a l p a r a s e l e c t i v i t i e s were f o u n d t o depend more on t h e t o t a l
c o n v e r s i o n t h a n on m, as i t i s g e n e r a l l y observed on l a r g e p o r e s t r u c t u r e s .
The i n f l u e n c e o f t h e A1 c o n t e n t was, by c o n t r a s t , o b v i o u s when f o l l o w i n g t h e
e v o l u t i o n s o f t h e p r o d u c t d i s t r i b u t i o n w i t h t i m e on stream. Examples o f such
e v o l u t i o n s a r e g i v e n i n F i g u r e s 8 and 9 f o r t h e o f f r e t i t e w i t h m=0.059.
I n i t i a l l y t h e main r e a c t i o n was d i s p r o p o r t i o n a t i o n ; among t h e xylenes, t h e
para isomer was s l i g h t l y f a v o u r e d .
The r a t e o f t o l u e n e d i s p r o p o r t i o n a t i o n decreased w i t h t i m e on stream
whereas t h a t o f a l k y l a t i o n i n c r e a s e d , r e a c h i n g r a p i d l y a s t a b l e v a l u e . As
t h e x y l e n e c o n v e r s i o n decreased t h e p r o p o r t i o n o f t h e p a r a isomer i n c r e a s e d
 69

whereas ethyltoluenes were always produced near their thermodynamic

e q u i l i b r i u m ( r e f . 2 5 ) . The decay o f t h e d i s p r o p o r t i o n a t i o n a c t i v i t y i s due t o
the r a p i d poisoning o f the strongest s i t e s o f t h e z e o l i t e . This r e a c t i o n
r e q u i r e s s t r o n g e r s i t e s t h a n e t h y l a t i o n ( r e f . 2 4 ) . The same i s t r u e f o r t h e
i s o m e r i z a t i o n o f xylenes compared t o t h a t o f t h e e t h y l t o l u e n e s (ref.26).
Since t h e r a t e o f d e a c t i v a t i o n i s r e l a t e d t o t h e aluminium f r a c t i o n ( t a b l e
2 ) ; t h e s e l e c t i v i t i e s o b t a i n e d a t each t i m e on stream were determined by
t h e c o m p o s i t i o n o f t h e z e o l i t e . Thus a f t e r t h r e e hours o f r e a c t i o n , t h e r a t -
i o a1 k y l a t i o n l d i s p r o p o r t i o n a t i o n and t h e percentage o f p a r a - x y l e n e i n c r e a s e d
from 4 t o 8 and 39 t o 80% r e s p e c t i v e l y when g o i n g f r o m m=0.133 t o 0.059,
r e s p e c t i v e l y , on o f f r e t i t e . The same t r e n d was n o t i c e d on m o r d e n i t e .

r - I -
h
X

-.-
C

0
'c
0
'0,
P
r" 5 0
r
Q)
c,
a
m
a ' 0
100 200 100 2 00
time (mi".) time (min.)
1
F i g s 8-9. R e a c t i o n r a t e s (mmol.g-".h- and s e l e c t i v i t i e s versus t i m e i n
t h e a l k y l a t i o n o f t o l u e n e by e t h a n o l a t 275°C on o f f r e t i t e .

CONCLUSIONS
I n t h i s work we have t r i e d t o emphasize t h e r o l e o f t h e aluminium con-
t e n t o f l a r g e - p o r e z e o l i t e s on t h e i r c a t a l y t i c b e h a v i o u r i n t h e c o n v e r s i o n
o f a r o m a t i c hydrocarbons. I n spite o f differences i n the origin o f the
parent z e o l i t e s and i n t h e structural and t e x t u r a l properties o f the
c a t a l y s t s , s e v e r a l common f e a t u r e s h a v e been p o i n t e d out, a l l o f them b e i n g
r e l a t e d t o changes i n t h e a c i d s i t e d e n s i t y and s t r e n g t h , which a r e s t r i c t l y
dependent on m. The aluminium c o n t e n t determines the stability i n the
d i s p r o p o r t i o n a t i o n o f t o l u e n e , t h e s e l e c t i v i t y i n t h e e t h y l a t i o n o f benzene
and t o l u e n e and, l a s t b u t n o t l e a s t , t h e a c t i v i t y in a l l cases. When t h e
r e a c t i o n r a t e s a r e expressed on a p e r - w e i g h t b a s i s , they f o l l o w volcano
c u r v e s w i t h t h e i r maxima a t m=0.1 f o r m o r d e n i t e and 0.12 f o r o f f r e t i t e . F o r
b o t h s t r u c t u r e s , t h e v a l u e o b t a i n e d s t r i c t l y corresponds t o t h e p o i n t where
t h e s i t e s would be i s o l a t e d and f u l l y e f f i c i e n t f o r c a t a l y s i s .
70

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F. Figueras and P . Geneste, F r i s t . I n t e r n Symp. Heter. C a t a l .
and F i n e Chem. P o i t i e r s France 1988. Stud. Surf. Sci. and Catal in
press.
24 P.A. Jacobs, i n "Carboniogenic A c t i v i t y o f Z e o l i t e s " E l s e v i e r , Amsterdam
(1977) p 58.
25 W.J. T a y l o r , D.D. Wagman, M.G. Williams, K.S. P i t z e r and F.D. R o s s i n i ,
.
J. Res. Nat Bur Standards, 37 ( 1946) 95.
26 R.H. A l l e n , L.D. Yats and D.S. Eberly, J.Amer.Chem.Soc., 82 (1960) 4853.
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

PARA-SELECTIVITY OF PENTASIL ZEOLITES

Jong-Ho KIM, S e i t a r o NAMBA. and T a t s u a k i YASHIMA

Department o f Chemistry, Tokyo I n s t i t u t e o f Technology,
Ookayama, Meguro-ku, Tokyo 152 (Japan)

ABSTRACT
The p e n t a s i l z e o l i t e s m o d i f i e d w i t h o x i d e s , coked, o r s t e a m e d e x h i b i t e d
much h i g h e r p a r a - s e l e c t i v i t i e s f o r t h e a l k y l a t i o n o f e t h y l b e n z e n e w i t h e t h a n o l
t h a n t h e p a r e n t z e o l i t e s . The m o d i f i c a t i o n s r e s u l t e d i n a r e d u c t i o n o f t h e
e f f e c t i v e p o r e dimension, a r e d u c t i o n i n a c i d s t r e n g t h , and an i n a c t i v a t i o n o f
t h e e x t e r n a l surfaces. The i n a c t i v a t i o n o f t h e e x t e r n a l s u r f a c e s improved t h e
p a r a - s e l e c t i v i t y t o some e x t e n t . The a c i d s t r e n g t h d e t e r m i n e d b y NH3-TPD
t e c h n i q u e was m o r e c l o s e l y r e l a t e d t o t h e p a r a - s e l e c t i v i t y t h a n t o t h e
e f f e c t i v e p o r e dimension d e t e r m i n e d by o-xylene a d s o r p t i o n experiments. It i s
found t h a t t h e improvement i n p a r a - s e l e c t i v i t y by t h e m o d i f i c a t i o n s i s
p r i m a r i l y due t o r e d u c i n g t h e s t r o n g a c i d s i t e s on w h i c h t h e i s o m e r i z a t i o n of
p-diethylbenzene as a p r i m a r y p r o d u c t proceeds p r e f e r e n t i a l l y .

INTRODUCTION
It i s w i d e l y known t h a t ZSM-5 z e o l i t e s m o d i f i e d w i t h o x i d e o f Mg r e f s . 1-
3). P ( r e f s . 2,3). o r B ( r e f s . 2.3) e x h i b i t a h i g h p a r a - s e l e c t i v i t : for the
a l k y l a t i o n o f alkylbenzenes. Kaeding e t a l . have proposed t h a t t h e h i g h para-
s e l e c t i v i t y o f m o d i f i e d ZSM-5 z e o l i t e s i s due t o "product s e l e c t i v i t y " , namely
t h e i n t r a c r y s t a l l i n e d i f f u s i v i t y o f para-isomer i s much h i g h e r t h a n t h a t o f
t h e o t h e r t w o i s o m e r s ( r e f . 2). On t h e o t h e r hand, we h a v e r e p o r t e d t h a t i n
t h e a l k y l a t i o n o f t o l u e n e w i t h methanol and o f ethylbenzene w i t h e t h a n o l on
HZSM-5, o n l y p a r a - i s o m e r i s a p r i m a r y p r o d u c t and t h a t t h e i m p r o v e m e n t i n
para-selectivity by t h e m o d i f i c a t i o n w i t h o x i d e s i s due t o t h e r e d u c t i o n o f
s t r o n g a c i d s i t e s which a c c e l e r a t e t h e i s o m e r i z a t i o n o f para-isomer (refs.
1,3). Moreover, P a p a r a t t o e t a l . have suggested t h a t i n t h e e t h y l a t i o n o f
t o l u e n e on HZSM-5 and HZSM-11, para-isomer i s formed s e l e c t i v e l y i n s i d e t h e
z e o l i t e channels, w h i l e t h e i s o m e r i z a t i o n proceeds o n l y on t h e e x t e r n a l
s u r f a c e s ( r e f . 4).
I n t h i s paper, we aim t o c l a r i f y t h e reason why m o d i f i e d p e n t a s i l z e o l i t e s
e x h i b i t the high para-selectivity. We choose t h e a l k y l a t i o n o f e t h y l b e n z e n e
w i t h e t h a n o l as a model r e a c t i o n , because t h e l a r g e r a l k y l groups a r e expected
t o provide c l e a r e r results.
12

EXPERIMENT
Catalysts
ZSM-5 (Si/A1=96) w i t h a s m a l l c r y s t a l s i z e (30-60 nm), and ZSM-11 ( S i / A l =
50) w e r e p r e p a r e d b y p u b l i s h e d p r o c e d u r e s ( r e f s . 1,5). These z e o l i t e s c a l -
c i n e d a t 823 K were t r a n s f o r m e d i n t o H-form by s e v e r a l exchanges w i t h l M HC1.
The HZSM-5 z e o l i t e s m o d i f i e d w i t h v a r i o u s amounts o f boron, phosphorus, and
magnesium o x i d e s were prepared by i m p r e g n a t i o n o f HZSM-5 w i t h aqueous s o l u -
t i o n s o f b o r i c a c i d , p h o s p h o r i c a c i d , and m a g n e s i u m a c e t a t e , r e s p e c t i v e l y ,
f o l l o w e d b y d r y i n g a t 373 K and c a l c i n e d a t 823 K f o r 1 8 h i n an a i r s t r e a m .
The steaming o f HZSM-5 was c a r r i e d o u t a t 1073 o r 1223 K f o r 1 h under atmos-
p h e r i c p r e s s u r e o f w a t e r vapor. The c o k e d HZSM-5 was p r e p a r e d b y t r e a t i n g
HZSM-5 w i t h a t m o s p h e r i c m e t h a n o l v a p o r a t 973 K f o r 1 h. Ferrierite
(Si/A1=9.8) was k i n d l y s u p p l i e d by Tosoh Co. and was t r a n s f o r m e d i n t o H-form
by c a l c i n i n g i t a t 823 K a f t e r s e v e r a l exchanges w i t h 1 M NH4C1. The s p e c i f i c
s u r f a c e area o f H - f e r r i e r i t e i s 390 m 2 /g.

Apparatus and procedure

The apparatus and procedure f o r t h e a l k y l a t i o n o f ethylbenzene w i t h e t h a n o l
are described i n t h e l i t e r a t u r e (ref. 3). The a l k y l a t i o n on s e l e c t i v e l y
poisoned z e o l i t e s was a l s o c a r r i e d o u t i n t h e presence o f 2.4-dimethylquino-
l i n e (2,4-DMQ) w h i c h s e l e c t i v e l y p o i s o n e d t h e a c i d s i t e s on t h e e x t e r n a l
surfaces (ref. 6). The c r a c k i n g o f 1,3,5-triisopropylbenzene (1,3.5-TIPB) at
673 K was p e r f o r m e d i n t h e p r e s e n c e o f 2.4-DMQ t o c h e c k t h e a c t i v i t y o f t h e
a c i d s i t e s on t h e e x t e r n a l surfaces. A l l t h e c a t a l y t i c r e a c t i o n s were c a r r i e d
o u t w i t h a continuous f l o w system a t 673 K under atmospheric pressure.
The measurement o f temperature-programmed d e s o r p t i o n f o r ammonia (NH3-TPD)
was c a r r i e d o u t as f o l l o w s . A f t e r t h e c a t a l y s t was evacuated a t 823 K f o r 1 h
and t h e n exposed t o 150 T o r r o f ammonia gas a t 423 K f o r 30 min, the catalyst
was e v a c u a t e d a t 423 K f o r 1 h and t h e n c o o l e d t o room t e m p e r a t u r e . The
t e m p e r a t u r e was b r o u g h t t o 823 K a t a c o n s t a n t r a t e o f 1 0 K m i n - ’ under
vacuum. The r e l a t i v e amount o f ammonia desorbed f r o m t h e c a t a l y s t was d e t e r -
mined by mass spectroscopy.
G r a v i m e t r i c measurements o f 0- o r p-xylene a d s o r p t i o n were p e r f o r m e d on a
h i g h l y s e n s i t i v e thermal microbalance. A f t e r z e o l i t e s a m p l e s (0.1 g) w e r e
e v a c u a t e d a t 823 K f o r 2 h u n d e r a p r e s s u r e o f l e s s t h a n Torr. the
measurement was p e r f o r m e d a t 393 K and a t an 0- o r p - x y l e n e p r e s s u r e o f 3.6
Torr.

RESULTS AND DISCUSSION

I n t h e a l k y l a t i o n o f ethylbenzene w i t h ethanol, diethylbenzenes, benzene,
 73

ethylmethylbenzenes and xylenes were observed as a r o m a t i c products. The main

p r o d u c t s o f t h i s a l k y l a t i o n were p- and m-diethylbenzenes. The a c t i v i t y and
t h e s e l e c t i v i t y o f t h e HZSM-5 o r HZSM-11 z e o l i t e d i d n o t change w i t h process
t i m e f o r 3 h. I n t h e case o f H - f e r r i e r i t e , however, the a c t i v i t y , decreased
s i g n i f i c a n t l y w i t h process time. The r e s u l t s o f t h e a l k y l a t i o n on HZSM-5,
HZSM-11 and H - f e r r i e r i t e a r e shown i n Table 1. The p a r a - s e l e c t i v i t i e s ( f r a c -
t i o n o f p-isomer i n t h e d i e t h y l b e n z e n e produced) o f t h e s e t h r e e z e o l i t e s were
low. The a l k y l a t i o n a c t i v i t y o f H - f e r r i e r i t e was e x t r e m e l y l o w compared w i t h
t h e o t h e r z e o l i t e s , p r o b a b l y because t h e e f f e c t i v e p o r e d i m e n s i o n o f H - f e r r i e -
r i t e was s m a l l e r t h a n those o f t h e o t h e r z e o l i t e s . The l o w a c t i v i t y and t h e
l o w p a r a - s e l e c t i v i t y o f H - f e r r i e r i t e s u g g e s t t h a t t h e a1 k y l a t i o n p r o c e e d s
m a i n l y on t h e e x t e r n a l surfaces.
I n o r d e r t o c l a r i f y w h i c h were t h e p r i m a r y p r o d u c t s i n t h e a l k y l a t i o n o f
ethylbenzene w i t h e t h a n o l on HZSM-11 o r H - f e r r i e r i t e , t h e change i n f r a c t i o n
o f each isomer i n t h e produced d i e t h y l b e n z e n e w i t h d e c r e a s i n g W/F was d e t e r -
mined. The r e s u l t s on HZSM-11 a t 673 K i n t h e d i e t h y l b e n z e n e y i e l d range o f
24 t o a b o u t 4 % a r e shown i n F i g . l ( a ) . I n t h e c a s e o f HZSM-11, t h e p r i m a r y
p r o d u c t i s suggested t o be e x c l u s i v e l y t h e p-isomer. This r e s u l t i s s i m i l a r
t o t h a t o f t h e a l k y l a t i o n on HZSM-5 ( r e f . 3). Therefore, t h e i s o m e r i z a t i o n o f
p-diethylbenzene formed as a p r i m a r y p r o d u c t must be suppressed t o i m p r o v e t h e
p a r a - s e l e c t i v i t y o f HZSM-11 a s w e l l as HZSM-5. A c t u a l l y , m o d i f i e d HZSM-5
catalysts, whose p a r a - s e l e c t i v i t y i s high, e x h i b i t low isomerization a c t i v i -
ties, and t h e o r d e r o f t h e p a r a - s e l e c t i v i t i e s o f a s e r i e s o f HZSM-5 z e o l i t e s
modified w i t h oxides i s exactly i n reverse order t o t h a t o f t h e i s o m e r i z a t i o n
a c t i v i t i e s (ref. 3). I n t h e case o f H - f e r r i e r i t e , t h e f r a c t i o n s o f m- and o-

T a b l e 1. T h e a l k y l a t i o n o n HZSM-5, HZSM-11 and H - f e r r i e r i t e a .

C a t a 1y s t HZSM-5 HZSM-11 H-ferrieri t e

Ethylbenzene
Conversion /% 43.5 48.4 3.2

Yield /Z
Benzene
Xyl ene
- 13.7
1.2
19.3
2.1
1.1
0.1
Ethylmethylbenzene 1.6 3.2 0.2
Oiethylbenzene 26.3 20.6 1.5

F r a c t i o n /%
o-Diethylbenzene 1.7 3.3 19.8
m-Diethylbenzene 59.1 63.5 32.7
p-Diethylbenzene 39.2 33.2 47.5

a R e a c t i o n t e m p e r a t u r e ; 673 K. W/F; 7.14 g h mol-l. Data a t

a p r o c e s s t i m e o f 0 . 5 h.
d i e t h y l b e n z e n e s s l i g h t l y decreased, b u t t h a t o f p - d i e t h y l b e n z e n e s l i g h t l y
i n c r e a s e d w i t h d e c r e a s i n g W/F as s h o w n i n F i g . l ( b ) . From t h e s e f a c t s , t h e
p r i m a r y p r o d u c t on H - f e r r i e r i t e c o u l d n o t be s p e c i f i e d .
I n o r d e r t o c l a r i f y t h e e f f e c t on p a r a - s e l e c t i v i t y o f t h e a c i d s i t e s on t h e
e x t e r n a l surfaces, t h e a l k y l a t i o n i n t h e presence o f 2,4-0MQ which could n o t
enter the pores (ref. 6) was c a r r i e d o u t a t 673 K. The r e s u l t s a r e summarized
i n Table 2. The c o m p l e t e p o i s o n i n g o f t h e a c i d s i t e s on t h e e x t e r n a l s u r f a c e s
was c o n f i r m e d by t h e i n a c t i v a t i o n o f t h e c a t a l y s t s f o r t h e c r a c k i n g o f 1,3,5-
TIPB w h i c h was a s u i t a b l e t e s t m o l e c u l e f o r d e t e r m i n i n g t h e a c t i v i t y o f t h e
external surfaces (ref. 7). Moreover, t h e m o d i f i e d HZSM-5 w h i c h e x h i b i t e d a

100 100-
\
\
\
(a) HZSM-11 (b) ti-ferrierite

ap 64
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c
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50
- c
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F i g . 1. Change i n f r a c t i o n o f 0- (m), m - (A) o r p - i s o m e r (0) i n d i e t h y l b e n z e n e

produced w i t h W/F i n a l k y l a t i o n o f e t h y l b e n z e n e w i t h e t h a n o l on HZSM-5 (a) and
H - f e r r i e r i t e (b) a t 673 K.

T a b l e 2. Selective poisoning of a c i d s i t e s on e x t e r n a l s u r f a c e s a .

Oiethyl- F r a c t io n b / % 113,5-TIPB
Catalyst benzene Conversion
Yield /x 0- m- P- 1%
HZSM-5 26.3 1.7 59.1 39.2 51.1
HZSM-5' 16.9 0 42.8 57.2 0
B(l0)HZSM-sd 14.2 0 0 100.0 0

HZSM-11 20.6 3.3 63.5 33.2 59.3

HZSM-I 1 15.3 0 58.9 41.1 0

H-ferrierite 1.5 19.8 32.7 47.5 11.8

H-ferrieritec 0.4 0 0 100.0 0

a R e a c t i o n t e m p e r a t u r e ; 6 7 3 K. W/F; 7.14 g h m o l - l .
b F r a c t i o n o f each isomer i n d i e t h y l b e n z e n e produced,
' P o i s o n e d w i t h 2,4-0MQ.
d S e e T a b l e 3.
 75

p e r f e c t p a r a - s e l e c t i v i t y was c o m p l e t e l y i n a c t i v e f o r 1,3,5-TIPB cracking. The

p a r a - s e l e c t i v i t i e s o f HZSM-5 a n d HZSM-11 w e r e t o some e x t e n t i m p r o v e d b y
s e l e c t i v e poisoning. However, t h e e f f e c t o f improvement i n p a r a - s e l e c t i v i t y
b y p o i s o n i n g t h e a c i d s i t e s on e x t e r n a l s u r f a c e s i s much s m a l l e r t h a n t h a t b y
m o d i f y i n g z e o l i t e s w i t h oxides, indicating t h a t the r o l e o f oxides i s not only
the i n a c t i v a t i o n o f the external surfaces b u t also the suppression o f the
i s o m e r i z a t i o n w h i c h p r o c e e d s e v e n i n s i d e t h e pores. On t h e o t h e r hand, i n the
case o f H - f e r r i e r i t e , a p e r f e c t p a r a - s e l e c t i v i t y was a c h i e v e d b y s e l e c t i v e
poisoning o f the external surfaces. This f a c t indicates t h a t the narrow
c h a n n e l s o f H - f e r r i e r i t e c a n accommodate o n l y p - d i e t h y l b e n z e n e .
The p a r a - s e l e c t i v i t y ( f r a c t i o n o f p - i s o m e r i n t h e diethylbenzene produced)
changed w i t h W/F. I n o r d e r t o compare t h e p a r a - s e l e c t i v i t i e s o f the pentasil
z e o l i t e s v a r i o u s l y m o d i f i e d , t h e p a r a - s e l e c t i v i t i e s a t an a l m o s t c o n s t a n t
y i e l d o f d i e t h y l b e n z e n e (15-20 X), t h a t is, a t an a l m o s t c o n s t a n t a l k y l a t i o n
activity. were d e t e r m i n e d and a r e s u m m a r i z e d i n T a b l e 3. The a l m o s t c o n s t a n t
a l k y l a t i o n a c t i v i t y was a c h i e v e d b y a d j u s t i n g W/F. The p a r a - s e l e c t i v i t y was
i m p r o v e d by e v e r y m o d i f i c a t i o n made here. Especially, the pentasil zeolites
m o d i f i e d w i t h a l o t o f boron o x i d e e x h i b i t e d an e x t r e m e l y h i g h p a r a - s e l e c t i v i -
ty. S i l i c a ZSM-5 m o d i f i e d w i t h b o r o n o x i d e d i d n o t e x h i b i t a n y a l k y l a t i o n
a c t i v i t y under o u r r e a c t i o n c o n d i t i o n s . Therefore, the alkylation a c t i v i t y o f
boron oxide i t s e l f i s ignored. I n order t o c l a r i f y t h e reason why t h e
modified pentasil zeolites exhibited the high para-selectivity, the adsorption
m e a s u r e m e n t s o f p - a n d o - x y l e n e s a n d NH3-TPD w e r e c a r r i e d o u t . I n t h e p-
x y l e n e a d s o r p t i o n e x p e r i m e n t s , e v e r y z e o l i t e was s a t u r a t e d w i t h p - x y l e n e
w i t h i n 30 m i n . T h e a m o u n t o f p - x y l e n e a d s o r b e d a t i n f i n i t e t i m e , A(p-X),,
w h i c h corresponds t o a k i n d o f p o r e volume, i s s h o w n i n T a b l e 3. The p o r e
volumes o f t h e p e n t a s i l z e o l i t e s were remarkably reduced b y t h e m o d i f i c a t i o n
w i t h o x i d e s , w h i l e s t e a m i n g o r c o k i n g had o n l y l i t t l e e f f e c t .
The r e s u l t s o f t h e a d s o r p t i o n measurements o f o - x y l e n e and NH3-TPD p r o v i d e
i n f o r m a t i o n o n t h e e f f e c t i v e p o r e d i m e n s i o n o f z e o l i t e s ( r e f . 8) a n d o n t h e
a c i d i c properties o f t h e c a t a l y s t s (refs. 3,9), respectively. The r e l a t i v e o-
xylene adsorption velocity, A(o-X)180/A(p-X), was o b t a i n e d f r o m t h e r a t i o o f
t h e amount o f o-xylene adsorbed a t 180 m i n t o t h a t o f p-xylene adsorbed a t
i n f i n i t e time. The r e l a t i v e o - x y l e n e a d s o r p t i o n v e l o c i t y d e c r e a s e d t h r o u g h
the modifications, i n d i c a t i n g t h a t t h e e f f e c t i v e pore dimension o f t h e penta-
s i l z e o l i t e s was r e d u c e d . The r e l a t i v e o - x y l e n e a d s o r p t i o n v e l o c i t i e s a r e
a l s o summarized i n T a b l e 3. The r e l a t i o n s h i p b e t w e e n t h e p a r a - s e l e c t i v i t i e s
and t h e r e l a t i v e o - x y l e n e a d s o r p t i o n v e l o c i t i e s i s shown i n Fig. 2. The p a r a -
s e l e c t i v i t i e s are roughly r e l a t e d t o t h e r e l a t i v e o-xylene adsorption v e l o c i -
ties. E s p e c i a l l y i n t h e c a s e o f HZSM-5 m o d i f i e d w i t h o x i d e s , a c l o s e r e l a -
 4
T a b l e 3. E f f e c t o f m o d i f i c a t i o n s on p a r a - s e l e c t i v i t y , a c i d s t r e n g t h and a d s o r p t i o n p r o p e r t i e s . m

Alkylationa NH3-TPDb Adsorption

No. Catalyst
D i e t h y l benzene Para- Temperature A(P-X),~ A(o-X)1 t e
Y i e l d 1% Selectivity 1% /K /mg g - l /A(p-fYmd 9i?n
~~ ~~

1 HZSM-5 19.8 43.2 563 118.5 0.639 2.1

2 P( 1 )HZSM-5f 20.1 49.3 538 91.4 0.430 12.1
3 B(3)HZSM-5; 18.8 55.3 52 3 91.3 0.392 17.4
4 Mg( 18)HZSM-5 19.9 72.4 498 74.4 0.247
5 P(5)HZSM-5f 16.3 89.8 48 3 70.0 0.233
6 B(9)HZSM-5; 18.3 97.1 483 67. a 0.147
7 B ( 10)HZSM-5 17.8 100.0 478 30.2 0.007

8 HZSM-11 19.4 40.1 568 125.5 0.719 1.4

9 B ( ~ O ) H Z S M - i~ f 18.4 89.2 463 45.1 0.390
10 B ( ~ O ) H Z S M -i~ f 16.7 98.7 473 21.9 0.046

11 Stm. (1073)g 15.7 68.9 493 100.0 0.528 4.5

12 Stm.(1223)h. 15.1 84.5 488 99.2 0.420 8.5
13 C o k e d HZSM-5' 16.2 64.2 508 105.6 0.449 3.1

a R e a c t i o n t e m p e r a t u r e : 6 7 3 K. W/F: 3.57 g h m o l - ' f o r HZSM-5. P ( l ) H Z S M - 5 . B(3)HZSM-5. Mg(18)HZSM-

5, a n d H S M 1 1 ; 7.14 g h m o l - ' f o r B(9)HZSM-5. B(lO)HZSMill, B(20)HZSM-ll. a n d C o k e d HZSM-5; 14.3
g h m o l - ' for B ( l O ) H Z S M - 5 , a n d S t m . ( 1 0 7 3 ) ; 21.4 g h m o l - f o r P(5)HZSM-5. a n d Stm.(1223). Para-
s e l e c t i v i t y : f r a c t i o n o f p-isomer i n t h e d i e t h y l b e n z e n e produced.
bPeak p o s i t i o n i n NH3-TPD p r o f i l e .
CAmount o f p - x y l e n e a d s o r b e d a t i n f i n i t e t i m e .
d R e l a t i v e o - x y l e n e a d s o r p t i o n v e l o c i t y ; ( A m o u n t o f o - x y l e n e a d s o r b e d a t 1 8 0 m i n ) / ( A m o u n t o f p-
xylene adsorbed a t i n f i n i t e time).
e
tTime t o r e a c h 30 % o f amount o f o - x y l e n e a d s o r b e d a t i n f i n i t e t i m e .
f M o d i f i e d w i t h o x i d e o f P, B o r Mg. Number i n p a r e n t h e s e s i n d i c a t e s t h e a m o u n t o f P. B o r Mg a d d e d
i n weight percent.
g S t e a m e d HZSM-5 a t 1 0 7 3 K.
h S t e a m e d HZSM-5 a t 1 2 2 3 K.
iHZSM-5 c o k e d w i t h m e t h a n o l a t 9 7 3 K .
 77

t i o n s h i p i s observed. I n t h e c a s e o f t h e s t e a m e d o r c o k e d HZSM-5. however,

t h e p a r a - s e l e c t i v i t i e s w e r e r e l a t i v e l y h i g h c o m p a r e d w i t h t h e r e l a t i v e o-
xylene a d s o r p t i o n v e l o c i t i e s .
Olson and Haag have r e p o r t e d t h a t t h e p a r a - s e l e c t i v i t i e s o f m o d i f i e d ZSM-5
z e o l i t e s f o r t h e d i s p r o p o r t i o n a t i o n o f t o l u e n e have a c l o s e r e l a t i o n s h i p t o
t i m e s t o r e a c h 30 % o f a m o u n t o f o - x y l e n e a d s o r b e d a t i n f i n i t e t i m e , t0.3
(ref. 8). The t O si3
s a d i r e c t measure o f t h e c r i t i c a l mass t r a n s f e r p r o p e r -
ty. Therefore, t h e y have proposed t h a t t h e p a r a - s e l e c t i v i t y f o r t h e d i s p r o -

0 0.5 1 .o
R e l a t i v e o-xylene adsorption v e l o c i t y

Fig. 2. R e l a t i o n s h i p between t h e p a r a - s e l e c t i v i t y
and t h e r e l a t i v e o-xylene a d s o r p t i o n v e l o c i t y .
The numbers a r e correspond t o t h o s e o f t h e c a t a l y s t s
i n Table 3.

A12

0 3
02

Fig. 3. R e l a t i o n s h i p between t h e p a r a - s e l e c t i v i t y
and t o 3. The numbers a r e c o r r e s p o n d t o t h o s e
of t h e ' c a t a l y s t s i n Table 3.
p o r t i o n a t i o n o f t o l u e n e on m o d i f i e d ZSM-5 z e o l i t e s i s due t o " p r o d u c t s e l e c t i -
vity". I n t h i s work, t0.3 v a l u e s f o r s e v e r a l z e o l i t e s were d e t e r m i n e d and a r e
shown i n T a b l e 3. F o r t h e o t h e r samples, i t required too long a time t o
o b t a i n t h e a m o u n t s o f o - x y l e n e a d s o r b e d a t i n f i n i t e t i m e , h e n c e tOm3
values
c o u l d n o t be determined. The r e l a t i o n s h i p between t h e p a r a - s e l e c t i v i t i e s for
t h e a l k y l a t i o n o f ethylbenzene w i t h e t h a n o l and t0.3 values i s shown i n Fig.

I ,--.
.

I
I \
'.

Temperature /K

323 423 523 623 723 823

Temperature /K Temperature /K
F i g . 4. P r o f i l e s o f NH3-TPD.
 79

3. The r e l a t i o n s h i p i s n o t c l o s e . Accordingly, i t i s d o u b t f u l t h a t t h e para-

s e l e c t i v i t y f o r t h e a l k y l a t i o n on m o d i f i e d p e n t a s i l z e o l i t e s i s d i r e c t l y
caused b y " p r o d u c t selectivity".
T h e p r o f i l e o f NH3-TPD c o r r e s p o n d s t o t h e s t r e n g t h d i s t r i b u t i o n o f a c i d
sites. F i g u r e 4 shows t h e p r o f i l e s o f NH3-TPD f o r p e n t a s i l z e o l i t e s v a r i o u s l y
modified. The HZSM-5 and HZSM-11 z e o l i t e s e a c h e x h i b i t e d o n l y one s y m m e t r i c a l
peak, a t 563 and 568 K, respectively. Every m o d i f i e d z e o l i t e a l s o e x h i b i t e d
o n l y o n e s y m m e t r i c a l p e a k e x c e p t Mg( 18)HZSM-5 and B(1O)HZSM-11. They e x h i -
b i t e d a peak w i t h a s h o u l d e r each. The peak p o s i t i o n s h i f t e d t o l o w e r t e m p e r -
a t u r e s by t h e m o d i f i c a t i o n s , as shown i n Fig. 4. This fact indicates t h a t the
a c i d s t r e n g t h i s weakened b y t h e m o d i f i c a t i o n s . The peak p o s i t i o n s i n NH3-TPD
p r o f i l e s f o r t h e m o d i f i e d z e o l i t e s a r e s u m m a r i z e d i n T a b l e 3. I n Fig. 5, t h e
r e l a t i o n s h i p between t h e p a r a - s e l e c t i v i t i e s and t h e peak p o s i t i o n s i n NH3-TPD
p r o f i l e s f o r t h e v a r i o u s l y m o d i f i e d p e n t a s i l z e o l i t e s i s shown. An e x t r e m e l y
close r e l a t i o n s h i p i s observed except f o r B(1O)HZSM-ll. The p e a k for
B(1O)HZSM-ll had a s h o u l d e r , i n d i c a t i n g t h a t t h i s z e o l i t e had a s m a l l number
o f strong acid sites. Consequently, t h e p a r a - s e l e c t i v i t y i s r e l a t e d more
closely t o the acid strength than t o the e f f e c t i v e pore dimension o r the
c r i t i c a l mass t r a n s f e r p r o p e r t y .
As mentioned before, t h e p r i m a r y p r o d u c t i n t h e a l k y l a t i o n o n HZSM-5 and
HZSM-11 i s p - d i e t h y l b e n z e n e . and t h e i s o m e r i z a t i o n o f p - d i e t h y l b e n z e n e m u s t be
suppressed t o improve t h e p a r a - s e l e c t i v i t y . I n t h e a l k y l a t i o n o f ethylbenzene
w i t h e t h a n o l a s w e l l as t h e a l k y l a t i o n o f t o l u e n e w i t h m e t h a n o l , the a c t i v i t y

Peak p o s i t i o n i n NH3-TPD p r o f i l e /K

Fig. 5. R e l a t i o n s h i p b e t w e e n t h e p a r a - s e l e c t i v i t y
and t h e peak p o s i t i o n i n NH3-TPD p r o f i l e .
The numbers c o r r e s p o n d t o t h o s e o f t h e c a t a l y s t s
i n T a b l e 3.
o f m o d i f i e d p e n t a s i l z e o l i t e s i s h i g h enough t o c o n v e r t c o m p l e t e l y t h e a l k y l a -
t i n g agent under c o n v e n t i o n a l r e a c t i o n c o n d i t T o n s . The m o d i f i c a t i o n s made
here r e s u l t i n a r e d u c t i o n i n a c i d s t r e n g t h o f p e n t a s i l z e o l i t e s and, conse-
q u e n t l y , i n t h e s u p p r e s s i o n o f t h e i s o m e r i z a t i o n . p r o b a b l y because i n t h e
n a r r o w p o r e s o f p e n t a s i l z e o l i t e s t h e i s o m e r i z a t i o n i s s u p p r e s s e d t o some
e x t e n t through " r e s t r i c t e d t r a n s i t i o n - s t a t e s e l e c t 1 v i t y " and r e q u i r e s s t r o n g
acid sites. compared w i t h t h e a l k y l a t i o n . T h i s i s t h e reason why t h e m o d i f i e d
pentasil zeolites exhibit high para-selectivity f o r the alkylation.

REFERENCES

T. Yashima. Y. S a k a a u c h i and S. Namba, Stud. S u r f . S c i . Catal.. 7 ( 1 9 8 1 )

739-751. '

W.W. Kaedinq. C. Chu, L.B. Young, B. W e i n s t e i n and S.A. B u t t e r , J. C a t a l . ,

67 (1981) 159-174.
J.-H. K i m , S. Namba and T. Yashima, B u l l . Chem. SOC. Jpn., 61 ( 1 9 8 8 ) 1 0 5 1 -
1055.
G. P a p a r a t t o . E. M o r e t t i , G. L e o f a n t i and F. G a t t i , J. C a t a l . . 1 0 5 ( 1 9 8 7 )
227-232.
G.T. K o k o t a i l o , P. Chu, S.L. L a w t o n and W.M. M e i e r , N a t u r e , 275 ( 1 9 7 8 ) 1 1 9 -
120.
S. Namba, S. N a k a n i s h l a n d T. Yashima, J. C a t a l . , 8 8 ( 1 9 8 4 ) 505-512.
S. Namba, A. Inaka and T. Yashima. Z e o l i t e s , 6 (1986) 107-110.
D.H. Olson and W.O. Haag. i n T.E. Whytes ( E d i t o r ) , C a t a l y t i c M a t e r i a l s , ACS
Symposium S e r i e s 248, San F r a n c i s c o , 1983, ACS. W a s h i n g t o n , D. C., 1984,
pp. 275-307.
U. K u r s c h n e r , B. P a r l i t z . E. S c h r e i e r . G. O h l m a n n a n d J. V o l t e r , A p p l .
C a t a l . , 3 0 ( 1 9 8 7 ) 159-166.
H.G. Karge, J. Weitkamp (Editors), Zeolites 0s Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

HYOROGEN SPILLOVER I N THE CONVERSION OF n-ALKANES ON ZEOLITES

K.-H. STEINBERG, U. MROCZEK and F . ROESSNER

Karl-Marx-Universitat L e i p z i g , Sektion Chemie, T a l s t r . 35,
L e i p z i g , 7010 ( G . 0. R . )

ABSTRACT
The hydroconversion o f n-hexane on H - e r i o n i t e takes p l a c e i n a batch reac-
t o r a t 493 K with a h i g h y i e l d o f C -, n-C4-,,and n-C - p a r a f f i n s b u t o n l y t r a c -
5
es o f methane and ethane. I f P t i s aresent, with l e s s conversion t h e s e l e c t i v i -
t y changes towards more formation o f methane, ethane and iso-hexanes. To cause
these changes i n a c t i v i t y and s e l e c t i v i t y i t i s s u f f i c i e n t t o admix some g r a i n s
o f a Pt/alumina c a t a l y s t (about 10 mg/g H - e r i o n i t e ) mechanically i n the H-erio-
n i t e bed. Poisoning o f the P t by CO leads t o r e c r e a t i o n o f t h e o r i g i n a l a c t i v i -
t y and s e l e c t i v i t y o f the H - e r i o n i t e .
The hydroconversion of n-butane i n a p l u g f l o w r e a c t o r a t 633 K leads t o hy-
drocracking and c r a c k i n g products ( C - t o C - p a r a f f i n s ) o n l y . I n the absence o f
P t iso-butane i s formed and fewer c r a c k i n g atoducts are observed. T f P t i s
present as some g r a i n s o f a Pt/alumina c a t a l y s t or supported up t o only 0.04 %
on the H-mordenite, the highest a c t i v i t y and s e l e c t i v i t y f o r the i s o m e r i z a t i o n
are observed. For such a change i n s e l e c t i v i t y i t i s s u f f i c i e n t t o p u t a few
g r a i n s o f the Pt/alumina c a t a l y s t as a t h i n l a y e r on top, a t the bottom o r ,
b e t t e r , i n the c e n t r e o f the H-mordenite bed. The H-mordenite remained w h i t e
(no coking) a f t e r a r u n o f 1 . 5 h over a d i s t a n c e o f some m i l l i m e t r e s from t h e
Pt/alumina l a y e r with, or even against, the f l o w d i r e c t i o n .
The a c t i v e hydrogen generated a t the P t and s p i l l i n g over t o t h e a c i d i c cen-
t r e s o f the H-zeolites regulates t h e r e a c t i o n pathway there: I f t h e supply o f
s p i l l o v e r hydrogen i s hjgh, hydrocracking i s favoured; i f i t i s low, the hydro-
i s o m e r i r a t i o n and the o l i g o m e r i z a t i o n o f o l e f i n i c intermediates are favoured;
i f i t i s zero (no P t being present, or N i n s t e a d o f H or P t poisoned),
c r a c k i n g and coking dominate. I n b o t h i n z e s t i g a t e d r e a e i i o n s the hydrogen
s p i l l o v e r i s a c t i v e over a distance o f about 10 mm.

TNTROOUCTTON
B i f u n c t i o n a l z e o l i t e s a r e a c t i v e and s e l e c t i v e c a t a l y s t s i n t h e hydrocon-
version of n-paraff i n s . P t / H - e r i o n i t e i s the a c t i v e and shape-selective compo-
nent o f the commercial shape-selective hydrocracking c a t a l y s t LEUNA-Kt. 9562
(ref. 1) f o r gasoline upgrading as w e l l as the backbone o f t h e SELECTOFORMING
process ( r e f . 2). Pt/H-mordenite i s used and claimed t o be a s e l e c t i v e l i g h t
p a r a f f i n e i s o m e r i z a t i o n c a t a l y s t ( r e f s . 3 - 8 ) . Usually noble metals h i g h l y
dispersed on the z e o l i t e s r e g u l a t e the hydrogenation/dehydrogenation a c t i v i t y ,
and the a c i d i c centres o f the z e o l i t e s - u s u a l l y protons - a r e r e s p o n s i b l e f o r
the C-C-bond rearranging r e a c t i o n s .
82

I n most cases the m e t a l c r y s t a l l i t e s are l o c a t e d o u t s i d e the z e o l i t e c r y s -

t a l s , e s p e c i a l l y i n narrow-pore z e o l i t e s l i k e e r i o n i t e and mordenite. There-
f o r e , even i n the case o f very h i g h metal d i s p e r s i o n a t l e a s t a d i s t a n c e o f a
few z e o l i t e u n i t c e l l diameters remains between the metal c r y s t a l l i t e s and t h e
a c i d i c centres, which has t o be overcome by t h e hydrogen a c t i v a t e d a t t h e rnet-
a1 t o avoid coking a t the a c i d i c c e n t r e s and/or t o p a r t i c i p a t e i n t h e r e a c t i o n
pathway there. This distance can be overcome by gas phase d i f f u s i o n or by
spillover.
To gain some i n s i g h t i n t o t h e p a r t i c i p a t i o n and t h e a c t i o n o f hydrogen
s p i l l o v e r i n the r e a c t i o n o f hydroconversion of n-alkanes, t h e shape-selective
n-hexane conversion on H - e r i o n i t e and t h e i s o m e r i z a t i o n o f n-butane on H-mor-
d e n i t e i n t h e presence 1or absence) o f p l a t i n u m and hydrogen have been s t u d i e d .

EXPERIMENT
0.93 NH4-erionite was prepared by repeated i o n exchange o f s y n t h e t i c Na,K-
e r i o n i t e ICKB, B i t t e r f e l d , G.D.R.) with a Si02/A1203 molar r a t i o o f 6.0. I t was
a c t i v a t e d i n - s i t u a u t o m a t i c a l l y by t h e program: h e a t i n g i n a i r with a f l o w r a t e
o f 3 l / h and with 10 K / m i n up t o 723 K, 3 h a t 723 K , c o o l i n g down i n N2-flow
t o 423 K, 6 h a t 423 K, h e a t i n g i n H2 with a f l o w r a t e o f 3 l / h with 10 K/min
up t o 723 K, reducing 3 h a t 723 K, c o o l i n g t o t h e r e a c t i o n temperature o f
493 K. Usually 1.0 g of dry H - e r i o n i t e , f r a c t i o n 0.2 - 0.31 mm, was i n v e s t i g a -
t e d i n a q u a r t z glass r e a c t o r w i t h gas r e c i r c u l a t i o n i n t h e conversion o f
n-hexane with an n-hexane/H molar r a t i o o f 1 : 50 a t a t o t a l pressure o f
2
0 . 1 MPa. I n some experiments P t was present, mechanically admixed as 0.5%Pt/)--
A1203 or supported on the H - e r i o n i t e 10.5 % P t by impregnation w i t h
[Pt1NH3)4]C12 s o l u t i o n ) .
0.99 NH4-mordenite was prepared by repeated i o n exchange o f s y n t h e t i c Na-
mordenite with a Si02/A1203 molar r a t i o o f 10 (CKE, B i t t e r f e l d , G . O . R . ) .
Usually 400 mg o f the dry c a t a l y s t ( f r a c t i o n 0.2 - 0.31 mm) was i n v e s t i g a t e d
i n a quartz glass p l u g f l o w r e a c t o r o f 6 mm diameter a f t e r a c t i v a t i o n according
t o t h e already described program. The molar H2/butane r a t i o was always 5 : 1.
The n-butane contained already 1 5 % o f iso-butane. The GHSV was c o n s t a n t l y
80 v/vh. Besides the H-mordenite, mechanical m i x t u r e s o f some 0.5%Pt/A1203 i n
the H-mordenite bed, e s p e c i a l l y arranged as "sandwich" l a y e r s , and Pt-supported
H-mordenites (impregnated with H2PtC16 s o l u t i o n ) were s t u d i e d . The product com-
p o s i t i o n was determined by o n - l i n e gas chromatography.
 83

RESULTS AND DISCUSSION

Hydroconversion of n-hexane
The conversion o f n-hexane i n t h e presence o f hydrogen on H - e r i o n i t e a t
-, n-C:4-, and n-C 5 - p a r a f -
493 K l e d , t o a l a r g e e x t e n t , t o t h e formation o f C
3
f i n s b u t n o t t o methane and ethane (only t r a c e s ) (Fig. l a ) . With i n c r e a s i n g
r e a c t i o n time the formed n-pentane s t a r t e d t o be converted too. T f P t was sup-
ported t o 0 . 5 w t . % on the H - e r i o n i t e , the c a t a l y s t was remarkably l e s s a c t i v e
and t h e s e l e c t i v i t y was d r a s t i c a l l y s h i f t e d towards the formation o f iso-hexa-
nes, less butane, no n-pentane, b u t more methane and ethane ( F i g . I b ) . Tn b o t h
cases the concentration o f o l e f i n s was lower than 0.2 w t . %.T f t h e P t on t h e
H - e r i o n i t e was poisoned by the i n t r o d u c t i o n o f about 1 v o l . % CO i n t h e r e c i r -
c u l a t i o n system, the a c t i v i t y was increased and the s e l e c t i v i t y o f the H-erio-
n i t e f r e e of P t was observed: no iso-hexanes, b u t n-pentane, n-butane, and
propane were the main products ( F i g . 1c).

0 b

n- C6 n- C6

, I

4 8 4 8

F i g . 1. Hydroconversion o f n-hexane a t 493 K, r e a c t o r with gas c i r c u l a t i o n ,

dependence of product composition on time. (a) 1 g H - e t i o n i t e . (b) 0.5 %
P t / H - e r i o n i t e . ( c ) 1 g 0.5 % P t / H - e r i o n i t e , 1 % CO i n t h e r e c i r c u l a t i o n sys-
tem.
84

Obviously, t h e presence o f a c t i v e P t d i r e c t s the r e a c t i o n towards t y p i c a l

hydroconversion products. I n t h e absence o f P t ( o r P t being poisoned) t y p i c a l
c r a c k i n g products (according t o t h e C-numberlare formed.
Probably, most o f t h e P t i s s i t u a t e d o u t s i d e o f t h e H - e r i o n i t e c r y s t a l s . The
8-membered pore openings o f t h e e r i o n j t e (0.36 x 0.52 nm) w i l l a t l e a s t h i n d e r
the d i f f u s i o n o f [Pt(NH,),I2' c a t i o n s i n t o t h e e r i o n i t e channels. Even i f t h e r e
were some P t i n s i d e t h e e r i o n i t e , due t o t h e low content t h e m a j o r i t y o f t h e
e r i o n i t e would remain f r e e o f P t . Therefore, i f t h e hydrogen a c t i v a t e d a t t h e
P t takes p a r t i n the r e a c t i o n a t t h e a c i d i c ( p r o t o n i c ) c e n t r e s o f t h e e r i o n i t e ,
i t must overcome the d i s t a n c e o f a number o f l a t t i c e u n i t s . To prove t h i s idea
we t e s t e d mechanical m i x t u r e s o f a 0.5%Pt/A1203 c a t a l y s t w i t h t h e H - e r i o n i t e
(Tab. 1). I n these experiments o n l y some m i l l i g r a m s (same g r a i n f r a c t i o n as the
H - e r i o n i t e ) were admixed i n t h e H - e r i o n i t e bed. The data i n Tab. 1 show t h a t
already f o u r mg o f t h e Pt/A1203 c a t a l y s t i n t h e bed were s u f f i c i e n t t o cause a
c a t a l y t i c behaviour s i m i l a r t o t h a t o f 0.5 % P t supported on the H - e r i o n i t e .
The less P t supplied, the more s t r o n g l y t h e c r a c k i n g dominated. A l i the r e s u l t s
given i n Tab. 1 show t h a t t h e hydrogen a c t i v a t e d a t t h e P t was a b l e t o over-
come l a r g e distances (some mrn) between i t s source and t h e p l a c e o f i t s a c t j o n .
That c o u l d happen p r i n c i p a l l y by gas phase d i f f u s i o n o r by s p i l l o v e r .

TABLE 1
Hydroconversion o f n-hexane a t 493 K, r e a c t o r with r e c i r c u l a t i o n , dependence
o f product composition on t h e amount o f 0.5 % Pt/A1203 c a t a l y s t mechanically
d i s t r i b u t e d i n I g H-erionite, after 7 h run

0.5 % Pt/A1203
amount, mg 4 10 50

n-hexane conversion, %
c r a c k i n g t o C1-C5,
iso-hexanes,
%
%
0.5
6.5
2.0
8.7
4.8
3.9
7.2
1.8
5.4
1
To d i s t i n g u i s h between t h e r e b o t h p o s s i b i l i t i e s we c a r r i e d o u t experiments
with d i f f e r e n t arrangements o f t h e Pt/A1203 c a t a l y s t ( F i g . 2 ) . We p u t 10 mg o f
the sample on top o r a t the bottom o f t h e H - e r i o n i t e , i n a basket hanging j u s t
over t h e H - e r i o n i t e (no s o l i d c o n t a c t ) , and as a l a y e r separated by a q u a r t z
glass powder l a y e r . For comparison t h e r e s u l t on 10 mg Pt/A1203 c a t a l y s t alone
i s given.
 85

arrangement

11
.....
..,...

......
.... ..
Ili _
!:..I-.*

......

n-hexane conversion, % 8.7 8.7 48.1 52.5 2.6

0.5%Pt/A1203 H-erionite quartz glass

F i g . 2 . Hydroconversion o f n-hexane a t 493 K , r e a c t o r with r e c i r c u l a t i o n ,

dependence o f conversion on arrangement o f 10 mg 0.5%Pt/A1 0 c a t a l y s t and
2 3
1 y o f H-erionite, a f t e r 7 h run

The r e s u l t s show t h a t the surface d i f f u s i o n of the a c t i v a t e d hydrogen ( i t s

s p i l l o v e r ) must be the reason f o r the s u r p r i s i n g a c t i o n o f P t being present
f a r away from the a c i d i c centres b u t p a r t i c i p a t i n g i n the hydroconversion o f
n-hexane there. Otherwise we should observe t h e same r e s u l t s i n cases a t o d
i n F i g . 2. Obviously, the hydrogen s p i l l o v e r takes p l a c e i n and against t h e
flow d i r e c t i o n on t h e H - e r i o n i t e b u t n o t through the gas phase ( c ) or on t h e
(poor i n surface) S i O glass (d).
2
I n a l l cases described above t h e maximal l e n g t h o f s p i l l o v e r a c t i o n was
about 10 mm (height o f the e r i o n i t e bed). To check t h e a c t i o n r a d i u s o f t h e
hydrogen s p i l l o v e r we c a r r i e d o u t experiments according t o F i g . 3. With a s e t
o f s p e c i a l quartz glass sample h o l d e r s described t h e r e i n we were a b l e t o change
the average distance between the 10 mg Pt/A1203 c a t a l y s t l a y e r on t o p and t h e
H - e r i o n i t e without changing the H - e r i o n i t e amount. The r e s u l t s show t h a t the
conversion degree o f the n-hexane s t a r t s t o increase i f the H - e r i o n i t e bed
h e i g h t i s greater than about 20 mm. That means t h e a c t i o n of the hydrogen
s p i l l o v e r becomes less and less as the d i s t a n c e i n t h e H - e t i o n i t e becomes
g r e a t e r ; then cracking dominates over hydrocracking.
86

y$LP
.....
.',..I.

......

I I

70 20 30 sample holder
I, mm

F i g . 3 . Hydroconversion of n-hexane a t 493 K, reactor with recirculation,

dependence o f conversion on distance 1 o f t h e 0 . 5 % Pt/A120j catalyst,
1 g H-erioriite, a f t e r 6 h run

Hydroconversion o f n-butane
Under the more severe c o n d i t i o n s o f the hydroconversion o f n-butane i n a
p l u g f l o w r e a c t o r a t 550 t o 640 K t h e hydrogen s p i l l o v e r leads t o s i m i l a r e f -
f e c t s . F i g . 4 shows t h e r e s u l t s on 400 mg H-mordenite (a) and a mechanical
m i x t u r e o f 40 mg 0.5%Pt/A1203 c a t a l y s t and 400 mg H-mordenite ( b ) a f t e r 0 . 5 h
t i m e on stream, On t h e pure H-mordenite l e s s i s o m e r i z a t i o n b u t more c r a c k i n g
t o C3 hydrocarbons take place, When 40 mg Pt/A1203 c a t a l y s t are admixed with-
i n t h e H-mordenite bed ( t h e same g r a i n f r a c t i o n s have been used), less n-butane
i s converted b u t t h e i s o m e r i z a t i o n i s p r e f e r r e d (and coking is suppressed as
w e l l ) . As i n the n-hexane hydroconversion on H - e r i o n i t e , o n l y the presence o f
some g r a i n s o f P t (as t h e Pt/A1203 c a t a l y s t ) i s s u f f i c i e n t t o i n f l u e n c e s t r o n g -
l y t h e a c t i v i t y as w e l l as t h e s e l e c t i v i t y o f the n-butane hydroconversion.
Again t h e a c t i v e hydrogen must s p i l l over from t h e P t onto the H-mordenite's
a c i d centres, t a k i n g p a r t t h e r e i n t h e r e a c t i o n .
To c c r r o b o r a t e our observations and i n t e r p r e t a t i o n o f t h e n-hexane e x p e r i -
ments we i n v e s t i g a t e d a s e t o f d i f f e r e n t m i x t u r e s o f Pt/A1203 and H-mordenite
( F i g . 5 ) and d i f f e r e n t arrangements o f b o t h c a t a l y s t s ( F i g . 6 ) i n t h e f l o w
r e a c t o r . F i g . 5 shows t h e r e s u l t of d i f f e r e n t amounts o f t h e Pt/A1203 cata-
l y s t i n the H-mordenite bed. A mechanical m i x t u r e of one p a r t o f Pt/A1203
 87

b
\ ISO- c
4
80

s 60 I n- c4 n - C4
' 40
2.4

ZG
Y4
-_
550 590
LJ C,'C
630

F i g . 4. Dependence of n-butane hydroconversion on temperature, plug flow

reactor. a ) 400 my H-mordenite. b ) 400 mg H-mordenite + 40 mg 0.5 % Pt/A1203

Fly. 5. Influence of the 0.5 % Pt/A120j amount (my) mechanically admixed

with 400 ng H-mordenite on the n-butane hydroconversion at 633 K

cracking products iso-butane selectivity of the

isomerization
88

and 10 p a r t s o f H-mordenite e x h i b i t s the h i g h e s t s e l e c t i v i t y f o r the isomeri-

z a t i o n a t r a t h e r h i g h t o t a l a c t i v i t y . Less P t i n t h e bed favours c r a c k i n g
(and coking, see below); more P t favours n o n s e l e c t i v e hydrocracking.

F i g . 6 . Influence o f d i f f e r e n t arrangements o f 40 mg 0 . 5 % Pt/A1203 c a t a l y s t

and 400 my H-mordenite on the ri-butane hydroconversion a t 633 K

40 rng 0 . 5 % Pt/A1203 400 mg H-rnordenite

0c r a c k i n g products iso-butane
s e l e c t i v i t y of the i s o m e r i z a t i o n

The arrangement o f the P t / A l 0 and the H-mordenite i s o f g r e a t importance

2 3
f o r the a c t i v i t y and t h e s e l e c t i v i t y . F i g . 6 shows some examples. If a l a y e r
of 40 my Pt/A1203 i s p u t on top or a t t h e bottom o f t h e H-mordenite, only a
weak i s o m e r i z a t i o n b u t an i n t e n s e c r a c k i n g takes p l a c e . D i v i d i n g of t h e
40 rng P t / A l 2 O j i n t o two l a y e r s improves t h e i s o r n e r i z a t i o n a c t i v i t y , and
d i v i d i n g i n t o four l a y e r s improves i t f u r t h e r .
 89

Obviously, t h e r e e x i s t s an o p t i m a l distance between P t and the a c i d i c cen-

t r e s i n the H-mordenite f o r supporting the isomerization. The reason can o n l y
be the hydrogen s p i l l o v e r again. Tn the very complex mechanism o f p a r a l l e l and
consecutive r e a c t i o n s i n the path o f the hydroconvetsion o f n-butane the unsat-
u r a t e d intermediates seem t o play a s p e c i a l r o l e f o r t h e coking r e a c t i o n .

F i g . 7. Photos o f the quartz glass r e a c t o r with c a t a l y s t arrangements according

t o F i g . 6 a f t e r 1 . 5 h hydroconversion of n-butane a t 633 K, f l o w from t o p t o
bottom
A H-mordenite 8 0.5 % Pt/Alz03

F i g . 7 shows photos o f the arrangements B, C, C ' , 0, and E. Arrangement B

(H-mordenite o n l y ) shows a s t r o n g l y coked c a t a l y s t bed ( b l a c k ) . I n arrangement
C a zone o f about 10 mm i n t h e f l o w d i r e c t i o n remains white/grey. The s p i l l o v e r
hydrogen i s able - n o t s u r p r i s i n g l y - t o avoid coking even a g a i n s t the f l o w d i -
r e c t i o n (case C'). About 5 mm remains white/grey. D i v i d i n g o f t h e Pt/A1203 ca-
t a l y s t i n t o two (0) or four ( E ) l a y e r s improves the r e s i s t a n c e of the H-morde-
n i t e t o f u r t h e r coking.
The i n t e r f e r e n c e of the s p i l l o v e r i n t h e r e a c t i o n p a t h o f n-alkane conver-
s i o n on z e o l i t e s needs P t and hydrogen as w e l l . I f the hydrogen i n t h e n-butane
conversion i s replaced by n i t r o g e n and t h e o t h e r r e a c t i o n c o n d i t i o n s are k e p t
constant, on H-mordenite as w e l l as on a m i x t u r e o f 10 mg 0.5%Pt/AlZO3 and
H-mordenite 48.5 % of cracking products are formed, the s e l e c t i v i t y f o r i s o -
m e r i z a t i o n i s l e s s than 10 %, and f a s t coking takes place ( f o r more d e t a i l s
see r e f . 9 ) .
90

CONCLUSIONS
S i m i l a r t o the hydroconversion o f n-heptane on H - e r i o n i t e ( r e f . 101, the
hydroconversion o f n-hexane on H - e r i o n i t e and o f n-butane on H-mordenite is
s t r o n g l y influenced i n i t s s e l e c t i v i t y and a c t i v i t y by the a c t i o n of hydro-
gen s p i l l o v e r . The a c t i v e hydrogen i s generated a t P t everywhere i n the ca-
t a l y s t bed and s p i l l s over t o the a c i d i c z e o l i t e c e n t r e s . There i t i n f l u e n c e s
the mechanjsm v i a c o n t r o l l i n g the c o n c e n t r a t i o n o f unsaturated intermediates
such as o l e f i n s , carbenium i o n s and coke precursors. Up t o 630 K t h e hydrogen
s p i l l o v e r a c t s over a distance of more than 10 mm. I f the supply o f s p i l l i n g
over hydrogen i s high, hydrocracking is favoured; i f i t is low ( l i t t l e P t p r e -
sent, P t f a r from the a c i d i c c e n t r e s ) , hydroisornerization i s favoured; i f i t
is zero (no P t present, P t poisoned or N2 i n s t e a d o f H ), c r a c k i n g and coking
2
(consecutive r e a c t i o n s o f o l e f i n s and/or carbeniurn i o n s ) dominate.

REFERENCES
1 K.-H. Steinberg, K. Becker, K.-H. N e s t l e r , Acta Phys. Chem. Univ. Szeged
31 (1985) 441
2 5.-0. Burd, J . Maziuk, Hydrocarbon Processing 51 (1972) 97
3 B r i t . Pat. 2 500 072, 10. 7 . 1975
4 B r i t . Pat. 2 712 996, 15. 6 . 1978
5 00 WP 240 503, 2 9 . 8. 1985
6 00 WP C07C/302 673 4 ( a p p l . )
7 A. Montes, G. Perot and M. Guisnet, React. K i n . C a t a l . L e t t . 13 (1980) 77
8 N. N. Krupkina, A. Z . OorogoEinski and A. L. Proskurnin, I z v e s t . Vyss.
UCebn. Sav., N e f t i Gaz 1985, 4 3
9 U. Mrocrek, Thesis, Karl-Marx-Universitat L e i p z i g , 1987
10 A. E l Tanany, G. M. Pajonk, K.-H. Steinberg, S. J . Teichner, Appl. Cat.
39 (1988) 89
H.G. Karge,J . Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

INTERMEDIATES IN THE FORMATION OF AROMATICS FROM PROPENE AND 2-PROPANOL ON

H-ZSM-5 ZEOLITES

H. LECHERT’, C.BEZOUHANOVA2, C. DIMITROV2 and V. NENOVA2

Institute of Physical Chemistry, University of Hamburg, Bundesstr.45,
$000 Hamburg 13 (Germany)
University of Sofia, Faculty of Chemistry, 1 Av.A.Ivanov, Sofia 1126,
(Bulgaria)

ABSTRACT
The aromatization o f propene and 2-propanol on H-ZSM-5 was studied on
samples with Si/Al-ratios of 50, 100, 140, 250, 500, and 1000 at temperatures
of the beginning of this reaction at 523 K and 573 K. The aim of these
experiments was the detection of possible intermediates of the aromatization.
The liquid reaction products contained beside a large fraction of hexane
isomers an appreciable amount of substituted cyclohexanes as trimerization
products. The first detectable trimeric aromat was 1,2,4-trimethylbenzene from
which the other aromatic compounds can be formed via subsequent disproportion-
ation and dealkylation reactions. The formation of the aliphatic trimer is
favoured for the propanol feed and for propene in the presence o f water.

INTRODUCTION
ZSM-5 zeolites are used as highly shape-selective catalysts in different
types of reactions. The peculiarities of these catalysts consist of a
combination of strong acid sites beside hydrophobic walls and a channel system
of specific size leading to special mechanisms of selectivity and very l o w
coking. The high Si/Al-ratio leads to high heat stability. Starting from
alcohols, aromatics (MTG) or olefins (MTO) are produced. In the recent time a
great variety of reactions has been reported starting from alcohols
(refs. 1-3). There is a considerable interest in the conversion of propene on
H-ZSM-5 zeolites in technical processes and many efforts have been made to
find conditions of high selectivity and to get a thorough understanding of the
mechanism (refs. 5-9).
In studies of Derewinski et al. (ref. 4) on the modification of the acidic
properties of pentasils by selective poisoning using pyridine or ion exchange
with different alkali metals showed that olefins are formed from alcohols on
very weak acid sites. The subsequent transformations to aromatic hydrocarbons
via oligomers and cyclopolyenes demand stronger acidity.
For the formation of benzene from propene a detailed reaction scheme
including subsequent dimers was given by Vedrine et al. (ref. 7).
92

Nevertheless, the aromatization of propene is usually not selective for the

formation of benzene. At relatively low temperatures an appreciable amount of
C9 products could be observed (ref. 6).
In connection with this work, in the present paper we report the catalytic
activity of ZSM 5 zeolites with a wide range of Si/Al-ratios connected with a
wide range of concentrations of acid sites for the conversion of propene and
2-propanol at 523 K and 573 K where the aromatization is just beginning and
precursors of this reaction may be detected.

EXPERIMENT
The ZSM-5 catalysts were synthesized with Si/Al ratios of s = 50, 100, 140,
250, 500, 1000. The batch composition was generally 14 NaOH * 100 Si02 * lOO/s
NaA102 * 5 TPABr * 1000 H20. s is a positive number which is chosen in the
experiments from about 20 to infinite. s is equal to the Si/Al-ratio in the
batch.
As silica source a precipitated product of Merck has been used. The alumina
was a sodium-aluminate solution from Riedel de Haen. The water content of the
batch for optimal crystallization i s dependent on the silica source and may
vary within a factor of 2. The crystallization was carried out in stainless
steel, teflon lined autoclaves at 423 K . The time necessary for complete
crystallization was 7 hours.
The crystallites were analyzed with respect to their Si/Al-ratio. For the
samples discussed in this paper the analyzed value was equal to the ratio
chosen in the batch.
The template was decomposed by heating for 6 hours in an air flow under
slowly increasing temperature by 4 K/min up to 723 K. The H-forms were
obtained by treating the synthesized zeolites with 0.6 M HC1 aqueous solutions
under stirring at room temperature.
For the catalytic experiments a fixed-bed flow reactor was used with 1 g
resp. 2 ml (1.25 - 2.5 mm fraction) of the zeolite previously pressed, crushed
and sieved. The activation and regeneration of the catalysts was performed at
723 K for 3 hours under an air flow. Before the experiments the catalysts were
flushed with Ar at the chosen temperature of the reaction.
The reaction products were analyzed by GC using a column with benzyl
cyanide t silver nitrate on Chromosorb PAW at room temperature for the gaseous
products and 3 m column 4mm in diameter containing 12% Benton 34 t
dodecylphthalat (1:l) on Celite at 353 K for the liquid products. The latter
products were also analyzed by GC-MS using for the separation a 50 m capillary
column with Carbowax.
 93

RESULTS
In preliminary experiments was found that samples of Na-ZSM-5 were
inactive for the chosen reactants and conditions.
The yields of liquid products from propene and from 2-prOpanOl as a
function of the zeolite composition are presented in Fig. 1. The product
distribution for propene for the different zeolites is shown in Table 1.
The product distribution for 2-propanol is qualitatively similar. Differen-
ces can be found in a distinctly increased yield of methyl-cyclopentane and in
the fraction of the substituted cyclohexanes. To get an impression of possible
changes of the catalyst by the released water the time dependency of the
product distribution was studied for the sample with Si/AI = 500 where the
highest selectivity effects may be expected. The results are given in Table 2.
In all liquid products according to a mass spectroscopic analysis the
presence o f C4H7 t (m/z=55) was observed (see also ref. 8).
For Si/Al = 1000 for propene no or low conversion could be observed at 573
K in various experiments. This sample has most probably an inhomogeneous
distribution of the A1 and will not be taken into account in the further
discussion.

1001

I
I
....
-7 I
I
....'*....'
40
0.
-0
.I+ 20
3
.z I,,, , , , , , , , , , , , , , , , , , ,
OO 5 10 15 20
1000#A1/ (SitAl)

Fig. 1. Yields of liquid products as a function of the composition of the

zeolites: A- propene at 573; 0 - 2-propanol at 523 K;O2-propanol at 573 K.
94

TABLE 1
Propene conversion on H-ZSM-5 Zeolites at 573 K, WHSV = 1.3 hour-', (x -
523 K , xx- Propene + Water, molar ratio 1:3), average values from 5 hours
stream
Si/Al 50' '05 50 100 140 250 500
Liquid.Prod,wt% 36.6 28.9 60.0 44.7 40.2 35.4 43.5
Coke, w t % of feed 1.6 0.5 1.4 1.8 2.0 1.3 -
C-6 1 29.8 10.7 3.3 - - -
C-6 2 - - 12.2 13.7 23.5 23.1 18.5
C-6 3 - - 1.3 17.9 26.9 27.7 26.9
n-Hexane 23.5 30.8 6.7 8.6 17.6 23.5 21.0
Unidentified 1 - - 4.8 - - - -
Methyl-cyclopentane 4.9 2.5 3.9 5.7 tr tr tr
Cyc1ohexane 4.9 2.5 6.0 6.1 5.8 5.7 6.4
Unidentified 2 - - 3.7 4.2 - - -
Unidentified 3 - - 1.8 - - - -
Subst.Cyclohexane 16.7 27.2 4.2 5.5 13.7 9.7 13.7
Benzene 7.6 7.3 3.0 3.5 3.4 3.1 4.4
Unidentified 4 9.8 18.5 1.3 1.6 9.0 6.2 9.1
Toluene 2.8 - 17.2 14.2 tr tr -
Ethylbenzene - - 4.1 1.9 tr 1.0 tr
p-Xylene - - 15.3 10.4 - - -
m-Xylene - - 3.7 6.7 - - -
o-Xylene - - 0.8 tr - - -
1,2,4-Trimethylbenzene - - 6.7 - - - -

TABLE 2
Composition of the liquid products iy wt% from 2-propanol on H-ZSM-5,
(Si/A1=500) at 573 K , LHSV = 1 hour , 32,5% liquid products of feed
Products Time on stream, min
30 90 120 150 180 210 240 270
C-6 1 - - tr 0.9 0.6 0.6 0.3 0.4
C-6 2 1.8 tr tr 1.3 1.7 1.5 0.7 0.7
C-6 3 19.9 7.5 7.0 10.0 14.3 14.5 11.3 8.5
n-Hexane 0.1 2.3 1.9 0.2 1.6 1.7 2.8 1.5
Methyl-cyclopentane 32.6 12.9 31.2 22.1 24.4 26.6 18.0 21.9
Cyclohexane 5.9 - 2.9 2.6 3.3 4.2 4.0 3.2
2-Propanol 5.4 7.5 0.5 2.9 3.3 4.1 3.8 3.3
Subst.Cyclohexane 18.4 35.8 23.4 19.7 21.6 19.8 25.3 19.2
Benzene 6.8 15.1 7 . 8 4.9 6.0 6.9 10.8 9.5
Unidentified 1 9.1 18.9 9.7 17.9 13.0 13.1 19.9 18.3
Toluene - - 2.9 4.3 2.8 3.5 2.0 5.0
Unidentified 2 - - 3.9 3.4 2.6 3.5 1.1 3.3
Ethylbenzene - - 6.8 7.2 3.1 - - 3.3
Unidentified 3 - - 1.9 2.5 1.4 - - 3.3
 95

DISCUSSION
Under the special conditions of reduced temperature used in our experiments
for propene the total amount of liquid products decreased with increasing
Si/Al-ratio. As expected, a high amount of dimers was observed as C6 fraction.
The relative amount of this fraction is about 15-20% higher for the samples
with Si/A1 = 140, 250, and 500 compared with the samples with Si/Al = 50 and
100. Cyclohexane and methyl-cyclopentane are present only in minor quantities.
The quantity of substituted cyclohexanes which can be regarded as trimer
products increased with increasing Si/Al-ratio.
This behaviour may be understood qualitatively from the following wellknown
effects. The olefin is adsorbed preferably at the acidic centers. At the
centers with the highest acid strength carbenium ions are formed which react
with olefin molecules additionally present in the channels.
A part of the resulting dimers adds a third propene molecule forming
trimeric olefins which undergo a cyclization giving the fraction of the
substituted cyclohexanes. Reactions of this kind have been discussed already
by Wolthusen et al. (ref. 5 ) .

CH
,. -CH=CH2
-
CH3\CH-CH2 -;H-CHj
Cy -tH-CH3 CH3’

Cycloalkanes with 7 - 9 carbon atoms have been found also in (ref. 6). These
species are present in the reactants in our experiments to about 10 - 15%,
except for the samples with Si/Al = 50 and 100. Exactly for these samples,
however, an appreciable amount of toluene and p-xylene could be observed
beside some ethyl-benzene and m-xylene.
For Si/Al = 50 additionally 6.7% 1,2,4-trimethylbenzene was found which
could be detected also in the mass spectroscopic experiments.
Other authors describe mesitylene or ethyl-toluenes as products in similar
experiments (ref. 15).
The amount of benzene in the reaction products is nearly constant at values
between 3 and 4.5% for all Si/Al-ratios independent of the formation of other
aromat i c s .
All these observations lead to the conclusion that substituted aromatics
found in the reaction products for the zeolites with Si/A1 = 50 and 100 are
96

not formed from dimerization, dehydrogenation to benzene and subsequent

alkylation, but rather from a cyclotrimer of the propene which undergoes
dehydrogenation and transalkylation reactions.
The source of the constant amount of benzene may be possibly dimers
dehydrogenated according to the scheme of Vedrine et al. (ref. 7).
To look for the possible source of benzene for Si/Al = 50 an experiment was
carried out, trying to convert cyclohexane into benzene under the given
conditions at 523 K. Beside some aliphats only a little methyl-cyclopentane
was observed.
The finding that the aromatization is favoured obviously at lower Si/Al-
ratios seems to suggest the assumption that for the hydrogen shift included in
that reaction two activated molecules with not a too large distance or one
activated and one strongly sorbed molecule seem to be necessary. If the
distance of both is too large the reaction stops at the stage of the
cyclotrimer under the temperature conditions of our experiments.
For 2-propanol a qualitatively similar product distribution was observed
with a reduced activity of the catalyst.
The striking difference was the high amount of methyl-cyclopentane and the
substituted cyclohexanes being observed in all experiments. The other dimers
are drastically reduced in comparison with the data for propene.
To get insight into the question whether this effect is due to a change of
the catalyst by the released water, for the sample with Si/Al = 500 with the
lowest activity the time dependency of the product distribution was studied
which is demonstrated in Table 2.
Obviously, the water released in the initial dehydration step influences
the formation of the oligomers. To prove this, with a sample of Si/Al = 50 an
experiment was carried out with a mixture of propene and an excess o f water
which is demonstrated in the second column of Table 1.
Also in this case the activity is reduced and the concentration of the
trimer is increased. The relative concentrations within the C6 fraction are
changed compared with the results with pure propene shown in the first column
in Table 1.
Comparing the results o f Table 2 with the last column of Table 1 a slightly
increased activity for the aromatization can be seen from a comparison with
column 1 in Table 1. The effect of the role o f the trimer as the origin of the
substituted aromats is, however, less pronounced.
For the mechanism of aromatization On0 et al.(ref. 9) found, that at 773 K
the molar ratio of alkanes to aromatics in the product over H-ZSM-5 was 2.9,
so confirming the scheme of Poutsma (ref. 13).
An analysis of the hydrogen balance of all identified substances gave no
 97

clear picture in our experiments.

On Zn-ZSM-5 Ono et al. suggest another mechanism involving dehydrogenation
on the zinc species. The final scheme of Ono et al.(ref. 9) for alkene
transformation offers two paths of aromatization - via allylic species in the
presence of dehydrogenation agents (zinc, gal 1 ium) and direct conversion of
the dimers to aromatics and alkanes with the participation of protons in
successive hydride transfer and deprotonation of carbenium ions. Our results
are consistent with the latter concept with the trimers as the important
intermediates. The dehydrogenation may also take place directly on the surface
of the walls of the ZSM 5 channels. Because o f this ability the ZSM 5 zeolites
are also called "pseudo-transition metals" in (ref. 14).
The formed 6 or 5 atom rings from the trimer are quite bulky. Therefore,
they probably transform further by methyl migration:

According to a mass-spectroscopic analysis 1,2,4-trimethylbenzene should

be the initial aromatic compound formed from propene. Toluene and xylenes are
formed from it by dealkylation, disproportionation and isomerization. Thus, C-
7 and C-8 aromatics are not a result of benzene alkylation, but originate
from the discussed trimers.
The picture is, in principle, not different in the case of 2-propanol feed.
Differences may occur in the formation of the initial carbenium ion. By the
contact of the alcohol with the acidic OH-groups of the zeolite the protona-
tion, formation of the oxonium salt and dehydration to the corresponding
carbenium ion may be discussed as an alternative way.

CONCLUSIONS
The production of aromats from propene on H-ZSM 5 zeolites proceeds mainly
via trimers and cyclotrimers. The benzene homologues are formed by further
disproportionation and dealkylation of the respective aromatized substances of
which 1,2,4-trimethylbenzenecould be detected.
The presence of the released water in case of the 2-propanol favours the
formation of cyclic compounds and influences also the aromatization reaction.
98

REFERENCES
1 Y. Matsumura, K. Hashimoto and S. Yoshida, J. Catal., 100 (1986) 392-400.
2 C. Bezouhanova, Chr. Dimitrov, H. Lechert, V. Nenova and M. Krusteva,
Proc.6th Int. Symp. Heterogeneous Catal., Sofia, 1987, part 2, p. 216.
3 W. Holderich, M. Hesse and F. Naurnann, Angew.Chernie, 100 (1988)232.
4 M. Derewinski, J. Haber and J, Ptaszynski, in Y. Murakami, A. Iijima and
J. W. Ward (Editors), New Dev. Zeol. Sci. Tech., Proc. 7 t h Int. Conf.,
1986, pp. 957-964.
5 J.P. Wolthuizen, J.P. van den Berg and J.H.C. van Hooff, in B. Imelik et
al. (Editors.), Catalysis by Zeolites, Elsevier, 1980, pp. 85-92.
6 K.G. Wilshier, P. Smart, R. Western, T. Mole and T. Behrsing,
Appl.Catal., 31 (1987) 339-359.
7 J.C. Vedrine, P. Dejaifve, E.D. Garbowski and E.G. Derouane, in B. Imelik
et al. (Editors), Catalysis by Zeolites, Elsevier, 1980, p. 29.
8 S. Bessell and D. Seddon, J. Catal., 105, (19871, 270-275.
9 Y. Ono, H. Kitagawa and Y. Sendoda, JCS Far. I , 83 (1987) 2913-2923.
10 H. Lechert, C. Bezouhanova, Chr. Dimitrov, V. Nenova and G. Taralanska,
J.Mol .Catal., 35 ( 1986), 349-354.
1 1 C. Bezouhanova, H. Lechert, Chr. Dimitrov, V. Nenova, J.Molec.Structure,
114 (1984),301-304.
12 G.A.Olah, Uspekhi Khimii, 44 (1975), 793.
13 M.L. Poutsma, in J.A. Rabo (Editor), Zeolite Chemistry and Catalysis,
ACS Monograph, Amer.Chem.Soc., Washington D.C. (1976),
14 W. Drenth, W.T. Andriessen and F.B. Van Duijneveldt, J.Molec.Catal.,21
(1983) 291-296.
15 F. Marscheider, Diplome Work, University of Hamburg 1988.
H.G. Karge, J. Weitkamp (Editors ), Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - P r i n t e d in T h e Netherlands

ZEOLITE AN0 M A T R I X STRUCTURES AND T H E I R ROLE I N CATALYTIC CRACKING

C.J. Groenenboom
Akzo C h e m i c a l s , Research C e n t r e Amsterdam
P . O . Box 1 5 , 1000 AA Amsterdam, The N e t h e r l a n d s

ABSTRACT
Some r e c e n t developments i n t h e s y n t h e s i s and m o d i f i c a t i o n o f Y - z e o l i t e s
and t h e i r i n f l u e n c e on t h e p e r f o r m a n c e o f c r a c k i n q c a t a l y s t s a r e r e v i e w e d . In
t h e s e c a t a l y s t s a l s o f u n c t i o n a l i n g r e d i e n t s a s a c t i v e a l u m i n a s and m e t a l t r a p s
a r e i n c o r o o r a t e d . The e f f e c t o f a l u m i n a on p o r e s i z e d i s t r i b u t i o n and t h u s on
t h e c r a c k a b i l i t y o f h e a v i e r f e e d s t o c k s i n d i s c u s s e d . F u r t h e r t h e mechanism o f
metal p a s s i v a t i o n i n o u t l i n e d .

I . INTRODUCTION
C a t a l y t i c c r a c k i n q o f h y d r o c a r b o n s on s o l i d a c i d s i s a l r e a d y a r a t h e r o l d
p r o c e s s . However, ma.jor chanqes have been c a r r i e d o u t d u r i n g t h e y e a r s ( r e f .1.)
A t t h e end o f t h e s i x t i e s a r e a l b r e a k t h r o u q h was r e a c h e d b v t h e a p p l i c a t i o n
o f c r y s t a l l i n e aluminosilicates o r z e o l i t e s (ref.2.3).As compared w i t h t h e
amOrDhOUS s i l i c a - a l u m i n a s . z e o l i t e c o n t a i n i n g c a t a l y s t s showed a h i q h e r
a c t i v i t y , a b e t t e r s t a b i l i t y and a b e t t e r s e l e c t i v i t y f o r g a s o l i n e .
The o n l y p e n a l t y t h a t has t o be p a i d was t h e l o w e r p r o d u c t i o n o f o l e f i n e s
r e s u i t i n g i n l o w e r o c t a n e numbers. A t t h a t t i m e , however t h i s was n o t considered
as a s e r i o u s problem. T h e r e f o r e z e o l i t e s r e p l a c e d a l m o s t c o m p l e t e l y t h e
amorohous c a t a l y s t s . T h i s r e s u l t e d i n a r a t h e r s t a b l e o p e r a t i o n d u r i n g s e v e r a l
y e a r s . However, t h e l e a d phase down. f i r s t i n t h e USA and now a l s o i n Europe.
has a m a j o r i m p a c t o n t h e r e f i n e r y w o r l d .
The c a t a l v s t m a n u f a c t u r e r s r e s p o n d e d on t h a t a n d t h e r e s u l t i s t h a t a l o t o f
new c a t a l y s t s were i n t r o d u c e d i n t h e m a r k e t t o i m p r o v e t h e g a s o l i n e o c t a n e s .
These c a t a l y s t s d i d n o t o n l y c o n t a i n i m p r o v e d z e o l i t e s . b u t a l s o t h e m t r i x
components were m o d i f i e d . I n t h i s p r e s e n t a t i o n some o f t h e m o s t i m p o r t a n t
d e v e l o p m e n t s w i l l b e d i s c u s s e d . However. b e f o r e t h a t t h e mechanism o f c a t a l y t i c
c r a c k i n q w i l l be o u t l i n e d b r i e f l v .

11. MECHANISM OF CATALYTIC CRACKING

D u r i n g f l u i d c a t a l y t i c c r a c k i n q many r e a c t i o n s a r e t a k i n g p l a c e , w h i c h have
been w e l l d e s c r i b e a i n some e x c e l l e n t r e v i e w s ( r e f . 1.4.5).
Summarizing. t h e mechanism o f c a t a l y t i c c r a c k i n q i s d o m i n a t e d by t h e c h e m i s t r y
o t t h e c a r b e n i u m i o n s . w h i c h a r e t o r m e d on t h e a c i d i c s i t e s o f c r a c k i n g
catalysts.
100

Reactions o f carbenium-ions t h a t a r e e s p e c i a l l y i m p o r t a n t f o r t h e c a t a l v t i c
c r a c k i n g process. a r e . c r a c k i n g , hydrogen t r a n s f e r and i s o m e r i z a t i o n . The f i n a l
c o m p o s i t i o n o f t h e c r a c k i n q p r o d u c t s depends on t h e r e l a t i v e r a t e s o f t h e
v a r i o u s competing r e a c t i o n s .
C r a c k i n g can o n l y proceed on t h e r e l a t i v e l y s t r o n g a c i d s i t e s . On t h e s e
s i t e s . t h e s k e l e t a l i s o m e r i z a t i o n o f carbenium i o n s i s a r a p i d p r o c e s s ( r e f . 6 ) .
Branched t e r t i a r y carbenium i o n s a r e more s t a b l e t h a n l i n e a r . p r i m a r y and
secondary carbenium i o n s . T h e r e f o r e , t h e c o m b i n a t i o n o f c r a c k i n g and i s m r i z a t i o n
l e a d s t o t h e f o r m a t i o n o f m a i n l y branched p r o d u c t s . T h i s i s a f a v o r a b l e a s p e c t
o f c a t a l y t i c c r a c k i n g , s i n c e branched COmDOUndS have h i g h e r octane numbers
than l i n e a r compounds.
Because. lonq c h a i n hydrocarbons a r e more r e a c t i v e t h a n s h o r t c h a i n hydrocarbons,
t h e r a t e o f t h e c r a c k i n q r e a c t i o n s decreases w i t h d e c r e a s i n g c h a i n l e n g t h and
f i n a l l y becomes v e r y slow, when i t i s no l o n g e r p o s s i b l e t o f o r m s t a b l e
t e r t i a r y carbenium i o n s . The c r a c k i n g r e a c t i o n s a r e t e r m i n a t e d by hydrogen
t r a n s f e r f r o m hydrogen donors t o t h e carbenium i o n s . V a r i o u s hydrogen donors
a r e mentioned i n l i t e r a t u r e , e.g. n a p h t h e n i c compounds which upon hydrogen
t r a n s f e r are transformed i n t o a r o m a t i c compounds and coke. Also, p a r a f f i n s
can t r a n s f e r a h y d r i d e i o n . I n t h i s way t h e c h a i n o f c r a c k i n g r e a c t i o n s i s
propagated. I n g e n e r a l , nydrogen t r a n s f e r r e a c t i o n s a r e much l e s s s e n s i t i v e t o
t h e a c i d s i t e s t r e n g t h o f t h e c a t a l y s t t h a n c r a c k i n g and i s o m e r i z a t i o n r e a c t i o n s
( r e f . 7 ) . However, hydrogen t r a n s f e r i s s t r o n g l y i n f l u e n c e d by t h e a c i d s i t e
d e n s i t y ( r e f . 8 ) and t h e c o n c e n t r a t i o n o f hydrogen donors ( r e f . 1 0 ) . An u n f a v o u r -
a b l e aspect of hydrogen t r a n s f e r i s t h a t i t l e a d s t o a l o w e r o l e f i n i c i t y and
t h e r e f o r e a 1ow RON o f FCC-gasol ine. N e v e r t h e l e s s , some hydrogen transfer a c t i v i t y
isneeded f o r g a s o l i n e s t a b i l i z a t i o n , i n o r d e r t o p r e v e n t e x c e s s i v e o v e r c r a c k i n g
( r e f . 9 , see scheme 1) and t h e f o r m a t i o n o f d i - o l e f i n s .

OLEFIN BRANCHEDOLEFIN

1I
HC --+ CARBENIUM
ION
ISOMERIZATION

FAST T
I
BRANCHED CARBENIUM
ION

BRANCHED SMALLER
PARAFFIN HC'S
IPAR. + 0LEF.I

RATIO I
KwTRANSFER Ine -DONOR1

Scheme 1
KCRACKING 1
 101

I n a d d i t i o n t o t h e r e a c t i o n s mentioned b e f o r e . a l s o c a t a l v t i c coke
f o r m a t i o n proceeds v i a carbenium i o n i n t e r m e d i a t e s . I t s h o u l d be n o t e d t h a t
t h e u n d e s i r a b i e coke f o r m a t i o n j u s t l i k e hvdrogen t r a n s f e r i s a " b i m o l e c u l a r "
r e a c t i o n . which i s enhanced bv a h i g h a c i d s i t e d e n s i t v . w h i l e c r a c k i n q and
i s o m e r i z a t i o n r e a c t i o n s a r e monomolecular. For t h i s reason a c a t a l v s t s c r e e n i n q
t e s t wasdevelopedin o u r l a b o r a t i e s . which makes use o f a model compound w i t h
p r o d u c t d i s t r i b u t i o n . which can d i s c r i m i n a t e between f a v o u r a b l e mnomolecular
and u n f a v o u r a b l e " b i m o l e c u l a r " r e a c t i o n s , v i z . o - x v l e n e ( r e f . 10 1.

111. C O M P O S I T I O N OF C R A C K I N G CATALYSTS
N o r m a l l v a c r a c k i n q c a t a l y s t i s composed o f a z e o l i t e , w h i c h d e t e r m i n e s t o
a l a r q e e x t e n t t h e a c t i v i t y and t h e s e l e c t i v i t y o f t h e c a t a l y s t . Besides t h e
z e o l i t e i n manv cases a l s o an alumina phase i s p r e s e n t . T h i s alumina i s
e s p e c i a l l v u s e f u l when l a r q e m o l e c u l e s . which can n o t e n t e r t h e z e o l i t e p o r e s
have t o be cracked. So. i t demands aluminas w i t h an a p p r o p r i a t e Dore s i z e
d i s t r i b u t i o n . F u r t h e r some c l a y i s p r e s e n t . T h i s i s a d i l u e n t . which a l s o
helps t o give the c a t a l y s t t h e desired density. I n order t o urepare micro-
spheres w i t h s u f f i c i e n t hardness, a q l u e i s necessary. T h i s q l u e can be s i l i c a
( r e f . 11). s i l i c a - a l u m i n a ( r e f 12. 1 3 ) o r can be c o m p l e t e l v basedonalumina
(ref. 14).
On t o p o f t h i s . a l s o o t h e r f u n c t i o n a l i n g r e d i e n t s can be i n c o r p o r a t e d i n t o
t h e c r a c k i n q c a t a l y s t . Examples o f t h e s e f u n c t i o n a l i n q r e d i e n t s a r e : m e t a l
t r a p s and components which reduce t h e SOx e m i s s i o n o f an FCC u n i t . Both
f u n c t i o n s w i l l be d i s c u s s e d l a t e r o n i n t h i s a r t i c l e .

I V . ZEOLITES I N CRACKING CATALYSTS

D u r i n g q u i t e a l o n q p e r i o d RE-exchanqed NaY z e o l i t e s have been used i n
c r a c k i n q c a t a l y s t s . These t y p e s o f z e o l i t e s a r e r e l a t i v e l y easy t o make(ref.15).
C a t a l y s t s c o n t a i n i n g REY z e o l i t e s a r e r e l a t i v e l v s t a b l e ( r e f . 1 6 ) a n d produce
a l o t o f q a s o l i n e . r h e r e a r e a l s o s e v e r a l d i s a d v a n t a q e s , i . e . t h e octane
numbers o f t h e g a s o l i n e i s r a t h e r low and t h e coke p r o d u c t i o n i s rather high
(ref.17). T h i s can be e x p l a i n e d bv t h e h i g h hvdrogen t r a n s f e r a c t i v i t v o f
t h i s type o f z e o l i t e s ( r e f . 18).
T h e r e f o r e u l t r a s t a b l e z e o l i t e s which have h i g h e r s i l i c a a l u m i n a r a t i o s ( = S A R I
and c o n s e q u e n t l y a l o w e r number o f aluminium s i t e s o e r u n i t c e l l ( =APC) a r e
D r e f e r a b l v used nowadays. I t may a l s o be mentioned t h a t an equal SAR o r APC
d o e s n ' t n e c e s s a r i l y mean t h a t t h e A l - s i t e d i s t r i b u t i o n s a r e a l s o t h e same.
T h i s can be v i z u a l i z e d i n f i g . 1 , where t h e c o n c e n t r a t i o n o f i s o l a t e d a c i d
s i t e s (=O-NNN) which r e p r e s e n t s t h e number A l - s i t e s w i t h o u t anv A 1 as n e x t -
n e a r e s t neiqhbours ( r e f . 8 ) . i s p l o t t e d a g a i n s t t h e APC.
102

T h i s has been done b o t h f o r a random and a w e l l - o r d e n e d d i s t r i b u t i o n . So. i t

can be concluded t h a t t h e a p D l i c a t i o n o f t h e most a p p r o p r i a t e s y n t h e s i s and
m o d i f i c a t i o n method can lead t o l a r q e advantages i n oerformance.

U J U I N U UPiR UNIT c n L (wc)

F i g . 1 . C o n c e n t r a t i o n o f 0-NNN s i t e s p e r u n i t s c e l l f o r a random A 1
d i s t r i b u t i o n and t h e most i d e a l Y z e o l i t e w i t h a maximum number
o f 0-NNN s i t e s .
A t t h e moment s e v e r a l methods t o o r e p a r e u l t r a s t a b l e z e o l i t e s a r e d e s c r i b e d i n
t h e I i t e r a t u r e ( r e f . 19 1. From these s t e a m c a l c i n a t i o n and isomorDhous sub-
s t i t u t i o n a r e t h e most i m p o r t a n t ones.

'I.S t e a m c a l c i n a t i o n .
T h i s orocess s t a r t s w i t h one o r more ammoniumexchanqe s t e p s , r o l l o w e d bv a
s t e a m c a l c i n a t i o n . 'The r e a c t i o n mechanism i s o u t l i n e d i n f i q . 2 ( s e e also ref.20.1
I t may be n o t i c e d t h a t as a r e s u l t o f t h e a p p l i e d method a secondarv p o r e
s t r u c t u r e w i t h a diameter o f ca. 1.5 up t o 10 nm i s formed.

I I
-si-
-I'
-p- + i O H ~ H O - $ i - t AI(OH)3

-51-
P
5 1 -
I I

F i g . 2 . Mechanism o f u l t r a s t a b i l i z a t i o n .
 103

T h i s may be advantageous f o r t h e c r a c k i n q r e a c t i o n s . F u r t h e r t h e d e a l u m i n a -
t i o n r e s u l t s i n t h e f o r m a t i o n o f n o n - f r a m e w o r k a l u m i n a s p e c i e s ( = NFA). T h i s
NFA can e x n i b i t a c i d i c p r o o e r t i e s and a l s o i n f l u e n c e s t h e z e o l i t e a c c e s s i b i l i t y .
R e c e n t l y Shannon e t . a l . ( r e f . 2 1 ) s p e c u l a t e d t h a t d u r i n g d e a l u m i n a t i o n t h e
a I umi n a s p e c i e s "condense" i n t h e zeo I it e s u p e r c a g e s t o f o r m boehmi t e 1 ik e
c l u s t e r s as shown c o n c e p t u a l l v i n f i g . 3.

F i q . 3. A b o e h m i t e - l i k e a l u m i n a c l u s t e r in t h e z e o l i t e Y s u p e r c a g e .

I n q e n e r a l t h e i n f l u e n c e o f t h e NFA o n t h e s e l e c t i v i t y i s n e g a t i v e ( r e f . 17).
M o r e o v e r t h i s e f f e c t i s enhanced s i n c e t h e NFA s p e c i e s a r e r a t h e r m o b i l e and
m i g r a t e t o t h e s u r f a c e o f t h e z e o l i t e c r y s t a l s . T h i s h a s been p r o v e n b y XPS
measurements c a r r i e d o u t by v a r i o u s r e s e a r c h g r o u p s ( r e f . 2 2 - 2 5 ) . These
measurements show t h a t v e r y h i g h c o n c e n t r a t i o n s o f NFA c a n b e r e a c h e d a t t h e
surface (see f i q . 4 ) .

- I

-
2
1,
120.
.
NFA migration

0" 100. totat Numinum per unit cell

c_
3
60
n ,,-.-i--r-
3 403r1*- Nay rtartinq material
5
I 20--/
t framework aluminum per unit call

0 5 10 15 20 25 30 35 3
ETCHING TIME (min.)

i i g . 4 . A1 d e p t h i n steamed z e o l i t e Y ( U S Y ) ; based on XPS d a t a .

 However. i t i s p o s s i b l e t o remove t h e s e NFA s p e c i e s . f o r i n s t a n c e b v a c i d
treatment of t h e z e o l i t e . T h i s g i v e s r i s e t o a much more f l a t p r o f i l e . I t
mav a l s o be m e n t i o n e d t h a t t h e r a t e o f m i g r a t i o n o f t h e NFA s t r o n g l y depends
on t h e RE c o n t e n t o f t h e z e o l i t e . R e c e n t w o r k ( r e f . 2 5 ) showed t h a t REY
d e a l u m i n a t e s m o r e s l o w l y t h a n USY and a l s o t h e m i g r a t i o n o f t h e NFA t o t h e
s u r f a c e i s h i n d e r e d . The USY z e o l i t e s t a r t s w i t h a A l / S i r a t i o a t the surface
o f 0 . 5 5 . w h i c h i n c r e a s e s up t o a f i g u r e s l i q h t l y o v e r 1 , a f t e r s t e a m i n q a t 500°C
f o r 65 h r s . F o r t h e REY z e o l i t e a r a t i o o f 0 . 5 6 was f o u n d f o r t h e s t a r t i n g
m a t e r i a l w h i c h i n c r e a s e s UP t o 0.77 u n d e r t h e same c o n d i t i o n s .

2. Isomorphous s u b s t i t u t i o n .
D e a l u m i n a t e d z e o l i t e s can a l s o be p r e p a r e d w i t h e x t r a n e o u s s i l i c a s o u r c e s ,
f o r i n s t a n c e w i t h (NH4)2 S i F 6 as d e s c r i b e d b y S k e e l s and B r e c k ( r e f . 2 6 ) o r
SiC14. a s a p p l i e d by B e y e r e t . a l . ( r e f . 2 7 ) . The f i r s t m e t h o d i s u s e d commer-
c i a l l y now ( r e f . 2 8 ) . A c c o r d i n g t o Rabo e t . a l ( r e f . 2 9 ) . t h i s method g i v e s r i s e
t o n e a r l y d e f e c t f r e e z e o l i t e s . They r e p o r t s u p e r i o r t h e r m a l and h y d r o t h e r m a l
s t a b i l i t y as compared w i t h a h i g h q u a l i t y ammonium exchanged and steam
s t a b i l i z e d Y z e o l i t e (see Table I ) .

TABLE 1
C o m p a r a t i v e p r o p e r t i e s of a l u m i n i u m d e f i c i e n t Y z e o l i t e s v e r s u s f r a m e w o r k
s i l i c a enriched z e o l i t e Y a f t e r severe nydrothermal t r e a t m e n t . 1

rel. retention (%)2

Zeolite Si02/A1203 ’ Na20 ( % ) Ao0) SA

NH4Y 5.0 0.36 24.79 25.8 12.5
Y82/USY 5.8 0.17 24.55 59.4 59.1
USY/HCl 9.1 0.33 24.30 23.2 30.3
extract.
FSE-Y 6.4 0.38 24.69 51.4 59.0
11.7 0.05 24.42 71.7 77.2

1. 16OOOF. 23% steam, 5 h r s . 15 p s i a .

2 . P e r c . r e l a t i v e r e t e n t i o n a f t e r s t e a m i n g v e r s u s unsteamed NH4Y s t a n d a r d .
3. Chemically determined.

However. a l o t o f d e b a t e i s g o i n g on a b o u t t h e d i f f e r e n c e s i n p r o p e r t i e s
and p e r f o r m a n c e o f b o t h t y p e o f z e o l i t e s . Macedo e t . a l . ( r e f . 30) concluded
f r o m I R and TPD measurements t h a t u l t r a s t a b l e z e o l i t e s p r e p a r e d b y isomorphous
s u b s t i t u t i o n posses more a c i d i c s i t e s t h a n t h o s e o b t a i n e d b y c o n v e n t i o n a l
steaming. M o r e o v e r t h e f o r m e r have a h i g h e r p r o p o r t i o n o f B r o n s t e d s i t e s
t h a n t h e l a t t e r , w h i c h may b e c o n s i d e r e d as f a v o u r a b l e f o r t h e c a t a l y t i c
cracking reactions.
 105

C r e i g h t o n e t a l . ( r e f . 3 1 ) p r e p a r e d c a t a l y s t s c o n t a i n i n g s t e a m s t a b i l i z e d and
c h e m i c a l l y d e a l u m i n a t e d ( i . e . ( N H 4 ) 2 S i F 6 ) z e o l i t e s and f o u n d i d e n t i c a l s e l e c t i -
v i t i e s . However t h i s was a f t e r a t h e r m a l d e a c t i v a t i o n s t e p and one may wonder
whether t h i s i s s t i l l r e p r e s e n t a t i v e f o r t h e f r e s h m a t e r i a l s . T h a t t h e f r e s h
z e o l i t e s r e a l l y show d i f f e r e n c e s has been p r o v e n by B e y e r l e i n e t . a l . ( r e f . 3 2 ) .
These a u t h o r s show t h a t " c l e a n framework" z e o l i t e s ( i . e . p r e p a r e d by i s o -
morphous s u b s t i t u t i o n w i t h (NH4)2SiF6 a r e low i n a c t i v i t y f o r i s o b u t a n e
cracking ( s e e T a b l e 1 1 ) . They a l s o f o u n d t h a t t h e a c t i v i t y i n c r e a s e d s t r o n g l y
a f t e r a h e a t t r e a t m e n t o f t h e z e o l i t e . T h i s was e x p l a i n e d by t h e f o r m a t i o n
o f super a c i d i t y , i . e . an i n t e r a c t i o n between B r o n s t e d a c i d s i t e s and non-
framework Lewis s i t e s .

TABLE I 1
Comparison o f t h e i s o b u t a n e c r a c k i n g a c t i v i t y o f ammonium h e x a f l u o r s i l i c a t e
d e a l u m i n a t e d Y and s t e a m s t a b i l i z e d z e o l i t e s .

Si/All Ao Na i-C Conversion r a t e s % Carb.

4
(Chem.ana1) (1) (wt %) ( m o l e / h / g x 10') Ion
Total Carb. I o n

SamDle
A . as p r e p a r e d 2 4.5 24.54 1.24 4.1 2.1 51
B . a f t e r NH4 5.1. 0.06 12.0 7.0 58
exchange o f A
LZY 482 ' 2.7 24.56 0.15 16.0 28.1 ia
USY 2.7 24.58 - 36.8 28.0 76

1. Chemically determined.
2. (NH ) SiF dealuminated.
3. Con!e$tiofial steamstabi 1 i z e d z e o l i t e .
4. Own made USY ( b y s t e a m s t a b i l i z a t i o n ) .

O t h e r i n t e r e s t i n g r e s u l t s a r e r e p o r t e d by Corma e t a1 .( r e f . 2 2 ) and K e y w o r t h
et.al. ( ref.23 1, who b o t h show t h a t isomorphous s u b s t i t u t e d z e o l i t e s have a
v e r y steep S i / A I g r a d i e n t (see f i g . 5 ) .
I f i t i s assumed t h a t a m a j o r p a r t o f t h e c r a c k i n g r e a c t i o n s . e s p e c i a l l y
with gasoil take p l a c e a t t h e o u t e r s u r f a c e o f t h e z e o l i t e , t h i s may a l s o
e x p l a i n t h e low a c t i v i t y f o u n d f o r t h i s t y p e o f z e o l i t e s . F u r t h e r i t may b e
n o t i c e d t h a t B e y e r l e i n e t . a l . found t h a t t h e i r m i l d l y s t e a m s t a b i l i z e d z e o l i t e s
demonstrate a c i d s i t e s o f equal e f f i c i e n c y f o r a l l Si/A1 r a t i o s T 5 .
A c c o r d i n g t o t h e a u t h o r s t h i s p o i n t i n t o t h e d i r e c t i o n o f an o r d e r e d
distribution o f acid sites ( c f . f i g . l ) .
106

-u
60-

0 5 10 15 20 25 30 35 3

ETCHING TIME (rnin )

F i g . 5 . Comparison between steamed and isomorphous s u b s t i t u t e d z e o l i t e Y .

T h i s i s i n agreement w i t n t h e r e s u l t s o b t a i n e d by Nieman and vanBroekhoven

( r e f . 10). They i n v e s t i g a t e d t h e a c i d s i t e d i s t r i b u t i o n o f a number o f z e o l i t e s
b o t h w i t h model compounds and 2 9 S i MAS NMR. A M a t h e m a t i c a l model was used t o
t r a n s l a t e t h e NMR d a t a i n t o t h e average number o f A l - s i t e s (=N"J.
Their
measurements i n d i c a t e t h a t t h e a c i d s i t e d i s t r i b u t i o n o f s e v e r e l y steamed
z e o l i t e s d e v i a t e s more t r o m t h e i d e a l one t h a n t h e more m i l d l y t r e a t e d
materials.

V . A C T I V E MATRICES
A f t e r i n t r o d u c t i o n o f t h e z e o l i t e s i n FCC. t h e o l d amorphous s i l i c a - a l u m i n a
c a t a l y s t s and so a l s o t h e a c t i v e m a t r i x was o m i t t e d . T h i s r e s u l t e d i n a d r a s t i c
s h i f t o f t h e c a t a l y s t p o r e s i z e d i s t r i b u t i o n as can be seen f r o m T a b l e 111. I t
i s c l e a r t h a t t h i s s h i f t has a l a r g e e f f e c t on t h e a c c e s s i b i l i t y o f t h e p o r e s
f o r l a r g e r hydrocarbons m o l e c u l e s .

TABLE 111
S i z e o f hydrocarbon m o l e c u l e s i n r e l a t i o n t o c a t a l y s t dimensions.

CJlalvsl

j <30APD 30 6 0 8 P O > 60 A P O

10

60

154

62 I 129

38 I 13

10
12

14
 107

Due to the increasing demand for lighter products, like gasoline and light
cycle oil, combined with a shrinking market for fueloil there is nowadays a lot
o f interest in processing heavier feedstocks, like residual oils. Therefore
active matrix components receive again a lot of attention now. What the
optimum pore size distribution is, however. is still a matter of discussion.
Ruchkenstein et.al. (ref. 33) calculated that the optimum pore diameter will
be approximately double the molecule size for the case that the molecules have
no difficulty in entering the pores. I f this is not the case, the optimum size
may be up to six times larger than the molecule size.
The concept of optimum pore size distribution was also stressed by Maselli
et a1 (ref. 3 4 ) . but these workers were not able to demonstrate the existence
of diffusion limitations in their fixed bed micro-activity test.
Young et a1 (ref. 3 5 ) separated cracking catalysts into different size
fractions and tested them with a heavy FCC feed in order to detect matrix
diffusion limitations. since increasing the particle size would increase the
diffusion resistance. They concluded that contrary to theoretical expectations
no diffusion limitations were observed.
Nevertheless, several authors (ref. 36.37) emphasize the importance of a
combination o f a large pore catalyst with a low hydrogen transfer molecular
sieve to convert bottoms into valuable products. Another effect that one has
to take into account is Pore mouth plugging (ref. 3 8 ) . which can reduce the
accessibility of the pores to a large extent. Especially for resid cracking
where metal contaminants are present, this effect will probably also play an
important role. An interesting model has been presented some time ago by
Takatsuka (ref. 3 9 ) who evaluated the performance o f three resid catalysts
in their pilot plant using hydroconverted OAO of Arabian Heavy Vacuum Residue
as feedstock. In Fig. 6 the product distributions are compared at the conversion
level of maximum gasoline yield.
The performance o f these catalysts are strongly correlated with the Pore
size distribution of the catalyst matrix. The author distinghuishes three
different regions o f pore sizes (see fig. 7 ) :

A-pores not accesable to large molecules

B-pores accessable. nigh SA contribution pore s ze 2 to 6 times of
molecular size
C-pores accessable. low SA contribution

However. it may be emphasized that the balance between zeolite and matrix
activity is also important for an optimal selectivity (ref. 3 7 . 4 0 ) .
108

1
1--
- ---
-- PI- - GAS

GASOLINE

LCO

HCO
COKE

COMPETITOR 1 COMPETITOR 2 M Z 11X

GAS t. LCO 430 650'F
GASOLINE C, 430°F HCO 650°F'

F i g . 6. FCC p r o d u c t s d i s t r i b u t i o n by v a r i o u s c a t a l y s t s
( a t maximum g a s o l i n e y i e l d ) .

F i g . 7 . E f f e c t o f p o r e s i z e d i s t r i b u t i o n on bottoms c o n v e r s i o n .
 109

V I . METAL TRAPS
The d e t r i m e n t a l e f f e c t s o f m e t a l s on t h e performance of c r a c k i n g c a t a l y s t s
a r e w e l l known now: N i i n c r e a s e s t h e gas ( e s p e c i a l l y H and coke p r o d u c t i o n .
2
whereas V l o w e r s t h e c o n v e r s i o n and s e l e c t i v i t y by d e s t r o y i n g t h e z e o l i t e
c r y s t a l l i n i t y , which i s a l s o r e f l e c t e d i n an i n c r e a s e d gas and coke make(ref.44.
N i p o i s o n i n g can be c o n t r o l l e d more o r l e s s by u s i n g antimony compounds.
which a r e added t o t h e f e e d s t o c k ( r e f . 4 2 ) . Another p o s s i b i l i t y t o suppress t h e
d e t r i m e n t a l dehydrogenation r e a c t i o n s i s t o use c a t a l y s t s w i t h a s i l i c a r i c h
m a t r i x ( r e f . 43, 4 4 ) .
F o r V p o i s o n i n g t h e s o l u t i o n i s l e s s c l e a r . Due t o i t s l o w m e l t i n g p o i n t ,
V205 i s v e r y m o b i l e under FCC condit1or.s ( ~ f . 4 5 ~ 4 6and
) can e a s i l y r e a c h t h e
z e o l i t e s . T h e r e f o r e , t n e mechanism o f t h e r e a c t i o n between V205 and t h e z e o l i t e
has been s t u d i e d e x t e n s i v e l y . From X-ray d i f f r a c t i o n and DTA measurements,
PomDe e t . a l ( r e f . 4 7 ) concluded t h a t V205 r e a c t s w i t h RE f r o m t h e z e o l i t e ,
g i v i n g r i s e t o t h e f o r m a t i o n o f RE-vanadates. T h i s vanadate f o r m a t i o n r e q u i r e s
more oxygen p e r RE atom t h a n can be s u p p l i e d b y V205.
T h e r e f o r e , t h e a u t h o r s assume t h a t e x t r a oxygen i s t a k e n f r o m t h e z e o l i t e
s t r u c t u r e . wbich l e a d s t o d e s t r u c t i o n o f t h e . l a t t i c e . However, such a
mechanism i s n o t so v e r y p r o b a b l y under o x i d i z i n g c o n d i t i o n s as a r e p r e s e n t i n
t h e r e g e n e r a t o r , as has been p o i n t e d o u t by Maug6 e t . a l ( r e f . 4 8 ) .
They c o n d u d e d t h a t t h e d e s t a b i l i z a t i o n o f t h e z e o l i t e i s m a i n l y due t o t h e
disappearance o f t h e s t a b i l i z i n g La-0-La b r i d g e s i n t h e s o d a l i t e cage b y
r e a c t i o n o f La 0 and V205 under f o r m a t i o n o f LaV04.
2 3
A c o m p l e t e l y d i f f e r e n t t h e o r y was i n t r o d u c e d b y Wormsbecher e t . a l . ( r e f . 46).
These a u t h o r s conclude t h a t under r e g e n e r a t o r c o n d i t i o n s V205 i s c o n v e r t e d
i n t o vanadic a c i d , H3V04, which may be c o n s i d e r e d as a s t r o n g a c i d analoqous
t o H3P04. T h i s H3V04 can d e s t r o y t h e z e o l i t e b y h y d r o l y s i s o f t h e z e o l i t e
Si02/A1203 framework. T h e r e f o r e t h e y propose b a s i c compounds as MgO o r CaO t o
n e u t r a l i z e t h e vanadic a c i d .
A s i m i l a r concept was developed b y Masuda e t . a l . ( r e f . 4 9 ) . These a u t h o r s a l s o
assume t h a t t h e a c i d i c - b a s i c p r o p e r t i e s o f t h e m e t a l o x i d e s a r e d e t e r m i n i n g
t h e i r u s e f u l l n e s s as V c a t c h e r . However, t h e s e t y p e o f conwounds a r e harmful
f o r t h e hydrothermal s t a b i l i t y o f the z e o l i t e . Therefore o n l y physical mixtures
c o u l d be used i n p r a c t i c e , whereby t h e z e o l i t e and b a s i c compound a r e i n
d i f f e r e n t p a r t i c l e s . Consequently, t h e z e o l i t e w i I 1 be l e s s e f f e c t i v e l y
p r o t e c t e d a g a i n s t vanadium.
A d i f f e r e n t approach was r e c e n t l y developed by G e i s l e r e t . a l . ( r e f . 5 0 ) . who
used compounds i n which t h e m e t a l o x i d e w i t h a h i g h a f f i n i t y t o V205 i s p r e s e n t
b u t as a p a r t o f a v e r y s t a b l e s t r u c t u r e .
110

T h i s means t h a t t h e m e t a l o x i d e i s b l o c k e d and d o e s n ’ t h u r t t h e z e o l i t e ,
whereas r e a c t i o n w i t h V205 under f o r m a t i o n o f h i g h m e l t i n g vanadates remains
p o s s i b l e . That t h i s concept worked o u t has been p r o v e n b o t h by performance
t e s t s and SEM s t u d i e s . The t e s t r e s u l t s f o r a c a t a l y s t w i t h and w i t h o u t m e t a l
t r a p a r e summarized i n T a b l e I V . F r o m t h i s T a b l e i t can be concluded t h a t t h e
c a t a l y s t w i t h m e t a l t r a p shows a much b e t t e r performance t h a n t h e c a t a l y s t
w i t h o u t t h i s t r a p o r w i t h an o l d e r one.

TABLE I V
MAT d a t a o f c a t a l y s t s w i t h an i n t e r m e d i a t e amount o f REY z e o l i t e ,
an i n e r t m a t r i x w i t h and w i t h o u t m e t a l t r a p s .

A. w l t h o u t m e t a l t r a p 8. m e t a l t r a p I C. metal t r a p I 1
no m e t a l s 1000 ppm N i b no m e t a l s 1000 ppm Nib no m e t a l s 1000 ppm Nib
3000 ppm V 3000 ppm V 3000 ppm V
Cow.. X wt 66.5 45.2 64.2 62.3
ROI . Y .gas01 i n e a 1.00 0.96 0.99 0.98
coke 1.11 2.00 1.01 1.22
“2 15.9 11.8 6.8

C a t a l y s t p r e t r e a t m e n t : s t e a m d e a c t i v a t i o n f o r 17 h r s a t 75OOC ( 1 b a r , 100 %
steam).
MAT c o n d i t i o n : r e a c t o r temperature : 483OC
Cat on o i l t i m e : 50 s e c .
WHSV : 12 h - 1
Feed : K u w a i t VGO

a. Re1.Y i s t h e p r o d u c t y i e l d r e l a t i v e t o MZ-7 s t a n d a r d c a t a l y s t a t equal

conversion.

b . Pore volume i m p r e g n a t i o n .

SEM s t u d i e s on e q u i l i b r i u m c a t a l y s t s c o n t a i n i n g t h i s new m e t a l t r a D were

a l s o c a r r i e d o u t . A c r o s s - s e c t i o n o f an FCC m i c r o s p h e r e can be seen i n F i g . 8 .
whereas F i g . 9 g i v e s t h e V d i s t r i b u t i o n i n t h a t p a r t i c u l a r particle.WDXA
a n a l y s i s shows t h a t t h e V c o n c e n t r a t i o n i n t h e m e t a l t r a p i s v e r y h i g h ( s e e
Table V 1.
TABLE V
R e l a t i v e vanadium d i s t r i b u t i o n o n c a t a l y s t w i t h m e t a l t r a p .

CATALYST LAB IMPREGNATED EQUILIBRIUM CAT

TOTAL VANADIUM 3000 pprn . 6084 ppm
~~ ~~

MATRIX 1.o 1 .o
ALUMINA 2.6 3.2
ZEOLITE 1.3 1.7
METALTRAP 26.1 18.3
 111

F i g . 8 . Cross s e c t i o n o f an FCC microsphere w i t h metal t r a p .

Fig.9. Vanadium d i s t r i b u t i o n o f an FCC microsphere w i t h m e t a l t r a p .

V I I . DESOX
I t i s w e l l recognized now t h a t t h e SOx emissions f r o m r e f i n e r i e s c o n t r i b u t e
t o a l a r g e e x t e n t t o t h e a c i d r a i n problem. T h e r e f o r e , a l l k i n d of r e g u l a t i o n s
f o r t h e SOx emissions a r e s e t up now. I n response t o t h i s , c a t a l y s t manufac-
t o r e r s developed adapted c a t a l y s t compositions o r s p e c i a l a d d i t i v e s t o reduce
SOx emissions o f FCC u n i t s . With these p r o d u c t s r e d u c t i o n s from ca. 20 up t o
70 %' a r e r e p o r t e d ( r e f . 51, 5 4 ) .
The mechanism o f t h e SOx t r a n s f e r has been o u t l i n e d by Habib ( r e f . 5 5 ) ,
whereas an e x c e l l e n t r e v i e w o f t h e s t a t e o f t h e a r t was r e c e n t l y p r e s e n t e d
by B e r t o l a c i n i e t . a t . (ref.56).
112

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H.G.Karge, J. Weitkamp (Editors),Zeolites (IS Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

EVALUATION OF NON-COMMERCIAL MODIFIED LARGE PORE ZEOLITES I N FCC

E. JACQUINOT, F. RAATZ, A. MACEDO and Ch. MARCILLY

INSTITUT FRANCAIS DU PETROLE, 1-4 r u e du B o i s Preau
BP311, 92506 Ruei 1 Malmai son, France

ABSTRACT
The c a t a l y t i c performances o f H-Y, H-Beta and H-Omega prepared by a
steaming-acid l e a c h i n g procedure, have been e v a l u a t e d i n cyclohexene and i n
Vacuum Gas O i l ( V G O ) t r a n s f o r m a t i o n . The l e a c h i n g i s a key s t e p , s i n c e
depending on t h e o p e r a t i n g c o n d i t i o n s i t can decrease o r i n c r e a s e t h e
c o n v e r s i o n l e v e l s . I n cyclohexene t r a n s f o r m a t i o n , t h e a c i d i t y o f t h e s o l i d s
controls the activity and the following ranking is obtained :
H-Beta)H-Y)H-Omega. I n c o n t r a s t , i n VGO c o n v e r s i o n a c c e s s i b i l i t y o f t h e a c i d
c e n t e r s has t o be taken i n t o account which means t h a t H-Y l e a d s t o t h e b e s t
r e s u l t s . Moreover, o p t i m i z a t i o n o f t h e a c i d i c p r o p e r t i e s o f H - Y t h r o u g h a
s e l e c t i v e a c i d l e a c h i n g improves s i g n i f i c a n t l y t h e c o n v e r s i o n l e v e l s .

INTRODUCTION
Y z e o l i t e s m o d i f i e d by two main techniques, i.e. hydrothermal treatment
(framework dealumination only) or isomorphous substitution (framework and
o v e r a l l dealumination), containing o r not containing r a r e earth cations, are
the a c t i v e component of commercial FCC catalysts (1, 2, 3). Indeed, a
tremendous amount o f d a t a i s a v a i l a b l e i n t h e l i t e r a t u r e on t h e b e h a v i o r o f
t h e s e sol i d s . However, o t h e r l a r g e - p o r e z e o l i t e phases a r e p o t e n t i a l c a n d i d a t e s
f o r t h i s a p p l i c a t i o n . Depending on whether o r n o t t h e aim i s t o f u l l y r e p l a c e
t h e a c t u a l a c t i v e component, and e x c l u d i n g any p r i c e c o n s t r a i n t , two t y p e s o f
s o l i d s c o u l d be a p r i o r i considered. As an a l t e r n a t i v e t o t h e a c t u a l main
a c t i v e component, o n l y l a r g e - p o r e z e o l i t e s w i t h m u l t i d i m e n s i o n a l porous systems
should be c o n s i d e r e d as p r o m i s i n g c a n d i d a t e s . I n t h i s c a t e g o r y we find Y
zeolite itself, but submitted to a conventional overall dealumination
(hydrothermal treatment followed by acid leaching), and other modified
structures such as ZSM-20 and zeolite Beta (4). Deal umi n a t e d 1 arge-pore
z e o l i t e s w i t h monodimensional porous systems, such as Omega and L, a r e more
l i k e l y t o be o n l y u s e f u l as secondary a c t i v e components ( 5 ) .
L i t t l e i s known about t h e c a t a l y t i c performances i n FCC o f t h e p o t e n t i a l
c a n d i d a t e s mentioned above ( 4 , 51, and most o f t h e s t u d i e s a l r e a d y p u b l i s h e d
have been devoted t o n o n - m o d i f i e d Beta z e o l i t e s . R e c e n t l y , A. Corma e t a l .
( 6 - 9 ) have e v a l u a t e d t h e c r a c k i n g p r o p e r t i e s o f Beta z e o l i t e s w i t h v a r i o u s
Si/A1 ratios, and o f c o n v e n t i o n a l l y dealuminated Y z e o l i t e s . Two i m p o r t a n t
c o n c l u s i o n s emerge f r o m t h i s work : i ) a t l e a s t f o r n-heptane c r a c k i n g H-Beta
i s superior t o H-Y, and i i )a m i l d a c i d l e a c h i n g o f steamed H-Y g i v e s r i s e t o a
116

decrease o f t h e a c t i v i t y i n g a s - o i l c r a c k i n g .
We aim h e r e t o e v a l u a t e t h e performances, i n a model t e s t r e a c t i o n and i n
t h e c r a c k i n g o f a VGO o f z e o l i t i c phases, which a r e o f p o t e n t i a l i n t e r e s t i n
FCC. Cyclohexene has been chosen as a t e s t molecule, since i t allows a r a p i d
e v a l u a t i o n of t h e hydrogen t r a n s f e r tendency o f t h e c a t a l y s t s , i . e . formation
o f benzene, cyclohexane and m e t h y l c y c l o p e n t a n e r a t h e r t h a n m e t h y l c y c l o p e n t e n e .
I n a f i r s t approach, we w i l l r e s t r i c t ourselves t o t h e study o f t h e f r e s h
c a t a l y s t s , which means t h a t h y d r o t h e r m a l a g i n g and p o i s o n i n g by metal w i l l n o t
be c o n s i d e r e d h e r e .

EXPERIMENT
SOL I D S
S t a r t i n g f r o m low-sodium (NaC400 ppm) NH4-Y (Si/Al = 2.81, NH4-Beta
( S i / A l = 14.0) and NH4-Omega ( S i / A l = 2.91, dealuminated s o l i d s have been
prepared by a t w o - s t e p procedure, i.e. hydrothermal t r e a t m e n t (100% steam) a t
v a r i o u s temperatures (823 t o 1123 K ) f o l l o w e d by an a c i d l e a c h i n g i n HC1
s o l u t i o n a t 373 K ( 1 and 3N f o r H-Y, 1N f o r H-Beta, 0.5N f o r H-Omega). The
sol i d s were c h a r a c t e r i z e d a t each s t e p o f t h e p r e p a r a t i o n procedures by
chemical a n a l y s i s , XRD, 29 S i MASNMR, I R spectroscopy and N2 adsorption.
Further d e t a i l s on t h e d e a l u m i n a t i o n procedures and t h e c h a r a c t e r i z a t i o n
t e c h n i q u e s can be found i n r e f . ( 1 0 ) . The o r i g i n a l Y z e o l i t e was p r o v i d e d by
Zeocat (Z-FlOO), w h i l e Omega and Beta were s y n t h e s i z e d by J.L. GUTH e t a1
( E c o l e N a t i o n a l e S u p c r i e u r e de Chimie, Mulhouse, F r a n c e ) .
CATALYTIC TESTS
MODEL MOLECULE. Cyclohexene t r a n s f o r m a t i o n was s t u d i e d u s i n g a Geomecanique
m i c r o t e s t u n i t a l l o w i n g v e r y l o w c o n t a c t t i m e s and a n a l y s i s o f t h e p r o d u c t s a t
v a r i o u s t i m e s on stream. The t e s t s were conducted a t atmospheric p r e s s u r e under
5
t h e f o l l o w i n g c o n d i t i o n s : cyclohexene p a r t i a l p r e s s u r e 0 . 2 0 ~ 1 0 Pa, c a r r i e r gas
n i t r o g e n , c o n t a c t t i m e s i n t h e 0.25 t o 3.0 s range, t e m p e r a t u r e 643 K, sampling
a t d i f f e r e n t t i m e s on s t r e a m ( 2 , 5, 8, 11 m i n ) .
VACUUM GAS OIL. Aramco 150 c r a c k i n g was s t u d i e d u s i n g a MAT u n i t a t 755 K under
atmospheric p r e s s u r e . W h i l e k e e p i n g a c o n s t a n t i n j e c t i o n t i m e ( 7 5 s ) , d i f f e r e n t
catalyst-to-oil weight r a t i o s were used (1.2 t o 5.3) i n order t o vary t h e
c o n v e r s i o n l e v e l s . P r i o r t o t h e MAT t e s t s , t h e z e o l i t e s (20 % i n w e i g h t ) were
blended w i t h an aged s i l i c a - a l u m i n a m a t r i x .

RESULTS
The main physicochemical characteristics of t h e modified zeolites are
reported i n table 1 together with the operating conditions applied f o r the
d e a l u m i n a t i o n procedures.
 117

TABLE 1
a ) Chemical and t e x t u r a l c h a r a c t e r i s t i c s o f dealuminated Y z e o l i t e s .
* C a l c u l a t e d f r o m t h e u n i t c e l l parameter, u s i n g t h e c o r r e l a t i o n g i v e n i n
r e f . (19)
** XRD c r i s t a l l i n i t y , t h e o r i g i n a l NH4-Y i s t a k e n as a r e f e r e n c e .
( S i /A1 )
P r e p a r a t i o n procedure (Si/Al % DX**
overall

Steaming 823 K
HCL 1 N
HC1 3N 57
::: 8I 4
9
00
%
69 %
0 %

Steaming 873 K
HC1 1N
HC1 3N 37
::: 10 80
11
>loo
%
72 %
69 %

Steaming 9 / 3 K T 85 %
HC1 1N
HC1 3N 43
42:; 16
41
79 %
93 %

Steaming 1043 K
HC1 1N
HC1 3N 44
::; 24
21
42
93 %
78 %
94 %

Steaming 1113 K > 50 91 %

HC1 1N 1:*8 > 50 87 %
HC1 3N 74 > 50 91 %

b ) Chemical and t e x t u r a l c h a r a c t e r i s t i c s o f dealuminated B e t a z e o l i t e s

I
I P r e p a r a t i o n procedure ( Si /A1 1 overall
I
I Steaming 873 K 18
I HC1 1N 62
I
I Steaming 973 K 14
I HC1 1 N 53
I
I Steaming 1073 K 14
I HC1 1 N 29
I
I Steaming 1123 K 74
I HC1 1 N 19
118

c ) Chemical and t e x t u r a l c h a r a c t e r i s t i c s o f dealuminated Omega z e o l i t e s .

* 29Si RMN s i m u l a t i o n a c c o r d i n g t o r e f ( 2 0 ) . 0
The c parameter i s n o t r e p o r t e d s i n c e i t o n l y v a r i e s between 7,51 and 7,55 A .
** XRD c r i s t a l l i n i t y , t h e o r i g i n a l NH4-0mega i s t a k e n as a r e f e r e n c e .

l p r e p a r a t i o n procedure ( S i / A l I V ) *% DX** a (i)

I
I Steaming 923 K 11 T 2 - r l-Kl-3-
I HC1 0,5 N 10 94 % ia,io
I
I
I
Steaming 913 K
HC1 0,5 N
18
ia
85%
90 %
m
18,06
I
I Steaming 1013 K 3068% 18;ar
I HC1 0,5 N 30 70 % 18,Ol
I
I
I Steaming 1123 K loo66% 77-38-
I HC1 0,5 N 100 66 % 18,OO
I

As expected, whatever the structure, the steaming at increasing

temperatures leads to a dealumination of the framework. The resulting
extra-framework species cause a r e d u c t i o n of t h e N2 a d s o r p t i o n c a p a c i t y o f H-Y
and H-Beta z e o l i t e s which do have a m u l t i d i m e n s i o n a l porous system (111, w h i l e
a complete b l o c k i n g o f t h e monodimensional porous system o f H-Omega o c c u r s .
Concerning t h e e f f e c t o f t h e p o s t - s t e a m i n g a c i d l e a c h i n g two s i t u a t i o n s have t o
be c o n s i d e r e d : i ) s e l e c t i v e a c i d l e a c h i n g g i v i n g r i s e t o an e l i m i n a t i o n o f
extra-framework species w i t h o u t any f u r t h e r framework d e a l u m i n a t i o n ( H - Y and
H-Omega treated in 1N and 0.5N HC1 solutions, respectively), and ii)
n o n - s e l e c t i v e a c i d l e a c h i n g r e s u l t i n g i n a s e v e r e framework d e a l u m i n a t i o n (H-Y
and H-Beta t r e a t e d i n 3N and 1N HC1 s o l u t i o n s , r e s p e c t i v e l y ) .
I n c o n t r a s t t o t h e steamed H - Y and H-Omega, steamed H-Beta appeared t o be
very s e n s i t i v e t o a c i d l e a c h i n g , s i n c e even a m i l d l e a c h i n g l e a d s t o v e r y h i g h
o v e r a l l S i / A 1 r a t i o s . T h i s i s l i k e l y t o be due t o t h e s i g n i f i c a n t amount o f
s t r u c t u r a l defects present i n t h i s z e o l i t e a f t e r t h e synthesis. Without going
i n t o t o o much d e t a i l , i t s h o u l d be n o t e d t h a t most of t h e s o l i d s have a h i g h
degree o f c r y s t a l l i n i t y , and t h a t f o r each s t r u c t u r e a wide range o f framework
and o v e r a l l S i / A 1 r a t i o s a r e covered. Thus, t h e i n f l u e n c e on t h e c a t a l y t i c
performances o f t h r e e v e r y important parameters namely the structure, the
framework and o v e r a l l S i / A l r a t i o s o f t h e s o l i d s can be s t u d i e d . Since i t i s
n o t always p o s s i b l e t o d e t e r m i n e w i t h good accuracy t h e framework S i / A l r a t i o
o f a l l t h e s o l i d s (H-Beta and a c i d leached s o l i d s c o u l d c o n t a i n many s t r u c t u r a l
d e f e c t s ) , we have chosen t o r e p o r t t h e c o n v e r s i o n l e v e l s versus t h e steaming
temperature o f t h e o r i g i n a l NH4-form, even f o r s o l i d s s u b m i t t e d t o a subsequent
acid leaching.
 119

HY-ZEOLITES
A f t e r steaming, t h e cyclohexene c o n v e r s i o n p r e s e n t s a f l a t optimum versus t h e
temperature employed f o r t h e steaming t r e a t m e n t (i.e. versus t h e framework
Si/Al r a t i o o f t h e s o l i d s , see t a b l e 1 ) and s e r i o u s l y decreases f o r steaming
temperatures h i g h e r t h a n about 900 K ( f i g u r e 1 ) . The most i m p o r t a n t p o i n t which
i s evidenced on f i g u r e 1 concerns t h e e f f e c t o f t h e a c i d l e a c h i n g . Depending on
whether o r n o t t h e l e a c h i n g i s s e l e c t i v e ( e x t r a - f r a m e w o r k A1 e x t r a c t i o n w i t h o u t
any f u r t h e r framework d e a l u m i n a t i o n , t a b l e 11, an i n c r e a s e o r a decrease o f t h e
cyclohexene c o n v e r s i o n l e v e l s i s observed. The same e f f e c t s a r e o b t a i n e d i n VGO
transformation ( f i g u r e 2 ) .

H-BETA ZEOLITES
Steaming a t i n c r e a s i n g temperatures l e a d s t o a monotonic decrease o f t h e
cyclohexene conversion levels (figure 1). I t should be n o t e d t h a t after
steaming, t h e cyclohexene c o n v e r s i o n l e v e l s o f H-Beta a r e h i g h e r t h a n t h o s e
o b t a i n e d f o r H-Y. The m i l d p o s t - s t e a m i n g a c i d l e a c h i n g r e s u l t s i n a severe
r e d u c t i o n o f t h e s e c o n v e r s i o n l e v e l s , whereas t h e same t r e a t m e n t has a p o s i t i v e
e f f e c t f o r H-Y ( f i g u r e 1 ) .
As i n t h e case of cyclohexene, t h e VGO c o n v e r s i o n i s s t r o n g l y a f f e c t e d by
steaming ( f i g u r e 2 ) b u t shows a d i f f e r e n t b e h a v i o r a f t e r a c i d l e a c h i n g . The
l a t t e r t r e a t m e n t g i v e s r i s e t o a small i n c r e a s e o f t h e VGO c o n v e r s i o n l e v e l s
( f i g u r e 21, which should be compared w i t h t h e n e g a t i v e e f f e c t evidenced f o r t h e
cyclohexene t r a n s f o r m a t i o n ( f i g u r e 1 ) . Moreover, i n VGO c o n v e r s i o n whatever t h e
p r e p a r a t i o n procedures we used, H-Beta gives lower performances t h a n H-Y
(figure 2 ) .

H-OMEGA ZEOLITES
C o n t r a r y t o H-Y and H-Beta, v e r y low cyclohexene c o n v e r s i o n l e v e l s a r e
o b t a i n e d f o r steamed H-Omega whatever t h e steaming t e m p e r a t u r e ( f i g u r e 1 ) . For
t h e s e s o l i d s even a v e r y m i l d and non-optimized a c i d l e a c h i n g l e a d s t o a severe
increase o f the conversion l e v e l s .
Similarly, t h e VGO c o n v e r s i o n level after steaming is very low and
i n c r e a s e s v e r y s i g n i f i c a n t l y a f t e r t h e a c i d l e a c h i n g ( T a b l e 2). However, w h i l e
for the acid-leached H-Omega the conversion levels in cyclohexene
i t i s no l o n g e r t h e case f o r t h e
t r a n s f o r m a t i o n a r e v e r y c l o s e t o t h o s e o f H-Y,
VGO t r a n s f o r m a t i o n f o r which H-Y appears t o be s u p e r i o r t o H-Omega ( f i g u r e s 1,
Table 2 ) .
120

75
H-Y

261 I 1
823 923 1023 1123 873 973 1073
STEAMING TEMPERATURE IKI STEAMING TEMPERATURE IK

-7 ti-BETA

01 I I I I 1 I
823 923 1 on 1123 873 973 1073
STEAMING TEMPERATURE (Kl STEAMING TEMPERATURE ( K 1
1w
H-OMEGA F i g u r e 2 : Conversion o f VGO
versus t h e steaming t e m p e r a t u r e
(,steamed + ; steamed and a c i d leached
+ HC1 1N ; + HC1 3N)
R e a c t i o n t e m p e r a t u r e = 755 K ; i n j e c -
t i o n t i m e = 75 s ; C/O = 3 ;
WHSV = 16 h-1
TABLE 2
MAT c o n v e r s i o n and y i e l d s of d i f f e r e n t
products o f gas-oil cracking f o r
H -Omeg a.

Preparation MAT Gasoline Gas Coke

procedure conv. yield yield
STEAMING TEMPERATURE (Kl
(wt.%) (wt.%) ;% !
(wt.%)
(wt.")

Fi ure 1 Conversion l e v e l o f c y c l o - Sti;!,"g 25.7 5.1 1.4

b e i s u s t h e steaming t e m p e r a t u r e HC1 0.5N 41.2 19,8 14.0 6.0
(steamed + ; steamed and a c i d leached
+HC1 0,5N ; + HC1 1N ; +HC1 3N)
Reaction t e m p e r a t u r e = 643K ; c o n t a c t
t i m e = 0,5 s ; t i m e on stream = 2 min.
 121

DISCUSSION
CONVERSION. Obviously, t h e framework d e a l u m i n a t i o n o c u r r i n g i n t h e c o u r s e o f
t h e steaming procedure i s r e s p o n s i b l e f o r t h e decrease o f t h e cyclohexene and
VGO c o n v e r s i o n l e v e l s . However, s e v e r a l i m p o r t a n t remarks have t o be made.
F i r s t , a t l e a s t i n t h e case o f H-Y t h e decrease i s non-monotonic, i.e a f l a t
optimum i s observed near 900 K . Since i t has been shown t h a t t h e s t r e n g t h o f
t h e framework a c i d s i t e s i n H - Y i n c r e a s e s w i t h t h e d e a l u m i n a t i o n l e v e l (12,131,
t h i s optimum i s l i k e l y t o r e s u l t f r o m two c o m p e t i t i v e e f f e c t s , i . e r e d u c t i o n o f
t h e number o f s i t e s and i n c r e a s e o f t h e i r a c i d s t r e n g t h . According t o t h e model
advanced by Barthomeuf (141, such an optimum i s n o t observed f o r z e o l i t e s ,
which a r e s y n t h e s i z e d w i t h t o o h i g h an i n i t i a l Si/A1 ratio. This i s for
example, t h e case w i t h H-Beta. Framework d e a l u m i n a t i o n c o n t r i b u t e s a l s o t o t h e
r e d u c t i o n o f t h e c o n v e r s i o n l e v e l s f o r H-Omega, b u t f o r t h i s s t r u c t u r e b l o c k i n g
o f t h e channels by extra-framework species p l a y s t h e m a j o r r o l e ( T a b l e 1 ) . T h i s
b e h a v i o r i s l i k e l y t o be t y p i c a l o f z e o l i t e s s y n t h e s i z e d w i t h low S i / A l r a t i o s
and possessing an u n i d i m e n s i o n a l porous system.
The most i m p o r t a n t p o i n t evidenced i n t h i s work i s l i k e l y t o concern t h e
e f f e c t o f t h e post-steaming a c i d l e a c h i n g , which c o u l d have a n e g a t i v e b u t a l s o
a s t r o n g l y p o s i t i v e i n f l u e n c e on t h e c o n v e r s i o n l e v e l s . Focussing on t h e d a t a
p r e s e n t e d here, i t appears t h a t s e l e c t i v e a c i d l e a c h i n g , which o n l y e x t r a c t s
extra-framework aluminium species, w i l l l e a d t o an i n c r e a s e o f t h e c o n v e r s i o n
levels. The r e v e r s e i s t r u e f o r n o n - s e l e c t i v e acid treatments, i.e. those
giving rise to a further framework dealumination. How can such behavior
r a t i o n a l i z e d ? Since t h e a c i d leaching could a f f e c t the acidity and t h e
accessibility o f the a c t i v e acid centers, two types of solids s h o u l d be
c o n s i d e r e d : i ) those possessing a m u l t i d i m e n s i o n a l porous system, and ii)
those h a v i n g a monodimensional porous s t r u c t u r e .
For s o l i d s w i t h a m u l t i d i m e n s i o n a l porous system ( Y , b e t a ) , o n l y a l i m i t e d
r e d u c t i o n o f t h e m i c r o p o r e volume occurs upon steaming, and t h e m i c r o p o r e
volume i s n o t i n c r e a s e d v e r y s i g n i f i c a n t l y by l e a c h i n g . Thus, the positive
e f f e c t on t h e c o n v e r s i o n l e v e l s o f s e l e c t i v e a c i d l e a c h i n g (H-Y t r e a t e d i n 1N
HC1 s o l u t i o n ) i s more l i k e l y t o be due t o an i n c r e a s e i n t h e a c i d i c p r o p e r t i e s
o f the s o l i d s r a t h e r than t o a b e t t e r a c c e s s i b i l i t y o f t h e a c i d s i t e s . This
statement i s s t r o n g l y supported by p r e v i o u s work which has shown, by v a r i o u s
complementary p h y s i c a l techniques, t h a t an i n c r e a s e i n t h e number o f s t r o n g
framework s i t e s occurs t h r o u g h t h e e l i m i n a t i o n , by s e l e c t i v e a c i d l e a c h i n g , o f
poisoning extra-framework aluminium c a t i o n s formed in the course of the
steaming procedure ( 1 2 ) . Extra-framework aluminium s p e c i e s which e x h i b i t a c i d i c
p r o p e r t i e s a r e a l s o e l i m i n a t e d by m i l d l e a c h i n g . However, these s i t e s o n l y
possess a moderate Bronsted a c i d i t y ( 1 2 ) and t h u s a r e n o t l i k e l y t o p l a y t h e
122

m a j o r r o l e i n t h e c a t a l y t i c performances o f t h e s o l i d s under t h e c o n d i t i o n s we
have employed. It s h o u l d be s t r e s s e d t h a t t o b e t t e r r e v e a l t h e b e n e f i t o f a
s e l e c t i v e l e a c h i n g o f H-Y i n VGO c o n v e r s i o n , t h e s o l i d has t o be t e s t e d w i t h an
a c t i v e m a t r i x so t h a t molecules which a r e t o o l a r g e t o e a s i l y e n t e r t h e z e o l i t e
crystals c o u l d r e a c t more rapidly. Otherwise t h e extra-framework material
l o c a t e d a t t h e e x t e r n a l s u r f a c e o f t h e z e o l i t e s c r y s t a l would h e l p i n t h e
t r a n s f o r m a t i o n o f such heavy molecules, and t h e s e l e c t i v e a c i d l e a c h i n g would
p o s s i b l y have a n e g a t i v e e f f e c t (8, 9). T h i s p o i n t remains t o be c o n f i r m e d .
On t h e contrary i n the case of Omega for which the unidimensional
microporous system i s n e a r l y c o m p l e t e l y b l o c k e d a f t e r t h e steaming s t e p , the
p o s i t i v e e f f e c t o f a s e l e c t i v e post-steaming a c i d leaching c l e a r l y r e s u l t s from
t h e e l i m i n a t i o n o f t h e extra-framework m a t e r i a l s located i n t h e pores. This
does n o t mean t h a t t h e a c i d i c p r o p e r t i e s of t h e framework a r e n o t m o d i f i e d by
l e a c h i n g , b u t t h e s e changes i n a c c e s s i b i l i t y a r e h e r e predominant.
C o n s i d e r i n g now n o n - s e l e c t i v e a c i d l e a c h i n g (H-Y and H-Beta t r e a t e d i n 3N
and 1N HC1 s o l u t i o n s r e s p e c t i v e l y ) , i t i s c l e a r t h a t framework d e a l u m i n a t i o n
o c c u r r i n g as a r e s u l t o f t h i s t r e a t m e n t i s r e s p o n s i b l e f o r t h e r e d u c t i o n o f t h e
conversion levels. Indeed, as shown by physical techniques, the acidic
p r o p e r t i e s o f s o l i d s s u b m i t t e d t o a n o n - s e l e c t i v e l e a c h i n g a r e v e r y low ( 1 2 ) .
However, H-Beta d i f f e r s f r o m H-Y, since non-selective leaching leads t o a
s t r o n g decrease o f t h e cyclohexene c o n v e r s i o n , w h i l e a small increase o f t h e
VGO c o n v e r s i o n occurs. To e x p l a i n such b e h a v i o r t h e r o l e o f a c c e s s i b i l i t y has
t o be t a k e n i n t o account.
Cyclohexene i s a s m a l l m o l e c u l e f o r which s t e r i c c o n s t r a i n t s a r e n o t v e r y
i m p o r t a n t , t h u s i t m a i n l y probes t h e a c i d i c p r o p e r t i e s o f t h e s o l i d s . From t h a t
p o i n t of view, t h e f o l l o w i n g r a n k i n g i s o b t a i n e d : steamed H-Beta > steamed
H-Yxteamed + a c i d leached H-Omega. T h i s r a n k i n g i s i n q u a l i t a t i v e agreement
w i t h t h e a c i d i c p r o p e r t i e s o f t h e s o l i d s as d e t e r m i n e d by p h y s i c a l t e c h n i q u e s ,
and indeed s t r o n g a c i d s i t e s a r e p r e s e n t i n steamed H-Beta ( 1 5 ) . On t h e o t h e r
hand i n VGO c o n v e r s i o n s t e r i c c o n s t r a i n t s cannot be n e g l e c t e d . T h i s would
suggest t h a t t h e m u l t i d i m e n s i o n a l channel system o f H-Beta i s n o t as a c c e s s i b l e
f o r l a r g e molecules as t h e microporous system o f H - Y . I n o t h e r words, i n a v e r y
f i r s t approximation, t h e a c c e s s i b i l i t y of t h e a c i d s i t e s r a t h e r t h a n t h e i r a c i d
s t r e n g t h c o n t r o l s t h e VGO c o n v e r s i o n l e v e l s o v e r H-Beta. This proposal is
s u p p o r t e d by a r e c e n t work ( 7 1 , a c c o r d i n g t o which t h e gas o i l c o n v e r s i o n o v e r
n o n - m o d i f i e d H-Beta does n o t depend much on i t s Si/A1 r a t i o , and by t h e n i c e
s t r u c t u r a l s t u d y o f TREACY e t a l . ( 1 1 ) which s t r o n g l y suggests t h a t t h e open
s t r u c t u r e of z e o l i t e Beta i s likely to contain structural defects. These
accessibility considerations would also explain why acid-leached H-Omega
p r e s e n t r a t h e r low VGO c o n v e r s i o n l e v e l s , w h i l e t h e i r cyclohexene c o n v e r s i o n
 123

CVCLOHEXENE CONVERSION lmol.%l -MAT CONVERSION (wt.%)

15
COKE

10
I

s.
-9
c
3

Y
>
5

0
25 35 45 55
CVCLOHEXENE CONVERSION lmol.%J MAT CONVERSION Iw1.X)

STEAMED (923 I0 AND ACID LEACHED ( 0.5 N)

H-OMEGA 0

CVCLOHEXENE CONVERSION (mol.%)

F i g u r e 3 : Comparison o f s e l e c t i v i t y F i g u r e 4 : Comparison o f s e l e c t i v i t y
curves f o r cyclohexene t r a n s f o r m a t i o n curves f o r VGO c r a c k i n g on t h r e e
over H-Y, H-Beta and H-Omeaa z e o l i t e s z e o l i t e s = (steamed H - Y (873K) -c :
( I s o m e r i s a t i o n + ; Hydrogen t r a n s f e r + ) steamed (97310 and a c i d leached (1Nj
H-Beta +; steamed (92310 and a c i d
leached (0.5N) H-Omega c 1.
124

l e v e l s a r e n o t t o o f a r f r o m t h o s e o f H-Y.
SELECTIVITY
CYCLOHEXENE. As described i n detail elsewhere (161, the selectivities in
cyclohexene t r a n s f o r m a t i o n o f m o d i f i e d H-Y are mainly determined by its
framework Si/A1 r a t i o . H - Y w i t h a u n i t c e l l parameter h i g h e r t h a n 24.27
f a v o r s hydrogen t r a n s f e r r e a c t i o n s (cyclohexane, benzene, methylcyclopentane
formation) r a t h e r than isomerisation (methylcyclopentene..), while H-Y w i t h a
0
u n i t c e l l parameter l o w e r t h a n 24.27 A i s c h a r a c t e r i z e d by v e r y l o w hydrogen
t r a n s f e r s e l e c t i v i t i e s (17, 1 8 ) ( f i g u r e 3 ) . T h i s b e h a v i o r c o u l d be r a t i o n a l i z e d
as f o l l o w s . Depending on whether o r n o t t h e s o l i d s c o n t a i n more t h a n about one
0
A1 per supercage ( u n i t c e l l parameter lower o r h i g h e r t h a n about 24.27 A), t h e y
w i l l o r w i l l n o t promote b i m o l e c u l a r r e a c t i o n s such as hydrogen t r a n s f e r . It i s
now i m p o r t a n t t o determine how t h e s e l e c t i v i t i e s o f m o d i f i e d H-Beta and H-Omega
towards hydrogen t r a n s f e r compare w i t h t h o s e o f m o d i f i e d H-Y. Considering t h e
s e l e c t i v i t y diagrams r e p o r t e d i n f i g u r e 3, i t appears t h a t t h e s e l e c t i v i t i e s o f
H-Beta and H-Omega w i t h r a t h e r low-framework S i / A l r a t i o s are very s i m i l a r t o
t h o s e o f h i g h l y dealuminated H-Y. T h i s would mean t h a t H-Beta and H-Omega do
n o t much promote b i m o l e c u l a r r e a c t i o n s . I t i s n o t c l e a r a t t h e moment whether
such b e h a v i o r d e r i v e s f r o m s t e r i c c o n s t r a i n t s (no cages a r e p r e s e n t i n Omega
and i n B e t a ) , o r f r o m a s p e c i f i c A1 s i t i n g . Since non dealuminated H-Mordenite
i s a l s o c h a r a c t e r i z e d by a l o w hydrogen t r a n s f e r s e l e c t i v i t y i n cyclohexene
c o n v e r s i o n (101, i t i s l i k e l y t h a t s t e r i c c o n s t r a i n t s a r e r e s p o n s i b l e f o r t h e
low hydrogen t r a n s f e r s e l e c t i v i t y o f H-Beta and H-Omega. The intermediate
s p e c i e s would be i n t h a t s p e c i f i c case t o o l a r g e t o e a s i l y f o r m i n 12-membered
r i n g z e o l i t e s which do n o t possess l a r g e cages.
VGO. As shown on f i g u r e 4, t h e s e l e c t i v i t i e s i n VGO c o n v e r s i o n o f H-Beta and
H-Omega v e r y s i g n i f i c a n t l y d i f f e r f r o m t h o s e of modified H-Y. H-Beta and
H-Omega produce v e r y h i g h y i e l d s o f light gases, the s e l e c t i v i t y towards
g a s o l i n e b e i n g r a t n e r l o w . However, H-Beta l e a d s t o a l o w coke l e v e l w h i l e t h e
r e v e r s e i s t r u e f o r H-Omega. From t h e l o w hydrogen transfer tendency of
H-Omega, one would have p r e d i c t e d a reduced coke f o r m a t i o n , which i s o b v i o u s l y
not t r u e . I n fact, i n VGO c o n v e r s i o n over these solids, as it has been
previously stressed, a c c e s s i b i l i t y c o n s i d e r a t i o n s a r e o f p r i m a r y importance
which means t h a t performances o b t a i n e d w i t h model molecules could not be
d i r e c t l y t r a n s f e d t o r e a l f e e d . The h i g h s e l e c t i v i t y f o r gases, f o r i n s t a n c e ,
i s l i k e l y t o be due t o an easy o v e r c r a c k i n g o f t h e g a s o l i n e f r a c t i o n i n s i d e t h e
n o t s u f f i c i e n t l y open channel system o f H-Beta and H-Omega.
CONCLUSION
The post-steaming a c i d l e a c h i n g has been shown t o p l a y a major r o l e i n t h e
c a t a l y t i c performances o f H-Y, H-Beta and H-Omega s i n c e i t can i n c r e a s e o r
 125

decrease t h e c o n v e r s i o n l e v e l s i n cyclohexene as w e l l as i n VGO t r a n s f o r m a t i o n .

I n t h e case o f v e r y open s t r u c t u r e s such as H-Y, the positive effect o f a
s e l e c t i v e l e a c h i n g m a i n l y r e s u l t s f r o m an i n c r e a s e o f t h e number o f s t r o n g a c i d
s i t e s ( e l i m i n a t i o n o f p o i s o n i n g aluminium s p e c i e s ) , w h i l e f o r s t r u c t u r e s w i t h a
monodimensional porous system such as H-Omega t h e a c c e s s i b i l i t y o f s i t e s i s o f
predominant importance ( i n c r e a s e i n t h e microporous volume). When a model t e s t
r e a c t i o n i s employed, a q u a l i t a t i v e r a n k i n g o f t h e s o l i d s a c c o r d i n g t o t h e i r
a c i d i c p r o p e r t i e s i s o b t a i n e d . I n t h a t r e g a r d , t h e c a t a l y t i c performances o f
H-Beta a r e b e t t e r t h a n t h o s e o f H-Y and H-Omega. However, t h i s r a n k i n g i s no
l o n g e r t r u e f o r VGO conversion. For such a t r a n s f o r m a t i o n o f heavy molecules
a c c e s s i b i l i t y c o n s i d e r a t i o n s have t o be t a k e n i n t o account, which means t h a n
t h e most open s t r u c t u r e , namely H-Y, leads t o t h e best performances. The
performances o f H-Y can be s i g n i f i c a n t l y improved when t h e a c i d i c p r o p e r t i e s o f
steamed H-Y a r e o p t i m i z e d t h r o u g h a s e l e c t i v e a c i d l e a c h i n g .

B I BLI OGRAPHY
1 . J . Scherzer, ACS Symposium S e r i e s 248, (19831, 157-200.
2. J.S. Magee, W.E. Cormier and G.M. m t e r m a n , K a t a l i s t i k s ' 6 t h Annual F l u i d
Cat. Cracking Symposium, Munich, Germany (19851, May 22-23.
3. Grupo Especializado de Catalisis, Madrid, Spain (19871,
September 28-October 1.
4. E.G. Campbell and P.A. Winthrop, European P a t e n t A p p l i c a t i o n , (19871,
n"243629.
5. F. Raatz and Ch. M a r c i l l y , European P a t e n t A p p l i c a t i o n , (19861, n o 206871.
6. A. Corma, V . Fornes, J.B. Monton and A.V. O r c h i l l e s , J o u r n a l o f C a t a l y s i s
107, (1987) 288-295.
7. E C o r m a , V. Fornes, F. Melo and J . Perez-Pariente, Symposium on advances
i n FCC, American Chemical S o c i e t y , New Orleans meeting, (19871, August 30
September 4.
8. A. Corma, E. H e r r e r o , A. M a r t i n e z and J. P r i e t o , Symposium on advances i n
FCC, American Chemical S o c i e t y , New Orleans meeting, (19871, August 30
September 4.
9. A. Corma, V. Fornes, A. M a r t i n e z , F. Melo and 0. P a l l o t a , Symposium on
" I n n o v a t i o n i n Z e o l i t e M a t e r i a l s Science", Stud. S u r f . S c i . Cat., Vol 37,
(19881, 495.
10. E. J a c q u i n o t , PhD, ENSPM, R u e i l Malmaison, France, i n p r e p a r a t i o n .
11. M.M. J . Treacy and J.M. Newsam, Nature, 332, (19881, March 17.
12. A. Macedo, PhD, ENSPM, R u e i l M a l m a i s o r France, (19881 and r e f e r e n c e s
there in.
13. R. Beaumont and D. Barthomeuf, J o u r n a l o f C a t a l y s i s , 26, (19721, 218-225.
14. D. Barthomeuf, M a t e r i a l s Chemistry and P h y s i c s , 11, ( l 3 8 7 1 , 49.
15. M. Maache and J.C. L a v a l l e y , i n p r e p a r a t i o n .
16. E. J a c q u i n o t , A . Mendes, F. Raatz, Ch. M a r c i l l y , F.R. R i b e i r o and J.
Caiero, a r t i c l e s u b m i t t e d f o r p u b l i c a t i o n .
17. L.A. Pine, P.J. Maher and W.A. Wachter, J o u r n a l o f C a t a l y s i s , g,
(19841,
466-476.
18. R.E. R i t t e r , J.E. C r e i g h t o n , T.G. Roberie, D.S. Chin, C.C. Wear, p r e s e n t e d
a t NPRA Annual Meeting, Los Angeles, paper AM 86-45, (19861, March 23.
19. H. F i c h t n e r - S c h m i t t l e r , U. Lohse, G. E n g e l h a r d t and V. Patzelova,
Cryst-Res-Tech. 1 1 , (19841, ( 1 1 .
20. A. Macedo, F. RaTtz, R. B o u l e t , J.C. L a v a l l e y and A. Janin, Symposium on
" I n n o v a t i o n i n Z e o l i t e M a t e r i a l s Science", Stud. S u r f . S c i . Cat, Vol 37,
(19881, 375.
This Page Intentionally Left Blank
H.G. Karge, J . Weitkamp (Editors 1, Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in T h e Netherlands

SURFACE-METALS INTERACTIONS IN FLUID CRACKING CATALYSTS DURING THE UPGRADING

OF VANADIUM CONTAMINATED GAS OILS*

M. L. Occelli(’) and J. M. Stencel(2)

’Unocal Corporation, P.O. Box 76, Brea, CA 92621 USA
2Kentucky Center for Energy Research, P.O. Box 13015, Lexington, KY 40512
USA

ABSTRACT
Laser Raman and x-ray photoelectron spectroscopy (XPS), together with
microactivity testing, x-ray diffraction (XRD) and BET surface area
measurements have been used to elucidate the interaction o f vanadium with
typical constituents of a fluid cracking catalyst. Cracking components 1 ike
HY or CREY (calcined rare-earth exchanged zeolite Y) are thermally stable in
air at 76O0C/5h even when loaded with 3-4% V. In the presence o f steam,
stability is greatly reduced. With less than 1% V, HY collapses with
formation of mullite (A1 Si 0 ) and silica (tridymite) whereas CREY
collapses with formation OF
2ed?um orthovanade (CeVO ) . The presence o f
lanthanide ions in the zeolite reduces V-toleradce at hydrothermal
conditions. Mullite formation was also observed on V-loaded gels. On
steam-aged Kaolin, aluminosilicate gels and HY, vanadium is present mainly
as bulk V205.
INTRODUCTION
In a previous paper (ref. l), interactions between the components (gel,
clay and zeolite) of a fluid cracking catalyst (FCC) with a metal
contaminant such as nickel have been studied in detail. In the reaction
zone (the riser) of a fluid cracking unit, metal-containing porphyrins and
similar complexes decompose, leaving Ni contaminants on the cracking
catalyst surface. Nickel catalyzes secondary cracking reactions, generating
light gases and coke at the expense o f gasoline yields.
Luminescence quenching of an artificially Ni -contaminated
(zeolite-rich) FCC have indicated that Ni, after deposition, covers the
catalyst zeolitic component without affecting its crystallinity (ref.2)
Steam aging causes some of the nickel t o migrate, thus restoring part of the
zeolite’s original luminescence intensity (ref. 2). Electron micrographs

*Based, in part, on a paper presented at the Spring Meeting o f the

California Catalysis Society, Menlo Park, CA, April 1988.
128

have shown t h a t steam-aging changes t h e s i z e o f t h e N i c r y s t a l l i t e s present

i n a manner c o n t r o l l e d by t h e nature (composition) o f t h e c a t a l y s t surface
( r e f s . 2,3). A f t e r c a l c i n a t i o n , n i c k e l was found t o be present mainly as a
N i O - l i k e phase on a l l the FCC components. However, f o l l o w i n g steam-aging,
n i c k e l i n t e r a c t s both w i t h t h e c l a y ( k a o l i n ) and w i t h t h e gel t o f o r m
surface compounds which are believed t o be l e s s d e l e t e r i o u s t o the cracking
process than supported N i O species ( r e f . 1).
It i s the purpose o f t h i s paper t o study and r e p o r t t h e i n t e r a c t i o n s o f
vanadium w i t h t h e t h r e e basic components o f a FCC. The o b j e c t i v e o f t h i s
work i s t o o b t a i n a b e t t e r understanding o f those V-surface i n t e r a c t i o n s
which can be useful i n designing V - t o l e r a n t cracking c a t a l y s t s .

EXPERIMENT
Reference ComDounds Preparation
A Ce-vanadate (CeV04) sample was prepared by pressing a 2Ce02.V205
mixture a t 10,000 l b s / l min and then heating the r e s u l t i n g wafer i n a i r a t
80O0C/2hr ( r e f . 5). A melt was obtained t h a t gave an x - r a y d i f f r a c t o g r a m
consistent w i t h JCPDS p a t t e r n No. 12-757 f o r CeV04; small amounts (51%) o f
unreacted Ce02 were a l s o present. S i m i l a r l y , by h e a t i n g a La203-V205 wafer
a t 80O0C/2hr, a compound w i t h an x - r a y d i f f r a c t o g r a m c o n s i s t e n t w i t h JCPOS
p a t t e r n No. 25-427 f o r LaV04 was obtained. A m i x t u r e ( w i t h an excess) o f
g i b s i t e and V205 when heated t o 600'C/air gave a compound w i t h an x - r a y
d i f f r a c t o g r a m s i m i l a r t o JCPDS p a t t e r n No. 31-34 f o r A1V04. Other
procedures f o r preparing A1V04 have been described elsewhere ( r e f . 6). A l l
powder d i f f r a c t i o n measurements were obtained w i t h a Siemens D-500
d i f f r a c t o m e t e r a t a scan r a t e o f l'/min using monochromatic Cu-km r a d i a t i o n .

Catalyst PreDaration and T e s t i n q

The amorphous a l u m i n o s i l i c a t e gel (AAA-alumina) used i n t h i s study
contains about 80.4% Si02, 19.4% A1203 and 0.056% Na20. Aluminum-27 MAS NMR
has shown t h a t aluminum i s present mainly as Al(V1) and t h a t a f t e r d r y i n g
(300°C/24h) i n a i r , t h e A l ( V I ) / A l ( I V ) r a t i o i s about 1.2. Mercury
2
porosimetry measurements have i n d i c a t e d a 479 m /g surface area and 1.67
cc/g pore volume; the average pore diameter o f t h e d r i e d gel was 134 A. The
k a o l i n i t e sample was obtained from t h e Georgia K a o l i n Company. The sample
o f c a l c i n e d r a r e - e a r t h (RE) exchanged Z e o l i t e Y (CREY) and t h e h i g h - a c t i v i t y
cracking c a t a l y s t (GRZ-1) were obtained from t h e Davison Company. The CREY
sample had a Si02/A1203 r a t i o o f 5.0, contained 7.6% Ce20j, 4.0% La20g,
 129

2.8% Nd203, 0.9% Pr203, 3.5% Na203 and had a BET surface area o f 749 mL/g.
The HY sample (Linde LZY-82) had a Si02/A120, r a t i o o f 5.4 and BET surface
2
area o f 761 m /g. LaY (containing 8.1% La203) was obtained by r e a c t i n g t h i s
HY w i t h 1M LaC13 solutions (prepared using LaC13.7H20 c r y s t a l s , from GFS
Chemicals) .
Catalyst evaluation was performed w i t h a m i c r o a c t i v i t y t e s t (MAT) using
conditions described elsewhere (4). Conversions are on a vol% f r e s h feed
(FF) basis and have been defined as [ V -V /V ] x 100, where Vf i s t h e volume
f P f
o f feed and V i s the volume o f product w i t h b.p. > 204'C.
P
Steam-aging was accomplished by passing steam a t 760'C over the
c a t a l y s t s f o r 5 hours. A s o l u t i o n o f vanadium naphthenate i n toluene was
used t o metal -load the various m a t e r i a l s according to an established
procedure ( 7 ) ; the naphthenate was obtained from P f a l t z and Bauer, I n c . and
contained 2.9 w t % V.

Catal v s t Characterization

(i)
XPS Measurements. The FCC and i t s components (AAA-alumina, k a o l i n ,
CREY o r HY) were analyzed by X-ray photoelectron spectroscopy (XPS) after
c a l c i n a t i o n (C), steaming (S) and a f t e r H2-treatment (H2). Powders were
pressed i n t o t h i n , 13-mm diameter wafers and then mounted on a heatable
sample probe attached t o a Leybold-Hereaus LHS-11 XPS/Auger/ISS instrument.
The instrument base pressure was 2 x lo-'' bar; samples were g e n e r a l l y
analyzed a t a pressure o f 2 x bar. During H2-treatment, m a t e r i a l s were
exposed t o 25 ml/min f l o w i n g H2 a t a pressure o f 2.5 bar and a t a
temperature o f 400°C f o r periods o f 15 t o 75 minutes i n a h i g h pressure-high
temperature r e a c t o r attached t o the side o f t h e LHS-11 a n a l y s i s chamber.
A f t e r exposure t o H2, the samples were cooled w h i l e the r e a c t o r . was
evacuated t o bar. Then the samples were moved i n t o a preparatory
chamber and f i n a l l y i n t o the analysis chamber. A t y p i c a l time t o cool,
evacuate and move the sample t o the analysis p o s i t i o n was 10 minutes. All
binding energies reported have been corrected f o r charging by assuming t h a t
t h e ubiquitous Cls band i s located a t 284.6eV.

(ii)Raman SDectroscooy.Raman spectra were recorded on a Spex Ramalog

1403 spectrometer (Spec Industries, Metuchen, NJ) equipped w i t h a cooled RCA
GaAs p h o t o m u l t i p l i e r tube (CA 31034-02). The 4880A l i n e o f a model 165 A r t
l a s e r (Spectra Physics, Mountain View, CA) was used t o generate Raman
130

scattered l i g h t . The l a s e r power i m p i n g i n g on t h e sample was l i m i t e d t o

ap p ro x ima t e ly 50 mW. A l l s p e c t r a were r e c o rded w i t h a s p e c t r a l r e s o l u t i o n
o f 5 cm-’ (350 p m s l i t w i d t h ) . S i g n a l p u l s e s f rom t h e p h o t o m u l t i p l i e r t u b e
were passed t h r o u g h a model 1182 amp1 i f i e r / d i s c r i m i n a t o r ( P r i n c e t o n A p p l i e d
Research, P r i n c e t o n , NJ) and counted by a N i c o l e t 1280 d a t a system ( N i c o l e t
I n s t r u m e n t Corp., Madison, WI). Typically, 50-100 scans p e r sample were
averaged i n o r d e r t o o b t a i n s p e c t r a w i t h adequate s i g n a l - t o - n o i s e r a t i o s . A
d a t a p o i n t was a c q u i r e d e v e r y 0.7 cm-’. Samples were prepared f o r Raman
measurements by g r i n d i n g t h e c a t a l y s t s i n an agat e m o r t a r and p e s t l e .
Samples c o n t a i n i n g KN03 ( t h e i n t e r n a l s t a n d a r d ) were prepared by g r i n d i n g
90% c a t a l y s t and 10% KN03 m i x t u r e s . The powdered samples were t h e n pressed
i n t o 1 cm d i a m e t e r w a f e r s under a p r e s s u r e o f a p p r o x i m a t e l y 1000 p s i . Each
waf e r was mounted i n a s p i n n i n g sample h o l d e r and p l a c e d i n t h e sample
chamber o f t h e spectrometer. The a n g l e between t h e i n c i d e n t l a s e r beam and
t h e sample s u r f a c e was 30’; samples were spun a t a p p r o x i m a t e l y 500 rpm t o
m i n i m i z e t h ermal m o d i f i c a t i o n s .

RESULTS AND DISCUSSION

Cat a l v s t T e s t i n q
The metal - f r e e , steam-aged amorphous a l u m i n o s i l i c a t e g e l (AAA-alumina)
and t h e z e o l i t e - r i c h commercial FCC (Davison’s GRZ-1) gave 61% and 84%
co nv ers io n, r e s p e c t i v e l y , when c r a c k i n g t h e same gas o i l under MAT
conditions ( r e f . 4). I n b o t h c a t a l y s t s , a c t i v i t y decreased m o n o t o n i c a l l y
w i t h V l e v e l s , Table 1 . W i t h 1.5% V, t h e z e o l i t i c FCC l o s t most o f i t s
u s e f u l a c t i v i t y ; w i t h 2.0% V, i t became i n a c t i v e . This irreversible
d e a c t i v a t i o n c o r r e l a t e s w e l l w i t h s u r f a c e a r e a and c r y s t a l l i n i t y l o s s e s w i t h
V l o a d i n g s , see Table 1 . Vanadium on t h e steam-aged c a t a l y s t was p r e s e n t
m a i n l y as a r e d u c i b l e o x i d e - l i k e V205. A t t h e h i g h t emperat ures encountered

TABLE 1
R e t e n t i o n o f S u r f a c e Area and C r a c k i n g P r o p e r t i e s i n t h e
Presence o f V ( M a t e r i a l s have been H y d r o t h e r m a l l y Aged) (4,12)

% W t % V on Gel )Jt%V on FCC (GRZ-1

Ret ent ion 0.5 1.0 1.5 2 .o 0.5 1.0 1.5 2ta
Conv ers io n 82.5 78.4 13.8 69.7 91.2 77.8 60.5 25.6
Gasoline 80.4 69.5 60.1 57.9 88.0 70.4 57.0 24.1
S u r f a c e Area 100.0 85.4 76.9 69.3 69.0 42.1 21.6 6.0
C r y s t a l 1i n i t y -_ -- _- -_ 75.7 51.3 37.8 13.5
 131

d u r i n g r e g e n e r a t i o n , V205, because o f i t s l o w (658'C) m e l t i n g p o i n t , became

a f l u i d c a p a b l e of m i g r a t i n g i n t o t h e c a t a l y s t pores where i t i n t e r a c t e d
w i t h t h e z e o l i t e c a u s i n g an i r r e v e r s i b l e r e d u c t i o n i n c r y s t a l l i n i t y and
cracking a c t i v i t y ( r e f . 12).
I n c o n t r a s t , V had l i t t l e e f f e c t on t h e amorphous c a t a l y s t p r o p e r t i e s
and a f t e r steaming, t h e 2% V l o a d e d g e l r e t a i n e d -70% o f i t s i n i t i a l s u r f a c e
a r e a (and -70% o f i t s i n i t i a l c o n v e r s i o n ) . Steaming o f t h e m e t a l - l o a d e d g e l
removed o c c l u d e d m a t e r i a l s ( p r o b a b l y s i l i c a ) c a u s i n g t h e p o r e volume o f t h i s
catalyst to increase s l i g h t l y t o 0.52 cc/g f r o m 0.46 cc/g (ref. 1).
Luminescence as w e l l as EPR d a t a ( r e f . 13) have shown t h a t a f t e r metal
deposition, vanadyl i o n s (YO2') were formed. These i o n s a r e q u i t e m o b i l e
( r e f . 14) and a b l e t o m i g r a t e t o charge compensate A l ( I V ) p r e s e n t i n t h e g e l
t h e r e b y f o r m i n g S i - 0 - A 1 (1V)-OV02' groups. Then, i n t h e r e g e n e r a t o r , t h e
o x i d a t i v e decomposition o f carbonaceous d e p o s i t s forms V205 which c o u l d coat
o r b l o c k access t o t h e g e l a c t i v e s i t e s t h u s c a u s i n g t h e decrease in
a c t i v i t y seen i n Table 1 .

Thermal S t a b i l i t y
The x - r a y d i f f r a c t o g r a m o f t h e steam-aged a l u m i n o s i l i c a t e g e l under
s t u d y show a weak, broad and f e a t u r e l e s s s h o u l d e r c e n t e r e d a t 28222' t y p i c a l
o f X - r a y amorphous m a t e r i a l s . However, a f t e r l o a d i n g t h e g e l w i t h 2% V and
c a l c i n a t i o n i n a i r ( a t 76OoC/5h), a d i f f r a c t o g r a m s i m i l a r t o JCPDS p a t t e r n
No. 15-776 f o r m u l l i t e (A16Si2013) was o b t a i n e d . The d i f f r a c t i o n l i n e s
almost doubled i n i n t e n s i t y when h e a t i n g ( a t 760°C/5h) was performed i n t h e
presence o f 100% steam. Steaming N i - l o a d e d (1-5% N i ) g e l s d i d n o t f o r m
mull i t e .
M u l l i t e has a s t r u c t u r e c o n s i s t i n g o f c h a i n s o f Al(V1) that are
p a r a l l e l t o t h e z - a x i s and c r o s s l i n k e d by t e t r a h e d r a c o n t a i n i n g b o t h S i and
Al. I t can be o b t a i n e d by h e a t i n g k a o l i n a t T ,lOOO'C o r by c a l c i n i n g
a l u m i n o s i l i c a t e g e l s a t temperatures w e l l above 1000°C ( r e f . 1 5 ) . Thus, i t
appears t h a t V a c t s as a m i n e r a l i z i n g agent, allowing the formation o f
m u l l i t e a t temperatures s i g n i f i c a n t l y l o w e r t h a n t h o s e u s u a l l y r e p o r t e d i n
t h e synthesis o f t h i s mineral. Partial incorporation o f V i n t o the mullite
structure and formation of V-0-A1 linkages could have occurred.
S u b s t i t u t i o n o f A1 w i t h Fe and T i i n m u l l i t e i s n o t uncommon, and n a t u r a l
i r o n - m u l l i t e s c o n t a i n i n g up t o 6% Fe20j have been r e p o r t e d ( r e f . 16).
S i l i c a - f r e e m u l l i t e t y p e phases have a l s o been s y n t h e s i z e d (ref. 17).
Formation o f A1V04 c o u l d n o t be observed b y XRD ( n o r by Raman) on any o f t h e
V-loaded a l u m i n o s i l i c a t e samples examined.
132

I n a t y p i c a l FCC, t h e desired cracking a c t i v i t y i s introduced by

i n c o r p o r a t i n g HY o r c a l c i n e d r a r e - e a r t h exchanged Y (CREY) c r y s t a l s i n t o a
gel-clay mixture. In an effort to investigate the mechanism of
V-deactivation o f a FCC, HY and CREY were metal-loaded w i t h up t o 5% V and
then heated f o r 5hr a t 760°C i n t h e presence o f a i r o r steam, see F i g s . 1-8.
With as much as 4% V, HY c r y s t a l s were t h e r m a l l y s t a b l e ( a t 760'C) when
heated i n t h e presence o f a i r , Figs. 1A-1E. With 5% V, t h e r e was a d r a s t i c
reduction i n surface area and c r y s t a l l i n i t y , and a new phase appeared, Fig.
1F. I n the presence o f steam, these c r y s t a l s became much l e s s stable, Figs.
2A-F. With 1% V, o n l y 45% o f t h e i r i n i t i a l surface area was r e t a i n e d and
w i t h 2% V, evidence o f the presence o f HY c r y s t a l s disappeared, Figs. 2B-C.
A new phase was formed which grew w i t h V-loadings, Figs. 2C-F. Vanadium ( a t
the hydrothermal c o n d i t i o n s used) seems t o have l i t t l e e f f e c t on the HY
c r y s t a l l i n i t y up t o t h e 0.6 w t % l e v e l , Figs. 3A-D. Following t h e collapse
o f the HY s t r u c t u r e , t h e x - r a y amorphous product forms m u l l i t e and smaller
amounts o f Si02, Fig. 4. The doublet a t 28 ~ 2 0 ' (d = 4.44A and d = 4.12A)
i d e n t i f i e s the Si02 formed t o be o f t h e t r i d y m i t e type.
Under hydrothermal conditions, l o s s o f c r y s t a l 1 i n i t y i n metal - f r e e HY
c r y s t a l s r e s u l t s from dealumination. Steaming V-loaded HY c r y s t a l s
generated a protonated species, probably HqV207 ( r e f . 18) (V205 t 2H20 =
H4V207), which accelerated A1 -removal and l a t t i c e collapse. E x t r a framework
aluminum could then r e a c t w i t h the r e s i d u a l x - r a y amorphous phase t o f o r m
m u l l i t e . I n f a c t , an A l ( V 1 ) - r i c h gel l i k e AAA-alumina ( A l ( V I ) / A l ( I V ) ratio
o f 1.2) forms mull i t e when heated i n the presence o f V .
L i k e HY, CREY c r y s t a l s w i t h as much as 4% V r e t a i n e d 62% o f t h e i r
i n i t i a l surface area and most o f t h e i r o r i g i n a l c r y s t a l l i n i t y when heated a t
760°C/5h i n t h e presence o f a i r ; Figure 5A and 5E. With 5% V, the c r y s t a l s
l o s t most o f t h e i r surface area and c r y s t a l l i n i t y and a new phase appeared.
As w i t h HY c r y s t a l s , heating a t 760'C/5h i n t h e presence o f steam reduced
the CREY s t a b i l i t y s i g n i f i c a n t l y , Fig.6. With o n l y 0.2-0.4% V, CREY became
e s s e n t i a l l y amorphous, Fig. 7. Thus, the i n t r o d u c t i o n o f r a r e - e a r t h ions
i n t o z e o l i t e s w i t h the f a u j a s i t e s t r u c t u r e decreased the c r y s t a l s '
hydrothermal s t a b i l i t y i n the presence o f vanadium. A t V-loading above 1%,
i t was p o s s i b l e t o observe t h e growth o f a new phase which had been
i d e n t i f i e d t o be cerium orthovanadate (CeV04); lanthanum compounds could n o t
be observed, Fig. 8.
 133

1
I I " '

Figure 1. X-ray diffractograms Figure 2. X-ray d i f f r a c t o g r a m s

o f HY c r y s t a l s heated i n a i r a t o f HY c r y s t a l s heated i n steam
760'C/5hr i n t h e presence o f : (A) a t 760'C/5hr i n t h e presence o f :
0, (B) 1.0, (C) 2.0, (D) 3.0, (A) 0, (B) 1.0, (C) 2.0, (D) 3.0,
(E) 4.0 and (F) 5.0% vanadium. (E) 4.0 and (F) 5.0% vanadium.

I l l 1 1 i I!

"1 I1

Figure 3 . X-ray diffractograms Figure 4. The formation o f

o f HY c r y s t a l s heated i n steam m u l l i t e and t r i d y m i t e a f t e r
a t 760eC/5hr i n the presence o f : steam aging HY c r y s t a l s
(A) 0, (B) 0.2, (C) 0.4, (D) 0.6, loaded w i t h 5% V.
(E) 0.8 and ( F ) 1.0% vanadium.

CREY i s u s u a l l y prepared by r e p e t i t i v e exchanges o f NaY w i t h a s o l u t i o n

containing a commercial r a r e - e a r t h (RE) c h l o r i d e mixture. I n i t i a l l y , the
a i r - d r i e d REY c r y s t a l s contain the various lanthanide ions i n t h e supercages
since hydrated lanthanide ions are t o o l a r g e t o d i f f u s e through a
0

six-membered window (2.5A i n diameter) and migrate d i r e c t l y i n t o the

s o d a l i t e cage o r i n t o the double-six r i n g u n i t s t h a t connect t h e s o d a l i t e
cages. However, on heating, these i o n s l o s e t h e i r water o f h y d r a t i o n and
i r r e v e r s i b l y migrate i n t o the small cages where they can have maximum
134

Figure 5 . X-ray diffractograms Figure 6. X-ray diffractograms

of CREY crystals heated in air o f CREY crystals heated in steam
at 760eC/5hr in the presence of: at 760'C/5hr in the presence o f :
(A) 0, (€3) 1.0, (C) 2.0, (D) 3.0, (A) 0, ( 6 ) 1.0, (C) 2.0, (D) 3.0,
(E) 4.0 and (F) 5.0% vanadium. (E) 4.0 and ( F ) 5.0% vanadium.

IWO I H E l l (DEGREE1 W O I H I I A (MGRIE)

Figure 7. X-ray diffractograms Figure 8. Cerium orthovanadate

o f CREY crystals heated in steam (CeV04) formation after steam-
at 760eC/5hr in the presence of: aging CREY crystals loaded with
(A) 0, (B ) 0.2, (C) 0.4, (D) 0.6, 5% vanadium.
( E ) 0.8 and ( F ) 1.0% vanadium.

coordination with framework oxygens (ref. 19-21). Repetitive exchanges with

1.OM NH4N03 solutions at 60'C did not remove any substantial amounts o f
lanthanide ions from CREY, and the RE-oxide content remained unchanged at
about 15.0%. At temperatures above 300'C, Ce(II1) oxidized to Ce(1V); the
oxidation to the tetravalent state was believed to retard Ce migration (ref.
20). Thus, it is possible that in CREY, La(II1) ions are preferentially
located in the small cages and Ce(IV) ions in the supercages where they can
more easily interact with vanadium and form stable orthovanadates.
 135

I t has been proposed t h a t vanadate f o r m a t i o n r e q u i r e s framework oxygen

t h u s l e a d i n g t o l a t t i c e c o l l a p s e ( r e f . 22). However, a t -7OO"C, t h e
apparent lanthanum charge i s 2.38 ( r e f , 19), i n d i c a t i n g t h e presence o f
r e s i d u a l La(0H)" i o n s which c o u l d r e a c t (under hydrot hermal c o n d i t i o n s )
w i t h V205 (2 La(OH)t2 t H20 t V205 = 2 LaV04 t 4Ht) g e n e r a t i n g a s t a b l e
vanadate and a c i d i t y . I n f a c t , LaY ( c o n t a i n i n g 8.1% La203) when steamed i n
t h e presence o f (1-5%) V c o l l a p s e d w i t h LaV04 f ormat ion, F i g . 100. H i g h l y
exchanged LaY c r y s t a l s have been shown t o c o n t a i n -La-(OH)-La- t y p e l i n k a g e s
between p a i r s o f La i o n s s t r e t c h i n g across t h e s o d a l i t e cages ( r e f s . 23,24).
Removal o f t h e s e l a n t h a n i d e i o n s when LaV04 i s formed d e s t a b i l i z e the
f a u j a s i t e s t r u c t u r e c o n t r i b u t i n g t o i t s c o l l a p s e ( r e f . 24).
The CREY c r y s t a l s under s t u d y c o n t a i n almost t w i c e as much Ce t h a n La
i n a d d i t i o n t o s m a l l e r amounts o f Nd and P r . A t t emperat ures above 300°C
( i n a i r ) , c e r i u m has an e f f e c t i v e charge near 2' which i s c o n s i s t e n t w i t h
t h e presence o f an oxycerium complex ( r e f . 20). Since i t i s known f rom EPR
( r e f . 13) t h a t even a f t e r t h e o x i d a t i v e decomposition ( i n d r y a i r ) o f t h e
naphthenate, vanadium i n t h e z e o l i t e i s p r e s e n t m a i n l y as vanadyl c a t i o n s
(VO"), i t i s proposed t h a t CeV04 i s formed d i r e c t l y by t h e f o l l o w i n g redox
scheme:

[Ce \o/ ce1t4

/O\ t 2 VOt2 t 4H20 = 2 Ce V04 t 8H'

Thus, removal o f l a n t h a n i d e i o n s d u r i n g vanadate formation, i n addition t o

d e s t a b i l i z i n g t h e z e o l i t e , generates p r o t o n s which c o u l d enhance framework
dealumin at io n. I n f a c t , i n d r i e d LaY ( w i t h 5% V), t h e A l ( V I ) / A l ( I V ) r a t i o
inc re as es t o 0.26 f r o m 0.20 upon c a l c i n a t i o n a t 54O0C/10hr i n d r y a i r .
Steaming causes a l o s s o f c r y s t a l l i n i t y ; t h e aluminum-27 MASNMR spectrum o f
the steamed material is similar to that of V-loaded amorphous
a l u m i n o s i l i c a t e g e l s l i k e AAA-alumina ( r e f . 25). A f t e r steaming LaY loaded
w i t h 5% V, the Al(VI)/Al(IV) r a t i o almost doubled i n value, suggest ing
e x t e n s i v e de-a l u m i n a t i o n . I t i s proposed t h a t t h e d e s t a b i l i z a t i o n r e s u l t i n g
f rom enhanced d e a l u m i n a t i o n and f r o m f o r m a t i o n o f vanadate i s r e s p o n s i b l e
f o r t h e r a p i d ( z i p p e r - l i k e ) ( r e f . 26) s t r u c t u r a l c o l l a p s e observed when CREY
c r y s t a l s a r e h y d r o t h e r m a l l y heated i n t h e presence o f small (0.2-0.4%)
amounts o f V, F i g . 7.

Raman R e s u l t s
The e f f e c t s o f steam-aging (760'C/5h, 100% steam) on V i n t e r a c t i o n s
w i t h a c r a c k i n g c a t a l y s t ( l i k e GRZ-1) and w i t h i t s components a r e shown i n
t h e Raman s p e c t r a i n Figs. 9-11. On t h e steam-aged clay (kaolin),
136

amorphous aluminosilicate gel and on the lanthanide-free HY crystals,

vanadium is present mainly as supported V205, Fig. 9. In contrast, the Raman
spectra of the V-loaded CREY crystals exhibit bands at 869, 803, 766, 470
and 370 cm-l which are characteristic of CeV04; see Figs. 108 and 1OC. A
surface vanadate species like A1V04 could not be observed.
The dependence of CeV04 formation on V loadings was examined by mixing
the steam-aged and V-contaminated CREY crystals with known quantities of
NaN03. Raman spectra were then obtained in which the intensity due to the
NO3 symmetric stretching vibrational band at 1050 cm-l could be compared to
the V04 symmetric stretching vibration at 870 cm-l. The increase in

Figure 9. Raman spectra of 5% V Figure 10. Raman spectra o f 5% V

loaded on: (A) kaolin and (B) gel on: (A) HY and (B) CREY crystals
after steam-aging. The reference after steam-aging. Reference
spectra for V205 is given in (C). spectra for CeV04 and LaVO are
shown In (C) and ( D ) , respgctively.

VANADIUM ON CRN (Wn)

Figure 11. The formation of CeV04 as a function of V loading.

intensities of this vibration as a function of V loading is shown in Fig.

11. The lower limit of CeV04 detection is at approximately 0.7% V; a
similar loading is required to observe CeV04 formation by XRD, Fig. 6.
Although Raman spectroscopy o f catalysts i s not generally considered
quantitative, recent studies have proven that with specially designed and
relatively simple experiments, quantitative data can be acquired (ref.
9,lO).
 137

The l i n e a r dependence o f CeV04 f o r m a t i o n on V l o a d i n g s a t

c o n c e n t r a t i o n s above a p p r o x i m a t e l y 0.7% V i m p l i e s t h a t Ce-V i n t e r a c t i o n s
c o n t i n u e t o o c c u r even i n c r y s t a l s i n which XRD d a t a has shown complete
c o l l a p s e o f t h e z e o l i t e s t r u c t u r e . Below 0.7% V, t h e s e n s i t i v i t y o f Raman
spectroscopy (and XRD) i s somewhat inadequate t o i d e n t i f y CeV04. However,
s i n c e even s m a l l amounts o f V s i g n i f i c a n t l y reduce CREY c r y s t a l l i n i t y , CeV04
p r o b a b l y forms a l s o a t l e s s t h a n 0.7% V l o a d i n g s . Alt hough CREY c o n t a i n e d
4.0% La203, LaV04 f o r m a t i o n c o u l d n o t be observed, suggest ing t h a t s i t e s a t
w hic h Ce i s l o c a t e d a r e more a c c e s s i b l e t o V a t t a c k t h a n t hose s i t e s
containing La and/or that CeV04 f o r m a t i o n i s more facile than LaV04
formation.

XPS R e s u l t s
Changes i n Si/A1 and V / ( S i t A l ) r a t i o s r e s u l t i n g f r o m steaming and/or
r e d u c t i o n ( i n H2) o f t h e c a l c i n e d V-contaminated m a t e r i a l s a r e shown i n
Table 2. Assuming a c o n s t a n t ( S i t A 1 ) s u r f a c e c o n c e n t r a t i o n , the V/(SitAl)
r a t i o s s hould i n d i c a t e t h e s u r f a c e o b s e r v a b i l i t y o f V independent o f Si/A1
r a t i o changes. The V / ( A l t S i ) r a t i o does n o t change appreciably a f t e r
thermal o r hydrothermal t r e a t m e n t o f t h e v a r i o u s components o f a c r a c k i n g
catalyst. I n c o n t r a s t , steaming a c r a c k i n g c a t a l y s t l i k e GRZ-1 causes a
l a r g e decrease i n t h i s r a t i o p r o b a b l y because o f V m i g r a t i o n i n t o t h e open
three-dimensional macroporosity o f t h e c a t a l y s t . M i g r a t i o n o f V t o Ce
and/or La c e n t e r s has been a l r e a d y r e p o r t e d ( r e f . 22).
Decreases i n Si/A1 r a t i o s a f t e r steaming a r e observed f o r t h e g e l ,
k a o l i n and CREY samples. The S i / A l r a t i o o f c a l c i n e d CREY i s 40% g r e a t e r
t h an t h e Si/A1 o f c a l c i n e d HY; o n l y upon steaming do t h e Si/ Al ratios of
t h es e z e o l i t e s become a p p r o x i m a t e l y equal, T able 2. The Si/ Al r a t i o o f HY
c r y s t a l s inc re a s e s upon steaming whereas l i t t l e change i n t h i s r a t i o i s
n o t e d f o r GRZ-1. V a r i a t i o n s i n Si/A1 v a l u e s (T able 2) may be a s s o c i a t e d
w i t h h y d r o l y s i s o f S i - 0 bonds, A1 m i g r a t i o n , and w i t h t h e presence o f
d i f f e r e n t V compounds, A f t e r l o a d i n g 2% V and steaming, HY forms s i l i c a
( t r i d y m i t e ) , m u l l i t e and V205 ( s e e F i g s . 3, 4 and 10) whereas CeV04 and an
x-ray amorphous component a r e observed i n CREY samples. Thus, silica
m i g r a t i o n t o t h e s u r f a c e i s p r o b a b l y r e s p o n s i b l e f o r t h e HY c r y s t a l s ' l a r g e
i n c r e a s e i n S i / A l r a t i o s whereas m i g r a t i o n o f e x t r a l a t t i c e A1 formed by
vanadates and a c i d i t y g e n e r a t i o n c o u l d have decreased t h e S i / A l r a t i o o f t h e
V-loaded CREY, g e l , and k a o l i n samples, Ta ble 2.
TABLE 2 TABLE 4
Atomic R a t i o s from XPS A n a l y s i s o f Several TABLE 3 Atomic 4 o f Vt5. Vt4 and Vt3 i n Several Suooorts
M a t e r i a l s ( l o a d e d w i t h 2 . W V) and Standard B i n d i n g E n e r g i e s (meV) o f Several Supports (Loaded w i t h 24'V) and Reference Compounds' a f t e r
Reference Compounds (Loaded w i t h 2% V) and Standard Reference Compounds R e d u c t i o n w i t h Hydrogen

SanDles 2p3/2 u u Sample 4 x 5 %fi %Y

Gel (C. AR) 4.00 0.011 -. Gel IC.ARl 517.7 103.1 74.7 Gel fCI 59 41 0
Gel (C. H ) 4.53 0.008 __ 517.6;
517.1
516.0 102.9
103.3
74.7
74.9
Gel ( S j 33 67 0
Gel (S, A#) 2.18 0.019 ..
CREY (C) 4a 52 0
Gel (S. H2) 2.44 0.015 .. 517.1; 515.2 103.2 74.9 CREY (5) 67 33 0
Kaolin (i,AR) 517.4 103.0 74.6
Kaolin (C,AR) 1.10 0.065 .. Kaolin (C H ) 517.0; 515.5 103.2 74.7 HY (C) 48 52 0
Kaolin (C,H ) 1.20 0.057 .. Kaolin (S:A$) 517.3 103.3 HY ( 5 ) 40 60 0
74.9
Kaolin (S,Aa) 0.82 0.052 .. Kaolin (S,H2) 516.9; 515.3 103.3 74.9 GRZ-1 ( C ) 45 55 0
Kaolin (S.H2) 0.82 0.044 .. GRZ-1 (5) 100 0 0
CREY (C,AR)- 517.4; 515.6 (w) 103.1 74.9
CREY (C,AR) 2.26 0.014 3.14 CREY (C H ) 517.2; 515.6 103.1 74.8 LaVO 95 5 0
CREV (C H ) 2.16 0.008 2.62 CREV rS:AaI 517.1 102.8 74.7 cevo4 61 39 0
CREV (S:A$) 1.51 0.015 1.80 517.0; 515.4 102.8 74.8 A1 VO: 69 31 0
CREV (S,H2) 1.54 0.012 1.18 HY (C,AR) V,O, 0 70 30
517.5 102.9 74.7
HY (C H ) 517.0; 515.5 102.9 74.8
HV (C.AR) 0.82 0.034 .. HV (S:Aa) 517.5 103.2 74.8
HV (C H ) 0.90 0.030 .. HV (S.HZ) 517.2; 515.4 103.2 74.8
HV (S:Aa) 1.54 0.036 ..
HV (S.H2) 1.63 0.038 __ GRZ-l
GRZ-l
(C,AR)
(C H )
516.8
516.8; 515.2
103.3
103.1
74.7
74.6
GRZ-l IC.ARI 3.25 0.044 9.7 GRZ-l (S:A$) 517.2 103.3 74.8
GRZ-I [ C ' H j 4.i5 0.037 6.7 GRZ-1 (S,H,) 517.1 103.2 74.7
GRZ-1 (S:Aa) 3.75 0.009 4.3 CeVO (AR) 517.5 .. -.
GRZ-1 (S,H2) 3.78 0.008 1.5 CeVO: (H?) 517.5, 515.4 __ ..

LaVO (AR) 516.9 .. ..

CeVO (AR) 5.15
CeVO: (ti2) 4.73 LaVO: (H?) 516.9, 515.6(w) -- ._
AlVO (AR) 517.2 .. ..
LaVO (AR) .. _. 1.41 AlVO: (H,) 517.2, 515.4 .. ..
LaVO: (H~) .. .. 1.41 517.2 .. ..

AlVO (AR) __ 0.43 ..

..
516.0. 514.7 .. ..

AlVO: (H?) .. 0.44

 139

Binding energies for the V-contaminated catalysts are listed in

T a b l e 3. The range o f t h e S i 2 p b i n d i n g energy i s 102.8-103.3 eV w h i l e t h e
A12p b i n d i n g energy i s near 74.8 eV. The S i 2p b i n d i n g e n e r g i e s range i s
smaller than t h a t previously reported f o r cracking c a t a l y s t s (ref. 18).
T h i s s m a l l e r range a f f e c t s t h e V2p b i n d i n g energy p o s i t i o n such t h a t i n
3/2
t h e c a l c i n e d o r steamed m a t e r i a l s i t i s a p p r o x i m a t e l y 517.2 f 0.4 eV. A f t e r
H2 t r e a t m e n t , t h e w i d t h o f t h e V 2p peak v a r i e d a c c o r d i n g t o whether
3/2
m u l t i p l e V o x i d a t i o n s t a t e s ( i n a d d i t i o n t o Vt5) were formed. As a r e s u l t
o f enhanced peak w i d t h s (and/or peak envelopes w i t h o b v i o u s s h o u l d e r s ) , t h e
V 2p3/2 envelope was f i t t e d t o a c o m b i n a t i o n o f peaks whose p o s i t i o n s a r e
l i s t e d i n Table 3.
All samples ( e x c e p t t h e c a l c i n e d CREY) b e f o r e HZ t r e a t m e n t can be
d e s c r i b e d t o c o n t a i n a s i n g l e t V 2p3,2 peak; i t s p o s i t i o n i s not highly
s e n s i t i v e t o d i f f e r e n t V s p e c i a t i o n i n a Vt5 oxidation state. Upon H2
t r e a t m e n t , t h e V 2p peak i n most m a t e r i a l s ( e x c e p t i n GRZ-1, V205 and
3/2
LaV04) can be r e p r e s e n t e d by two peaks a t a p p r o x i m a t e l y 517.0 eV and 515.5
eV, see Table 3. R e p r e s e n t a t i v e s p e c t r a o f r e f e r e n c e vanadates and V-loaded
m a t e r i a l s a r e d i s p l a y e d i n F i g s . 12-16. A f t e r H2 t r e a t m e n t , t h e spectrum o f
steamed GRZ-1 and o f LaV04 c o n t a i n a V 2p peak w h i c h i s almost e n t i r e l y
3/2
r e p r e s e n t e d by a s i n g l e t a t 517.0 eV, whereas t h e V205 spectrum has a V
2p3/2 peak r e p r e s e n t e d by two peaks a t a p p r o x i m a t e l y 516.0 eV and 514.7 eV.
Peak p o s i t i o n s , a t 517.0, 516.0 and 514.7 eV, have been a t t r i b u t e d t o Vt5,
Vt4 and Vt3, respectively.
The percentage c o n t r i b u t i o n o f Vt5, Vt4 and Vt3 t o t h e V 2ppeak o f
3/ 2
H - t r e a t e d samples i s l i s t e d i n Table 4. The V205 samples c o n t a i n Vt4 and
V
$3 . I n contrast, t h e o t h e r samples a f t e r H2 t r e a t m e n t do n o t c o n t a i n
Vt3 species which suggests t h a t t h e V i s somewhat d i f f e r e n t f r o m b u l k V205.
Such XPS-derived r e d u c i b i l i t y d a t a i s , a t f i r s t i m p r e s s i o n , i n disagreement
w i t h Raman r e s u l t s p r e s e n t e d i n F i g s . 9-10. However, s l i g h t b u t s i g n i f i c a n t
d i f f e r e n c e s i n t h e Raman s p e c t r a o f V-loaded k a o l i n , g e l and HY c r y s t a l s a r e
present. F o r example, t h e 997 cm-l V=O s t r e t c h i n g mode f o r V205 i s narrow
and w e l l d e f i n e d . I n t h e l a n t h a n i d e - f r e e samples, t h i s band i s broadened
and c o n t a i n s a h i g h - f r e q u e n c y s h o u l d e r . The Raman bands i n t h e 700-850 cm-’
r e g i o n f o r b u l k V205 a r e t h e r e s u l t o f V-0-V b r i d g e d oxygen s t r e t c h i n g modes
( r e f . 11). These bands a r e s u b s t a n t i a l l y d i f f e r e n t i n shape and r e l a t i v e
i n t e n s i t y i n V-loaded g e l , k a o l i n and HY. These d i f f e r e n c e s suggest
d i s t o r t i o n o f some o f t h e V205 o r f o r m a t i o n o f a s u r f a c e V205 phase which
decreases V - r e d u c i b i l i t y under H2 atmosphere.
140

There i s l i t t l e d i f f e r e n c e between t h e r e d u c i b i l i t y o f V i n steamed o r

c a l c i n e d HY and k a o l i n . However, a l a r g e decrease i n V r e d u c i b i l i t y e x i s t s
between steamed and c a l c i n e d GRZ-1 and CREY samples. Hence, V s t a b i l i t y
against reduction is enhanced in catalysts containing La and/or Ce.
Steaming inc re as e s t h e r e d u c i b i l i t y o f V-loaded g e l s , p r o b a b l y because o f
V-migration t o t h e g e l surface; i n f a c t , t h e V / ( S i t A l ) r a t i o increases t o
0.019 f rom 0.011 upon steaming, Ta b l e 2. I n c o n t r a s t , steaming causes a
l a r g e decreases i n V - r e d u c i b i l i t y i n CREY and i n a CREY-containing c a t a l y s t
l i k e GRZ-1, p r o b a b l y because o f vanadate f o r m a t i o n , T a b l e 4.

C.VO.

BINDING ENERGY (eV)

F i g u r e 12. XPS d a t a f o r t h e V 2p peak o f LaVO ,
A1V04 and CeV04 i n a s - r e c e i v e d (A&f2and reduced fgrrns

v)

BINDING ENERGY lev1 BINDING ENERGY lev1

F i g u r e 13. XPS d a t a f o r t h e V F i g u r e 14. XPS d a t a f o r t h e V

2p peak o f 2% V / k a o l i n , 2p peak o f 2% V/CREY,
cafC?ned (C) and steamed (S), ca?C?ned ( C ) and steamed ( S )
i n a s - r e c e i v e d (AR) and reduced i n a s - r e c e i v e d (AR) and reduced
forms. forms.
 141

BlNOlNG ENERGY lev1 BlNOlNG ENERGY lev1

F i g u r e 15. XPS d a t a f o r t h e V F i g u r e 16. XPS d a t a f o r t h e V

peak o f 5% V/AAA, c a l c i n e d 2p peak o f 2% V/GRZ-1,
&a n d steamed ( S ) , i n as-
r e c e i v e d (AR) and reduced forms.
ca!&ed ( C ) and steamed (S),
i n as-received (AR) and reduced
forms.
+4
The r e f e r e n c e LaV04 c o n t a i n s 5% Vt4 whereas CeV04, c o n t a i n s -39% V
a f t e r H2 t re at me n t , Table 4. S i m i l a r l y , steamed CREY (which by Raman
a n a l y s i s has CeV04) c o n t a i n s -33% Vt4 a f t e r H2 t r e a t m e n t . The s t a b i l i t y
a g a i n s t r e d u c t i o n o f V-loaded CREY resembles t h a t o f CeV04 whereas t h a t o f
t h e c r a c k i n g c a t a l y s t more c l o s e l y resembles t h a t o f LaV04, T able 4. T h i s
enhanced s t a b i l i t y i n hydrogen i s p o s s i b l y t h e r e s u l t o f d i s t o r t i o n o f t h e
vanadates formed w i t h i n t h e z e o l i t e s t r u c t u r e .

CONCLUSIONS
T y p i c a l c r a c k i n g components (such as HY o r CREY) o f f l u i d i z e d c r a c k i n g
c a t a l y s t s e x h i b i t s i m i l a r s t a b i l i t y t o V - d e a c t i v a t i o n when heated i n d r y a i r
a t 76OoC/5h. When t h i s thermal t r e a t m e n t i s repeat ed i n t h e presence o f
steam, s t a b i l i t y i s d r a s t i c a l l y reduced and HY i s more h y d r o t h e r m a l l y s t a b l e
tha n CREY a t t e s t c o n d i t i o n s .
I n t h e presence o f steam, the collapse o f the f a u j a s i t e structure
occurs by two mechanisms. In CREY, i t has been a t t r i b u t e d t o
d e s t a b i l i z a t i o n due t o CeV04 g e n e r a t i o n and t o enhanced d e a l u m i n a t i o n caused
by p r o t o n s r e s u l t i n g from vanadate f o r m a t i on. I n HY, p r o t o n a t e d species
(such as H4V20,) promote d e a l u m i n a t i o n and c r y s t a l l i n i t y losses; after
l a t t i c e c o l l a p s e , m u l l i t e and t r i d y m i t e a r e observed.
Vanadium i m p u r i t i e s have l e s s e r e f f e c t s on t h e s u r f a c e (and c a t a l y t i c )
p r o p e r t i e s o f an a l u m i n o s i l i c a t e m a t r i x ( g e l ) c o n t a i n i n g b o t h A1 ( V I ) and
A l(1 V ). As with HY, V induces mullite formation at t emperat ures
s i g n i f i c a n t l y l o w e r t h a n those used i n s y n t h e s i z i n g t h i s m i n e r a l . M u l l i t e
f o r m a t i o n was n o t observed when V was r e p l a c e d by N i . Raman spectroscopy
and XRD have been p a r t i c u l a r l y u s e f u l i n m o n i t o r i n g phase changes and
vanadate genera t i o n .
142

ACKNOWLEDGMENTS
The many u s e f u l discussions and s u p p o r t r e c e i v e d f r o m t h e Unocal
A n a l y t i c a l Department s t a f f a r e g r a t e f u l l y acknowledged. Special thanks are
due D r . E. G o l d i s h and Dr. P. R i t z f o r h e l p i n g w i t h r e f e r e n c e compound
p r e p a r a t i o n , x - r a y and Raman measurements.

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Rock Forming Minerals,"'Langman, p. 37 ( 1 9 - 3 ) .
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24 F . Maiige, J. C . C o u r c e l l e , Ph. Engelhard, G a l l e z o t , P. and Grosmangin,
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H.G. Karge, <J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

HIGHLY DISPERSED Pt AND Pt-Cr CLUSTERS I N PENTASILS AND THEIR ACTIVITY IN

TRANSFORMATIONS OF LOWER ALKANES

E.S. S H P I R O ~ ,G.J. T U L E U O V A ~ ,v I. Z A I K O V S K I I ~ ,O.P. T K A C H E N K O ~ ,T.V. V A S I N A ~ ,

O.V. BRAGIN' and KH.M. MINACHEV'
lN.0. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR,
MOSCOW V-334, USSR
zInstitute of Catalysis, Novosibirsk, USSR

ABSTRACT
Pt and Cr electronic states, reduction degrees and metal dispersion in pen-
tasils have been determined by XPS, TEM, XRD and chemisorption techniques. The
formation of Pt(S+) and Pt-Cr clusters significantly affects the catalytic acti-
vity in hydrogenolysis of alkanes (C Hs,C,H*) and aromatization: the former fa-
cilitats these reactions while the lafter suppresses the activity.

INTRODUCTON
The study of the regularities of Group VIII metals behaviour in pentasils is
of great importance since these systems are rather promising in various cataly-
tic processes, for example. aromatization of lower alkanes (refs. 1-3). T o pro-
vide high activity in the aromatization reaction small metallic clusters should
be formed in the vicinity of acidic centers which was confirmed by a significant
dependence of the Pt/H(Ga)-ZSM-5 activity on preparation and pretreatment con-
ditions (refs. 1 , Z ) . On the other hand, highly dispersed Pt particles in fauja-
sites are known to be stabilized in the presence of other cations, in particular
Cr3+ (ref. 4). Alternatively, Cr3+ to CrD reduction and possibly Pt-Cr interme-
tallic formation, as found on y-AlpO3 (ref. 5 ) . can lead to the same effect.
This paper deals with the study of electronic states of Pt and Cr, their
dispersion and interaction in Pt, Cr and Pt-Cr catalysts based on pentasil zeo-
lites as a function of preparation and pretreatment conditions and their perfor-
mance in the transformations (ethane and propane hydrogenolysis and aromatiza-
tion) of lower alkanes. An attempt was also made to elucidate the relationship
between the surface characteristics and catalytic properties of metal zeolite
catalysts in these reactions.

EXPERIMENT
Catalysts containing 0.5. 1.0, 1.75% Pt; 0.75% Cr and 0.5% Pt plus 0.75% Cr
were prepared via ionic exchange of NH4ZSM-5 (Si02/A1203=33) with Pt(NH3)4Clz,
Cr(N03)3 or (Cr03)x solutions and subsequent impregnation by the rest of these
144

solutions. Along with the initial chromium compounds, the pH and the sequence of
Pt and Cr introduction were varied in the bimetallic zeolites (Table 1). Before
spectral and catalytic experiments the specimens were exposed to the following
treatments: air, 520°C (a); air, 520°C + H2, 400°C (b); air, 520°C + H2, 520°C
(c); Hp, 520°C (d).
Sample characterization
XPS spectra were recorded with an AEI ES 2006 spectrometer according to the
technique given in ref. 6. The Pt 4f lines, overlapping with the A1 2p peak and
the Cr 2p doublet, were resolved into individual components by a standard peak
synthesis routine. The pretreated samples were transferred Into the spectrometer
in inert atmosphere according to the procedure described in ref. 1. The electron
microscopy measurements were performed with a JEM lOOCX instrument; the reso-
lution was 0.2 nm (ref. 7). CO chemisorption was studied by the pulse chromato-
graphy method. X-ray analysis was performed with a powder diffractometer DRON-3
equipped with a high-temperature chamber.
Catalrt i c exper iments
Ethane and propane hydrogenolysis were studied in a microflow reactor opera-
ting in the differential mode at alkane conversions below lo%, hydrocarbon/H2
equal to 1/10. The C2H6 aromatization was investigated in pulse and flow units
according to ref. 8.

RESULTS AND DISCUSSION

1. The state and dispersion of Dlatinum in monometallic zeolite catalysts.
In starting samples platinum was located in the channels and partially on
the external surface as [Pt(NH3)4I2+ cations characterized by the Pt 4f7/2 bin-
ding energy (B.E.) of 73.9 - 74.1 e.V. Air calcination resulted in the decom-

-
positon of the complex cations, Pt2+ migration into channels and partial reduc-
tion of Pt2+ Pto with NH3 evolved (B.E. of reduced Pt state equalled to 72.0 -
72.6 eV and its fraction amounted to 35%). Hp treatment led to additional Pt
reduction. Two different states could be evaluated from the spectra: one with a
positive shift of 0.8 - 1.2 eV, the fraction of which is maximum for a sample
with a low percentage of Pt, and the other close to pure Pt metal. Since at this
temperature the degree of Pt reduction is close to 100% (ref. 9) the Pt 4f doub-
let with higher B.E. could be attributed to small Pt particles (PtS+) which exhi-
bit some electron deficiency due to the interaction with acidic centers of the
zeolite. On the contrary, only the state of Pto close to the bulk metal was ob-
served upon direct Hp treatment. The Pt/Si enhancement indicated substantial Pto
migratlon onto the external surface in the course of this treatment.
 145

TABLE 1
Preparation conditions and composition o f c a t a l y s t s studied

N Wt.% Sequence o f c a t i o n I n i t i a l compound PH

Pt Cr introduction

1 0.5 0.75 P t then C r (CrO ) * P t ( N H )4Cl 5

2 0.5 0.75 simultaneously Cr(Nd37;; Pt(N&)&?z 8-8.5
0.5 0.75 P t then C r Cr(N0 )3; Pt(NH3)dClz 4
3
4
5
0
0.5
0.75
0
- (CrO 3 4.5
6
6 1.0 0 - PP tt ((Na374cl2
NH3 4c12 6
7 1.75 0 Pt( NH3 4c12 6

The conclusions drawn from XPS studies are i n close agreement w i t h t h e P t

d i s p e r s i o n derived from TEM, CO chemisorption and XRD data (Table 2). Two main
f a c t o r s govern the P t dispersion: the mode o f treatment and P t concentration.
The treatment (b) gives r i s e t o widely dispersed Pt" c l u s t e r s (0.6 - 1.4 nm)
located i n s i d e the s t r u c t u r e , w h i l e treatment (d) r e s u l t s i n P t o m i c r o c r y s t a l -
l i t e s w i t h a broad s i z e d i s t r i b u t i o n ranging from 2 t o 16 nm. The increase i n P t
concentration leads also t o a decrease o f the P t o d i s p e r s i o n although t o a
lesser extent than i n the f i r s t case.
2. The states o f P t and C r i n b i m e t a l l i c z e o l i t e c a t a l y s t s .
P t 2 + and P t 4 + were found i n the s t a r t i n g specimens (Table 3). The l a t t e r
s t a t e probably appeared as the r e s u l t o f incomplete t r a n s i t i o n o f H2PtC16 t o
Pt(NH3)4C12 i n the s t a r t i n g solution. Chromium i n c a t a l y s t s 1, 3 and 4 was found
as Cr6+ and Cr3+, and i n c a t a l y s t 2 i t e x i s t e d as C r 3 + only. The d i f f e r e n t sta-
b i l i t y o f Cr6+ ions seemed t o be r e l a t e d t o d i f f e r e n t pH values i n the solu-
tions. Surface concentrations o f both elements were higher than i n the bulk,
which i s t y p i c a l f o r metal/pentasil systems ( r e f . 10). When P t and C r were i n -
troduced from a common s o l u t i o n t h i s e f f e c t became more pronounced. Probably,
j o i n t d i f f u s i o n o f both components i n t o the channels was more s t r o n g l y hindered.
The a i r c a l c i n a t i o n o f Pt-Cr/HZSM-5 r e s u l t e d i n the appearance o f Cr6+ in
c a t a l y s t 2 and increased i t s f r a c t i o n i n c a t a l y s t 1 w h i l e i n Cr/HZSM-5 the
Cr6+/Cr3+ r a t i o remained a c t u a l l y the same. Platinum, which was reduced by t h i s
treatment from P t 4 + t o Pt2+, supposedly s t a b i l i z e d chromium i n i t s h i g h e s t o x i -
d a t i o n state, which i s known t o be r a t h e r unstable and can be reduced under X-
r a y i r r a d i a t i o n d u r i n g spectra recording ( r e f . 11). C r , i n turn, stabilized P t
i n i t s i o n i c s t a t e (Tables 2 and 3).
The H2 treatment o f Cr/HZSM-5 gave r i s e t o a new chromium s t a t e w i t h B.E. of
571.7 - 572.6 eV which probably corresponds t o supported Cro ( r e f . 5). The nega-
t i v e s h i f t r e l a t e d t o pure metal (574.0 eV) can be t e n t a t i v e l y explained by two
f a c t o r s ( r e f . 5): an i n t e r a c t i o n w i t h electron-donor s i t e s o f the support and a
TABLE 2
The effect of pretreatment conditions and Pt content on metal state,surface composition and dispersion

Catalyst Pretreatment B.E. Pt 4f7/2. eV -

Pt Pt/Si (XPS) Pt dispersion,
_____ %
103
Si Pt/Si(AAS) (av. crystal size, nm)
conditions PtO ptS+ pt2+ (XPS) XRD CO/Pt TEM

0.5 % Pt X - - 73.9(100%) 1.94 1.18 - - -

NH4ZSM a 72.0( 36%) - 74.0(64%) 1.72 1.05 - - -
C 72.1(29%) 72.9(71%) - 1.15 0.70 - 61(1.8) al(0.8)
d 72.5( 100%) - - 2.22 1.35 amorph. - 16(7.0)

1.0 % Pt X - - 74.1(100%) 2.60 0.84 - - -

NH4ZSM a 72.6(31%) - 73.&(69%) 2.58 0.83 - - -
C 72.3(44%) 73.1(56%) - - - amorph. 40(2.8) -
d 72.6(100%) - - 4.31 1.39 g(13.2) ZZ(5.1) -

-1.75
_- % Pt X - - 74.0(100%) 4.70 0.86 - - -
NHqZSM a 72.5 (37%) - 73.9(63%)- 4.12 0.76 - - -
C 72.0( 61%) 73.2( 39%) - 3.33 0.61 - 31(3.6) -
d 72.4(100%) - - 8.97 1.65 B(14.7) - -

x initial
TABLE 3
The effect of pretreatment conditions on the electronic state of Pt and Cr

Catalyst Pretreatment Cr6+ ~r3+ Cr*+ CrO pt4+ Pt2+ PtO

B.E.,e.V. % B.E.,e.V. % B.E.,e.V. % B.E.,e.V. % B.E.,e.V. % B.E..e.V. % B.E.,e.V. %

1 X 500.0 39 578.0 61 - - - - 76.1 63 73-3 37 - -

a 500.2 49 577.2 51 - - - - 76.1 23 73.3 77 - -
C - - 570.0 72 - - 573.0 20 - - 73.2 63 72.0 37
d - - 570.0 63 - - 573.0 37 - - 73.6 19 72.2 01
2 X - - 577.7 100 - - - - 76.2 37 73-4 63 - -
a 579.7 22 577.7 70 - - - - 75.5 32 73.5 60 - -
C - - 570.1 69 575.9 31 - - - - 73.0 43 71.8 57
d - - 577.0 60 576.2 32 - - - - 73.2 30 72.0 70
3 X 579.2 20 577.4 72 - - - - 76.7 55 73.5 45 - - >
4 X 579.4 44 577.4 56 - - - - - - - - - -
a 579.2 42 577.4 50 - - - - - - - - - -
C - - 577.5 06 - - 572.9 14 - - I - - - -
d - - 577.6 70 - - 572.6 22 - - - - - -
TABLE 4
The catalytic properties of Pt and Pt-Cr/HZSM-5 in C2H6 and C3H8 hydrogenolysis

Catalyst C2H6 hydrogenolysis C3H8 hydrogenolysis

Pretreatment conditions
~

air + HE H2 air + H p
Rate, Wx103, TON, Activ. WXlOj, TON, Ea. ~~103. Ea* SCZH~~)
mol e/gpt S-1 energy,Ea, rnole/gpts S-' kJ/mole mole/gpts kJ/mole %
400°C 400 C kJ/mo 1 e 400°C 400°C 350°C
300-400°C 300-450°C 300-400°C

0.5% Pt
HZSM-5 7.2 1.74b) 134 0.25 0.30b) 199 - - -
2.31')
1 9 ) - 134 - - - 2.9 76 92.5
1.0% Pt
HZSM-5 3.3 1.58') 133 0.19 0. 17') 188 - - -
1.75% Pt
HmI-5- 2.4 1.54') 125 0.14 0.34') 120 - - -
0.5%Pt-0.75%Cr
HZSM-5 0.36d) 232 - - - 0.28 120 65.7
(N 1)
0.5XPt-0. 75%Cr
HZSM-5 0.45d) - 160 - - - 0.55 132 90.3

a)selectivity was determi d as (C Hg/CH4 + C2H ) x 100 X; b*c)the number of Pt surface atoms was calculated from: TEM (b)
or CO chemisorption (c); aTreact. (emperatwe 3 b " C .
 149

differential charging effect. A similar signal of Cr 2p with slightly higher

B.E. (573.5 eV) was observed for Pt-Cr/HZSM-5 (catalyst 1). These results differ
from those known for Cr-zeolite catalysts (ref. 11) which gave evidence in
favour of Cr2+ formation under Hp treatment. Similarly. a new Cr 2 ~ 3 1 2line with
B.E. of 575.9 eV, observed during reduction of catalyst 2, can be attributed to
Cr2+.
The differences in precursors of reduced Cr (Cr6+ or Cr3+) as well as their
dispersion can cause different reduction behaviour of Cr species in the samples
studied. Indeed, TEM data suggest that catalyst 2 contains a substantial portion
of Cr as a hardly reduced CrzO3 phase on the external surface (aggregated into
blocks larger than 10 nm ) whereas the Cr dispersions in catalysts 1 and 4 seem
to be substantially higher. Comparison of the degree of Cr reduction for Pt-
Cr/HZSM-5 (catalyst 1) and Cr/HZSM-5 (catalyst 4 ) indicates a prominent Pt-pro-
moting effect similar to that observed for Pt-Cr/y-Alp03 (ref. 5). The diffe-
rence between Cr 2 ~ 3 1 2B.E. in Pt-Cr and in Cr-zeolites can be related to Pt-Cr
interaction which eliminates the negative shifts obtained for supported Cro
systems. The less understandable experimental fact is the suppression of the re-
duction of Pt to Pto in the presence of Cr (Table 3). According to XPS intensity
ratios and TEM data, Pto i s , in both types of Pt-Cr samples (catalysts 1 and 2)
stabilized, as very fine particles with 0.5 - 1.0 nm size, mainly located inside
the zeolite channels.
When Pt-Cr samples were directly reduced in H2 flow, the promoting effect of
Pt was also observed (Table 3): the degree of reduction in catalyst 1 reached
37% vs. 22% in catalyst 4. Again, as in the case of Pt/HZSM-5 zeolite, Pto mi-
gration was more pronounced under these conditions but the Pt/Si increase was
not so dramatic. This probably reflects the enhancement of the Pto dispersion in
the presence of chromium even under these unfavourable conditions.
3. The effect of Pt state and disDersion on catalytic DroDerties of Pt- and Pt-
Cr/HZSM-5 in alkane transformations
3.1. Ethane and propane hydroqenolysis. Pt/HZSM-5 samples pretreated accor-
ding to (b) possessed rather high and stable activity in C2H6 hydrogenolysis
whereas directly reduced catalysts had low activity (Table 4 ) . The reaction rate
(per gpt) dropped also when the Pt content increased, but the turnover numbers
noticably decreased when dispersion decreased due to a change of the pretreat-
ment mode ("d" instead of "c"). The introduction of chromium into Pt/HZSM-5
strongly influenced the catalytic activity in alkane hydrogenolysis: the reac-
tion rate decreased and the activation energy increased. Taking into account the
rather high Pt dispersion for all samples treated in air and H2, the observed
changes in activity can be assigned to a Cr doping effect. As seen from Table 4,
the changes in activity and selectivity (C3H8 hydrogenolysis) were more pro-
nounced when Cr was reduced to Cro and possibly formed intermetallic compounds
with Pt (catalyst 1).
 3.2. The activltv in alkane aromatization. The highly dispersed Pt, located
in the vicinity of Br0nsted centers, provided the most effective system among
Pt-containing catalysts for ethane and propane aromatization (refs. 1-3). One of
the factors responsible for such catalytic behaviour i s that small P t o particles
can be easily modified under reaction conditions. This might result in an in-
crease of the positive charge on clusters in parallel with an enhanced yield of
aromatics upon increasing pulse numbers (ref. 1).
Platinum exhibited similar properties on being introduced together with Cr
into HZSM-5 (Flg. 1). It should be noted that Cr/HZSM-5 possesses a low aromati-
zation activity, comparable with that of HZSM-5 (ref. 1). Some differences in
the activity level were observed as a function o f the preparation procedure
(catalysts 1-3). but in all cases the yield of aromatics did not exceed that ob-
tained with Pt/HZSM-5. In a flow reactor, Pt-Cr zeolites were rather efficient
in both C2H6 and C3Hg aromatization. Yields of aromatics amounted t o 17 - 22 %
(C2Hs) and 5 5 % (C3Hg). As in the case of Pt/HZSM-5 (ref. 1). the activity deve-
lopment in the pulse mode was accompanied by the change of the electronic state
o f Pt (Fig. 1). During the first pulses the cationic form of Pt was reduced to
Pto, but then a growing positive charge o n Pt clusters was observed as well.

\ v )

-
U
I-
4 12 -

0-

NUMBER OF C,HI P U L S E S

F i g . 1. Development o f Pt- and Pt-Cr/HZSM-5 and modification of the electronic

state o f Pt in the course of ethane aromatization: a - Pt-Cr/HZSM-5 (Cat. Z),
b - Pt/HZSM-5 (Cat. 1 ) . c - Pt-Cr/HZSM-5 (Cat. 3), d - Pt/HZSM-5 (Cat. 5).

These data suggest some correlations between activities in alkane aromatiza-

tion and hydrogenolysis performed under H2 flow. At first glance this is a ra-
ther confusing result, but if we take into account that both alkane dehydrogena-
tion (first stage of aromatization) and hydrogenolysis proceed via the common
step of C2Hx intermediate formation (ref. 12). the similarity becomes more un-
derstandable. The small Pt clusters with some electron deficiency are the best
 151

candidates for this step, and further pathways of C2H, transformations are con-
trolled by reaction temperature, H2 content and acidity of the zeolitic support.
The activity in both reactions is likely to depend not only on cluster dimen-
sions but on its structure as well. When located inside the channels such
clusters can be stabilized in an icosahedron structure (ref. 13), which posses-
ses highly reactive sites for hydrogenolysis and dehydrogenation. The following
changes in local surface structure have been supposed to be responsible for a
decreasing hydrogenolysis activity in PtCr zeolites: (a) extremely high Pt dis-
persion reached in the presence of chromium; (b) formation of Pt-Cr interme-
tallic compounds leading to a dilution of Pt aggregates by Cr, which probably
replaces most reactive Pt centers.
Concerning the lower aromatization activity, one can speculate that only PtS+
centers are involved in the catalysis and not Pt-Cr sites. However, this assump-
tion needs further confirmation.

CONCLUSION
The electronic state, distribution and dispersion of Pt in pentasil-type
zeolites depend on the mode of pretreatment, metal concentration and the pre-
sence of a second element (chromium). Precalcination of Pt/HZSM-5 leads t o a
more uniform Pt2+ distribution in the channels and subsequent Pto stabilization
in a finely dispersed form. Chromium provided the same effect via possible for-
mation o f Pt-Cr intermetallic compounds or stabilizing of Pt by Cr3+. A variety
of cationic Cr species, viz. Cr(VI), Cr(III), Cr(I1) and Cr(O), were found in
pentasil zeolites. The activity in ethane and propane hydrogenolysis was influ-
enced by the state of Pt, Pt-dispersion and its modification by Cr. The correla-
tion between the charge of Pt species and the yield of aromatics observed for
both Pt/HZSM-5 and Pt-Cr/HZSM-5 permits the conclusion that at least alkane de-
hydrogenation is catalyzed by highly dispersed PtS+ species.

REFERENCES
O.V. Bragin, E.S. Shpiro. A.V. Preobrazhensky, S.A. Isaev, T.V. Vasina. 6.8.
Dysenbina, G.V. Antoshin and Kh.M. Minachev, Appl. Catal., 27 (1986) 219-
231.
T. Inui, Y. Makino, F. Maganos and A. Miymoto, Ind. Eng. Chem. Res. and
Develop., 26 (1987) 647-652.
C.W.R. Engelen, J.P. Wolthuizen, J.H.C. Hoof and H.W. Zundbergen, Proceed.
7th Int. Zeolite Conf., 1986, pp. 709-716.
M.S. Tzong, H.J. Jiang and W.M.H. Sachtler, React. Kinet. Catal. Lett., 35
(1987) 207-218.
W. Grunert. E.S. Shpiro. R. Felthaus, K. Anders, G.V. Antoshin and Kh.M.
Minachev, J. Catal., 100 (1986) 138-148.
Kh.M. Minachev, G.V. Antoshin and E.S. Shpiro, Photoelectron Spectroscopy
and its Application in Catalysis, M., Nauka, 1981.
Yu.A. Ryndin, V.I. Chernyshev, V.I. Zaikovskii, E.N. Yurchenko and Yu.1.
Yermakov. React. Kinet. Catal. Lett., 21 (1982) 125-129.
O.V. Bragin. A.V. Preobrazhensky and A.L. Liberman, Izv. Akad. Nauk SSSR,
Ser. Khim., 12 (1974) 2751-2757.
152

9 T.R. Felthouse and J.A. Murphy. J . Catal., 98 (1986) 411-433.

10 Kh.M. Minachev and E.S. Shpiro, Kinetica 1 Kataliz, 27 (1986) 824-837.
1 1 B. Wichterlova, L. Krajcihova, Z. Tvaruzkova and S. Beran, J . Chem. SOC.
Faraday Trans. I, 80 (1984) 2639-2645.
12 J.H. Sinfelt, Catal. Rev., 3 (1969) 175-205.
13 B. Moraweck. J . Ckugnet and A. Renouprez, Surf. Sci., 9 1 (1981) 631.
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

CONVERSION OF LIGHT ALKANES INTO AROMATIC HYDROCARBONS. 3. AROMATIZATION OF

PROPANE AND PROPENE ON MIXTURES OF HZSM5 AND OF Ga203

N.S. GNEP, J.Y. DOYEMET and M. GUISNET

UA CNRS 350, C a t a l y s e en Chimie Organique, U n i v e r s i t S \ de P o i t i e r s , 40, avenue
du Recteur Pineau, 86022 P o i t i e r s Cedex, FRANCE

ABSTRACT
The a c t i v i t i e s f o r propane a r o m a t i z a t i o n o f p h y s i c a l m i x t u r e s o f HZSM5 ( 2 5
mg) and Ga 0 ( 5 t o 200 mg) a r e much g r e a t e r t h a n t h e sum o f t h e a c t i v i t i e s
o f t h e p u r 6 zomponents. T h i s s y n e r g i c e f f e c t i s c h a r a c t e r i s t i c o f a r e a c t i o n
i n which c a t a l y t i c s i t e s o f t h e two components ( b i f u n c t i o n a l c a t a l y s i s )
p a r t i c i p a t e . Experiments w i t h model r e a c t a n t s propane, propene, 1-hexene,
1-heptene, methylcyclohexene and methylcyclohexane c o n f i r m t h a t g a l l i u m o x i d e
c a t a l y z e s t h e dehydrogenation o f alkanes i n t o o l e f i n s and o f naphthenes i n t o
a r o m a t i c s b u t i s n o t a c t i v e f o r o l i g o m e r i z a t i o n and c y c l i z a t i o n r e a c t i o n s .
The a r o m a t i z a t i o n o f propane on t h e m i x t u r e o c c u r s i n t h e f o l l o w i n g way : on
g a l l i u m o x i d e propane i s dehydrogenated i n t o propene; propene d i f f u s e s f r o m
g a l l i u m o x i d e t o HZSM5, on which i t undergoes o l i g o m e r i z a t i o n and t h e n c y c l i -
z a t i o n ; naphthenic compounds d i f f u s e f r o m HZSM5 t o g a l l i u m o x i d e where t h e y
a r e dehydrogenated i n t o C6-C8 aromatics.

INTRODUCTION
An i n t e r e s t i n g means o f i n c r e a s i n g t h e v a l u e o f l i g h t alkanes would b e t o
transform them into aromatics (1,2). HZSM5 is active for propane
t r a n s f o r m a t i o n i n t o C6-Cg aromatic products (3-5). A r e a c t i o n a l scheme has
a l r e a d y been proposed t o e x p l a i n t h i s t r a n s f o r m a t i o n ( 4 , 5 ) . The f i r s t stage
is t h e formation of propene; this olefin, by a series of reactions
--01 i g o m e r i z a t i o n , c y c l i z a t i o n , hydrogen t r a n s f e r f r o m naphthenes t o o l e f i n i c
compounds-- l e a d s t o aromatic hydrocarbons. The c r a c k i n g o f o l i g o m e r s g i v e s
l i g h t o l e f i n s which, l i k e propene, p a r t i c i p a t e i n t h e f o r m a t i o n o f a r o m a t i c s .

Kitagawa e t a l . (4) have shown t h a t t h e exchange o f HZSM5 by Ga3+

i n c r e a s e s t h e r a t e o f propane c o n v e r s i o n and improves g r e a t l y t h e s e l e c t i v i t y
towards aromatics. The o n l y r o l e o f g a l l i u m s p e c i e s would b e t o i n c r e a s e t h e
154

r a t e o f a r o m a t i z a t i o n o f t h e lower o l e f i n s ; t h e s e species do n o t have a

d i r e c t e f f e c t on t h e a c t i v a t i o n o f propane ( s t e p 1 ) . T h i s i s c o n t e s t e d by
Gnep e t a l . ( 6 ) . A c c o r d i n g t o t h e s e a u t h o r s propane a r o m a t i z a t i o n on GaHZSM5
c a t a l y s t s can be c o n s i d e r e d as a b i f u n c t i o n a l process i n which gallium
species c a t a l y z e m a i n l y s t e p 1 (propane a c t i v a t i o n ) and s t e p 5 ( a l i c y c l i c
compound a r o m a t i z a t i o n ) w h i l e t h e a c i d s i t e s o f HZSM5 c a t a l y z e m a i n l y s t e p s 2
t o 4. The n a t u r e o f t h e a c t i v e g a l l i u m s p e c i e s i s n o t w e l l known. Indeed,
g a l l o s i l i c a t e s w i t h a p e n t a s i 1 s t r u c t u r e a r e a l s o good c a t a l y s t s f o r propane
a r o m a t i z a t i o n ( 7 1 , and we have shown i n a p r e l i m i n a r y n o t e ( 8 ) t h a t Ga20j
added t o HZSM5 produces e f f e c t s s i m i l a r t o t h o s e produced by exchange o f
HZSM5.
The aim o f t h i s paper i s t o show how t h e a d d i t i o n o f g a l l i u m o x i d e t o
HZSM5 a f f e c t s propane and propene a r o m a t i z a t i o n . We c o n f i r m , namely, that
g a l l i u m species p l a y no r o l e i n s t e p s 2 t o 4 o f t h e s u c c e s s i v e r e a c t i o n
scheme b u t p a r t i c i p a t e i n s t e p s 1 and 5.

EXPERIMENT
HZSM5 ( S i / A l = 40) was s y n t h e s i z e d a c c o r d i n g t o M o b i l P a t e n t s ( 9 ) . G a l l i u m
o x i d e (Ga203, Bform, 99.99 % pure, BET a r e a equal t o 4 m 2 g - l ) was s u p p l i e d b y
A l d r i c h Chemical Co. P r i o r t o use, c a t a l y s t s were p r e t r e a t e d f o r 10 h o u r s a t
530°C under d r y n i t r o g e n f l o w .
Propane ( 99.95 % p u r e ) and propene ( > 9 9 % p u r e ) were Alphagaz p r o d u c t s .
The main i m p u r i t y i n propane was propene. Propene c o n t a i n e d propane ( < 4 0 0 0
ppm), ethane (<1500 ppm) and ethene ( ~ 1 5 0ppm). Propane and propene t r a n s f o r -
mations were c a r r i e d o u t i n a f l o w r e a c t o r under t h e f o l l o w i n g c o n d i t i o n s :
r e a c t i o n temperature, 530°C; propane o r propene p r e s s u r e , 1 b a r ; WWH ( w e i g h t
o f r e a c t a n t i n j e c t e d p e r u n i t w e i g h t o f c a t a l y s t and p e r h o u r ) between 0.5
and 80 i n o r d e r t o o b t a i n a wide range o f c o n v e r s i o n r a t e s ( 1 - 4 0 % f o r
propane and 1-80 % f o r propene). R e a c t i o n p r o d u c t s were analyzed on l i n e b y
gas chromatography; t h e c o n d i t i o n s f o r a n a l y s i s a r e r e p o r t e d elsewhere ( 5 ) .

RESULTS
1. Propane t r a n s f o r m a t i o n
The c o n v e r s i o n o f propane was c a r r i e d o u t under i d e n t i c a l c o n d i t i o n s ( T =
530°C, p propane = 1 b a r , f l o w r a t e o f propane = 0.018 mole h - ' ) , on p u r e
HZSM5 ( 2 5 mg), on p u r e Ga203 (200 mg) and on mechanical m i x t u r e s o f HZSM5 ( 2 5
rng) and Ga203 (5, 25, 75 o r 200 mg).
D e a c t i v a t i o n i s always v e r y slow. F i g u r e 1 shows t h a t t h e t o t a l c o n v e r s i o n
on t h e mechanical m i x t u r e s i n c r e a s e s a t f i r s t when t h e amount of Ga203
i n c r e a s e s and t h e n reaches a p l a t e a u f o r amounts of Ga203 above 75 mg. Except
 155

f o r t h e m i x t u r e w i t h 200 mg o f Ga203 t h e t o t a l c o n v e r s i o n i s p r a c t i c a l l y
equal t o the sum o f the conversions that can be expected w i t h pure
components. On a l l t h e m i x t u r e s t h e c o n v e r s i o n i n t o C6-C8 a r o m a t i c s i s much
h i g h e r t h a n t h o s e found on HZSM5 and on Ga203. As i s t h e case w i t h t h e t o t a l
conversion, i t i n c r e a s e s a t f i r s t w i t h t h e amount o f Ga203 added t o HZSM5 and
t h e n reaches a p l a t e a u ( F i g u r e 1 ) .

2
c.
8e
Y

-
c.
w
x 1
x
t

0 100 200
Ga203 (mg)

F i g . 1. Propane t r a n s f o r m a t i o n on mechanical m i x t u r e s o f HZSM5 ( 2 5 mg) and o f

g a l l i u m o x i d e Ga 0 . T o t a l c o n v e r s i o n X ( % I and c o n v e r s i o n i n t o a r o m a t i c s XAr
( % ) as f u n c t i o n s 2 0 ? t h e amount o f Ga203.

On pure Ga203, t h e p r o d u c t s a r e composed m a i n l y o f propene (70 w t % ) and

o f an equimolar m i x t u r e o f e t h y l e n e and methane. On HZSM5 and on a l l t h e
mechanical m i x t u r e s t h e p r i m a r y p r o d u c t s a r e methane, e t h y l e n e and propene;
t h e o t h e r p r o d u c t s --ethane, butanes, butenes, a l i p h a t i c o r a l i c y c l i c C5-C6
compounds and C6-C8 a r o m a t i c s - - r e s u l t f r o m t h e secondary t r a n s f o r m a t i o n o f
propene and o f e t h y l e n e . F i g u r e s 2 - 4 show, however, t h a t t h e r e are great
d i f f e r e n c e s between t h e p r o d u c t d i s t r i b u t i o n s on HZSM5 and on t h e m i x t u r e s .
The a d d i t i o n o f g a l l i u m o x i d e t o HZSM5 causes t h e f o l l o w i n g :
- An i n c r e a s e o f t h e i n i t i a l p r o d u c t i o n o f propene ( F i g u r e 2 ) : a t low
c o n v e r s i o n ( < l o % ) t h e g r e a t e r t h e amount o f g a l l i u m o x i d e i n t h e m i x t u r e t h e
g r e a t e r t h e s e l e c t i v i t y f o r propene. F i g u r e 2 shows a l s o t h a t t h e secondary
transformations o f propene a r e much f a s t e r with the mixtures than with
HZSM5 : t h e maximum y i e l d i n propene i s l o w e r and o b t a i n e d f o r l o w e r v a l u e s
o f conversion; on t h e o t h e r hand,on Ga203 propene does n o t seem t o undergo
secondary t r a n s f o r m a t i o n s .
- An i n c r e a s e i n t h e s e l e c t i v i t y f o r C6-C8 aromatics: the greater the
amount o f g a l l i u m added t o HZSM5, t h e g r e a t e r t h e s e l e c t i v i t y ( F i g u r e 3 ) .
 Fig. 2

0 10 20 30 0 10 20 30
X(%) X(%)

F i g s , 2 and 3. Propane t r a n s f o r m a t i o n on mechanical m i x t u r e s o f HZSM5 and o f

Ga 0 . Percentages o f propene and o f a r o m a t i c s ( w t % ) as f u n c t i o n s o f t h e
t o ? a ? c o n v e r s i o n X ( % ) , HZSM5 ( 0 ; 25 mg HZM5 t 5 mg Ga O3 ( *
) ; 25 mg
*
HZSM5 t 25 mg Ga O3 ( ) ; 25 mg HZSM5 t 75 mg Ga203 ( A ) ; 1 5 mg HZSM5 t 200
mg ~ a ( +~ I ;02a203 ~ (21).

- A decrease i n t h e s e l e c t i v i t y f o r methane, ethane, e t h y l e n e , butanes,

butenes, a l i p h a t i c o r a l i c y c l i c C5-C6 compounds ( F i g u r e s 4).
- An i n c r e a s e o f t h e isobutane/n-butane r a t i o . Moreover, when t h e c o n v e r -
s i o n i n c r e a s e s t h i s r a t i o i n c r e a s e s on HZSM5 and decreases on t h e m i x t u r e s .
I n b o t h cases i t approaches i t s e q u i l i b r i u m v a l u e (0.55 a t 530°C (10)) a t
high conversion.
On t h e c o n t r a r y , on a l l t h e c a t a l y s t s t h e butene d i s t r i b u t i o n i s t h e same
as t h e d i s t r i b u t i o n o f t h e thermodynamic e q u i l i b r i u m even a t low c o n v e r s i o n .
The d i s t r i b u t i o n o f a r o m a t i c s i s t h e same on a l l t h e c a t a l y s t s when i t i s
determined f o r t h e same v a l u e s o f a r o m a t i c y i e l d s .
The p r o d u c t i o n o f hydrogen can be e s t i m a t e d f r o m t h e d i f f e r e n c e between
t h e hydrogen c o n t e n t o f t h e r e a c t i o n p r o d u c t s and o f t h e r e a c t a n t . F i g u r e 5
shows t h a t t h e y i e l d i n hydrogen i s more s i g n i f i c a n t on t h e Ga203 (200 mg)-
HZSM5 ( 2 5 mg) m i x t u r e t h a n on HZSM5. About 4.2 moles o f hydrogen a r e formed
p e r mole o f a r o m a t i c hydrocarbon f r o m propane t r a n s f o r m a t i o n on t h e m i x t u r e
as a g a i n s t about 2 moles on HZSM5.
 157

'O1
41
I

i a
2
Y

0)
c
10
c
c,
W

py,
0 10 20 30
X(%)

3 !
+
j
P
:
e
a.
1

0 10 20 30 0 10 20 3b

io 20 30 0 10 20 30
X(%) X(%)

Y J'

L
F i g . 4. Propane t r a n s f o r m a t i o n on HZSM5 ( * j , on a m i x t u r e o f 25 mg HZSM5 and
200 mg Ga 0 ( ttt 1 and on 6GaHZSM5 ( A 1. Percentages o f t h e p r o d u c t s ( w t X ) as
functions'o? t h e t o t a l c o n v e r s i o n X ( % I * ( a ) methane ; ( b ) ethane ; ( c )
ethene ; ( d ) propene ; ( e l butanes ; i f ) butenes ; ( 9 ) a l i p h a t i c and
a l i c y c l i c C5-C6 compounds (non-aromatics C5+) ; ( h ) aromatics.
158

0 50 100
X(%)

F i g . 5. Propane t r a n s f o r m a t i o n on HZSM5 (+I,on a m i x t u r e o f 25 mg HZSM5 and

200 mg Ga 0 ( * ) and on 6GaHZSM5 ( A ) . ( a ) Hydrogen y i e l d ( H as a f u n c t i o n
o f t h e to?aq c o n v e r s i o n X ( % ) . ( b ) Hydrogen/aromatic m o l a r r a ? i o ( H 2 / A ) as a
f u n c t i o n o f t h e c o n v e r s i o n i n t o a r o m a t i c s XAr (%I.

2. Propene t r a n s f o r m a t i o n
The c o n v e r s i o n o f propene was c a r r i e d o u t on p u r e HZSM5 ( 2 5 mg), on p u r e
Ga203 (200 mg) and on a mechanical m i x t u r e o f HZSM5 ( 2 5 mg) and o f Ga203 (200
mg) under t h e same o p e r a t i n g c o n d i t i o n s as f o r propane c o n v e r s i o n .
On Ga203 t h e r e a c t i o n r a t e i s t h r e e t i m e s l o w e r t h a n w i t h propane, t h e
main p r o d u c t s b e i n g propane ( 3 0 w t %I and C5-C7 a l i p h a t i c compounds (30
wt %I ; small amounts o f methane, ethane, ethylene, butanes, butenes and
a r o m a t i c s a r e a l s o formed. On HZSM5 and on t h e m i x t u r e propene r e a c t s about
5 0 t i m e s more r a p i d l y t h a n propane. T a b l e 1 shows t h a t t h e a d d i t i o n o f Ga203
t o HZSM5 i n c r e a s e s s l i g h t l y t h e t o t a l c o n v e r s i o n o f propene b u t i n c r e a s e s
s t r o n g l y i t s c o n v e r s i o n i n t o C6-C8 a r o m a t i c s . The r e a c t i o n p r o d u c t s a r e t h e
same as t h o s e o b t a i n e d i n propane t r a n s f o r m a t i o n b u t t h e d i s t r i b u t i o n s a r e
q u i t e d i f f e r e n t . The a d d i t i o n of Ga203 t o H E M 5 has p r a c t i c a l l y no e f f e c t on
t h e f o r m a t i o n o f methane, o f ethane, o f e t h y l e n e , o f propane, o f butenes and
o f butanes b u t causes a decrease i n t h e p r o d u c t i o n o f non-aromatic C5-C6
p r o d u c t s ( F i g u r e 6 ) and an i n c r e a s e i n t h e p r o d u c t i o n o f C6-C8 aromatics
(Figure 7 ) .
On HZSM5 and on t h e m i x t u r e t h e i s o b u t a n e / n - b u t a n e r a t i o i s always h i g h e r
t h a n i t s thermodynamic e q u i l i b r i u m v a l u e (0.55 a t 530°C ( 1 0 ) ) . F o r t h e same
v a l u e of c o n v e r s i o n t h i s r a t i o i s h i g h e r on t h e m i x t u r e t h a n on HZSM5 : e.g.
a t 30 % c o n v e r s i o n 1.6 on t h e m i x t u r e as a g a i n s t 1 on HZSM5; a t 80 %
c o n v e r s i o n about 2 on t h e m i x t u r e as a g a i n s t 1.4 on HZSM5. No s i g n i f i c a n t
d i f f e r e n c e s between t h e two c a t a l y s t s a r e observed i n t h e b u t e n e and i n t h e
C6-C8 a r o m a t i c d i s t r i b u t i o n s .
 159

F i g s . 6 and 7. Propene t r a n s f o r m a t i o n on HZSM5 ( + 1, on a m i x t u r e o f 25 mg

*
HZSM5 and 200 mg Ga 0 ( ) and on 6GaHZSM5 ( A). Percentages o f non-aromatic
C ( w t % ) and o f & h a t i c s (wt % ) as f u n c t i o n s o f t h e t o t a l conversion X
(2J.
The y i e l d i n hydrogen i s c l o s e t o zero on HZSM5. On t h e m i x t u r e o f HZSM5
and o f Gap03 i t becomes s i g n i f i c a n t f o r h i g h conversion l e v e l s ; whatever t h e
conversion l e v e l , about 1.8 mole o f hydrogen i s formed p e r mole o f aromatic
hydrocarbon.

TABLE 1
Propene conversion a t 530°C, p propene = 1 bar, molar f l o w r a t e = 0.018
mol.h-', X = t o t a l conversion, XAr = conversion i n t o C6-C8 aromatics.

Catalysts I x (%I I XAr (XI

I I
HZSM5 (25 mg) I 79 I 17.8
Ga203 (0.2 4) I 4.4 1 0.3
HZSM5 (25 mg) t Ga203 (200 mg) I 81.3 I 28.8
6GaZSM5 ( 2 5 mg) I 81.6 I 31.3
I I

3. Conversion o f model r e a c t a n t s on Ga2c3

I n order t o discuss t h e r o l e played by Ga203 on steps 2 t o 5 t h e t r a n s f o r -
mation o f f o u r model r e a c t a n t s --1-hexene, 1-heptene, methylcyclohexane and
methylcyclohexene-- was c a r r i e d o u t on 200 mg o f Ga203 under t h e f o l l o w i n g
o p e r a t i n g c o n d i t i o n s : t = 530"C, p hydrocarbon = 1 bar, m o l a r f l o w r a t e o f
about 0.018 mol .h-'.
160

Table 2 shows t h a t w i t h a l l t h e r e a c t a n t s i s o m e r i z a t i o n and c r a c k i n g are

t h e main r e a c t i o n s . The o l e f i n i c compounds are more r a p i d l y transformed
(conversion between 58-70 % I t h a n methylcyclohexane (conversion o f about
10 % I , Aromatics are formed f r o m a l l t h e r e a c t a n t s . However, only
methylcyclohexane and, above a l l , methylcyclohexene lead to significant
amounts; i n both cases t o l u e n e i s p r a c t i c a l l y t h e o n l y aromatic product.

TABLE 2
Conversion o f model r e a c t a n t s on Ga203 (200 mg) a f t e r 5 m i n u t e s ' r e a c t i o n a t
530°C, p hydrocarbon = 1 bar, molar f l o w r a t e = 0.018 mol.hr-'

Reactant I * I
X ( % ) 1X c r a c k i n g X Isomers (%)I X Aromatics (%I
I [Products (%I I I
-1 I I I
1-hexene I 67 1 21 I 46 I < 1
1-heptene I 58 1 50 I 8 I < 1
methylcyclohexane I 9-10 I 5 I 3 I 1-2
methylcyclohexene 170-72 I 12.5 I 57.5 I 10-12
-1 I I I
X : t o t a l conversion, * conversion i n t o C1-C5 products f r o m 1-hexene and i n t o
C1-C6 products from t h e o t h e r r e a c t a n t s .

DISCUSSION
The a c t i v i t i e s f o r propane a r o m a t i z a t i o n o f t h e m i x t u r e s o f HZSM5 and
Ga203 are much g r e a t e r than t h e sum o f t h e a c t i v i t i e s o f t h e pure components
( F i g u r e 1 ) . T h i s s y n e r g y s t i c e f f e c t i s c h a r a c t e r i s t i c o f r e a c t i o n s i n which
t h e c a t a l y t i c s i t e s o f t h e two components ( b i f u n c t i o n a l c a t a l y s i s ) p a r t i c i -
pate. F i g u r e s 2-7 show t h a t on t h e m i x t u r e Ga203 (200 mg) - HZSM5 (25 mg) t h e
s e l e c t i v i t i e s f o r propane and f o r propene t r a n s f o r m a t i o n s are s i m i l a r t o
those obtained on 6GaHZSM5, a c a t a l y s t w i t h 6 w t % g a l l i u m prepared by
impregnation o f HZSM5 w i t h g a l l i u m n i t r a t e ( 6 ) . Therefore, on b o t h c a t a l y s t s
the gallium species participating i n the aromatization are identical,
probably g a l l i u m oxide. However, we cannot exclude t o t a l l y t h a t t h e r e a r e no
r e a c t i o n s between HZSM5 and g a l l i u m o x i d e under t h e o p e r a t i n g c o n d i t i o n s
( h i g h temperature, presence o f hydrogen). The r a t e o f propane t r a n s f o r m a t i o n
i s h i g h e r on 6GaHZSM5 than on t h e m i x t u r e . Thus under i d e n t i c a l c o n d i t i o n s
t h e conversion o f propane on 25 mg o f 6GaHZSM5 i s equal t o 20 % as a g a i n s t
o n l y 8.5 % on t h e m i x t u r e . T h i s can be e x p l a i n e d by a c l o s e r i n t i m a c y between
t h e two components o f t h e a r o m a t i z a t i o n c a t a l y s t HZSM5 and g a l l i u m oxide.
 161

R o l e o f a a l l i u m soecies
G a l l i u m o x i d e causes a s i g n i f i c a n t i n c r e a s e i n t h e r a t e s o f a r o m a t i c and
of hydrogen p r o d u c t i o n . It a c t s t h e n as a dehydrogenating c a t a l y s t . T h i s i s
shown c l e a r l y i n propane t r a n s f o r m a t i o n on Ga203: t h e main p r o d u c t i s
propene. T h i s dehydrogenating e f f e c t i s p r o b a b l y r e s p o n s i b l e f o r most o f t h e
i n c r e a s e i n t h e propane t r a n s f o r m a t i o n r a t e caused by t h e a d d i t i o n o f g a l l i u m
o x i d e t o HZSM5 ( F i g u r e . 1 ) . Indeed, on HZSM5 t h e t r a n s f o r m a t i o n o f propane
i n t o propene which r e q u i r e s s t r o n g a c i d s i t e s i s one o f t h e slower s t e p s o f
( 3 ) . Gallium oxide also catalyzes step 5 o f t h e
propane a r o r n a t i z a t i o n
r e a c t i o n scheme as shown i n t h e t r a n s f o r m a t i o n s o f methylcyclohexane and
above a l l o f methylcyclohexene ( T a b l e 2 ) . T h i s e f f e c t o f g a l l i u m s p e c i e s on
s t e p 5 e x p l a i n s t h e h i g h e r s e l e c t i v i t y f o u n d f o r propane and f o r propene
a r o m a t i z a t i o n and t h e i n c r e a s e i n t h e r a t e o f propene consumption shown i n
f i g u r e 2 : t h e maximum y i e l d i n propene f o r m a t i o n i s lower w i t h t h e m i x t u r e
o f Ga203 t HZSM5 t h a n w i t h HZSM5 and i s o b t a i n e d f o r a lower c o n v e r s i o n .
I t i s i n t e r e s t i n g t o e s t i m a t e how g a l l i u m o x i d e on one hand and t h e HZSM5
a c i d s i t e s on t h e o t h e r i n f l u e n c e t h e r a t e s o f steps 1 and 5. F o r s t e p 1 t h i s
can be deduced f r o m t h e i n i t i a l r a t e s o f propene p r o d u c t i o n on HZSM5 and on
t h e m i x t u r e s : on HZSM5 t h e r a t e i s about 4 t i m e s l o w e r t h a n on t h e m i x t u r e
Ga203 (200 mg) t HZSM5 ( 2 5 mg) o r on 6GaHZSM5. We can t h u s c o n c l u d e t h a t
about 7 5 % o f t h e propene p r o d u c t i o n comes f r o m Ga203 as a g a i n s t about 2 5 %
from t h e acid s i t e s . For step 5 t h e formation o f aromatics through d i r e c t
dehydrogenation o f naphthenes i s more s i g n i f i c a n t than their formation
t h r o u g h hydrogen t r a n s f e r . Indeed f o r propene c o n v e r s i o n on t h e m i x t u r e o f
Ga203 and HZSM5 t h e p r o d u c t i o n o f one mole o f a r o m a t i c hydrocarbon is
accompanied by t h e f o r m a t i o n o f 1.8 mole o f hydrogen w h i l e on HZSM5 t h e
f o r m a t i o n o f hydrogen i s n e g l i g i b l e . I f t h e a r o m a t i c s were produced t h r o u g h
naphthene dehydrogenation about 3 moles o f hydrogen would be formed p e r ,mole
o f aromatic hydrocarbon ( c o n s i d e r e d as t o l u e n e ) . We can t h u s c o n c l u d e t h a t
dehydrogenation on g a l l i u m s p e c i e s i s r e s p o n s i b l e f o r about 60 % o f t h e
t r a n s f o r m a t i o n o f naphthene i n t o aromatics, hydrogen t r a n s f e r on t h e a c i d
s i t e s o f HZSM5 b e i n g r e s p o n s i b l e f o r t h e o t h e r 40 %.Another e s t i m a t i o n made
from t h e p r o d u c t i o n o f a r o m a t i c s and o f hydrogen d u r i n g propane transforma-
t i o n g i v e s about 7 0 % f o r dehydrogenation as a g a i n s t 30 % f o r hydrogen
transfer .
G a l l i u m s p e c i e s have no s i g n i f i c a n t e f f e c t on s t e p 4 s i n c e t h e r e is
p r a c t i c a l l y no p r o d u c t i o n of benzene f r o m 1-hexene o r o f toluene from
1-heptene. Cracking o f large olefins such as I-hexene, 1-heptene and
methylcyclohexane occurs on g a l l i u m o x i d e ; however, we have checked t h a t
t h e s e r e a c t i o n s a r e c o n s i d e r a b l y f a s t e r on H E M 5 ( o v e r 100 t i m e s ) . D u r i n g t h e
162

a r o m a t i z a t i o n o f propane on t h e Ga20g t HZSM5 m i x t u r e s o r on 6GaHZSM5, t h e

p a r t i c i p a t i o n o f g a l l i u m s p e c i e s i n c r a c k i n g r e a c t i o n s and t h e n i n the
r e v e r s e r e a c t i o n (i.e. o l i g o m e r i z a t i o n ) i s t h e r e f o r e almost n e g l i g i b l e ; t h e s e
r e a c t i o n s o c c u r m a i n l y on t h e HZSM5 a c i d s i t e s .

Scheme o f propane t r a n s f o r m a t i on on Ga/HZSM5 c a t a l y s t s

Propane t r a n s f o r m a t i o n on c a t a l y s t s a s s o c i a t i n g g a l l i u m s p e c i e s a c t i v e i n
dehydrogenation and HZSM5 a c i d s i t e s can be c o n s i d e r e d as a b i f u n c t i o n a l
process such as expressed by Weisz ( 1 1 ) . G a l l i u m s p e c i e s c a t a l y z e s t e p s 1 and
5 of t h e successive r e a c t i o n scheme and t h e a c i d s i t e s o f HZSM5 s t e p s 2 t o 4.
Besides t h e s e chemical steps t h e b i f u n c t i o n a l process r e q u i r e s d i f f u s i o n
s t e p s o f t h e i n t e r m e d i a t e s p e c i e s : propene d i f f u s i o n f r o m t h e g a l l i u m a c t i v e
s i t e s t o t h e a c i d s i t e s and naphthene d i f f u s i o n f r o m t h e a c i d t o t h e g a l l i u m
s i t e s . The v a r i a t i o n o f t h e c o n v e r s i o n o f propane i n t o C6-C8 aromatics w i t h
t h e amount o f g a l l i u m o x i d e ( F i g u r e 1 ) i s q u i t e c h a r a c t e r i s t i c o f t h i s t y p e
o f b i f u n c t i o n a l process :
- For small amounts of gallium oxide, the limiting steps are the
dehydrogenation o f propene ( s t e p 1 ) o r t h a t o f a l i c y c l i c compounds ( s t e p 51,
and t h e c o n v e r s i o n o f propane i n t o a r o m a t i c s i n c r e a s e s p r o p o r t i o n a l l y t o t h e
amount o f g a l l i u m o x i d e .
- F o r l a r g e amounts, r e a c t i o n s 1 and 5 become f a s t e r compared t o r e a c t i o n s
2-4 which a r e t h e n t h e r a t e - l i m i t i n g steps; and t h e c o n v e r s i o n o f propane
i n t o a r o m a t i c s no l o n g e r depends on t h e amount o f g a l l i u m o x i d e .

REFERENCES
1 J.R. Mowry, R.F. Anderson, J.A Johnson, O i l and Gas J o u r n a l (1985) 128.
2 J.R. Mowry, D.C. M a r t i n d a l e , A.H.P. H a l l , The A r a b i a n J o u r n a l f o r Science
and E n g i n e e r i n g 10 (1985) 367.
3 T. I n u i , F. Okazumi, J . C a t a l . 90 (1984) 366.
4 H. Kitagawa, Y . Sendoda and Y. Ono, J. C a t a l . 101 (1986) 12
5 N.S. Gnep, J.Y. Doyemet, A.M. Seco, F.R. R i b e i r o and M. G u i s n e t , Appl.
C a t a l . 35 (1987) 93.
6 N.S. Gnep, J.Y. Doyemet, A.M. Seco, F.R. R i b e i r o and M. G u i s n e t , A p p l .
C a t a l . 43 (1988) 155.
7 T. I n u i , A . Miyamoto, H. Matsuda, H. Nagata, Y. Makino, K . Fukuda and F.
Okazumi, Proc. 7 t h I n t e r n . Z e o l i t e Conference, Y. Murakami e t a l . (Eds.)
Kodansha, Tokyo, 1986, p. 859.
8 N.S. Gnep, J.Y. Doyemet and M. G u i s n e t , J . Mol. C a t a l . 45 (1988) 281.
9 R.G. Argauer and G.R. L a n d o l t , U.S. Pat., 3.702.886 (1972).
10 D.R. S t u l l , E.F. Westrum and G.C. Sinke, The Chemical Thermodynamics o f
Organic Compounds, J. Wiley, New York, 1969.
11 P.B. Weisz, Advances i n C a t a l y s i s , D.D. E l e y e t a l . ( E d s . ) , Academic
Press, London, 13 (1962) p . 137.
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

SHAPE-SELECTIVE CATALYSIS I N ZEOLITES WITH ORGANIC SUBSTRATES CONTAINING

OXYGEN

R.F. P art on, J.M. Jacobs, D.R. Huybrechts and P.A. Jacobs
La b ora t o riu m voor Oppervlaktechemie, KU Leuven, 92 K a r d i n a a l M e r c i e r l a a n B-
3030 Leuven (Heverlee), Belgium

INTRODUCTION AND SCOPE

With the advent of acid 10-membered ring (10-MR) zeolites as
heterogeneous c a t a l y s t s i n hydrocarbon t r a n s f o r m a t i o n s , s e v e r a l new concepts
on s e l e c t i v i t y such as t r a n s i t i o n s t a t e and p r o d u c t shape s e l e c t i v i t y , to
name t h e most i m p o r t a n t ones, were developed [ l - 8 1 . I n t h e meantime i t was
e s t a b l i s h e d t h a t t h e s e concepts were s u i t a b l e f o r d a t a r a t i o n a l i s a t i o n and
property p r e d i c t i o n n o t o n l y on a c i d c a t a l y s t s b u t on met al [9, l o ] ,
b i f u n c t i o n a l [ 8 ] and even b a s i c c a t a l y s t s [ll]o f z e o l i t i c o r i g i n as w e l l .
The aim o f t h e p r e s e n t r e v i e w was t o examine whether t hese concepts a r e v a l i d
when o t h e r t h an hydrocarbon s u b s t r a t e s a r e c o n v e r t e d on t h e mentioned shape-
s e l e c t i v e z e o l i t e s and r e l a t e d m a t e r i a l s .
The r e a c t i o n s o f molecules c o n t a i n i n g hetero-atoms on z e o l i t e s have a l r e a d y
been t h e s u b j e c t o f s e v e r a l r e v i e w s [12-211. S e l e c t i v e chemical c o n v e r s i o n o f
o r g a n i c molecules on c l a y m i n e r a l s has been reviewed as w e l l [22]. From t h i s
wealth o f information, i t seems t h a t f o r e v e r y o r g a n i c r e a c t i o n a z e o l i t e
and/or c l a y can be found, c a t a l y s i n g i t w i t h a more o r l e s s good a c t i v i t y and
selectivity. T he r e f o r e , the following two editorial constraints on the
p r e s e n t r e v i e w seem j u s t i f i e d : ( i ) o n l y t h e r e a c t i o n s o f oxygenates should be
cons idere d, and ( i i ) t h e d a t a s h o u l d be arranged i n a way g o i n g beyond a mere
enumeration o f r e a c t i o n s . The p r e s e n t work on t h e c a t a l y t i c c o n v e r s i o n o f
oxygenates on z e o l i t e s and c l a y s w i l l , as a r e s u l t , n o t be e x h a u s t i v e b u t
o n l y deal w i t h a few s e l e c t e d t o p i c s , on w hich a c c o r d i n g t o t h e a u t h o r s ’
o p i n i o n a c o n s i s t e n t s e t o f d a t a a r e a v a i l a b l e o r which i n t r o d u c e new
concepts.

ALKYLATION OF PHENOLIC COMPOUNDS

P henolic compounds such as c r e s o l s [23-251, l o n g c h a i n a l k y l phenols
[26] and alkyl aryl ethers [27-301 find increasing industrial use as
i n t e r m e d i a t e s . Product p u r i t y i s a p r e r e q u i s i t e f o r t h e i r use. F or t h e moment
o n l y o - c r e s o l and 2 , 6 - x y l e n o l can be made i n a r a t h e r s e l e c t i v e way by d i r e c t
164

a l k y l a t i o n f r o m phenol u s i n g e i t h e r a b a s i c [31] o r an alumina c a t a l y s t [26!.

However, t h e s e l e c t i v e c a t a l y t i c s y n t h e s i s o f p - and m-cresol remains a
c h a l l e n g e g i v e n t h e expensive d i s t i l l a t i o n and c r y s t a l l i s a t i o n o p e r a t i o n s
needed f o r t h e i r s e p a r a t i o n .
As t h e a l k y l a t i o n o f t o l u e n e w i t h methanol o v e r a c i d 10-MR z e o l i t e s i s
very s u i t a b l e t o o b t a i n para-enriched a l k y l a t e , t h e m e t h y l a t i o n o f phenol
and/or a n i s o l e o v e r t h e same z e o l i t e s i s an obvious way t o achieve enhanced
yields of para alkylates. Most alkylation reactions reported in the
l i t e r a t u r e a r e c a r r i e d o u t w i t h phenol i n t h e vapour phase a t atmospheric
pr e s s ure and a t t e m p e r a t u r e s between 413 and 673 K u s i n g p e n t a s i l and
f a u j a s i t e - t y p e z e o l i t e s as c a t a l y s t s . An o verview o f work i n t h i s area i s
g i v e n i n Table 1. A l k y l a t i o n r e a c t i o n s o f p h e n o l i c compounds a r e more complex
th an t hos e o f t h e c o r r e s p o n d i n g a r o m a t i c hydrocarbons, as n o t o n l y carbon ( C -
) b u t a l s o oxygen (0-) a l k y l a t i o n i s p o s s i b l e . It i s , t h e r e f o r e , e s s e n t i a l t o
have a good comprehension o f t h e r e a c t i o n n et work i n t h e a l k y l a t i o n o f phenol
and t h e i n f l u e n c e o f t h e z e o l i t e s t r u c t u r e and a c i d i t y on i t .

Table 1
D i f f e r e n t a l k y l a t i n g agents used w i t h phenol on z e o l i t e s i n t h e vapour and
i q u i d pha:
reaction a l k y l a t i n g agent z e o l i t e type reference
medi um
vapour methanol X, Y, Mordenite, TSVM, 27-29, 32-38, 40-42,
phase ZSM-5, ZSM-11, 45, 47, 51, 53-54
h i g h e r a1 cohol s X, Y, ZSM-5 23, 56
o le fins X, Y, ZSM-5 23, 38, 62-64
anisole X, Y, ZSM-5, ZSM-11 43-44
a1 k y l benzenes X, Y, Tseokar-2 57-61
a1 k y l c h l o r i d e x, y 38
d i a1 k y l c a r b o n a t e unspecified 30

1i q u i d methanol X, Y, M o r d e nit e, ZSM-5 39, 46, 55

phase h i g h e r a1 cohol s Y 67
methyl i o d i d e X 65
benzylchl o r i d e x, Y, L 66

1. M e c h a n i s t i c aspects
For t h e a l k y l a t i o n o f phenol or benzene w i t h ethene on z e o l i t e REX,
Venuto et al. [38,64] reported a decreased reactivity of the f ormer
substrate, which is opposite to their respective nucleophilicities.
C o m p e t i t i v e a d s o r p t i o n measurements showed an i n c r e a s e d a d s o r p t i o n o f phenol
compared t o benzene and ethene [68]. The o f a Rideal type
operation
mechanism, c omp l i c a t e d by a c o m p e t i t i v e a d s o r p t i o n o f phenol f o r t h e
a l k y l a t i n g agent, was proposed [68,69]. Indeed, an a r o m a t i c compound adsorbed
 165

on a Brensted s i t e w i l l be p o s i t i v e l y charged and p o o r l y s u s c e p t i b l e t o an

e l e c t r o p h i l i c attack. Such an e l e c t r o p h i l i c aromat ic s u b s t i t u t i o n r e a c t i o n
can be viewed as t h e r e a c t i o n o f an adsorbed e t h y l c a t i o n formed f rom ethene
w i t h a f r e e aro m a t i c :

F i g . 1. Mechanism o f t h e a l k y l a t i o n o f phenol w i t h ethene on z e o l i t e s .

Recently, i t was e s t a b l i s h e d [51,70] t h a t phenol i s more a c t i v e t han

benzene on Y and p e n t a s i l z e o l i t e s w i t h methanol as a l k y l a t i n g agent. It
seems, t h e r e f o r e , t h a t more p o l a r a1 k y l a t i n g fragments compete more
f a v o u r a b l y w i t h phenol f o r a d s o r p t i o n .

loo I
80
c.
8
Y
E S 3 A
E 60
.-
0
r E m 6
tc 40

s
20

0
0.5 1 1.1 2 2.1 s 5.1 4

MethanollPhcnol (mollmol)
F i g . 2. Phenol c o n v e r s i o n versus t h e methanol/phenol m o l a r r a t i o i n t h e
reac i o n o f phenol w i t h methanol: (A), on H-K-Y a t 523 K w i t h W/F0=324 kg s
mol-' i n t h e vapour phase and a f t e r 60 min ( d e r i v e d f rom [ 47] ) and (6) on H-
ZSM-5 a t 643 K i n t h e l i q u i d phase and a f t e r 70 min ( d e r i v e d f rom [ 46] ).

The competition between substrate and a1 k y l a t i n g agent is further

evidenced i n F i g . 2. Indeed, u s i n g an i n c r e a s i n g molar excess o f methanol t h e
c o nv ers io n in c re a s e s on b o t h p e n t a s i l and Y z e o l i t e s . The e x i s t e n c e o f t h e
s t r o n g a d s o r p t i o n o f phenol on p e n t a s i l z e o l i t e s can a l s o be d e r i v e d from
T a ble 2. On s i l i c a l i t e , phenol and t h e c r e s o l isomers adsorb homogeneously
thro ughout t h e c r y s t a l s as e v e r y p o r e i n t e r s e c t i o n i s occupied by
appro x ima t e ly one molecule. On t h e c o n t r a r y , on h i g h - a l u m i n a H-ZSM-5 o n l y a
min or amount o f phenol i s adsorbed. Presumably, phenol interacts strongly
with the surface hydroxyl groups, and consequently, relatively small
q u a n t i t i e s o f phenol a r e a b l e t o b l o c k t h e pores and p r e v e n t complete f i l l i n g
o f the intersections.
166

Ta ble 2
Is on p e n t a s i l z e o l i t e s a .
adsorbent adsorbate adsorbat e p e r
pore i n t e r s e c t i o n
H-ZSM-5( 19) phenol 0.15
s i licali t e phenol 0.72
s i 1 i c a l it e p-cresol 0.91
s i licali t e m-cresol 1.03
s i licali t e o-cresol 0.84

2. C a t a l y t i c s t a b i l i t y o f z e o l i t e s

SO

--
bp 40
E
0 IAl
:
I-

>
E
s 20

0
0 10 20 SO 40

Time an dream (h)

F i g . 3. I s o m e r i s a t i o n o f o - c r e s o l on H-ZSM-5 a t 653 K and 6 MPa a g a i n s t t i m e

on stream w i t h ( a ) hyflrogen and ( b ) n i t r o g e n as c a r r i e r gas. W/Fo values a r e
339 and 113 kg s m o l - i n p a r t (A) and (B), r e s p e c t i v e l y ( d e r i v e d f rom [so]).

The i s o m e r i s a t i o n r e a c t i o n s o f c r e s o l s and t h e a l k y l a t i o n r e a c t i o n s o f
p h e n o l i c compounds always s u f f e r f r o m d e a c t i v a t i o n by coke d e p o s i t i o n on t h e
zeolite catalysts, but air regeneration easily restores their initial
c a t a l y t i c a c t i v i t y [28,40-41,44-45,52-53,561. Some a u t h o r s [27,39-41,47-491
use an i n e r t d i l u e n t f o r t h e feed, w h i l e o t h e r s [28,43-45,50-521 take
hydrogen f o r t h i s purpose as i t was found t h a t t h e decay o f t h e c a t a l y s t
a c t i v i t y i s c o n s i d e r a b l y s l o w e r i n t h e l a t t e r case [45,50]. This i s
i l l u s t r a t e d i n F i g . 3 f o r t h e i s o m e r i s a t i o n o f o - c r e s o l . Such a f a v o u r a b l e
e f f e c t o f hydrogen has been r e p o r t e d by Barthomeuf e t a l . [72-731 i n t h e
i s o o c t a n e c r a c k i n g on Y z e o l i t e s and e x p l a i n e d l a t e r by t h e presence o f
i m p u r i t y Fe2+ w i t h h y d r o g e n - a c t i v a t i n g p r o p e r t i e s 1761. I n t h e c o n v e r s i o n o f
a c e t y l e n e ov er H-ZSM-5, hydrogen i s a l s o n o t an i n e r t d i l u e n t and can r e a c t
 167

w i t h v i n y l c a t i o n s upon f o r m a t i o n o f ethene t h u s a v o i d i n g p o l y m e r i s a t i o n o f
a c e t y l e n e and c o k i n g o f t h e c a t a l y s t [74].
Minachev e t a l . [75] observed a f a v o u r a b l e e f f e c t o f carbon d i o x i d e on
t h e c onv ers io n o f a n i s o l e on z e o l i t e s . The e f f e c t i s more pronounced f o r
alkaline earth than for alkali ion-exchanged faujasites. A similar
enhancement o f t h e i s o p r o p a n o l d e h y d r a t i o n a c t i v i t y was r e p o r t e d and
a t t r i b u t e d t o t h e g e n e r a t i o n o f new B r a n s t e d a c i d s i t e s and s u r f a c e carbonate
[761.
I n t h e a l k y l a t i o n o f phenol w i t h methanol on z e o l i t e s , Marzewski e t a l .
[34] proved t h a t a t a g i v e n c o n v e r s i o n t h e s e l e c t i v i t y remained unchanged
i r r e s p e c t i v e o f whether t h i s c o n v e r s i o n was reached by changing c o n t a c t t i m e
or during a decay experiment. Consequently, selectivity changes on a
d e a c t i v a t i n g c a t a l y s t w i t h i n c e r t a i n conversion l i m i t s w i l l allow
d e t e r m i n a t i o n o f t h e r e a c t i o n network. T h i s i s an a p o s t e r i o r i v e r i f i c a t i o n
o f a procedure used i n o t h e r work [51].

3. Oxvqen versus carbon a l k v l a t i o n i n t h e Dhenol a l k v l a t i o n w i t h methanol

Typical p r i m a r y p r o d u c t s o b t a i n e d i n t h e a l k y l a t i o n o f phenol w i t h
methanol are anisole, 0- and p - c r e s o l . F o r t h e f o l l o w i n g reasons i t i s
e v i d e n t t h a t a n i s o l e i s formed by 0- and t h e c r e s o l s by C - a l k y l a t i o n :
* A t l o w c o nv er s i o n s t h e y a r e t h e o n l y p r o d u c t s o b t a i n e d [34,46,51].
* A t medium c o n v e r s i o n s x y l e n o l s , m e t h y l a n i s o l e s and m-cresol appear [34,51].
As expected f o r an e l e c t r o p h i l i c a r o m a t i c s u b s t i t u t i o n , m-cresol i s not a
p r i m a r y pro duc t .
There is a quite general belief among d i f f e r e n t authors that C-
alkylation requires stronger acid sites t han t hose responsible for 0-
a1 k y l a t i o n [27,51,67]:
* I n a s e r i e s o f H-Na-Y z e o l i t e s w i t h v a r y i n g sodium c o n t e n t , the anisole
y i e l d decreases g r a d u a l l y w i t h i n c r e a s i n g p r o t o n c o n t e n t ; a t t h e same t i m e
t h e number o f weak a c i d s i t e s determined b y n - b u t y l a m i n e t i t r a t i o n decreases
i n a p a r a l l e l way [47].
* On a H-Na-ZSM-5 z e o l i t e t h e a n i s o l e s e l e c t i v i t y i s h i g h e r t h a n on sodium
f r e e H-ZSM-5 [46].
* I n p a r a l l e l t o t h e decreased e l e c t r o n e g a t i v i t y and consequent ly decreased
average a c i d s t r e n g t h o f H-K-Y compared t o H-Na-Y, t h e f o r m e r z e o l i t e i s more
s e l e c t i v e f o r a n i s o l e f o r m a t i o n [47].
* As i n the zeolite literature i t i s g e n e r a l l y accepted t h a t pentasil
z e o l i t e s have s t r o n g e r a c i d s i t e s t h a n f a u j a s i t e s , t h e l a t t e r z e o l i t e s should
have h i g h e r s e l e c t i v i t y f o r a n i s o l e . There i s ample experiment al evidence f o r
t h i s [28,39-42,46,51,53-55].
168

T h i s dependence o f C - a l k y l a t i o n s e l e c t i v i t y upon Brransted a c i d s t r e n g t h

has a l s o been observed f o r metal phosphate c a t a l y s t s , as a c o r r e l a t i o n
between r i n g a l k y l a t i o n s e l e c t i v i t y and e l e c t r o n e g a t i v i t y o f t h e metal i o n
has been e s t a b l i s h e d [77]. I n t h i s r e s p e c t Marczewski e t a l . [ 34] r e p o r t
c o n f l i c t i n g evidence, s i n c e i n a s e r i e s o f u l t r a s t a b l e Y z e o l i t e s w i t h
de c reas ing alumina c o n t e n t t h e a n i s o l e s e l e c t i v i t y does n o t decrease. The
a u t h o r s assume t h a t d e a l u m i n a t i o n decreases t h e b a s i c i t y o f t h e framework and
t h a t a d s o r p t i o n o f phenol on b a s i c s i t e s o f i n c r e a s i n g s t r e n g t h f avours
electrophil i c substitution.
As w i l l be e x p l a i n e d l a t e r , t h e l o w a n i s o l e s e l e c t i v i t y observed on ZSM-
5 [28,40,51] compared t o more open z e o l i t e s [51] i s due t o t h e f a c t t h a t
a n i s o l e i s c a t a l y t i c a l l y l e s s s t a b l e i n 10-MR t h a n i n l a r g e p o r e z e o l i t e s
[51]. H igh a n i s o l e s e l e c t i v i t i e s on p e n t a s i l z e o l i t e s [27,34,45-461 can be
a t t r i b u t e d t o t h e presence o f e x t r a - f r a m e w o rk aluminium [ 27] o r impregnated
phosphor o x i d e s [34,53] and are, t h e r e f o r e , r e l a t e d t o p r o d u c t shape
s e l e c t i v i t y which would f a v o u r t h e d e s o r p t i o n o f l i n e a r molecules [ 34] .

2.50 1 J 100

1.50 60

1.00 40

0.50 ¶O

0.00 0
4 7 3 498 623 648 673 6B8 6 2 5 648 6 7 s

Temperature (K)

F i g . 4. Conversion and a n i s o l e / c r e s o l - r a t i o versus r e a c t i o n t emperat ure i

t h e r e a c t i o n o f phenol w i t h methanol (A) on H-K-Y w i t h W/Fo= 324 k g s mol- P
i n t h e vapour phase and a f t e r 60 min ( d e r i v e d f rom [ 47] ) and (B) on H-ZSM-5
i n t h e l i q u i d phase, w i t h methanol/phenol m o l a r r a t i o o f 2 and a f t e r 70 min
( d e r i v e d f rom [ 46 ] ) .

The following evidence clearly indicates that part of the cresol

f r a c t i o n must be o f a secondary n a t u r e as t h e a n i s o l e / c r e s o l r a t i o increases
when:
* t h e r e a c t i o n temperature i s decreased [27-28,35,40-41,46-47,671( t h i s i s
t r u e f o r ZSM-5 as w e l l as f o r Y z e o l i t e s ( F i g . 4 ) ) ;
* t h e c o n t a c t t i m e decreases [28,35,47] as shown i n F i g . 5;
 169

WlFO (kg 8 mOl-1) WlFO (kg e mol-1)

F i g . 5. Conversion and a n i s o l e / c r e s o l - r a t i o versus c o n t a c t t i m e (W/Fo) i n t h e
r e a c t i o n o f phenol w i t h methanol i n t h e vapour phase (A) on H-K-Y a t 523 K
and a f t e r 60 min ( d e r i v e d f r o m [ 4 7 ] ) , (B) on H-TSVM a t 623 K ( d e r i v e d from
[351) *

* t i m e on stream i n c r e a s e s and t h u s t h e c o n v e r s i o n decreases f rom h i g h t o

v e r y l o w values [32,45-47,511.
The i n f l u e n c e o f an i n c r e a s i n g methanol/phenol r a t i o on t h e p r o d u c t
s e l e c t i v i t y and more p a r t i c u l a r l y on t h e a n i s o l e / c r e s o l r a t i o i s shown i n
F i g . 6. For Y z e o l i t e s t h i s r a t i o decreases [47], b u t f o r ZSM-5 z e o l i t e s i t
inc re as es [28,46,55]. I n the former case t h i s can be e x p l a i n e d b y t h e
c ons ec ut iv e f o r m a t i o n a t i n c r e a s i n g c o n v e r sions o f c r e s o l s f rom a n i s o l e and
x y l e n o l s f rom c r e s o l s . As a r e s u l t o f t h e a l r e a d y mentioned p r o d u c t shape
s e l e c t i v i t y i n ZSM-5, i n c r e a s i n g amounts o f a n i s o l e a r e expected t o desorb
when an excess o f methanol i s used.

1.00 L 100

- 80
0.80

0.60
- 10

0.40
- 40

0.20
- 20

0.00 -0
0.s 1 1.6 2 2.6 5 5.1 4

Yethanol/Phenol (mol/mol)

Fig . 6. Phenol c o n v e r s i o n and a n i s o l e / c r e s o l r a t i o versus t h e methanol/phenol

mo lar r a t i o i n t h e r e a c i o n o f phenol w i t h methanol: (A), on H-K-Y a t 523 K
w i t h W/Fo=324 kg s mol-' i n t h e vapour phase and a f t e r 60 min ( d e r i v e d from
[47]) and (B ) on H-ZSM-5 a t 643 K i n t h e l i q u i d phase and a f t e r 70 min
( d e r i v e d f rom [46]).
170

Thus c r e s o l s a r e n o t o n l y p r i m a r y b u t a l s o secondary product s, whereas

a n i s o l e i s o n l y o f primary nature. T h i s s t r o n g l y suggests t h a t t h e r e i s
f o r m a t i o n o f c r e s o l s f r o m a n i s o l e . I n o r d e r t o c l a r i f y t h e r e l a t i o n between
a n i s o l e and c r e s o l s i n the r e a c t i o n network, it i s necessary t o have
i n f o r m a t i o n about t h e isomer d i s t r i b u t i o n o f t h e c r e s o l s and t h e r e a c t i v i t y
o f a n i s o l e as s u b s t r a t e .

4. C re s ol isomer s e l e c t i v i t v i n t h e a l k v l a t i o n o f Dhenol w i t h methanol

T a ble 3
Comparison o f t h e d i s t r i b u t i o n o f c r e s o l isomers f r o m phenol a l k y l a t i o n w i t h
!than01
Catalyst Ref. Temp. Conversion C r e sol ortho meta para
selectivity
(KI (%I (%I (%I (%I (%I
H-Y 45 523 46.9 64.2 60.0 22.0 18.0
H-Y 34 473 6.0 29.0 58.6 0.0 41.4
H-USY 51 473 20.2 63.9 38.9 1.3 59.8
H-La-Y 45 523 49.7 46.3 52.0 8.9 39.1
H-K-Y 47 523 32.0 57.5 33.0 6.0 61 .O
H-Na-Y 47 523 66.0 70.2 33.3 9.1 57.6
P-ZSM-5 34 413 6.0 10 .o 65.0 0.0 35.0
P-ZSM-5 53 723 26.6 43.2 60.9 7.0 32.1
H-ZSM-5 46 573 13.5 31.3 68.6 0.0 31.4
H-ZSM-5 51 413 10.2 73.3 65.3 0.0 34.1
H-TsVM 35 573 11.5 30.3 68.9 3.4 27.7
Pd - H -TsVM 15 573 16.7 66.5 62.4 3.3 34.3

As t h e h y d r o x y l group o f phenol i s o / p - d i r e c t i n g , m-cresol, alt hough

be ing t h e most thermodynamically s t a b l e isomer, can o n l y be formed v i a a
secondary 1 , 2 - a l k y l s h i f t . Ta b l e 3 shows t h a t a t l o w and medium conversions
t h e m-c re s ol s e l e c t i v i t y i s v e r y l o w indeed. I t f u r t h e r shows t h a t t h e r e i s
always a h i g h s e l e c t i v i t y f o r o - c r e s o l , w h ich i n most r e p o r t s i s h i g h e r on
p e n t a s i l z e o l i t e s t h a n on z e o l i t e Y. T h i s b e h a v i o u r was unexpected because i n
t h e a l k y l a t i o n o f t o l u e n e w i t h methanol l o w o/p r a t i o s i n t h e x y l e n e f r a c t i o n
a r e i n v a r i a b l y o b t a i n e d on p e n t a s i l z e o l i t e s [78]. Alt hough t h e d i f f e r e n c e i n
k i n e t i c diame t e r between t h e 0 - and p - i s o m e r s i s s m a l l e r f o r c r e s o l s t han f o r
xyle nes , t h i s does n o t i m p l y t h e absence o f s h a p e - s e l e c t i v e f o r m a t i o n o f p -
c r e s o l . As shown i n F i g . 7 f o r t h e i s o m e r i s a t i o n o f m - c r e s o l , z e o l i t e H-ZSM-5
e x h i b i t s a s h a p e - s e l e c t i v e e f f e c t because t h e f o r m a t i o n o f p - c r e s o l i s
fa v oure d o v er t h e o-isomer, d e s p i t e t h e f a c t t h a t t hermodynamically t h e p-
isomer i s about 5 t i m e s l e s s s t a b l e t h a n t h e o-isomer. Moreover, i n t h e
i s o m e r i s a t i o n of o - c r e s o l t o m- and p - c r e s o l [49-501 o v e r H-ZSM-5 a d e f i n i t e
shape s e l e c t i v e f o r m a t i o n of p - c r e s o l i s e ncount ered ( F i g . 8). The enhanced
 171

0 - c r e s o l s e l e c t i v i t y i n t h e a l k y l a t i o n of phenol w i t h methanol must,

t h e r e f o r e , be o f o t h e r t h a n j u s t a s h a p e - s e l e c t i v e o r i g i n . On amorphous
c a t a l y s t s [24-25,43-44,79-811 u s u a l l y no shape s e l e c t i v i t y i s p r e s e n t and o-
c r e s o l s e l e c t i v i t i e s as h i g h as 100% can be obt ained.

loo[ . J 60

40

60 30

40

20
- 10

0
0 10 20 SO 40

Time on stream (h)

F i g . 7. I s o m e r i s a t i o n of m - c r e s o l and t h e p / ( o t p ) - c r e s o l r a t i o a g a i n s t t i m e
on s ream on H-ZSM-5 a t 653 K and 6 MPa. W/Fo values a r e 339 and 113 kg s
mol-' i n p a r t (A) and (B), r e s p e c t i v e l y ( d e r i v e d f rom [SO]). The s o l i d l i n e
r e p r e s e n t s t h e thermodynamic e q u i l i b r i u m .

100 i6 0

80

60

40

20

0
0 10 20 SO 40

Time on stream (h)

F i g . 8. I s o m e r i s a t i o n o f o - c r e s o l and t h e p / ( m t p ) - c r e s o l r a t i o a g a i n s t t ime
on s ream on H-ZSM-5 a t 653 K and 6 MPa. W/Fo v a l u e s a r e 339 and 113 kg s
mol-' i n p a r t (A) and ( B ) , r e s p e c t i v e l y ( d e r i v e d f rom [ 5 0 ] ) . The s o l i d l i n e
r e p r e s e n t s t h e thermodynamic e q u i l i b r i u m .

I n 1i t e r a t u r e t h e r e appear t h r e e hypotheses which can e x p l a i n t h i s h i g h

o r t h o s e l e c t i v i t y , a l t h o u g h o n l y one o f them g i v e s an e x p l a n a t i o n f o r t h e
h i g h e r p ara s e l e c t i v i t y on z e o l i t e Y compared t o p e n t a s i l z e o l i t e s .
172

The first hypothesis was advanced by Tanabe et al. [79-811 based on a

comparison o f the I.R. spectra o f adsorbed phenolic compounds on MgO and
silica-alumina with the catalytic results o f the alkylation of phenol with
methanol. On a basic surface such as MgO, phenol is adsorbed perpendicularly,
its ortho-position being close t o the surface and alkylation occurring
predominantly in this position. On acid catalysts, the B r ~ n s t e d sites will
interact with the aromatic nucleus of the adsorbed phenol thus bringing it
closer t o the surface and permitting alkylation in the para position, in this
way explaining the decreased o-cresol selectivity on silica-alumina.
In a second hypothesis advanced by Beltrame et al. [43-441 for acid
catalysts, strongly adsorbed anisole, eventually formed in the phenol
alkylation, reacts with phenol from the gas phase by an Eley-Rideal
mechanism, enabling the phenol OH group t o interact with the activated '0
center of adsorbed anisole and bringing the ortho position o f phenol closer
and more accessible t o an attack o f the methyl group than the para position.
Such transition state is schematically represented in Fig. 9.

Fig. 9. Possible transition state o f the alkylation o f phenol by anisole.

The basic arguments for this hypothesis are the zero and first order in
anisole and phenol, respectively, observed in the reaction of anisole with
phenol over Y zeolites and gamma-alumina [43-441.
Neither hypothesis, however, can predict the lower o-cresol selectivity
obtained with Y compared t o pentasil zeolites. Jacobs et al. [51] derived
that in the alkylation of phenol with methanol, anisole is an intermediate
for the formation of a major part o f the o-cresol, because:
* in the anisole conversion, o-cresol is a primary product as it is formed
with very high selectivity in the cresol fraction at low conversions [52];
* in the reaction o f anisole with methanol also high o-cresol selectivity is
observed [51] ;
* the initial selectivity for o-cresol on pentasil and USY zeolites is
substantially higher in the alkylation o f anisole with methanol than of
phenol [51];
Given ( i ) the direct formation o f o-cresol from anisole, ( i i ) the higher
selectivity for o-cresol in pentasils compared t o faujasites, and ( i i i ) the
suppression o f the rate of all bimolecular reactions in the reaction network
 173

s t a r t i n g f rom phenol and methanol i n p e n t a s i l s [51], i t i s l o g i c a l t o assume

t h a t t h e t r a n s f o r m a t i o n o f a n i s o l e i n t o o - c r e s o l occurs i n t r a m o l e c u l a r l y [51]
and is f a v our e d in the constrained environment of pentasil zeolites.
Mechanistically this can be viewed as a transformation of an oxygen
p r o t o n a t e d a n i s o l e t o an oxygen p r o t o n a t e d o - c r e s o l ( f i g . 10).

f i g . 10. I n t r a m o l e c u l a r rearrangement o f a n i s o l e t o o - c r e s o l .

A l s o i n homogeneous medium t h e e l e c t r o p h i l i c s u b s t i t u t i o n a t t h e o r t h o
p o s i t i o n s o f phenols " i s r a r e l y found t o be a normal r e a c t i o n " [ 82] and
o rt h o/ p ara r a t i o s much h i g h e r t h a n t h e s t a t i s t i c a l l y 2/1 a r e found.

5. Z e o l i t e s t r u c t u r e and s e l e c t i v i t y i n t h e a l k y l a t i o n of phenol and a n i s o l e

w i t h methanol
5.1. S u m r e s s i o n i n D e n t a s i l z e o l i t e s o f b i m o l e c u l a r r e a c t i o n s
A ma jor i n f l u e n c e o f t h e z e o l i t e s t r u c t u r e on t h e p r o d u c t s e l e c t i v i t y
f rom t h e r e a c t i o n o f methanol w i t h a n i s o l e and/or phenol i s t h e suppression
o f t h e b i m o l e c u l a r r e a c t i o n s i n p e n t a s i l compared t o Y z e o l i t e s [51]. This
can be i l l u s t r a t e d as f o l l o w s :
* Z e o l i t e Y i s more a c t i v e t h a n ZSM-5 i n t h e r e a c t i o n o f phenol w i t h methanol
because a l l primary reactions are o f bimolecular nature, whereas i n t h e
a l k y l a t i o n o f a n i s o l e w i t h methanol t h e o p p o s i t e i s t r u e because some o f t h e
p r i m a r y r e a c t i o n s a r e monomolecular ( F i g . 11).

80

60

40

20

0
0 5 10 15 20 25

Time (h)

F ig. 11. Conversion versus t i m e on stream o f (a) a n i s l e and (b) phenol i n

t h e a l k y l a t i o n w i t h methanol w i t h W/F = 1736 kg s mol-' and 278 kg s mol- ,
r e s p e c t i v e l y , on u l t r a s t a b l e Y and ti-Z!M-5 a t 473 K ( d e r i v e d f rom 1511).
174

* The phenol selectivity in the methylation o f anisole is substantially

higher on pentasil than on Y zeolites, whereas for the methylanisole and
xylenol selectivity the opposite is observed (Fig. 12). T h e dealkylation o f
anisole is o f monomolecular nature, while the alkylation o f both anisole and
cresols to methylanisoles and xylenols, respectively, is bimolecular.

H-USY H-ZSY-5

Fig. 12. Pie-chart representation of the product selectivities in the

a1 kyl ation of anisole wi h methanol on ultrastable Y and H-ZSM-5 at 473 K
with W/Fo= 1736 kg s mol-' (derived from [51]).

* The o-cresol selectivity in the methylation o f phenol and anisole is

highest on pentasil zeolites [51]. This has been explained in a previous
sect ion.
In contrast to what has been claimed recently [48], for all these
reasons it is, therefore, not unexpected t o obtain high o-cresol
selectivities from anisole on pentasil-type zeolites and at intermediate
conversions.

5.2. Para selectivities in the Droduct fractions

An obvious way t o enhance the p-cresol selectivity would be the use of
10-MR zeolites with smaller pore dimensions than those of pentasil zeolites.
However, it was reported that on H-Ferrierite and H-ZSM-22 the anisole
conversion proceeds predominantly on the outer surface of the crystals, thus
forming high amounts of o-cresol [52]. Anisole itself undergoes self-
alkylation with higher para selectivity on ZSM-5 [52-531 than on faujasite-
type zeol i tes [75].
In Table 4 product selectivities for the alkylation o f phenol with
methanol are compared over various zeolitic and amorphous catalysts. For all
zeolites the para selectivity in the methylanisole and cresol fractions as
well as the selectivities of (2,4 t 2,5)-xylenols in the xylenol fraction are
substant i a1 ly higher than the corresponding selectivities obtained on
amorphous catalysts. Moreover, when the data on ZSM-5 and Y zeolites are
 175

compared, for obvious sterical reasons a further enhancement of the

selectivity for p-methylanisole and (2,4 t 2,5)-xylenol is observed for
ZSM-5. Methylanisoles are formed by C-alkylation of anisole [34] or
0-alkylation of cresols [27] or both together [43-45,511.

Table 4
Comparison of the distribution of cresol, methylanisole and xylenol isomers
-~
Catalysts A1203 MgO AlP04 Si1.- H-ZSM-5 H-USY P-ZSM-!
alum.^^-
Reference 39 81 24 55 51 51 53
Temoerature(K1 533 771 523 523 473 473 723
Conversion (%l 65.9 11.2 19.9 30.0 44.0 56.1 26.6

ani sol e 65.8 80.7 0.0 9.3 22.8 44.0

methylanisoles 2.5 5.5 22.7 3.0
cresol s 22.9 92.0 19.3 86.0 82.3 40.7 41.4
xylenol s 8.9 8.0 14.0 2.9 13.8

ortho 100.0 98.1 95.1 70.5 65.3 38.9 60.9

meta 0.9 1.3 7.0
para 1.0 4.9 29.5 34.7 59.8 32.1
Selectivity in the methylanisole fraction (%1
ortho
meta
100.0 53.5a
3.sa
I 28.3 12.5
para 43. Oa 100.0 1 71.7 87.5
Selectivity in the xylenol fraction (%
226
2,4t2,5 100.0

selectivities obtained from reaction of anisole with methanol [53]

6. Overall reaction network

The overall reaction network for the alkylation o f phenol given in Fig.
13 is valid for all catalysts, including zeolites as well as amorphous
solids. Primary products are formed and partially transformed into secondary
ones via either C- or 0-alkylation. On less acidic catalysts 0-alkylation
dominates, but possibly protonated anisole rearranges on the catalyst surface
to o-cresol. This, together with o/p-directing C-alkylation, will result in
ortho selectivities higher than the statistical 2/1 o/p-ratios. In zeolites,
C-alkylation will be more para-selective when the reaction occurs in a more
constrained environment. Parallel to this more o-cresol is formed via
protonated anisole and consequently p-cresol selectivity will never be very
176

high. The formation of the more bulky secondary products is strongly

influenced by the sterical constraints of the environment and therefore,
gives rise to high para-selectivities in zeolites. On amorphous catalysts the
ortho-isomers are formed predominantly.

j 3Hc75
T

Fig. 13. Overall reaction network for the alkylation of phenol with methanol.
Dashed arrows represent direct o-alkylation. Dominant products on amorphous
and zeolite catalysts are surrounded by solid or crenate frames,respectively.

There are two major differences between pentasil and faujasite zeolites
caused by the more constrained environment o f the former zeolites:
Bimolecular reactions as well as diffusion of anisole are suppressed in
 177

p e n t a s i l z e o l i t e s , r e s u l t i n g i n a p r e f e r r e d intramolecular rearrangement o f
ani sol e t o o-cresol .
* For obvious s t e r i c a l reasons, t h e methylation o f the primary products w i l l
be more para selective on pentasil zeolites. This results in higher
s e l e c t i v i t i e s f o r p-methylanisole and 2,4-xylenol.

7. Reaction o f Dhenolic comDounds w i t h bulky a l k v l a t i n s aqents

I n the a l k y l a t i o n o f phenolic compounds w i t h b u l k y a l k y l a t i n g agents
i n v a r i a b l y a bulky t r a n s i t i o n s t a t e i s required. Thus w i t h z e o l i t e s i t w i l l
be p o s s i b l e t o o b t a i n high para s e l e c t i v i t i e s i n t h i s r e a c t i o n . As shown i n
Table 5 f o r ZSM-5 the o / p - r a t i o o f i-propylphenol i s more than 20 times lower
than f o r cresols. I n t h e same way t h e para s e l e c t i v i t y on Y z e o l i t e s
increases i n the f o l l o w i n g order:
t-butylphenol > i-propylphenol > cresol .
The formation o f the more bulky dialkylphenols i s suppressed and o n l y the
l e s s bulky isomer i s obtained, which i n the case o f d i - t - b u t y l p h e n o l i s the
2,4-isomer [67]. For very bulky side chains i t i s even p o s s i b l e t o o b t a i n a
para-enriched a l k y l a t e i n the i n t e r l a m e l l a r space o f a c t i v a t e d clays.

Table 5
o/p-Ratio i n the alkylphenol f r a c t i o n obtained w i t h d i f f e r e n t a l k y l a t i n g
on zeol it e s .
z e o l i t e type a l k y l a t i n g agent a1 k v l Dhenol o/p - r at io reference
H-Y methanol cresol 3.33 45
H-USY methanol cresol 0.65 51
H-Na-Y methanol cresol 0.58 47
P-ZSM-5 methanol cresol 1.86 34
H - ZSM- 5 methanol cresol 1.88 51
Tseokar-2 cumene i-propylphenol 0.4 57
H- ZSM - 5 i-propano1 i-propyl phenol 0.08 23
H - ZSM- 5 propyl ene i-propyl phenol 0.08 23
H-Y t-butanol t - b u t y l phenol 0.2 67
act. clay C - 5 alkenes t-amylphenol 0.2 83

When phenol r e a c t s w i t h 1-octanol on 12-MR z e o l i t e s , o n l y p- and o-

a l k y l a t i o n occurs [84]. As even a t high conversions m-isomers are completely
absent, deviations from thermodynamic e q u i l i b r i u m i n t h e d i s t r i b u t i o n o f the
products w i l l r e f l e c t t r a n s i t i o n s t a t e shape-selective e f f e c t s . For energetic
reasons t h e primary carbenium i o n formed from 1-octanol w i l l isomerise t o t h e
more s t a b l e 2-, 3- and 4 - o c t y l cations. I n the absence o f geometric
c o n s t r a i n t s i t i s n o t expected t h a t l e s s 4-octylphenol will be formed
compared t o the o t h e r isomers. As 4 - o c t y l i s a more b u l k y s u b s t i t u e n t on
phenol than 3 - o c t y l , which i n t u r n i s more bulky than 2 - o c t y l , two kinds of
178

shape-selective e f f e c t s can be expected w i t h t h i s a l k y l a t i n g agent: regio

s e l e c t i v i t y along t h e hydrocarbon chain and p o s i t i o n a l s e l e c t i v i t y on t h e
aromatic nucleus.

Fig. 14. S e l e c t i v i t y and p/(pto) r a t i o f o r t h e d i f f e r e n t octylphenols

obtained i n t h e a l k y l a t i o n o f phenol w i t h 1-octanol on 12-MR z e o l i t e s
(derived from [84]).

As shown i n Fig. 14 p r e f e r e n t i a l para s u b s t i t u t i o n occurs f o r each

octylphenol and a l l 12-MR z e o l i t e s used. For the l e s s b u l k y 2-octylphenol t h e
preference f o r t h e para isomer i s about equal f o r H-RE-Y, H-Mordenite and H-
ZSM-12. For t h e more bulky 3- and 4-octylphenol t h e p/(pto) r a t i o i s about
0.6 on Y z e o l i t e , whereas 100% para s e l e c t i v i t y i n t h e 3-octylphenols and no
4-octylphenol i s observed i n H-ZSM-12 and H-Mordenite. I n z e o l i t e Y equal
amounts o f 2-, 3- and 4-octylphenols are formed and t h e r e f o r e no r e g i o
s e l e c t i v i t y i s observed, whereas on H-ZSM-12 and H-Mordenite no 4-octylphenol
and two times more 2-octylphenol than 3-octylphenol is detected. The
s e l e c t i v i t y d i f f e r e n c e s between H-Mordenite and H-ZSM-12 which apparently are
present should be considered w i t h c a u t i o n as no i n d i c a t i o n o f t h e coke
content o f t h e two samples i s given.
I n any case, i t i s i l l u s t r a t e d t h a t a f t e r proper choice o f a l k y l a t i n g
agent and z e o l i t e s t r u c t u r e , r e g i o as w e l l as p o s i t i o n a l s e l e c t i v i t y can be
influenced by d i f f e r e n c e s i n environmental c o n s t r a i n t s , even among 12-MR
zeol it e s .

ACYLATION OF AROMATICS
The F r i e d e l - C r a f t s a c y l a t i o n o f aromatic hydrocarbons by carboxyl i c
acids o f various chain l e n g t h has been studied by Geneste e t a l . [85-881 on
Y-zeolites, M o n t m o r i l l o n i t e and AlC13. A summary o f t h e p e r t i n e n t r e s u l t s f o r
t h e a c y l a t i o n o f toluene i s shown i n Fig. 15.
On molecular sieves, on clays as w e l l .as w i t h homogeneous c a t a l y s t s ,
para-acylation i s favoured. The data on t h e p a r a - s e l e c t i v i t y do n o t a l l o w one
t o conclude t h a t s i g n i f i c a n t d i f f e r e n c e s e x i s t between AlC13 and A13+-
Montmorillonite. However, a much stronger preference f o r p - a l k y l a r y l ketones
 179

on Ce-Y i s observed. As expected f r o m a l k y l a t i o n r e a c t i o n s on z e o l i t e s t h e

s e l e c t i v i t y o f t h e p a r a isomer i n c r e a s e s w i t h t h e c h a i n l e n g t h t o v e r y h i g h
v a lues , even t o 100% f o r behenic a c i d (n=20).

n
F i g . 15. P a r a - s e l e c t i v i t y and y i e l d o f t h e a c y l a t e d p r o d u c t s i n t h e r e a c t i o n
o f c a r b o x y l i c a c i d s (CH3-(CH2),-COOH) w i t h t o l u e n e ( d e r i v e d f rom [85-871).

F i g . 15 shows a second s t r i k i n g d i f f e r e n c e between z e o l i t e s , c l a y s and

homogeneous c a t a l y s t s . I n homogeneous a c y l a t i o n t h e y i e l d i s o n l y s l i g h t l y
dependent on t h e c h a i n l e n g t h o f t h e c a r b o x y l i c a c i d [85-671. On t h e o t h e r
hand, on c l a y s as w e l l as on Y z e o l i t e s a s t r o n g dependence on c h a i n l e n g t h
is observed. With acetic acid no acylation occurs [85-871. On A13+-
M o n t m o r i l l o n i t e t h e y i e l d i n c r e a s e s w i t h c h a i n l e n g t h , whereas on CeY t h e r e
i s a maximum y i e l d f o r dodecanoic a c i d . The decrease o f t h e y i e l d f o r l o n g e r
c h a i n s can be due t o d i f f u s i o n a l l i m i t a t i o n s on z e o l i t e Y, a l t h o u g h according
t o Geneste e t a l . [85] l a r g e c a r b o x y l i c a c i d s would n o t be a b l e t o p e n e t r a t e
t h e c a v i t i e s o f z e o l i t e Y . It i s n o t c l e a r why t h e y i e l d i n c r e a s e s w i t h c h a i n
l e n g t h because such phenomenon i s n o t encountered i n homogeneous F r i e d e l -
Crafts catalysis.

SHAPE SELECTIVITY I N THE FORMATION OF ACETOPHENONES

1. F r i e s rearranqement o f Dhenvl a c e t a t e

Table 6
ries rearr
catalyst Conversion S e l e c t i v i t y of t h e o:p-ratio o f
(molX) F r i e s rearrangement ( X ) hydroxyacetophenones
H -Y 4.5 75 12.6: 1.O
A1203-F 6.6 58 13.6: 1.8
H - ZSM- 5 4.2 20 1.8: 1.5
180

Perot et al. [89] studied the transformation o f phenyl acetate into

hydroxyacetophenones. The inter- and intramolecular Fries rearrangement is
shown in Fig. 16.

*\ ,c=o
+ ___)

Chc=, cf;3 -7
Fig. 16. Inter- (A) and intramolecular ( 6 ) Fries rearrangement o f phenyl
acetate.

As shown in Table 6 and for obvious steric reasons the selectivity for
the Fries rearrangement is higher on Y than on ZSM-5 zeolite. The increase o f
the o:p-ratio o f the hydroxyacetophenones in Y compared to alumina can be
explained by a suppression o f the bimolecular reactions in the zeolite.
However, on H-ZSM-5 the rate o f the bimolecular Fries reaction remains low
and the strongly decreased o:p-ratio is exclusively the result of the low
rate o f formation of the o-isomer. On the contrary, in the rearrangement o f
anisole where a methyl group is involved which is less bulky than an acetyl
substituent, the bimolecular reactions are suppressed in pentasil zeolites.

2. Acetoalkoxvlation of phenol.
Ortho- (I) and para-methoxyacetophenones (11) in a ratio of 1 t o 10 are
formed as acetoal koxylation products of phenol with 1,l'-dimethoxyethane
( 1 1 1 ) on H-ZSM-5 [ g o ] . This ratio is considerably lower than that obtained
for the hydroxyacetophenones on the same zeolite (Table 6) and must be the
result o f geometric constraints of the intracrystall ine pore volume.

I I11
 181

ZEOLITES AS ENZYME M I M I C S
Two d i f f e r e n t approaches a r e r e p o r t e d i n t h e l i t e r a t u r e on t h e use o f
z e o l i t e s as mimics f o r enzymes i n o x y g e n a tion r e a c t i o n s . The p r e p a r a t i o n and
c a t a l y t i c use o f m e t a l l o p h t a l l o c y a n i n e (MPc) complexes encaged i n f a u j a s i t e
supercages has been reviewed [91-961. Fenton's r e a c t a n t was het erogenised i n
z e o l i t e s A, X and Y i n an a t t e m p t t o mimic cytochrome P450 [97-981.

1. Encaqed D h t a l l o c v a n i n e s
Among o t h e r s [94,95], an i m p o r t a n t advantage t h a t z e o l i t e s o f f e r over
amorphous s upp o r t s and homogeneous c a t a l y s t s i s shape s e l e c t i v i t y . Indeed,
w i t h FePc imm o b i l i s e d i n z e o l i t e Y a pronounced r e a c t a n t shape s e l e c t i v e
e f f e c t was r e p o r t e d i n a c o m p e t i t i v e o x i d a t i o n experiment w i t h cyclododecane
and cyclohexane as s u b s t r a t e [97,98]. With homogeneous FePc as c a t a l y s t b o t h
r e a c t a n t s a r e o x i d i s e d e q u a l l y w e l l . However, w i t h sodium exchanged X o r Y
z e o l i t e c o n t a i n i n g encaged FePc, the r a t e o f oxidation o f the less bulky
cyclohexane i s i n c r e a s e d by a f a c t o r o f about 2 [97]. T h i s shape s e l e c t i v e
e f f e c t can be f u r t h e r i n c r e a s e d by exchange o f c a t i o n s w i t h proper
dimensions. As shown i n F i g . 17 when t h e s i z e o f t h e c a t i o n increases from
Lit to Rb' the ratio of the rates of oxidition of cyclododecane to
cyclohexane decreases f r o m 1.4 t o 0.14. Thus t h e s i z e o f t h e supercage
c a t i o n s i s a v e r y s e n s i t i v e paramater t o t a i l o r s u b s t r a t e s e l e c t i v i t y .

u
I
a
X
0
c
-0
1.00
*
0
\
0
c
(D
0
0
'0 0.50
0

-ur
P
0

0 A

0.05 0.10 0.15 0.20

ionic radius (nm)

F i g . 17. Dependence o f s u b s t r a t e s e l e c t i v i t y i n t h e simult aneous o x i d a t i o n of

cyclododecane and cyclohexane on t h e s i z e o f a l k a l i c a t i o n s exchanged i n
z e o l i t e X lo ade d w i t h FePc ( d e r i v e d from [ 9 8 ] ) .

I n t h e o x i d a t i o n o f n-octane, r e g i o s e l e c t i v i t y i s e x e r t e d by FePc
immobilis ed i n f a u j a s i t e z e o l i t e s . I n F i g . 17 i t i s shown t h a t w i t h encaged
FePc t h e o x i d a t i o n a t p o s i t i o n 2 i s p r e f e r r e d over t h a t a t p o s i t i o n 4. T h i s
182

i s e x p l a i n e d b y t h e e x i s t e n c e o f an o r i e n t i n g i n f l u e n c e o f t h e z e o l i t e
framework on t h e s u b s t r a t e , so t h a t t h e more t e r m i n a l carbon atoms a r e more
a c c e s s i b l e for t h e a c t i v e i r o n - o x o a c t i v e c e n t e r [97].

F i g . 18. R a t i o o f o c t a n e o x i d a t i o n i n p o s i t i o n 2 t o p o s i t i o n 4 w i t h
homogeneous FePc and FePc encaged i n z e o l i t e s X and Y, c o n t a i n i n g 1 and 2 Fe
atoms p e r supercage, r e s p e c t i v e l y ( d e r i v e d f rom [ 9 7 ] ) .

S t e r e o s e l e c t i v e o x i d a t i o n w i t h FePc i n z e o l i t e Y has been r e p o r t e d by

Herron e t a l . [97,98] and i s i l l u s t r a t e d i n Table 7 . T h i s i s anot her example
o f s t e r e o s e l e c t i v i t y imposed by t h e z e o l i t e o r o f an o r i e n t i n g i n f l u e n c e o f
t h e z e o l i t e framework on t h e s u b s t r a t e r e s u l t i n g i n a d i f f e r e n t p r e f e r e n c e
f o r o x i d a t i o n a t one o f t h e two d i a s t e r e o t o p i c hydrogen atoms.

Table 7
'om [ 97] )
substrate product r a t i o FePc-Y FePc
methyl c y c l ohexane trans:cis ( I ) -alcohol 2 1.1
norbornane exo ( I I I ) :endo (11) norborneol 6 9
I
 183

2 . Completely i n o r q a n i c mimic o f enzymes

A c omp let e l y i n o r g a n i c mimic o f cytochrome P450 has been developed by
H erron and Tolman [99-lOO]. The mimic p r o v i d e s remarkable r e g i o s e l e c t i v i t y
in the partial oxidation of octane and substrate selectivity i n the
c o m p e t i t i v e o x i d a t i o n o f octane and cyclohexane i n Fe-exchanged z e o l i t e 5A
under m i l d c o n d i t i o n s ( Fi g . 19). However, t h e o x i d a t i o n p r o d u c t s a r e s t r o n g l y
adsorbed in the intracrystalline volume of the zeolite. With several
treat ment s , t he s e a u t h o r s a r e a b l e t o desorb p a r t l y o r even c o m p l e t e l y t h e
o x i d i s e d pro duc t s : w a t e r a d d i t i o n , a c i d d i s s o l u t i o n o f t h e z e o l i t e , p o i s o n i n g
w i t h 2,2’-bipyridine o f t h e acid z e o l i t i c residues a f t e r a c i d d i s s o l u t i o n
( F i g . 19). The r a t i o o f t h e o x i d a t i o n p r o d u c t s f rom oct ane and cyclohexane
in c reas es f rom about 1 on s i l i c a - a l u m i n a t o 190 on z e o l i t e 5A. On Fe-A
z e o l i t e a t e n - f o l d i n c r e a s e o f t h e o x i d a t i o n o f t h e p r i m a r y compared t o t h e
secondary carbon atoms o f o c t a n e i s observed w i t h r e s p e c t t o F e - s i l i c a -
alumina ( F i g . 19).

1.00 )J
C
0 Addition of I
/
I

X
0

10 C
4: meld + blpyrldlnr (A
X
0
c
- 0
V
9.
1 V
%
Q
C
C
a
V
0
0.1

catalysts
F i g . 19. S e l e c t i v i t i e s i n t h e o x i d a t i o n a t p r i m a r y t o secondary carbon o f
oc t a ne as w e l l as i n t h e c o m p e t i t i v e o x i d a t i o n of oct ane w i t h cyclohexane on
(1) F e - s i l i c a - a l u m i n a , (2) Fe-5A a f t e r w a t e r a d d i t i o n , (3) Fe-5A a f t e r a c i d
d i s s o l u t i o n and (4) Fe-5A a f t e r a c i d d i s s o l u t i o n and a d d i t i o n o f 2 , 2 ’ -
b i p y r i d i n e as p o i s o n ( d e r i v e d f r o m [99,100]).

Furthermore, i t i s c l e a r f r o m F i g . 20 t h a t a l l r a t i o s o f 1- t o x - o c t a n o l
(- o n) a r e about 0.04 f o r t h e amorphous c a t a l y s t , whereas on z e o l i t e A t h i s
r a t i o inc re as es s t r o n g l y f o r l a r g e r v a l u e s o f x, when t h e o x i d i s e d carbon i s
l o c a t e d more towards t h e c e n t e r on t h e hydrocarbon c h a i n . The same remains
t r u e i r r e s p e c t i v e o f t h e c h a i n l e n g t h o f t h e alkane s u b s t r a t e ( F i g . 20).
Moreover, the relative reactivity at the terminal C-atoms increases
s i g n i f i c a n t l y w i t h t h e c h a i n l e n g t h o f t h e n-alkane. T h i s again i s an example
184

o f a s p e c i f i c zeolite-induced r e g i o - s e l e c t i v e o x i d a t i o n . I n a competitive
o x i d a t i o n experiment o f 2-methylpentane and n-pentane on z e o l i t e 5A, the
latter substrate is oxidised 200 times faster, indicating that also
s e l e c t i v i t y among alkane substrates e x i s t s .

1.20 I J 1.20

1.00 -

0.80 - 0.80
-.. -
I-
0.60 0.60
9
0.40 ~

0.40

0.20 - 0.20

0.00 - 0.00
2 4 5

position of oxidissd C atom

Fig. 20. Regio-selective o x i d a t i o n o f alkanes on Fe-A z e o l i t e : T : I . , r a t i o o f

terminal t o i n t e r n a l C atoms oxidised; N.R., normalised r a t i o o f terminal t o
i n t e r n a l C atoms ( = carbon number/2 - 1) (derived from [99,100]).

SELECTIVE OXIDATION OF HYDROXYARENES

D i r e c t o x i d a t i o n o f aromatic compounds f o r t h e synthesis o f phenol,
cresol s, hydroquinone and resorcinol is of considerable industrial
importance. The i n t r o d u c t i o n o f shape s e l e c t i v e z e o l i t e c a t a l y s t s i n t h i s
area r e c e n t l y proved t o be very successful. Indeed, a non-acidic t i t a n i u m -
s i l i c a l i t e , denoted as TS-1, catalyses the H202 o x i d a t i o n o f aromatics and
o t h e r organic substrates [101-1101. TS-1 has already found an i n d u s t r i a l
a p p l i c a t i o n i n t h e production o f hydroquinone and catechol from phenol [102].

1-b
+ Fe2+
0-H* Fenton's reagent
/ +H+ +
H202 H-O-9-H peroxonium i o n
H
M
,, or MOOH transition metal peroxo complexes
M

F i g . 21. Schematic representation o f t h e mechanisms f o r h y d r o x y l a t i o n o f

arenes w i t h H202.

Hydroxylation w i t h H202 can occur v i a t h r e e d i f f e r e n t mechanisms which

are shown i n Fig. 21. Surface t i t a n i u m peroxo compounds are proposed t o be
 185

t h e actual oxidants i n TS-1 c a t a l y s e d oxidations [102]. It i s f u r t h e r

s pec ulat e d t h a t t h e t i t a n i u m atoms have a reduced r a t e f o r H202 decomposition
due t o t h e i r p e r f e c t i s o l a t i o n from each o t h e r . A Fenton's reagent made o f
Fe2+ and Co2+ i s used i n t h e B r i c h i m a process f o r t h e h y d r o x y l a t i o n o f phenol
[112]. The RhBne-Poulenc process u s i n g s t r o n g m i n e r a l a c i d s such as HC104 and
H3P04 [113], and t h e h y d r o x y l a t i o n on HZSM-5 [lll], proceed v i a t h e f o r m a t i o n
o f a peroxonium i o n .

1.00 -

0
rn 18-1 (1021
0 Fe2+. C 0 2 + [1121
E
0 0.80 - Fa-Y [991
N
E H3C104, H3P04 11 131
0
P
*
x 0.60 -
RE-Y [I101

e H-ZSM-6 11111
U
* 0.40 -
c
U
A

+n
0 -
Y
0.20
\
n

0.00 -
1 2 5 4 5 6

catalysts

F i g . 22. p - S e l e c t i v i t y i n t h e h y d r o x y l a t i o n o f phenol w i t h H202.

The p - s e l e c t i v i t i e s o f processes u s i n g H202 f o r t h e h y d r o x y l a t i o n o f

phenol a r e compared i n F i g . 22. I t i s r e a d i l y seen t h a t p - s e l e c t i v i t i e s o f
50% and h i g h e r can be o b t a i n e d u s i n g TS-1 z e o l i t e s . Furthermore, unwanted
side reactions, such as t h e f o r m a t i o n o f p o l y n u c l e a r aromat ic compounds, are
l i m i t e d . The h y d r o x y l a t i o n o f phenol w i t h H202 was a l s o performed on a c i d
z e o l i t e c a t a l y s t s . I n t h e presence o f a f a u j a s i t e , phenol i s c o n v e r t e d t o a
m i x t u r e o f hydroxybenzenes and t a r s [110], w i t h a p - s e l e c t i v i t y comparable t o
t h a t o b t a i n e d on TS-1 ( Fi g . 22). When t h e r e a c t i o n i s c a r r i e d o u t on Fe-Y, a
heterogeneous analog o f Fenton's reagent, a l s o good s e l e c t i v i t y i s obt ained
[98]. On H-ZSM-5 almost 100% p - s e l e c t i v i t y i n t h e dihydroxybenzenes was
r e p o r t e d w i t h H202 [lll].
No t a r f o r m a t i o n was mentioned.
Thus i t seems t h a t i n t h e h y d r o x y l a t i o n o f phenol, t h e r e a c t i o n
mechanism as w e l l as t h e p o r e a r c h i t e c t u r e a r e s e l e c t i v i t y - d e t e r m i n i n g
parameters. Therefore, the reaction seems to be anot her example of
t r a n s i t i o n - s t a t e shape s e l e c t i v i t y .
O x i d a t i o n o f 2,6-dimethylphenol by t - b u t y l h y d r o p e r o x i d e v i a a r a d i c a l
o x i d a t i o n - r e d u c t i o n mechanism occurs i n a s e l e c t i v e way on COX z e o l i t e , i t s
poly me ri s a t i o n r e a c t i o n i n t o p o l y (2,6-dimethy1-1,4-phenylene ether) ( I 11)
186

being suppressed and its dimerisation into 3,3’,5,5’-tetramethy1-4,4’-

diphenoquinone (11) being reduced compared t o amorphous supports [114]. The
resultant selectivity for 2,6-dimethyl -p-benzoquinone (I) is high but
dependent on the partial pressure of the peroxide.

ZEOLITES AS CHIRAL HYDROGENATION CATALYSTS

Heterogeneous hydrogenation catalysts that produce optically active
products contain always an active center next t o an optically active ligand
molecule [115]. Dessau reported on the arrangement o f both components in the
pores o f ZSM-5 [116]. First a Pt-loaded H-ZSM-5 was prepared and subsequently
the chiral template was fixed in the zeolite pores by adsorption of optically
active S-( -)-alpha-methylbenzylamine and anchored as the corresponding
alkylammonium ion in the pores after its protonation via surface O H groups.
Acetophenone can be hydrogenated into optically active 1-phenylethanol . The
tailored active site and the hydrogenation reaction are represented in Fig.
23.

El
.......................

H4!-CH3
+NH3
-
//////Al///////////////

Fig. 23. Schematic representation o f the active entities in a ZSM-5 chiral

catalyst (A) and hydrogenation o f acetophenone (B) [derived from [116]).

SELECTIVE DIELS-ALDER CYCLOADDITIONS

Diels-Alder addition of 0-containing double bond compounds (dienophiles)
t o 1,4 conjugated dienes has received considerable attention on clays and
occasionally also on zeolites [117-1191. In general, with both types o f
catalysts cycloaddition rates are very much enhanced with dienophiles that
 187

o t h e r w i s e r e a c t s l u g g i s h l y i n homogeneous phase and r e q u i r e e x t r e m e l y h i g h

r e a c t i o n pre s s u r e s (up t o 1,500 MPa). Enhanced r e g i o s e l e c t i v i t i e s a r e
r e p o r t e d as w e l l . A t y p i c a l example i s t h e a d d i t i o n o f m e t h y l v i n y l k e t o n e t o
c y c lopent a diene [ 118,1191 :

END0 EX0

Re ac t io n selectivities obtained in homogeneous phase [120], with

Fe(II1)- M o n t m o r i l l o n i t e and Cu(1)-Y z e o l i t e a r e compared i n F i g . 24. I n
homogeneous phase ENDO-addition is f a voured with cyclic dienes for
stereochemical reasons [121]. I n t h e i n t e r l a m e l l a r space o f t h e c l a y and much
more i n t h e supercage o f z e o l i t e Y, t h e r e l a t i v e r a t e o f ENDO-addition i s
further enhanced. Mechanistically, a one-electron transfer f rom the
d i e n o p h i l e t o t h e t r a n s i t i o n metal seems t o be i n v o l v e d , f o l l o w e d by i t s
reaction w i t h t h e d i e n e and r e t u r n o f t h e e l e c t r o n t o t h e r a d i c a l . The
B r ~ n s t e ds i t e s p r e s e n t on t h e c a t a l y s t s seem t o p r o t o n a t e t h e more p o l a r C=O
i n t h e d i e n o p h i l e r a t h e r t h a n t h e d o u b l e bond o f t h e diene, t h u s keeping t h e
d i e n o p h i l e more s t r o n g l y i n t h e c o o r d i n a t i o n sphere o f t h e t r a n s i t i o n metal
[118], and hence a v o i d i n g i t s secondary i n t e r m o l e c u l a r r e a c t i o n s .

Fa-Yontmorillonite

1 2

catalysts

F ig. 2 4 . R a t i o o f t h e END0:EXO c y c l o a d d i t i o n o f m e t h y l v i n y l k e t o n e t o
c y c lo pent a diene i n homogeneous medium [120], F e - M o n t m o r i l l o n i t e c l a y [118]
and Cu(1)-Y z e o l i t e [117].
188

MISCELLANEOUS SHAPE-SELECTIVE EFFECTS

O t h er i n d u s t r i a l l y r e l e v a n t s h a p e - s e l e c t i v e e f f e c t s o f z e o l i t e s have
been r e p o r t e d as w e l l :
* The s h a p e - s e l e c t i v e a c i d - c a t a l y s e d PRINS r e a c t i o n between formaldehyde and
is o but e ne, f o r s t e r i c a l reasons, drastically restricts the formation o f
4,4’-dimethyl-1,3-dioxane ( I ) i n f a v o u r o f m e t h y l b u t e n o l s (11), and
m e t h y l b u t a n e d i o l s (111) a r e condensed i n p e n t a s i l compared t o Y z e o l i t e s and
m i n e r a l a c i d s [122,123].

* On z e o l i t e s c o n t a i n i n g t h e E r i o n i t e cage, a CAGE EFFECT has been r e p o r t e d

i n t h e a c i d - c a t a l y s e d c o n d e n s a t i o n o f b u t y r i c a c i d i n t o 4-heptanone [124].
Only zeolites with this structural element limit the reaction to
dimerisation, p r o v i d e d t h e p r o d u c t formed c o n t a i n s 7 o r 8 C atoms. I n a l l
o t h e r cases a c i d - c a t a l y s e d a l d o l c o n d e n s a t ion o f t h e ketones o b t a i n e d occurs
in an uncontrolled way, resulting in rapid and complete catalyst
deactivation.
* S h ape-s e lec t ive base c a t a l y s i s was r e p o r t e d f o r t h e a l d o l condensat ion o f
aceton c a t a l y s e d by sodium metal clusters encaged i n t h e supercages o f
z e o l i t e Y and t h e p o r e s o f z e o l i t e L [125]. On t h e l a t t e r z e o l i t e l e s s o f t h e
b u l k i e r c y c l i c t r i c o n d e n s a t e ( i s o p h o r o n e ) i s formed, r e s u l t i n g i n an enhanced
s e l e c t i v i t y f o r t h e d i -condensate ( m e s i t y l o x i d e ) .

CONCLUSIONS
From t h e s h a p e - s e l e c t i v e e f f e c t s mentioned i n t h e l i t e r a t u r e t o occur
m a i n l y w i t h medium-pore z e o l i t e s [124] which were d e r i v e d f o r a c i d - c a t a l y s e d
hydrocarbon t r a n s f o r m a t i o n s , r e s t r i c t e d t r a n s i t i o n - s t a t e s e l e c t i v i t y seems t o
be t h e dominant e f f e c t when t h e c o n v e r s i o n o f o x y g e n - c o n t a i n i n g s u b s t r a t e s i s
concerned. With b u l k y s u b s t r a t e molecules t h e e f f e c t s e x i s t w i t h l a r g e - p o r e
z e o l i t e s as w e l l ; and t h e y a r e a l s o n o t l i m i t e d t o a c i d - c a t a l y s e d r e a c t i o n s
b u t o c c u r w i t h redox and b a s i c c a t a l y s i s as w e l l . From t h e p o i n t o f view o f
o r g a n i c c hemis t r y , t h e z e o l i t e , i n F r i e d e l - C r a f t s a1 k y l a t i o n s and a c y l a t i o n s
o f aro ma t ic s , i s a b l e t o change t h e normal o r t h o : p a r a s e l e c t i v i t y b u t can
enhance t h e y i e l d o f meta-products o n l y by secondary a c i d - c a t a l y s i s . New
s h a p e - s e l e c t i v e e f f e c t s such as r e g i o and even s t e r e o s e l e c t i v i t y e x i s t ,
which d o n o t oc c u r w i t h t h e usual hydrocarbon s u b s t r a t e s .
 189

I t i s f u r t h e r shown t h a t i n t h e case o f phenol m e t h y l a t i o n s , t h e

r e a c t i o n network i s e n t i r e l y determined b y t h e a v a i l a b l e i n t r a c r y s t a l l i n e
space. Z e o l i t e s seem t o be a b l e t o s e rve as mimics f o r enzymes, when
m e t a l l o p h t a l l o c y a n i n e s a r e encaged i n t h e cages o f f a u j a s i t e , and even a
ze ol i t e - b a s e d c o m p l e t e l y i n o r g a n i c mimic o f cytochrome P540 e x i s t s .

ACKNOWLEDGMENTS
The aut h ors acknowledge t h e B e l g i a n Government f o r support o f t h i s work i n
t h e frame o f a Concerted A c t i o n on C a t a l y s i s . One o f us, PAJ, acknowledges
t h e B e l g i a n N a t i o n a l Fund o f S c i e n t i f i c Research (NFSR) f o r a p o s i t i o n as
Research D i r e c t o r . DRH i s g r a t e f u l t o NFSR f o r a g r a n t as Research A s s i s t a n t .

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H.G. Karge, J. Weitkamp (Editors), Zeolites (IS Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THE USE OF ZEOLITE CATALYSTS FOR THE SYNTHESIS OF NITROGEN-CONTAINING ORGANIC

INTERMEDIATES

W. HOELDERICH
F.
BASF Aktiengesel lschaft, Amnoniaklaboratorium, D-6700 Ludwigshafen, FRG

ABSTRACT
Nitrogen-containing intermediates and fine chemicals play an important role
in the chemical industry, e. g. in the synthesis of active substances and the
production of dyestuffs as well as solvents. Thus, attempts are continually
being made to synthesize new nitrogen-containing compounds and to devise
improved routes to known products. In this connection zeolites with their
numerous adjustable catalytic properties can be an useful instrument. This
article describes in particular the preparation of cyclic and heteroaromatic
compounds as well as reactions (e. g. alkylation, isomerization and rearrange-
ment) of these compounds in the presence of zeolite catalysts.

INTRODUCTION
New and wide-ranging possibilities for using zeolites in catalytic processes
are being discovered all the time. Zeolitic catalysts find a broad spectrum o f
applications, including acid, non-acid and base-catalysed organic reactions
leading to intermediates (ref. 1 - 10). The reasons for the rapid expansion of
this field include the easily reproducible production of well defined zeolite
surfaces, the considerable advances made in the synthesis o f new zeolitic and
nonzeolitic molecular sieves and of isomorphously substituted materials, the
high activity, the transition-state and product-diffusion shape selectivity of
zeolites, the possibilities of varying and regulating the properties of zeolitic
catalysts - including bi- and polyfunctional catalysts - , and last but not
least, the better understanding of the nature of the active sites o f such
materials.
Of all the numerous types of zeolite-catalysed reactions, the topic which has
been chosen for this presentation is the synthesis o f nitrogen-containing
organic compounds, in particular cyclic and heteroaromatic intermediates. On the
basis o f examples taken from reviews of academic studies and from the patent
1 iterature an attempt wi 1 1 be made to examine to what extent zeol it ic catalysts
are superior to conventional catalysts, and to which extent the acidity and
structural features of such catalysts determine the reaction path. Furthermore,
attention will also be directed to the question as t o whether the principles
derived for reactions of hydrocarbons on zeolites can also be applied to the
reactions of N-containing compounds.
194

NUCLEOPHILIC SUBSTITUTION OF ALCOHOLS WITH AMMONIA

Methylamines, which are of considerable technical importance, can be produced
from methanol and ammonia by means of nucleophilic substitution. The aim is in
most cases to achieve a reaction product having a composition differing from the
equilibrium distribution and containing as high a proportion as possible of
mono- or dimethylamine (MMA or DMA). Different zeolites have been used to meet
this challenge (e. g. ref. 4). The elimination of me3N is related to the pore
size of the zeolite. R. D. Shannon and coworkers recently discovered that the
small-pore zeolites HRHO, HZK-5 and chabazite show higher DMA selectivities than
other zeolites (refs. 1 1 , 12). At 325 "C and WHSV = 2 hr-' up to 63 % selec-
tivity of DMA at 90 % methanol conversion can be obtained. In comparison, the
thermodynamic equilibrium predicts only 21 % DMA. H-mordenite apparently has a
pore size that allows the formation and movement of the mono- and disubstituted
amines, but not the triamine (refs. 13, 20). The Y-zeolite has pores large
enough to allow the formation of me3N. Nevertheless, it is not yet possible to
control the reaction to give only one of the methylamines, but the composition
of the product mixture can be controlled better than in the classical reaction
on A1203 (e. g. refs. 14, 15).
The production of 2 - 8 C containing amines by vapour-phase catalytic
amination of alcohols or ethers occurs only at low conversion (e. g. ref. 16).
EtNH2 is formed at 550 "C and 18 bar with a selectivity of 85 % at 6 % con-
version. At higher conversion, i. e. at higher temperature, the formation of
ethene and other hydrocarbons reduces the selectivity for the amine.
The amination of alcohols on zeolite catalysts is not restricted to simple
molecules. It has been shown, for instance, that nucleophilic substitution of
the OH-group in ethanolamine with NH3 yields ethylenediamine (ref. 17). The
reaction involves the utilization o f a dealuminated (HC1-treated Si:Al = 7.2)
rare earth or hydrogen ion-exchanged mordenite as the catalyst. With ethanol-
amine and ammonia in a molar ratio of 1 : 4 as feed and at 300 "C and 4860 psig
ethylenediamine is obtained with 84 % selectivity at 15 % conversion. As by-pro-
duct aminoethylethanolamine was formed exclusively with 16 % selectivity. This
behavior contrasts with that of many conventional hydrogenation catalysts such
as Co, Ni, Cu/Cr, P t on supports where selectivity to ethylenediamine is sacri-
ficed in favor of conversion.
Analogous to cyclic ethers, cyclic or bicyclic amines can be prepared from
corresponding educts by elimination of H20 or NH3. Thus, 1,4 diazabicyclo-
,l2,2,2 1 octane (DABCD) has been prepared, e. g. from N-hydroxy- or N-amino-
ethylpiperazine, by intramolecular nucleophilic substitution. The industrially
used catalysts for that reaction are silica, alumina or tungsten catalysts.
Because of the severe reaction conditions (T 3 400 " C ) , the said catalysts
promote cracking and condensation reactions of the reactants and the desired
 195

DABCO, resulting in small yields. Because of the wide variety of undesired

products like piperazines, N-alkylpiperazines and pyrazine derivatives, expen-
sive purification of DABCO via distillation or fractional crystallization is
required.
Therefore it is desirable to find a more selective catalyst. It has been
reported (ref. 18) that high-silica zeolites having preferably silica-to-alumina
ratios in the range of 35 to 55, such as ZSM-5, ZSM-11, ZSM-12 or ultrastabi-
lized Y-zeolite, provide increased selectivities when the reaction is carried
out between approx. 250 "C and 550 OC and at pressure between 0.5 to 2 atm in
the vapor phase and contact times between ca. 0.2 and 3 sec. At 400 O C 10 %
conversion and 87 % selectivity are achieved using HZSM-5. Under the same
reaction conditions using a conventional alumina catalyst only 47 % selectivity
but a much higher conversion rate of about 96 % are obtained. The only advantage
of the silica-rich zeolite is the reduction in the amount of difficultly
separable by-products, because in this case, the only by-product is piperazine.
Increasing the conversion rate from 10 to 21 % leads to the formation of not
only piperazine (10 % ) but also other by-products ( 3 %). The selectivity for
DABCO still remains at 87 %.
It is also possible to use ethanolamine as starting material for the prepara-
tion of DABCO (ref. 19). At 400 OC and SV = 10 hr-', 64 % yield of DABCO is
attained using ZSM-5. This method provides an alternative to the aforementioned
route.
The synthesis of anilines is of industrial interest. The preparation by
reaction of alicycl ic alcohols like cyclohexanol, or ketones like cyclohexanone
with ammonia is carried out in the presence of a crystalline silicate catalyst
having the structure of ZSM-5 which contains a metal promotor having dehydro-
genation activity (ref. 20). Using NiHZSM-5 at 480 OC and 200 psig only 16.2 %
aniline selectivity is observed. Higher heterocyclic compounds such as diphenyl-
amine and carbazole are preferentially formed.
Since amination and simultaneous dehydrogenation proceed with only moderate
yield, it is preferable to choose phenol as starting material for the synthesis
of aniline. In the presence of HZSM-5 in an autoclave at 510 OC and 28 atm a
phenol conversion o f 92 % and an aniline selectivity of 99 % (ref. 21) are
achieved. The reaction is also catalysed by Y-, X- and mordenite zeolites, but
these catalysts display a markedly shorter lifetime than HZSM-5, and in the case
of X - and Y-zeolites the conversion is lower (refs. 21 - 23). By-products such
as diphenylamine and carbazole, which are obtained in the presence of non-
zeolitic alumina-si1 ica according to the Halcon-Scientific Design process are
suppressed or eliminated by virtue of the shape selectivity of the ZSM-5 cata-
lyst.
Amonolysis of anisole on zeolites of the faujasite type yields aniline. The
196

conversion is approx. twice as high (60 % at ca. 400 "C) as in the case of
phenol. The lifetime of these catalysts is also short (refs. 22, 23). Sur-
prisingly, however, the ammonolysis of anisole in the presence of HZSM-5 at 400
"C leads exclusively t o phenol. The conversion is 95 % (ref. 22). Although the
authors point to the markedly higher conversion of anisole (95 % ) compared with
phenol (35 % ) , they do not comment on the unexpected formation of phenol instead
of aniline.
The reaction of chlorobenzene and ammonia to aniline in the presence of
zeolite catalysts leads to low conversion rates and short service time because
of the formation and deposition of nonvolatile aniline hydrochloride on the
catalyst (ref. 22).
On the basis of the foregoing results the only suitable route for the
synthesis of aniline is the nucleophilic substitution of phenol with ammonia in
the presence of HZSM-5. Substitution of conventional heterogeneous catalysts
such as non-zeolitic alumina-silica, mixtures of manganese and boron oxides and
alumina-titania by shape-selective ZSM-5 catalysts yields advantages with regard
to aniline selectivity. In comparison to the homogeneous, Lewis-acid-catalysed
Halcon Process (ref. 241, the use of pentasil zeolites opens up an environ-
mentally and energetically more favourable route such as is the case in the
Mobil Badger Process (refs. 25, 26).
Condensation reactions, in particular of the intramolecular type, are known
(refs. 27 - 30) for the preparation of nitriles by means of zeolite catalysts.
They can be prepared from amides or from formaldehyde/alcohols in the presence
of amines (refs. 27, 28). The preparation of aliphatic dinitriles, such as
adipodinitrile, from dicarboxylic acids and ammonia is carried out in the gas
phase, for example, on a boron zeolite doped with Na and P (ref. 29). As shown
by comparison with a catalyst based on Si02, the content of cyclic by-products
is reduced, resulting in an increased selectivity for adipodinitrile - from 83 %
to 94 %. The transition-state shape-selectivity of the zeolite, which does not
permit the cyclization reaction, is evidently responsible for this.
Even HCN as an inorganic compound i s manufactured by reaction of CO with NH3
in the presence of HZSM-5 as catalyst, whereby the water-gas-shift reaction can
be avoided (ref. 30). This example also demonstrates how useful zeolite cata-
lysts can be in the synthesis of nitriles.
 197

REARRANGEMENT REACT1ONS
Beckmann rearrangement
The most important industrial example of the Beckmann rearrangement is the
reaction of cyclohexanone oxime to E-caprolactam. This is a valuable starting
material for plastics, in particular for synthetic fibres like Nylon. The
classical synthetic route involves the oximation of cyclohexanone with hydro-
xylamine-sulphate and the subsequent rearrangement of the oxime in concentrated
sulfuric acid. Approx. 4 - 5 t (NH4)2S04 per t caprolactam are inevitably
obtained as co-product (ref. 31 ). Further problems encountered include hand1 ing
a large amount of fuming sulfuric acid and corrosion of the apparatus caused by
that acid. In order to eliminate these problems and the formation of the co-pro-
duct, which can only be taken up by the fertilizer industry to a limited extent,
attempts have been made for many years to switch from a homogeneous to a hetero-
geneous catalytic process.
There are a number o f references concerning the use of heterogeneous cata-
lysts like alumina, heteropoly acids, boronphosphate, phosphoric acid or Lewis
acids on inert carriers, silica-alumina and boric-acid on alumina for the
rearrangement of a variety of ketoximes to amides (refs. 31, 32).
As long ago as the 1960s P. S. Landis and P. B. Venuto attempted to use
zeolites for this purpose (refs. 1, 26). X - and Y-zeolites as well as mordenite
in the H-form or doped with rare-earth or transition metals are employed; e. g.
cyclohexanone oxime (30 wt% dissolved in benzene) is converted at 380 "C and
WHSV = 1.2 hr-' to E-caprolactam with 76 % selectivity and 85 % conversion
during the first two hours. The principal by-product is 5-cyanopent-1-ene
together with traces of cyclohexanone and cyclohexanol. As the reaction is
continued, the overall conversion decreases to about 30 % after 20 hrs with a
drop to 50 % selectivity for caprolactam. According to the authors' findings the
optimum reaction temperature for high caprolactam selectivity is between 250 " C
and 380 "C with the selectivity increasing with increasing temperature. Above
400 "C caprolactam decomposition is observed. Atmospheric pressure is favored,
since at elevated pressure 5-cyano-pent-1-ene is formed as principal product.
Non polar solvents such as cyclohexane, benzene or toluene are much more favour-
abie than the more polar solvents. Nitrogen and particularly carbondioxide as
nonbasic carrier gas are very useful for the Beckmann rearrangement. As far as
the mechanistic considerations are concerned, a protonic catalysed reaction is
assumed, whereby probably an initial adsorption of the ketoxime at a catalyst
acid site is involved.
Investigations using HNaY-zeolite catalysts with different levels of exchange
of Na' show (refs. 33, 34) that the Beckmann rearrangement of cyclohexanone
oxime is catalysed by strong Bronsted acid sites of pKa 4 1,5 and that, in
198

competition to this reaction, the selectivity-reducing by-product 5-cyano-pent-

1-ene is formed on acid sites as well as on Na' ions. Furthermore, the catalyst
deactivation is assumed to be caused by poisoning of the acid sites by the basic
products such as aniline and methylpyridine rather than by coke formation on the
catalyst surface, because after reaction the color of the catalyst is still
almost white.
Generally the greatest limitations of the rearrangement of the ketoxime using
Y- and X-zeolites as well as mordenite were the rapid catalyst aging and low
selectivity for the caprolactam. It is not possible to avoid these disadvantages
even by employing the strongly acidic, hydrophobic HZSM-5 with Si0,/Al2O3 = 78
(ref. 35); a 14 % solution o f cyclohexanone oxime in benzene at 350 "C, 1 atm
and LHSV = 1.7 hr-' was nearly quantitatively converted for a period of up to 15
hr. Afterwards the conversion drops rapidly to about 40 % at 21 hr on stream.
Therefore, in recent years, considerable interest has focussed upon zeolite
catalysts of reduced acidity, in particular on the outer surface and upon other
weakly acidic microporous materials (refs. 36 - 40). H. Sato and coworkers
demonstrated (refs. 37, 38) that both the catalytic activity and the selectivity
of lactam formation increase with increasing Si/Al ratio in HZSM-5 catalysts. By
measuring the amount of 4-methyl-quinoline (4-MQ) adsorbed on HZSM-5, the amount
of acidic sites on the outer surface of these samples with various Si/Al ratios
can be determined. It was found that both the activity and the selectivity
increase as the quantity of 4-MQ adsorbed on the outer surface decreases. This
and other quoted results indicate that the rearrangement takes place on the
outer surface or at the pore mouth of the pentasil zeolites. The relatively
large molecular diameter of the cyclohexanone oxime and the E-caprolactam are
probably responsible for that. Even HZSM-5 catalysts with a Si/Al ratio of more
than 2000 show high activity. Furthermore the service life of the catalysts
increases with the increase o f the Si/Al ratio. But even these catalysts lose 50
% of their activity in the course of 12 h. Generally speaking the weaker the
acidic centers on the outer zeolite surface the better are the results.
The same research group (ref. 39) reduced the acidity of the external surface
of HZSM-5 catalysts by treatment with organometall ic compounds such as chloro-
trimethylsilane. The comparison, given in Table 1 , of silanated with nonsilanat-
ed HZSM-5 shows the advantageous effects of this silanation treatment on the
service life of the catalyst and the selectivity for &-caprolactam.
The service life can also be improved, but only slightly, by selectively
covering the outer surface of a boron pentasil zeolite with Na ions (ref. 36).
This is achieved by making the pore volume of the silicate inaccessible with an
organic compound, in particular an aromatic hydrocarbon like toluene (saturation
the pore volume), and by subsequently contacting such a sample with a deacti-
vating agent such as an alkali metal ion, preferably Na, in a polar solvent. For
 199

example, a gas mixture o f cyclohexanone oxime, toluene, C02 and H20 in a molar
ratio 1:3:7:1 is converted quantitatively at 340 "C and WHSV = 0.8 hr-I to
E-caprolactam with 58 % selectivity using such a treated boron zeolite. The
service life of this catalyst is more than 15 hr and more than three times
longer than that o f an untreated boron zeolite; however, in this case the
selectivity is very poor because 5-cyano-pent-1-ene may be formed preferably as
by-product on Na' ions according t o A. Aucejo et al. (refs. 33, 34).

TABLE 1
Comparison of silanated with nonsilanated HZSM-5 in the reactiona of cyclo-
hexanone oxime to E-caprolactam
catalyst time on conversion selectivity
stream [hrl C%l C%l
si lanatedb 3,3 100 95 ,O
31 ,O 98,2 95,O
nonsilanated 3,3 100 79,7
27,O 95,8 89,4

areaction conditions: 8 wt% solution o f oxime in benzene, 350 "C, WHSV = 11.7
hr-1 , 1 atm, C02 as carrier gas, oxime/C02/benzene = 1/5.6/18.3 mol
bHZSM-5 with Si/Al :: 1600, treated with chlorotrimethylsilane at 350 "C for 4 hr

Pursuing the idea of reducing the acidity of the zeolite in order to get high
selectivity and long lifetime of the catalyst, micro-porous materials such as
the weakly acidic non-zeolitic molecular sieves (e. g. the middle-pore-sized
SAPO-11 or SAPO-41) are used for the Beckmann rearrangement (ref. 40). Using
SAPO-11, a 5 wt% solution of cyclohexanone oxime in acetonitrile is converted at
350 "C, atmospheric pressure and WHSV = 10.8 hr-l, to E-caprolactam with 95 %
selectivity at 98 % conversion rate.
However, also in the latter case, it must be pointed out that the Beckmann
rearrangement of cyclohexanone oxime by means of zeolites or other non-zeolitic
molecular sieves does not at present, for reasons of service life, constitute an
alternative to the homogeneous process now practiced. Generally, the development
of heterogeneous catalysts based on middle-pore-sized zeol itic and non-zeolitic
molecular sieves for the rearrangement of cyclohexanone oxime indicate that the
reaction does not necessarily take place at the acidic centers as active sites,
whereas it was generally considered so in former times. Only rather weak
acidity, or no acidity, is required in order to achieve high selectivity at high
conversion and long catalyst service life.
The rearrangement of other ketoximes such as acetone oxime or acetophenone
200

oxime to the corresponding amides using HY-zeolites has been reported (ref. 32).
For example, a mixture of 20 wt% acetophenone oxime in benzene reacts at 300 OC
to acetanilide with 95 % selectivity and N-methylbenzamide with 5 % selectivity.
In this case the migration of the phenyl group is favoured over methyl group
migration in the aldehyde-ketone isomerization (ref. 3 ) .

Rearrangement of ani 1 ines

The synthesis of picol ines by rearrangement of aminated arenes constitutes an
interesting reaction. There, aniline can be converted at 510 "C, 2860 KPa and
WHSV = 1.1 hr-' to d-picoline in the presence of NH3 (NH3/aniline = 1.5 molar)
using HZSM-5. Conversion of 13 % and selectivity of 52 % for
c(-picoline are obtained (ref. 41). The presence of NH3 is necessary to attain a
high picoline yield, because in the absence of NH3 diphenylamine is found as the
main product.
In a similar way the very interesting rearrangement of 1,3-diaminobenzenes to
a mixture o f 2- and 4-amino-pyridines occurs in the presence of acid catalysts
(ref. 42). A mixture of 1,3-diaminobenzene and NH3 (molar ratio 1;60) is con-
verted at 350 "C and 190 bar on HZSM-5 to 2-amino-6-methylpyridine with 83 %
selectivity at 43 % conversion. A comparison with silica-alumina or alumina
under the same reaction conditions (16 - 29 % conversion, 57 - 89 % selectivity)
shows the superior properties of the zeolite over other acid catalysts not
possessing zeolite structure. This is an useful new route for aminopyridines,
compounds which were hitherto only available by complicated reaction of sodium
amide with pyridine.
With these exciting reactions in mind, it is astonishing that an aromatic
ring can be opened at elevated temperature and pressure in the presence o f NH3
and an acid heterogeneous catalyst.

CYCLOCONDENSATION WITH AMMONIA

Aldol condensations of aldehydes and ketones on zeolitic (refs. 1 , 3, 4, 6,
10) and on non-zeolitic molecular sieves (ref. 43) have been extensively
described. Such condensation reactions, which are preferably carried out in the
gas phase, lead in the presence of NH3 to pyridine and alkylated pyridines
(refs. 44 - 51).
For example, acetaldehyde with or without formaldehyde, in the presence of
NH3 on HZSM-5 or Cd-HZSM-5 (ref. 44) or Cd-Y-zeolite (refs. 45, 46) at 300 -
400 O C reacts to form pyridine and picolines in yields of 20 % to 68 % in a
relatively unspecific manner. Furthermore, the catalyst deactivates very rapid-
ly. On the other hand, the acid-catalysed reaction o f acetaldehyde with ammonia
in the liquid phase at 150 "C - 250 O C yields 2-methyl-5-ethylpyridine (e. g.
ref. 46).
 201

Acetaldehyde, formaldehyde, NH3 and H20 (molar ratio 1:1:1.5:1.7) give an 83

- 90 % yield of a mixture of pyridine and 8-picoline (molar ratio approx. 2 : l )
when the reaction is carried out at 450 "C on alumino-silicate catalysts of the
pentasil type in the acidic H-form (ref. 49). The yield of pyridine in such a
reaction can be increased by using ZSM-5 zeolites doped with T1, Pb and Co,
respectively (ref. 50); e. g. a mixture of acetaldehyde, formaldehyde and
ammonia (molar ratio 2:1:4) was passed at 450 "C and GHSV = 1000 hr-' over
TI-ZSM-5 (Si/Al = 90 1 resulting in 63 % yield of pyridine and a 81 % total
yield of pyridine and picolines.
A synthesis of O-substituted pyridines is based upon the reaction of mixtures
of acrolein and alkanals with ammonia in the presence of zeolite catalysts (ref.
51). For instance, if such a mixture of ammonia, acrolein and alkanal R-CH2CH0
in a molar ratio of 3:l:l is allowed to react on an HF-treated borosilicate
pentasil zeolite at 400 OC and WHSV = 3 hr-1 , one obtains 0-ethyl-pyridine with
72 % selectivity (R = C2H5), 0-butylpyridine with 78 % selectivity (R = C4Hg)
and 8-hexylpyridine with 90 % selectivity ( R = C6H,3). In all cases conversion
is complete and catalyst lifetime > 48 hs. The increasing selectivity with
increasing chain length of the fi-substituent is surprising, because more
extensive cracking of the long-chain alkanals would have been expected. The
transition-state shape selectivity of the pentasil zeolite is probably respon-
sible for this effect, since the long-chain alkanals are restricted in their
movements within the zeolite channels and adopt definite positions in relation
to the other reaction partners.
These cyclocondensation reactions of aldehydes and ketones in the presence of
ammonia demonstrate once again the superiority of zeolite catalysts over con-
ventional Al2O3- or Si02-based catalysts.

O/N-REPLACEMENT IN CYCLIC COMPOUNDS

As is known from other acid heterogeneous catalysts, the reaction of cyclic
ethers and lactones with ammonia also gives cyclic imines or lactams using
zeolite catalysts (refs. 1 , 8, 52 - 57). Tetrahydrofuran in the presence of NH3
(molar ratio 1:7) is converted at 350 "C into pyrrolidine on HL-zeolite with a
selectivity of 91 % at 53 % conversion and on HY-zeolite with a selectivity o f
82 % at 61 % conversion. The conversion of THF increases with increasing tem-
perature up to 360 "C, but drops down sharply at higher temperatures. Alumina
and silica-alumina are also active in this reaction, but only poor selectivity
is obtained. The alkali forms of the L- and Y-zeolite are not active at all,
indicating that Bronsted acid sites are responsible for this O/N-replacement
(ref. 53).
HL- and HY-zeolites are not very suitable for the conversion of tetrahydro-
pyran to piperidine. However, dealumination of these zeolites improves the
202

activity and selectivity for this ring transformation (ref. 55); at 460 OC the
HL-zeolite (Si/Al = 3.2) gives a 24 % conversion and a piperidine selectivity of
58 %, whereas the dealuminized catalyst (Si/Al = 6) results in 25 % conversion
and an 80 % selectivity.
The ring conversion, e. g. of THF, is possible with alkylated amines, too.
THF reacts with propylamine on HY-zeolite doped with A1 at 360 OC to l-propyl-
pyrrolidinone with 75 % selectivity at 61 % conversion (ref. 52).
In contrast, selective O/N-replacement of aromatic compounds such as trans-
formation of furan into the corresponding N-containing compound pyrrole takes
place only on zeolites with modest acidity such as NaX-zeolite (ref. 1 ) or
Bay-zeolite (ref. 56). In the latter case 14 % conversion and 100 % selectivity
for pyrrole are attained.
FButyrolactone and NH3 (molar ratio 1:5) are converted in the vapor phase
into 2-pyrrolidinone on Cay-, KY- and CuY-zeolites. The highest activity (31 %
conversion) and selectivity of 80 % are achieved at 260 "C (ref. 57). For this
reaction the alkali cation zeolites are equally as active as the acid zeolites,
indicating that acidic sites are not necessarily required.
It has been mentioned in the patent literature that caprolactam can be
obtained by the reaction of caprolactone and NH3 using HY-zeolites (ref. 58) or
HZSM-5 (ref. 59). However, exact data are not disclosed. On the contrary, it was
found (ref. 60) that in this reaction no O/N-replacement occurs, but instead
there is cleavage of the ring system and dehydration to form hexennitrile. For
instance, caprolactone and NH3 (molar ratio 1:7) are converted at 400 OC to
hexennitrile with 66 % selectivity using a boronsilicate zeolite and 82 %
selectivity using a alumina-silicate zeolite both of the pentasil type and 75 %
using a HY-zeolite. If this reaction is carried out in the presence of a con-
ventional catalyst such as A1203, only poor yields of the hexennitrile are
obtained because the reaction stops at the intermediate 6-hydroxycapronitrile.
The question arises as to why we obtain hexennitrile instead of caprolactam
in the conversion of caprolactone with NH3. If this result were in agreement
with the idea of shape selectivity, i. e. the less bulky hexennitriles pre-
ferentially formed rather than the bulky caprolactam, then caprolactone would
have to migrate in the pores of the pentasil type zeolite. On the other hand, it
is known from the investigation of the Beckmann rearrangement (refs. 37 - 39)
that caprolactam formation takes place at the outer surface because of the bulky
compounds. There may be two explanations for the formation of hexennitrile.
First, the ring opening of the caprolactone occurs at the pore mouth and then
the stretched fragment migrates partially inside the zeolite pore to react with
NH3, or second it is just a question of the reaction rate, i. e. that after the
ring opening under addition of NH3 the dehydration to hexennitrile occurs faster
than the ring closure to form the caprolactam, and shape selectivity is not
involved at all.
 203

OX IDATI O N REACTIONS
With hydrogen peroxide and ammon i a
The discovery of the titanium-silicate TS-1 has enabled remarkable progress
to be made in oxidation reactions with H202 in recent years (refs. 61, 62). Such
a titanium-zeolite can also be used for the preparation of cyclohexanone oxime
by the reaction of cyclohexane with ammonia and hydrogen peroxide in the liquid
phase (ref. 63). Such a mixture i s heated in an autoclave to 60 "C ( - 700 mm Hg
above atmospheric pressure), giving 95 % conversion o f the cyclohexanone, 80 %
selectivity of the oxime and 15 % selectivity of peroxy-di-cyclohexyl-amine.
Surprisingly, using a zirconium-silicalite or a boronsilicate zeolite,
analogous results are obtained. This cyclohexanone-oxime formation rate avoids
the co-production o f ammonium sulphate, as is obtained in the classical reaction
of cyclohexanone and hydroxylammonium sulphate, and hence it can be of in-
dustrial interest.

With oxvqen and ammonia

As has already been shown, the reaction of ethanol with ammonia on zeolite
catalysts leads to ethylamine. If, however, the reaction is carried out in the
presence o f oxygen, then pyridine is formed (refs. 64, 65). H. Van Bekkum and
coworkers recognized that H-boron zeolite with S i / B = 42, i. e. 2.2 boron atoms
per unit cell or Fe-containing ZSM-5-type catalysts, are particularly suitable
for this purpose. Thus, a mixture of ethanol, NH3, H20 and O2 (molar ratio
3:1:6:9) reacts on H-boralite at 330 "C and a WHSV 0.17 hr-' to yield pyridine
with 48 % selectivity. The conversion is 24 %. It is possible to improve the
conversion by increasing the number of boron atoms per unit cell, i. e. the
number of acid sites, or by raising the temperature. At 360 "C the conversion is
81 % but there is increased ethylene formation at the expense of pyridine.
Further by-products include diethylether, acetaldehyde, ethylamine and C02. In
the case of Fe-containing aluminosilicate ZSM-5 catalyst the conversion in-
creases with increasing Fe content. An FeHZSM-5 with Si/Fe = 189 and Si/Al = 71
leads to a 48 % pyridine selectivity at 28.5 % conversion. A mechanism starting
with partial oxidation of ethanol to acetaldehyde followed by aldol ization,
reaction with ammonia, cyclization and aromatization can be envisaged,
The oxidative ammonolysis of olefines in the presence of e. g. Ag, Cr, Fe or
Mn cation-exchanged X - and Y-type zeolites yields unsaturated nitriles (ref.
66).
The ammoxidation of toluene and related aromatics to the corresponding
nitriles can be achieved by means of X-zeolite (ref. 1) or ZSM-5 zeolites (ref.
204

67). Doping with transition metals such as Zn, Cu, Ag and Fe increases the
activity. Whereas, for example, ZnX-zeolite deactivates within 7 hrs, the
CU-H-ZSM-5 is much more stable and shows also higher selectivity and activity
than ZnX. The ion-exchange of H-ZSM-5 to CU-H-ZSM-5 results in a substantial
increase of the activity and selectivity. Using CU-H-ZSM-5 with 0.6 wt.-% Cu as
catalyst, toluene reacts with NH3 in H20 (mol ratio 1:2:6) at 230 OC and WHSV =
0.17 hr 1 t o benzonitrile with 86 % selectivity at 70 % conversion. Water has a
beneficial influence on the activity and selectivity. On the other hand, H-ZSM-5
yields only 35 % selectivity and 7 % conversion. The temperatures required for
the ammoxidation are substantially lower in the case of the zeolites than for
conventional catalysts like silica-alumina, -zirconia or -titania.
Acetonitrile is produced with high yield by ammonolysis o f propane at about
600 "C when a pentasil zeolite with Si02/A1203 = 25 - 200 is employed as cata-
lyst (ref. 68).

OLIGOMERIZATION REACTIONS
Oligomerization reactions of olefins on zeolites, which have been the subject
of numerous studies, generally yield mixtures of dimers, trimers and tetramers
(e. g. ref. 4, 69). On the other hand, oligomerization reactions in the presence
of NH3 have received little attention. One of the infrequent examples is the
synthesis of dimethylphenylpyridine by cotrimerization of phenylacetylene and
acetonitrile in the presence of a Co-doped Y-zeolite which had been specially
reduced with NaBH4 in the reaction mixture (ref. 70). At 100 OC an 80 % yield of
diphenylmethylpyridine is obtained. In this case the heterogeneous catalyst is
superior to the homogeneous monovalent Co complexes for reasons of separation
and product work-up.

ISOMERIZATION REACTIONS
The excellent isomerization capacity of pentasil zeolites is also applicable
to aromatic compounds bearing N-containing substituents such as toluidines
(refs. 71 - 74) and methylbenzonitriles (ref. 75).
A zirconium-doped pentasil zeolite is particularly suitable for the iso-
merization of 0- or p-toluidine in mixtures of the 0-, m- and p-isomers and is
superior to the HZSM-5 catalyst in terms of both product yield and catalyst
lifetime (ref. 71). At 430 "C o-toluidine is converted on the zirconium zeolite
to an 0 - , m-, p-mixture in a weight ratio of 37:45:15; on the other hand, the
HZSM-5 zeolite yields a mixture of isomers in a weight ratio of 52:32:10.
Toluidine is produced by the hydrogenation of nitrotoluene mixtures of
approximate composition by weight 63 % 0-, 4 % m- and 33 % p-isomers. It is,
however, the m-isomer which is of greatest importance as an intermediate for
dyestuffs and agrochemicals. In the foregoing nitration-reduction process the
 205

toluidine mixture contains only 4 % of the m-isomer. In order to increase the

proportion of the desired in-isomer the 0- or p-isomer is isolated from the
hydrogenation product, and in a subsequent isomerization process converted on a
pentasil zeolite to a toluidine mixture rich in the m-isomer. Surprisingly, in
contrast to the isomerization of xylene, this toluidine isomerization does not
yield preferentially the para but the meta isomer (e. g. refs. 1 , 4).
A compari son of the isomerization of to1 un i tri les and d imethy 1 benzon i tri les
shows that, in the case of tolunitrile, the three isomers are distributed in
accordance with the thermodynamic equilibrium (ref. 75), whereas in the case of
the dimethylbenzonitriles the shape selectivity results in a product distri-
bution such that no 1,2,3-isomersor 1,3,5- isomers are formed. This limitation
does not apply to trimethylbenzenes; in this case the 1,2,3-isomer and the
1,3,5- isomer are formed from 1,2,4-trimethylbenzene in a ratio between 1.3:1
and 2.7.1 (ref. 76).

ALKYLATION REACTIONS

Alkvlation of heteroaromatics
The alkylation of the aromatic nucleus (e. g. ref. 4, 26, 77, 78) or of the
side-chain (refs. 4, 79 - 82) of alkylbenzenes are competing reactions which
have been extensively studied. In contrast, perhaps because such systems are
apparently intrinsically more complex, only few references dealing with alky-
lation of N-containing heteroaromatics are known (ref. 83).
Pyridines can be alkylated in the nucleus using faujasites, with the R-
position being preferentially attacked when H-Y or Li-Y-zeolites are used, and
the cc- and Zpositions in the case of alkali-earth Y-zeolite catalysts. On H-Y 3
% d-, 12 % R- and 3 % Fpicoline are obtained at 32 % conversion, whereas on
Ba-Y 23 % &-, 4 % R- and 8 % Fpicoline are produced at 63 % conversion (re-
action conditions: 400 "C, methano1:pyridine = 8 mol, LHSV 1.3 hr-1 , N2).
Isomers of lutidine are formed as by-products.
On the other hand, when pyridine is treated with methanol in the presence of
X- and Y-zeolites ion-exchanged with alkali metals (not Li), side chain alky-
lation is also oberved as a consecutive reaction. The principal products are
ethylpyridine and vinylpyridine as well as isomers of picoline and lutidine.
When, for example, Cs-Y-zeolite is used as catalyst (reaction conditions: 450
"C, LHSV = 1.3 hr-', methanollpyridine = 8 mol) the yield of ethylpyridine is
approx 27 % at 82 % conversion. In the side-chain methylation of picolines the
following order of reactivity is observed: CC > r>
fi, with B-picoline being
almost inert. Thus, the maximum yield of 2-ethylpyridine (approx. 30 %, together
with 3 % 2-vinylpyridine at 83 % conversion and 450 " C ) is obtained by treating
OC-picol ine with methanol on Cs-Y-zeolite. Conversely the yield of 2-vinyl-
206

pyridine is highest (10 %, 425 "C) when Cs-zeolite is used.

The above examples indicate how it is possible to suppress or to induce
consecutive reactions during the alkylation of pyridine merely by means of the
appropriate choice of dopant in the zeolite catalyst. The examples also show how
the selectivity can be influenced by the type of zeolite employed. In contrast
to the side-chain alkylation of toluene using alkali-earth-doped faujasites, it
is characteristic of the side-chain alkylation of picolines that alkylation of
the nucleus also occurs (e. g. ref. 4).

Alkylation of aromatic amines

The alkylation of aromatic amines includes the reaction of aniline with
methanol (refs. 84, 85) or with olefins (refs. 86 - 88) in the presence of
zeolitic and nonzeolitic molecular sieves. In principle, reaction can take place
at the N-containing groups forming N-alkylated compounds or at the nucleus
forming C-alkylated compounds. In other words, the methylation of aniline, for
example, yields toluidine, N- methylaniline and N,N-dimethylaniline. All are
useful intermediates for dyestuffs, agrochemicals and drugs as well as for the
organic synthesis.
A mixture of aniline and methanol in a molar ratio 1:3 reacts at 350 "C and
WHSV = 0.8 hr-' with 51.4 % selectivity for N-methylaniline and 20.1 % for
toluidine using HZSM-5 with Si02/A1,03 = 60. The conversion is 70 %. That means
the acid HZSM-5 already favours N-alkylation over C-alkylation. By impregnating
or moulding with, e. g. MgO, thereby reducing the acidity, the amount of N-
alkylate can be increased; N-methylaniline was formed with 86.5 % selectivity at
85.5 % conversion. However, only 3,5 % toluidine selectivity was obtained.
The alkylation of aniline with olefines such as propylene can be carried out
employing H-mordenite (ref. 86), dealuminated mordenite or Y-zeolite (ref. 87)
or SAPO 37 (ref. 88). In contrast to the alkylation with methanol, in all these
cases C-alkylation is favoured especially in the ortho-position. Using H-
mordenite, aniline and propylene in a 1:l molar ratio are converted at 250 C'
and LHSV = 0.35 hr-' to o-alkylate with 84 %, p-alkylate with 4 % and N-alkylate
with 15 % selectivity. 32 % conversion is obtained. Using dealuminated mordenite
the conversion rate can be increased to 76 % whilst maintaining a similar
product distribution, and using SAPO 37 a further increase up to 93 % is
possible. In the latter case, however, only 64 % o-alkylate selectivity and 12 %
p-alkylate selectivity are achieved. The selectivity for N-alkylate is 21 %.
In the author's opinion a concerted reaction between aromatic amine and
olefine (ref. 86) is responsible for ortho-alkylation being favoured over
para-alkylation.As far as the thermodynamics are concerned the para-alkylates
are the most stable, as is demonstrated by the fact that their selectivity
increases with higher temperatures demonstrates.
 207

CONCLUSION
This presentation is intended to underline once again the versatility of
zeolites for both synthesis and reactions of N-containing compounds. Some
examples demonstrate that existing processes can be improved merely by replacing
the conventional heterogeneous catalyst. Other examples show the advantages of
the change from homogeneously catalysed processes to heterogeneous catalysis if
environmental and process engineering problems occur in the separation and
work-up. However, in other cases, like the Beckmann rearrangement to produce
caprolactam, the results obtained by homogeneous catalysts can not be achieved
by zeolitic or non-zeolitic molecular sieves up to now. Considerable effort is
still necessary in order to solve this problem.
The principles derived from reactions of hydrocarbons on zeolites can
generally be applied to the reactions of N-containing compounds. However, there
can be a few differences, too, as the alkylation of pyridine or aniline in
comparison t o the alkylation of benzene or toluene has shown. Nevertheless,
there are some promising results in the chemistry of N-containing organic
compounds which encourage us to proceed further along the road of shape-selec-
tive catalysis.

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This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

COMPARISON OF THE ALKYLATION OF ANISOLE AND PHENOL WITH METHANOL ON PENTASIL

AND ULTRASTABLE ZEOLITES

RUDY F. PARTON, JULIA M. JACOBS, HEIDI VAN OOTEGHEM and PETER A. JACOBS
Laboratorium voor Oppervlaktechemie, KU Leuven, Kardinaal Mercierl aan 92, B-
3030, Heverlee (Leuven), Belgium

ABSTRACT
The alkylation of anisole and phenol with methanol was measured in a
microreactor at 473 K and at different contact times, using as catalysts
pentasil and H-USY zeolites. Activity and selectivity results showed that
monomolecular reactions are favoured on pentasil and bimolecular reactions on
large-pore zeolites. The high selectivity o f o-cresol observed on the ten-
membered-ring compared to H-USY zeolites is explained by the intramolecular
rearrangement of anisole to o-cresol .

INTRODUCTION
The acid-catalysed a1 kylation of toluene with methanol over ten-
membered-ring (10-MR) zeolites to obtain a para-enriched a1 kylate is now well
established industrial practice [l-31. The methylation of phenol with
methanol [4-91 or anisole [lo, 111 on zeolites gives a mixture of anisole,
xylenols and cresols, rich in the ortho-isomer. Evidently, the selectivity of
p-cresol is not improved by the use of pentasil-type zeolites. On H-ZSM-5,
the o/p-cresol ratio is always higher than one whereas on Y zeolites o/p
ratios significantly lower than one have been reported [12-141. On the
contrary, a high p-selectivity in the methylanisole fraction is observed in
the self-alkylation of anisole on H-ZSM-5 [15] as well as in the methylation
of anisole with methanol [14].
In order to make p-cresol selectively by the use of shape selective
zeolite catalysts, it is desirable to know the reaction network of the
methylation of phenol with methanol and the influence of the zeolite
structure on the different pathways. Recently, for A1P04-Ti02 catalysts an
overall scheme of the phenol and anisole alkylation was reported [16, 171. On
H-ZSM-5 a detailed study of anisole conversion showed three primary pathways
[15]. The main pathway of cresol formation is the intramolecular
rearrangement of anisole to o-cresol .
When the influence of the zeolite structure and acidity on the reaction
network of the alkylation of phenol with methanol is known it should be
possible to select and modify zeolite catalysts in order to obtain the
desired isomer with high selectivity.
EXPERIMENT
M a t e r i a1 s
Two batches, (1) and ( 2 ) , o f ZSM-5 and a sample o f ZSM-11 w i t h a Si/A1
r a t i o o f 100 were s y n t h e s i z e d a c c o r d i n g t o e s t a b l i s h e d l i t e r a t u r e procedures
[18, 191. A f t e r a i r c a l c i n a t i o n a t 823 K, subsequent ammonium exchange a t
r e f l u x c o n d i t i o n s was done. A sample o f H-USY w i t h a framework S i / A l r a t i o o f
20 was r e c e i v e d f r o m Toyo Soda. A n o t h e r sample o f H-USY was prepared by
steaming o f NH4-Y, purchased f r o m V e n t r o n as Nay, w i t h a Si/A1 r a t i o o f 2.46.
Bot h samples are denoted as H-USY(T) and H-USY(V), respectively. The
framework Si/A1 r a t i o o f USY(V) was 4.3 as det ermined b y 2 9 S i NMR. Bef ore
reaction a l l z e o l i t e s were c a l c i n e d i n s i t u i n f l o w i n g oxygen. Anisole,
phenol and methanol w i t h a p u r i t y o f a t l e a s t 99% were purchased f rom Janssen
Chimica.

Reac t io n procedure
Time-on-stream (ToS) e x p e r i m e n t s i n t h e vapour phase were c a r r i e d o u t i n
hydrogen, u s i n g a f i x e d - b e d c o n t i n u o u s f l o w r e a c t o r a t d i f f e r e n t c o n t a c t
times , W/Fo, and atmospheric p r e s s u r e . W s t ands f o r c a t a l y s t weight and Fo
f o r mo lar f l o w r a t e o f t h e f e e d a t t h e r e a c t o r e n t r a n c e . The z e o l i t e powder
was pressed, crushed, s i e v e d and t h e 0.25-0.50 mm f r a c t i o n retained for
f u r t h e r use. The vapour p r e s s u r e o f a n i s o l e , phenol and methanol was 1.3 kPa.
The r e a c t i o n p r o d u c t s were analysed o n - l i n e by gas chromatography on a 2 m
packed column from Supelco c o n t a i n i n g 0 . 1 % SP-1,000 on Carbopack C .

RESULTS and DISCUSSION

O v e r a l l a c t i v i t y i n t h e a l k v l a t i o n o f a n i s o l e w i t h methanol

100

-aR 80
.-C0
2
0
60
>
e
0
V
40
-
0
0
.-mC 20
<

0 5 10 15 20 25

l i m e (h)

F i g . 1. A l k y l a t i o n o f a n i o l e w i t h methanol on d i f f e r e n t H - z e o l i t e s a t 473 K
w i t h W/Fo= 1,736 kg s mol -7 .
 213

Fig. 1 shows t h a t i n the a l k y l a t i o n o f a n i s o l e w i t h methanol the anisole

conversion decreases w i t h ToS f o r a l l c a t a l y s t s investigated, probably as a
r e s u l t o f coke deposition. Although these data h a r d l y a l l o w a d i s t i n c t i o n t o
be made between i n i t i a l a c t i v i t y , the f o l l o w i n g statements can be made: i.
t h e r e p r o d u c i b i l i t y o f the conversion i s s u f f i c i e n t as shown f o r t h e two
batches o f H-ZSM-5; ii. H-ZSM-5 i s more a c t i v e than t h e u l t r a s t a b l e z e o l i t e s ;
iii. the a c t i v i t y d i f f e r e n c e between the two u l t r a s t a b l e z e o l i t e s i s i n l i n e
w i t h the d i f f e r e n c e i n Si/A1 r a t i o o f t h e i r framework; i v . H-ZSM-11 shows
i n i t i a l l y a lower a c t i v i t y than H-ZSM-5 b u t seems t o be l e s s susceptible t o
deactivation. USY(V) contains more Brensted s i t e s which a r e o f lower strength
than i n USY(T). Indeed, the S i / A l r a t i o o f USY(T) i s h i g h e r as w e l l as i t s
a c t i v i t y i n the hydroisomerisation o f long-chain alkanes [20]. Therefore, the
alkylation o f phenol and anisole can p o s s i b l y occur over sites with
r e l a t i v e l y weak a c i d strength.

Overall s e l e c t i v i t y i n the a l k v l a t i o n o f a n i s o l e w i t h methanol

TABLE 1
Product s e l e c t i v i t y i n the methanol a l k y l a t i o n o f anisole a t 473 K, w i t h W/Fo
=

Catalysts I
1,736 kg s mol-' and a f t e r 3 hours on stream.
H-USY(T) 1 H-USY(V) 1 H-ZSM-5 I H-ZSM-11

Conversion o f anisole (%l

I 30.0 I 58.4 I 60.9 I 49.6

Phenol 51.9 32.5 79.3 84.3

Cresol s 12.6 23.8 15.3 11.6
Xyl enol s 0.0 6.8 0.0 0.0
Methylanisoles 35.5 36.9 5.4 4.1

I 30*4 I I 41*4 I 36.1

Products obtained i n a l l cases are cresols (Cr), methylanisoles (mAn)

and phenol (Ph) (Table 1). H-ZSM-5 and H-ZSM-11 show similar product
s e l e c t i v i t i e s w i t h Ph being present i n l a r g e excess over C r and mAn. Compared
t o t h e p e n t a s i l z e o l i t e s , t h e r e i s l e s s Ph and more mAn obtained on H-USY.
The decreased Ph s e l e c t i v i t y on H-USY(V) i s t h e r e s u l t o f a conversion
effect, as secondary a l k y l a t i o n products l i k e xylenols (Xy) and C r a r e
favoured on the more a c t i v e H-USY(V). The d i f f e r e n c e i n s e l e c t i v i t y between
H-USY and p e n t a s i l z e o l i t e s cannot be explained by such an e f f e c t . As the
214

methanol conversion t o dimethylether i s h i g h e r on t h e 10-MR z e o l i t e s i t i s

p o s s i b l e t h a t the h y d r o l y s i s o f An by water t o Ph proceeds t o a greater
e x t e n t on t h e p e n t a s i l z e o l i t e s than on H-USY. Supplementary evidence i s
found i n Fig. 2 where i s shown t h a t t h e An conversion i n the presence o f
water y i e l d s about 10% more Ph a t t h e expense o f mAn. However, t h e a d d i t i o n
o f l a r g e amounts o f water r e s u l t s i n a minor product change. Therefore,
h y d r o l y s i s alone cannot e x p l a i n t h e d i f f e r e n c e between USY and p e n t a s i l
zeol ites.
Possibly monomolecular r e a c t i o n s are favoured on 10-MR z e o l i t e s , whereas
bimolecular r e a c t i o n s dominate on H-USY as a result o f differences in
c o n s t r a i n t s o f the pores. Indeed, Ph can be formed v i a a monomolecular
d e a l k y l a t i o n r e a c t i o n , as reported p r e v i o u s l y [15], and should be favoured on
the p e n t a s i l z e o l i t e s , whereas mAn can o n l y be formed by a bimolecular
r e a c t i o n . Also i n t h e An conversion Ph was formed i n l a r g e excess [15] over
pentasi 1 zeol ites.

Time (h)

Fig. 2. Product s e l e c t i v i t y f o r a n i s o l e conversion on H-ZSM-5 i n t h e presence

(open p o i p t s ) and absence ( f u l l p o i n t s ) o f water a t 473 K, w i t h W/Fo = 1,736
kg s mol- and a molar anisole/water r a t i o o f 1.

Cresol S e l e c t i v i t y i n the a l k v l a t i o n o f a n i s o l e w i t h methanol

F i g . 3 shows t h e o-Cr s e l e c t i v i t y against conversion o f An i n the An
methylation. I n no case i s m - C r observed. Although t h e data are t r a n s i e n t
measurements and do not represent initial or steady state conversions
obtained a t d i f f e r e n t contact times, t h e f o l l o w i n g conclusions can be s a f e l y
drawn: i. o-Cr i s a primary product necessarily formed v i a a monomolecular
r e a c t i o n whereas t h e p-isomer i s o f secondary nature and obtained by a
bimolecular reaction; ii. t h e bimolecular formation o f p-Cr i s suppressed i n
the p e n t a s i l compared t o t h e Y z e o l i t e s . I n Fig. 4 i s given the o-Cr
 215

s e l e c t i v i t y i n the Ph a l k y l a t i o n w i t h methanol over p e n t a s i l z e o l i t e s . Again

no m - C r i s formed, the o-isomer dominates and t h e s e l e c t i v i t i e s are hardly
conversion (and ToS) dependent. I n contrast t o what i s observed f o r 0- and p-
xylenes, the ZSM-5 pores are unable to influence significantly the
distribution o f 0- and p-Cr by product shape s e l e c t i v i t y . From Figs. 3 and 4
i t f o l l o w s t h a t t h e o-Cr s e l e c t i v i t y i s lower i n t h e Ph than i n t h e An
alkylation with methanol. All this indicates that the intramolecular
rearrangement o f An t o o-Cr i s a major primary pathway. The same was reported
f o r t h e An conversion on H-ZSM-5 i n absence o f methanol [15].

100

90
A H-ZSY-6

80 C H-USV(V)

0 H-ZSY-11
70

60

50
0 20 40 60 80

Conversion (%I

Fig. 3. o-Cresol selec i v i t y i n the methylation o f anisole a t 473 K and w i t h

W/Fo = 1,736 kg s mol- . f
100

--
;P 80
*
--
c
.-0
u
0
60
a 0 0 0
0

-
Po

0
40 0
0
Po
0
t 20

0
0 10 20 30 40 50

Conversion (%)

Fig. 4. C r e s o l - s e l e c t i v i t y from the methylation o f Ph w i t h methanol a t 473 K,

w i t h o-Cr (open p o i n t s ) , p-Cr ( f u l l p o i n t s ) and W/Fo = (a) 1,736 and (b) 278
kg s m o l - l .
216

Methvlanisole sel e c t i v i t v i n the a l k v l a t i o n o f a n i s o l e w i t h methanol

Table 2
Comparison o f the d i s t r i b u t i o n o f methylanisoles from a n i s o l e a l k y l a t i o n w i t h

Catalysts I
methanol a t 473 K, 3 hours on stream and w i t h W/F,

H-USY(T) I H-USY(V)
=

I
1,736 kg s m o l - l .
H-ZSM-5 I H-ZSM-11 1
Conversion o f anisole I%)
I 30.0 I 58.4 I 60.9 1 49.6
S e l e c t i v i t y i n the mAn-fractiona
ortho
para

am-mAn i s n o t detected.
1 20.4
71.6 I 30.5
69.5 1 0.1
99.9 1 0.0
100.0

As can be seen from Table 2, the p-mAn s e l e c t i v i t y i s almost 100% on

p e n t a s i l z e o l i t e s and much lower on z e o l i t e Y. Thus t h e s e l e c t i v i t y i n the
carbon a l k y l a t i o n r e a c t i o n o f An i s determined by t h e presence o f the s t e r i c
c o n s t r a i n t s exerted by the z e o l i t e pore s t r u c t u r e .

Overall a c t i v i t y i n t h e a l k v l a t i on o f DhenOl w i t h methanol

60

-
3
E
.-0 40
t
2e
0

-c
0

0 20
0
c
P

0
0 5 10 15 20

Time (h)

P.
Fig. 5. Phenol conversion i n t h e r e a c t i o n o f phen 1 w i t h methanol a t 473 K
and W/Fo = (a) 1,736, (b) 695 and (c) 278 kg s mol-

Fig. 5 shows t h a t H-USY(V) i s more a c t i v e than t h e p e n t a s i l z e o l i t e s and

H-USY(T), which have the same a c t i v i t y . Only the a c t i v i t y sequence between
USY and p e n t a s i l z e o l i t e s i s d i f f e r e n t from t h a t observed i n t h e a l k y l a t i o n
o f An. I n t h e r e a c t i o n o f Ph w i t h methanol all primary r e a c t i o n s are
bimolecular and thus favoured on Y z e o l i t e s , whereas i n t h e a l k y l a t i o n o f An
 217

some o f the major pathways are monomolecular, such as t h e d e a l k y l a t i o n and

intramolecular rearrangement o f An, and t h e r e f o r e favoured on p e n t a s i l
zeolites. All t h i s explains t h e d i f f e r e n c e i n r e l a t i v e a c t i v i t y o f the
z e o l i t e s i n the Ph and An a l k y l a t i o n . L i k e i n t h e a l k y l a t i o n o f An, H-USY(V)
i s more a c t i v e than H-USY(T), and H-ZSM-11 apparently shows an increased
resistance against deactivation.

Overall s e l e c t i v i t v i n the a l k v l a t i o n o f ohenol w i t h methanol

Table 3 i n d i c a t e s t h a t the product s e l e c t i v i t y between the two p e n t a s i l
z e o l i t e s i s only s l i g h t l y d i f f e r e n t and can be a t t r i b u t e d t o a conversion
e f f e c t : when the contact time decreases the An s e l e c t i v i t y increases a t the
expense o f C r , Xy and mAn. Xylenols and mAn are secondary products and t h e i r
formation i s suppressed a t lower contact times. Cresols are p a r t l y secondary
products because they are formed e i t h e r by the a l k y l a t i o n o f Ph o r the
intramolecular rearrangement o f An. On the contrary, An can o n l y be formed by
a primary reaction.

An 15.3 32.9 22.8 40.9 42.6 9.3 26.7 14.1 23.1

Cr 52.4 58.4 40.7 42.2 43.0 82.3 73.3 79.3 76.9
XY 7.2 4.8 13.8 9.0 8.4 2.9 0.0 1.8 0.0
mAn 25.1 3.9 22.7 7.9 6.0 5.5 0.0 4.8 0.0

For the USY z e o l i t e s Table 3 shows s i g n i f i c a n t d i f f e r e n c e s i n An, mAn

and C r s e l e c t i v i t i e s . A t equal conversion and d i f f e r e n t contact times, o r
v i c e versa, always more An and l e s s C r i s formed on H-USY(V), i n d i c a t i n g t h a t
0 - a l k y l a t i o n i s p r e f e r r e d over the z e o l i t e w i t h t h e lower Brrnsted a c i d
strength. I t i s n o t unexpected t o observe t h i s as the e l e c t r o n d e n s i t y o f the
oxygen i n Ph i s higher than on t h e o/p p o s i t i o n s o f t h e aromatic nucleus.
218

Table 3 also shows t h a t a t the same contact t i m e t h e s e l e c t i v i t y f o r C r

i s higher on p e n t a s i l than on z e o l i t e s H-USY. For An, mAn and Xy t h e opposite
i s observed. A p o s s i b l e explanation could be t h e presence o f stronger a c i d
s i t e s on p e n t a s i l z e o l i t e s , favouring carbon a l k y l a t i o n . On t h e other hand,
An i n p e n t a s i l s could be p r e f e r e n t i a l l y consumed v i a a monomolecular r e a c t i o n
which c o n t r i b u t e s t o t h e formation o f o-Cr.

Cresol s e l e c t i v i t v i n t h e a l k v l a t i o n o f DhenO1 w i t h methanol

1.50

1.00
11
t

* *

0.50
0 20 40 60

Conversion (%I

Fig. 6 . The o/p r a t i o o f c r e s o l s agyinst conversion a t 473 K w i t h W/Fo = (a)

1,736, (b) 695 and (c) 278 kg s mol- .
Fig. 6 shows t h a t t h e o/p r a t i o i n t h e C r - f r a c t i o n i s higher on p e n t a s i l
than on H-USY z e o l i t e s . Apparently, o-Cr i s a primary product. However, it
cannot be excluded t h a t the lower d i f f u s i o n r a t e o f An i n p e n t a s i l z e o l i t e s
favours the monomolecular rearrangement o f An t o o-Cr. Indeed, as shown i n
previous sections, t h e intramolecular rearrangement o f An t o o-Cr proceeds
f a s t e r on p e n t a s i l z e o l i t e s .
The o/p r a t i o decreases f o r t h e p e n t a s i l z e o l i t e s w i t h ToS. Possibly
t h i s i s t h e r e s u l t o f coke d e p o s i t i o n decreasing t h e e f f e c t i v e pore s i z e
e i t h e r by a mechanism o f pore-mouth b l o c k i n g o r by a homogeneous deposition
throughout t h e c r y s t a l .
I r r e s p e c t i v e o f t h e contact t i m e and t h e amount o f coke, a s i n g l e curve
i s found f o r each USY sample. The o/p r a t i o i s determined by t h e conversion
and n o t by t h e coke content. On those z e o l i t e s t h e o/p r a t i o increases when
the conversion decreases. It seems t h a t p-Cr i s p a r t l y a secondary product
and probably the r e s u l t o f Ph methylation w i t h An. The d i f f e r e n c e i n t h e o/p
r a t i o between the two USY samples over t h e whole conversion range can be
explained by t h e i r d i f f e r e n c e i n a c i d strength. Indeed, on H-USY(T), because
 219

of its higher acid strength, carbon alkylation dominates over oxygen

a l k y l a t i o n , r e s u l t i n g i n lower o/p r a t i o s .

Methvlanisole and xvlenol selectivitv i n the a l k v l a t i o n o f Dhenol w i t h

methanol

Table 4
Comparison o f t h e d i s t r i b u t i o n o f methylanisole and xylenol isomers from
phenol a l k y l a t i o n w i t h methanol a t 473 K, a f t e r 1 hour on stream and a t
d i f f e r e n t contact times.

Catalysts 1 H-USY(T) 1 H-USY(V) 1 H-ZSM-5 1 H-ZSM-11

l,&-, (kq s m o l - l l
I 695 278 I 695 278 204 11,736 278 11,736 278
Conversion o f phenol (%l
1 29.2 13.1 I 56.1 30.1 24.7 1 44.0 10.2 I 24.5 7.6

ortho 21.2 33.1 28.3 33.1 33.0 0.0 0.0 0.0 0.0
meta 4.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
para 74.2 66.9 71.7 66.9 67.0 100.0 0.0 100.0 0.0

100.0
0.0
0.0
0.0
100.0
0.0 0.0
O*O I
w e l l as on H-USY z e o l i t e s
the l e s s bulky isomers o f mAn and Xy are p r e f e r e n t i a l l y formed. As a r e s u l t
2,4-Xy and p-mAn are almost e x c l u s i v e l y obtained on the 10-MR z e o l i t e s ,
whereas on USY minor amounts o f 2,6-Xy and o-mAn are formed i n a d d i t i o n .

Comoarison o f Dentasil w i t h USY z e o l i t e s i n t h e anisole and Dhenol a l k v l a t i o n

Based on t h e r e s u l t s obtained, an o v e r a l l r e a c t i o n scheme i s proposed
f o r p e n t a s i l and H-USY z e o l i t e s . It i s shown t h a t bimolecular r e a c t i o n s are
favoured on H-USY compared w i t h 10-MR z e o l i t e s . Oxygen (1) and carbon (2)
a l k y l a t i o n o f Ph are f a s t e r on H-USY z e o l i t e s . Once An i s formed, it is
rearranged faster on p e n t a s i l than on H-USY zeolites by monomolecular
reactions, such as d e a l k y l a t i o n t o Ph (-1) o r intramolecular rearrangement t o
o-Cr (3). I n t h e An a l k y l a t i o n the important primary reactions are o f
monomolecular nature and t h e conversion on USY compared w i t h p e n t a s i l
z e o l i t e s i s suppressed. The o-Cr s e l e c t i v i t y i s improved on 10-MR z e o l i t e s .
Methylanisoles are obtained by t h e a l k y l a t i o n r e a c t i o n o f An (4) and C r (5)
220

and favoured on large-pore zeolites. On pentasil zeolites a high p-

s e l e c t i v i t y i s obtained, b u t d e a l k y l a t i o n i s favoured on those z e o l i t e s .

lpentasil zeolites1

..'..'
4

..
T
( 4 ) MeOH
( 4 b&.fMeOH
..*..' I
( 5 ) MeOH

Q-./

CONCLUSION
I t i s shown t h a t bimolecular r e a c t i o n s are favoured on H-USY and
monomolecular r e a c t i o n s on p e n t a s i l z e o l i t e s . I n t h e a l k y l a t i o n o f anisole
w i t h methanol, d e a l k y l a t i o n and i n t r a m o l e c u l a r rearrangement o f a n i s o l e are
primary reactions. For t h i s reason t h e conversion on p e n t a s i l z e o l i t e s i s
increased i n t h e a l k y l a t i o n o f a n i s o l e w i t h methanol compared t o the
a l k y l a t i o n o f phenol. The opposite i s observed on H-USY. The 10-MR z e o l i t e s
are l e s s a c t i v e i n t h e phenol conversion than H-USY. As t h e rearrangement o f
anisole t o o-cresol i s favoured on 10-MR z e o l i t e s , t h e s e l e c t i v i t y f o r o -
cresol i s higher on those z e o l i t e s compared w i t h H-USY f o r both a n i s o l e and
phenol a l k y l a t i o n . Differences i n a c t i v i t y and s e l e c t i v i t y between H-USY
z e o l i t e s w i t h d i f f e r e n t framework alumina content i s explained by d i f f e r e n c e s
i n acidity. A higher Brdnsted a c i d s t r e n g t h o f t h e z e o l i t e framework i s
responsible f o r more carbon a1 k y l a t i o n .
 221

ACKNOWLEDGMENTS
The authors are g r a t e f u l t o the Belgian Government, Programmatie
Wetenschapsbeleid, f o r sponsoring t h i s research i n the frame o f a "Concerted
Action on Catalysis". P.A.J. acknowledges as a p o s i t i o n as Research D i r e c t o r
from the National Fund f o r S c i e n t i f i c Research (Belgium).

REFERENCES
1 T. Yashima, Y. Sakaguchi and S. Namba, 7 t h I n t . Congr. Catal., Tokyo,
Ed. by T. Seiyama and K. Tanabe, E l s e v i e r (Amsterdam), (1980) 739-751.
2 L.B. Young, S.A. B u t t e r and W.W. Kaeding, J. Catal., 76 (1982) 418-432.
3 D.D. Do, Am. I n s t . Chem. Eng. J., 31 (1985) 574-580.
4 R. Pierantozzi and A.F. Nordquist, Appl. Catal., 21 (1986) 263-271.
5 A.A. Agaev and D.B. Tagiev, 2. P r i k l . Kh., 58 (1985) 2734-2735.
6 J. Yamawaki, T. Ando, Chem. Letters, (1979) 755-758.
7 P.D. Chantal, S. Kaliaguine and J.L. Grandmaison, Appl. Catal., 18 (1985)
133-145.
8 M. Renaud, P.D. Chantal and S. Kaliaguine, Can. J. Chem. Eng., 64 (1986)
785-791.
9 M. Marczewski, G. Perot and M. Guisnet, Proc. o f 1 s t I n t . Symp. Heterog.
Catal. and Fine Chem., P o i t i e r s , (1988) P80-P89.
10 P. Beltrame, P.L. Beltrame, P. C a r n i t t i , A. C a s t e l l i and L. Forni, Appl.
Catal., 29 (1987) 327-334.
11 P. Beltrame, P.L. Beltrame, P. C a r n i t t i , A. C a s t e l l i and L. Forni, Gazz.
Chim. It., 116 (1986) 473-474.
12 S. Balsama, P. Beltrame, P.L. Beltrame, P. C a r n i t t i , L. Forni and 6 .
Z u r e t t i , Appl. Catal., 13 (1984) 161-170.
13 S. Namba, T. Yashima, Y . I t a b a and N. Hara, Stud. Surf. Sci. Catal., 5
(1980) 105-111.
14 L.B. Young and N.J. Skillman, U.S. Pat. 4,371,714 (1983), assigned t o
Mobil O i l Corporation.
15 J.M. Jacobs, R.F. Parton, A.M. Boden and P.A. Jacobs, Proc. o f 1 s t I n t .
Symp. Heterog. Catal. and Fine Chem., P o i t i e r s , (1988) C70-C79.
16 J.M. Campelo, A. Garcia, D. Luna, J.-M. Marinas and M.-S. Moreno, B u l l .
SOC. Chim. France, (1988) 283-292.
17 J.M. Campelo, A. Garcia, D. Luna, J.-M. Marinas and M.-S. Moreno, Proc. o f
1 s t I n t . Symp. Heterog. Catal. and Fine Chem., P o i t i e r s , (1988) P54-P63.
18 P.A. Jacobs and J.A. Martens, Stud. Surf. Sci. Catal., 33 (1987) 19,
r e c i p e 10.b.
19 P.A. Jacobs and J.A. Martens, ibid., 20-21, r e c i p e 11.
20 Unpubl ished r e s u l t s
This Page Intentionally Left Blank
H.G. Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
Amsterdam - Printed in The Netherlands
0 1989 Elsevier Science PublishersB.V.,

ACIDITY EFFECT OF ZSM-5 7lEOLITES ON PHENOL METHYLATICN RFACI'ION

N.S. CHANG, C.C. CHEN, S.J. CHU, P.Y. CHEN and T.K. CHUAhG
Union Chemical Laboratories, ITRI
321, Kuang F'u Road, Sec.2, Hsinchu, %iwan, R.O.C.

ABSrRAm
Vapr-phase phenol alkylation with methanol over ZSM-5 zeolites and modified
ZSM-5 zeolites was studied. The main products of the reaction were cresols.
?he shape-selective effect w a s obscure in cresol fonnation, and strong acid
sites were responsible for m-cresol fonnation. fithemre, the strong acid
sites on the external surface played a major role in cresol isanerization.

INTRODUCTION
Cresols are important intermediates for producing phosphate
plasticizers, phenolic resins and antioxidants in the chemical
industry. With increasing demand and limited supplies from
petroleum refinery waste and coal tar, the development of new
synthesis processes for cresol is increasingly important (ref. 1).
The alkylation of phenol with methanol over solid catalyst has
been considered to be an interesting process. There were different
types of catalysts, including metal oxides and zeolites, t o be
investigated in the vapor phase (refs. 2-6). Metal oxides with
acid-base properties, such as MgO or FezOs-ZnO, were recently
reported to promote the direct ortho-substitution to yield an
ortho-methylated product without passing through anisole as an
intermediate (ref. 4). However, alkylation of phenol with methanol
over zeolite proceeded via 0-methylation and C-methylation to
produce anisole and cresols respectively (ref. 2), as follows:

OCH 3
A

bH
224

The present paper compares various kinds of catalyst for

phenol methylation and concerns mainly the acid sites that in-
fluence the cresol formation. Finally, a reaction pathway is
postulated according to the investigation.

EXPERIMENT
Catalyst preparation
(i) Zeolite synthesis: NaZSM-5 zeolites with different SiOz/
A1203 ratios (30-680) and zeolite-@ with SiOz/Alz03 ratio of 30
were prepared in our laboratory, according to the well-known Mobil
patents (ref. 7 - 8 ) . Details on the preparation of Na-form and H-
form zeolite could be found elsewhere (ref. 9).
(ii) Zeolite modifications
Impregnation: HZSM-5 zeolite was first soaked in its
impregnation solution overnight, then dried and calcined at 550°C
for six hours.
Ion exchange: HZSM-5 was ion-exchanged with 0.1 M magnesium
nitrate or calcium nitrate many times until the maximum exchange
capacity was reached and then filtered, washed and dried.
Vapor deposition: Tetraethyl orthosilicate (Si(OCzH,))
was employed as modification reagent. 300 vl of Si(OCaH,) was
pulsed and vaporized with NZ stream into the reactor at 400°C
prior to the reaction test.

Catalyst characterization
The crystallinity of the prepared zeolite was checked by X-ray
diffraction. The chemical composition analysis of the prepared
zeolite was carried out following the procedure of Hillebrand
et al. (ref. 10). Prior to acidity measurement, all the catalysts
were activated under air stream at 550°C for 2 hours and purged
with helium for one hour. The total acidity was determined by
the temperature-programmed desorption (T.P.D.) of NH3 as shown
previously (ref. 11).

Catalyst evaluation
Reactions were carried out in a fixed-bed reactor (7 mm i.d.)
containing 0.5 g of 20-30 mesh catalyst. The catalysts were
preheated in a stream of air at 500°C for 3 hours before reaction.
Reactants were fed by a syringe pump, vaporized and mixed with
preheated carrier gas N Z by flowing downward to the catalyst bed.
 225

The reaction effluents were cool and collected in a cold trap

(-5°C). The non-condensable gas flow was measured by a wet-test
meter and analyzed by gas chromatography using a Porapack Q column.
The collected liquid products were analyzed by a HP-5730A gas
chromatograph with a Carbopack C/O.l% SP-1000 glass column.
The catalytic activity and selectivity were expressed by
(moles of reacted phenol/moles of supplied pheno1)xlOO and (moles
of reacted product/moles of supplied phenol)x100, respectively.

RESULT AND DISCUSSION

Catalytic activitv and selectivitv
The alkylation of phenol with methanol was studied initially
by comparing various kinds of catalyst. The reaction occurred
to give a reaction mixture of cresol isomers as the principal
products, and results were summarized in TABLE 1. Methanol was
very reactive over zeolites (ref. 12), and Cz-C3 olefin produced
in this manner also reacted with phenol to form undesired aromatic
compounds. Those would be all lumped in the "other" term speci-
fied in TABLE 1.

TABLE 1
Catalytic activity and selectivity of various catalysts
~ ~~~

Catalyst' a ' T - A L O ~ --5(35) Zeolite-C(30) HZSH-5(60) HZSH-5(150)

Acidity
(mmoleig cat.)
weak sites 0.206 0.833 1.029 0.745 0.355
(70-400"C)
strong sites 0.024 0.037 0.301 0.337 0.214
(400-600"C)
total sites 0.230 0.870 1.330 1.082 0.569
s/w 0.117 0,044 0.293 0.452 0.603
PhOH conv. (molX) 48.8 39.1 45.0 49.5 55.2
Prod. s e l . (molX)
anisole 7.4 12.6 3.8 0.0 0.0
o-cresol 58.1 37.9 35.1 26.3 26.3
a-cresol 0.9 16.1 16.6 30.1 28.2
p-creso 1 2.3 16.6 11.6 11.3 10.8
DNP' b , 17.1 11.6 12.6 13.1 18.5
others' 14.1 5.2 20.3 19.2 16.6
(a) The molar ratio of SiOs/AlsOa during preparation is shown in the parentheses
(b) 2.6-dimethylphenol for 7-AlnOs, 2,4- and 2,5-dimethylphenol for zeolites
(c) lnclude methylanisole, alkylbenzenes and DHP other than those described in (b)
Condition:
reaction temp. 400"C, WHSV 0.98-1.04 hr-' (based on phenol)
PhOH/NeOH/HsO = 1/1/5, time on stream 3-4 hrs, carrier Nu 390 Nml/hr
226

NaZSM-5(35) or r-Al~.Oawith relatively weak acid sites, as

shown in TABLE 1 , readily catalyzed the methylation of phenol.
However, the conversion of phenol did not increase when the number
of total acid sites increased and seemed to be proportional to the
ratio of strong acid sites to weak acid sites ( S J W ) . This indicat-
ed that strong acid sites might be responsible for some kinds of
reaction. Presumably, o-cresol and p-cresol were preferable formed
in an electrophilic substitution reaction, and the secondary reac-
tion (such as isomerization and transalkylation) was confined due
t o the limited number of strong acid sites. On the other hand,the
fact that 0- and p-cresol were thermodynamically unfavored (TABLE
2 , ref. 1 3 ) resulted in the reduction of phenol conversion.

TABLE 2
Equilibrium concentrations of cresol isomers
T ("lo 298.16 400 500 600 700 800
m-cresal 78.1 69.9 63.2 58.6 54.2 51.7
p-cresol 2.6 4.7 6.5 7.7 9.2 10.0
o-cresol 19.3 25.4 30.3 33.7 36.6 38.3

The selectivity of anisole decreased with increasing S/W ratio

which inferred that anisole was also the primary product produced
on weak acid sites, as proposed by other workers (ref. 5). The
high selectivity of ortho-substituted phenol over Y-A1203 could be
well elucidated by a mechanism in which a dissociative adsorption
of phenol on the surface was assumed. The ortho-position of the
surface phenoxides was easily attacked by the proximately adsorbed
alcohol (refs. 14-15).
The o-cresol predominance indicated that in our study the shape-
selective effect was obscure in cresol formation. Accordingly, a
plausible mechanism was considered analogous to the mechanism of
toluene methylation over ZSM-5 proposed by Kaeding et al. (ref.16).
The oxoniom ion was formed by the protonation of methanol, but
somehow both ortho- and para-position of phenol could be attacked
without steric hindrance.
Nevertheless, 2,4-and 2,5-dimethylphenol had a smaller minimum
dimension than the other isomers and were produced in significant
excess. This was consistent with the isomers expected for reactions
occurring within a restricted space of zeolite.
 227

To suppress the formation of anisole under specified conditions,

further studies were carried out on the relationship between the
selectivity of cresol isomers and acidity of ZSM-5 zeolites.

Effect of Si02/A1~03ratio
HZSM-5 zeolites with SiOz/Alz03 ratios from 60 to 680 were
employed to afford an insight into the nature of acidity on phenol
methylation. Generally, the acid strength of zeolite increased
with increasing SiOz/A1~03ratio, and the number of acid sites
decreased correspondingly. The crystallite size of ZSM-5 bacically
increased with increasing SiOz/A1203 ratio. As a result, the
number of strong acid sites on external surface would increase
when the A1 content increased. Fig. 1 shows the influence of
strong acid sites on the composition of cresol isomers. The m-
cresol isomers increased from 20.2% to 44.5% by increasing the
number of strong acid sites. Only a small change was observed in
para-isomer (20.4%-15.9%), and was higher than the equilibrium
value (7.7%-9.2%, TABLE 2). It was suggested that m-cresol iso-
mers were formed by the isomerization of o-cresol on the strong
acid sites. More details would be discussed later.

0
0
+J

0"
4o I HZ (255).
. m-cresol
pcresol

(150).

HZ (150)
r(60)
HZ (100)
HZ (60)

I I I I I

0.1 0.3
strong acid sites (mnol/g Z. )
'

Fig. 1. Effect of strong acid sites on the formation of

cresol isomers.
Reaction conditions are described in TABLE 1
228

Effect of modification
During our studies with various modified catalysts to enhance
p-cresol selectivity, no matter what impregnation or ion exchange
method was used, shape-selection was still vague in p-cresol
formation except for MgO-HZSM-5 and SiOzfHZSM-5.

TABLE 3
Effect of HZSM-5 catalyst modification

t,ata!ysr' dZSH-5 F.C,/HZ H g O , H Z BLOJ!iiZ La,O,/HZ HE-HZ Ck-HZ SlO.,'HZ

Imprg amoun? - 3 1 u t 5 8 . 9 wt% 3 5 ut9, 5.0 wt% -
(meta! 0 x 2 2 )
Ac:d:ty
(mmo1e.g c a t . )
strong s i t e s G.;14 0.085 0.197 0.216 0.060 0.225 0 . 1 2 3 -
(70-400"Cj
weak sites 0.355 0.406 0.746 0.459 0.504 0.779 0.486 -
i4 0 0- 6 0 0*' C )

Hodi f . met hod - imprg. imprg. imprg. imprg. ion- ion- vapor
exc. EXC. dep.
P h O H conv.(moli) 55.2 59.8 40.5 54.5 53.1 57.4 58.0 29.9
Prod. SEl.(mol%)
ani so l e -- 1.3 5.2 - 5.8
cresols E3.1 63.7 69.0 67.0 70.1 66.1 63.4 78.7
DI(pl h i 18.5 21.7
2 1.115
15.8.817.0 u 20.1 20.7
20 . u
72 0 . 1 12.5
Cresol ccomp.
o w . (%)
m-c re s o l 43.5 24.5 19.3 37.8 36.9 40.1 39.1 17.9
P-cresol 15.9 17.3 24.5 15.4 14.6 14.6 14.8 27.7
0-c reso 1 40.6 58.2 56.: 46.8 48.5 45.3 46. 54.4
(a) The molar r a t i o of SiOa/A1.03 i s 150
!b) 2.4- and 2,5-dimethylphenol
Reaction c o n d i t i o n s are described i n TABLE 1

As seen in TABLE 3 , vapor deposition of Si(OCzH,) reduced

both the activity of the catalyst and the fraction of m-cresol.
It was believed that this material might react with silanol
hydroxyls on the external surface to form a surface layer without
active sites (ref. 18). As a result, the covering and deactiva-
tion of the external surface reduced the isomerization of products
formed within the pore structure without significantly blocking
the diffusion of molecules in and out the catalyst.
The external surface of ZSM-5 could be partially covered by
impregnation of MgO to a certain degree as reported earlier (ref.
9). Modification of phosphoric acid was also shown to convert
strong acid sites into weak acid sites without changing the overall
 229

acid-base properties(ref. 19). All those treatments reduced the

isomerization of o-cresol to m-cresol on the external acid sites,
and slighly enhanced the formation of p-cresol. However, the
zeolite modified by Bz03 exhibited less modification effect than
that modified by MgO. This might be attributed to the less amount
of Bz03 used and the smaller ionic radius of boron.
La203/HZ, Mg-HZ and Ca-HZ catalysts showed similar activity to
the parent zeolite, regardless of the S/W ratio. This was probably
due to the creation of new active sites by hydrolysis of modified
elements under H,O-enriched environment (ref. 20). Further experi-
ments are needed to verigy this point.
We believe that strong acid sites on the external surface
played a major role in m-cresol formation. Therefore it could be
concluded that the alkylation of phenol with methanol over ZSM-5
zeolite proceeded via fast 0-methylation t o anisole and C-alkyla-
tion to p-/o-cresol, followed by isomerization to m-cresol on
strong acid sites (mostly on the external surface), towards ther-
modynamic equilibrium.

REFERENCES
1. “Toluene, the Xylenes and Their Industry Derivatives” Chemical
Engineering Monograph 15, 1982. p. 209
2. S. Balsama, P. Beltrame, P.L. Beltrame, P. Carniti, L. Forni
and G. Zuretti, Applied Catalysis 13, 161(1984)
3. P. Beltrame, P.L. Beltrame, P. Carniti, A. Castelli and L.
Forni, Applied Catalysis 29, 327(1987)
4. K. Tanabe, Catalysis by Acids and Bases, Elsevier, Amsterdam,
1985, pp. 1-13
5. S. Namba, T. Yashima, Y. Itaba and N. Hara, Catalysis by
Zeolites, Elsevier, Amsterdam, 1980, pp.105-111
6 . F. Nozaki and I. Kimura, Bull. Chem. SOC. Japan 50, 614(1977).
7. R.J. Argamer, U.S. Patent 3702886 (1972).
8. R.L. Wedlinger, U.S. Patent 3308069 (1967).
9. P.Y. Chen, M.C. Chen, H.Y. Chu, N.S. Chang and T.K. Chuang,
Proc. Int. Zeolite Conf., 7th, Tokyo (1986), pp. 739-746
10.W.F. Hillebrand, C.E.F. Lundell, H.H. Bright and J.H. Hoffman,
Applied Inorganic Analysis, John Wiley and Sons, New York, 1953
ll.K.J. Chao, B.H. Chiou, C.C. Chu and S.Y. Jeng, Zeolites 4, 2
(1984)
12.C.D. Chang and A.J. Silvestri, J. Catal. 47, 249(1977)
13.J.H.S. Green, Chemistry and Industry Sep. 1 , 1575(1962)
14.S.V. Kannan and C.N. Pillai, Indian J. Chem. 8, 1144(1970)
15.S. Oae and R. Kiritani, Bull. Chem. SOC. Japan 39, 611(1966)
16.W.W. Kaeding, C. Chu, L.B. Young, B. Weinstein and S.A. Butter,
J. Catal. 67, 159(1981)
17.N. Takamiya, T. Kondo and S. Murai, Weseda University Report, 21
(1975)
230

18. M. Niwa, S. Morimoto, S. Kato, T. Hattori and Y. Murakami, J.

Chem. SOC. Faraday Trans. 1. 80, 3135(1984)
19. J.A. Lecher and G. Pumplmayr. Applied Catalysis 25, 215(1986)
20. C.J. Plank. Proc. Intern. Congr. Catal., 3rd Amsterdam, 1964,
p. 727
H.G. Karge, J. Weitkamp (Editors), Zeolites 0s Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

A NEW CATALYST F(x1 MIEX SYNTHESIS --- PALLADIUM (3N ZS-5 ZElOLITES

P.Y. CHEN, S.J. CHU, N.S. CHMG, T.K. CHUANG and L.Y. UBN
Union Chenical Laboratories, I'IRI
321, Kumg Fu Road, Sec. 2, Hsinchu, Taiwan, R. 0.C.

AEsrRAm
The one-step vapour phase synthesis of methyl isobutyl ketone (MIBK) was
extensively studied on supported bifunctional W catalysts. Effects of support
acidity and W metal dispersion on both acetone conversion and MIBK selectivity
were examined. It was found that ZSM-5 dified by exchange with alkali metal
cation, especially C s ions, would enhance the selectivity of MIEX. 'lhe results
indicated that MIEX selectivity as high as 82% with the conversion of acetone
about 42% at 250°C could be obtained.

INTRODUCTION
Methyl isobutyl ketone (MIBK) is commercially produced by two
different processes. The conventional three-stage process includes
(1) aldol condensation of acetone to form diacetone alcohol which
is catalysed by a base, ( 2 ) dehydration of the alcohol to r n c S i t V 1
oxide with an acid catalyst, and ( 3 ) hydrogenation of the unsatu-
rated ketone to MIBK with nickel or copper chromite catalyst(1-3).
Recently, i t was reported that the selective one-step synthesis
of MIBK was performed on palladium-exchanged resins (4-5), which
not only cannot tolerate a temperature higher than 160°C but which
also induce polymer formation easily. It is therefore not suitable
for practical application.
In this study Pd/ZSM-5 catalysts modified by alkali metal were
employed for MIBK production.

EXPERIMENT
1. Catalyst preperation
Zeolite synthesis
The ZSM-5 zeolites with different SiOz to AlaO3 ratios were
prepared by adding aqueous aluminum sulfate to water glass and
tetrapropylammonium bromide solutions. After agitating for three
hours, the solution was allowed to crystallize, at 160"C, according
to hydrothermal process. The products were then filtered, washed
232

and dried before calcination in a stream of air at 550°C for 16

hours. The crystallinity of ZSM-5 was checked by X-ray diffrac-
tion.

ZSM-5 modification
HZSM-5 zeolite was ion-exchange with 0.1 M alkali nitrate
solution ( o r 0.01 M Pd(NH4)C12 solution) many times until the
maximum exchange capacity was reached. Subsequently,the material
was filtered, washed and dried.

Supported Pd catalyst
The ZSM-5 zeolite was first soaked in Pd(NH4)C12 solution over- '

night, then dried, calcined and reduced at 400°C for eight hours
in hydrogen atmosphere.

2. Catalyst characterization
The chemical analysis of the prepared zeolites was carried out
according to the procedure of Hillebrand et al. (6). The acidity
was determined by the temperature-programmed desorption (T.P.D.)
of NH3 as shown previously (7-8), and the Pd metal dispersion was
measured by chemisorption of CO (9-10) with a Micromeritics pulse
chemisorb 2700.

3. Catalyst activity evaluation

The reaction was carried out in a fixed-bed reactor at 150-300
"C under one atmosphere pressure. The 3/8" cylindrical reactor
contained 1.7 g of 12-20 mesh catalyst. The reactor effluents
were cooled and collected in a cold trap. The collected liquid
products were analyzed by a HP-5840 gas chromatograph with a 10%
carbowax 20 M f 2% Bentone 34 on chromosorb W HP/ 2% KOH column.

RESULTS AND DISCUSSION

I. Influence of various catalyst supports
The conversion of acetone and the selectivity of each component
over various supported Pd catalysts are shown in Table 1. The
activity shows the sequence Pd/ r-Al203 > > Pd/NaNZ3!1-5,Pd/NaX >
Pd/HZSM-5, Pd/Nap> Pd/USY, Pd/Si02, Pd/TiO2 which indicates that
the activity was highly dependent on the acid strength of the sup-
port. In order to obtain a good acetone converion , a support
with proper acid strength such as y-A1203,NaHZSM-5 and NaX should
 233

be chosen. The selectivity for MIBK varied between 21.1% and

71.1%. No significant relationship could be found between acid
strength and MIBK selectivity. The major by-products were diiso-
butyl ketone (DIBK), light hydrocarbons and isopropyl alcohol.
The highest MIBK selectivity was obtained on Pd/NaHZRr.l-5 and Pd/
HZSM-5, which might be due to the shape effect of ZSM-5 channels
(5.2 x 5.6 i).The large molecular by-product DIBK, which was
formed by trimeric condensation of acetone, would be minimized
due to the narrowness of the ZSM-5 channel.

Table 1. Influence of various catalyst supports .

-~ - .F - -

Acid Conv. of Product selectivity, wle %

Catalyst strength of acetone IpA MIBK Mesityl DIBK Light
supports mole % Oxide hydrocarbons
1% Pd/USY 14.4 7.3 21.1 - - 71.6
1% Pd/HZSM-5 27.6 - 64.7 - 1.4 33.9
1% Pd/Nap 22.6 - 27.1 2.3 - 69.6
1% Pd/NaHZSM-5 41.0 - 71.3 - t 28.7
1% Pd/NaX a 36.9 17.0 39.3 - 3.8 39.3
a,
m
1% Pd/ T-Al207 d 77.9 3.2 33.7 1.1 31.6 30.6
a,
1% Pd/ 7 -Al2O3* 0
k 39.9 15.9 49.9 - 15.0 19.1
1% Pd/SiO2
a,
a 15.1 24.4 29.4 - - 46.2
1% Pd/TiO:! t 13.2 8.9 46.6 2 . 8 - 41.7
* Reaction temperature: 150°C (others were 25OOC); WHSV: 2 hr-l
H2/Acetone=l/l; time on stream: 4 hours

11. Catalytic properties of ZSM-5-supported Pd catalyst for MIBK

synthesis
(1) Influence of the Al/Si ratio of ZSM-5 supports
As shown in Fig. 1,the activity of 1% Pd/NaHZSM-5 was raised
from around 646 to 42% by increasing the Al/Sl ratio of NaHZSM-5.
The conversion of acetone seemed to be proportional to acidity
of NaHZSM-5 while there were enough metal active sites on the
catalyst. Generally, the acidity of ZSM-5 increased with increas-
ing Al/Sl ratio. The selectivity for MIBK also showed the same
tendency as that observed for the conversion of acetone, whereas
the isopropyl alcohol behaved in an opposite manner. It decreased
drastically when the Al/Si ratio was higher than 4. This might be
due to the fact that in the one-step process condensation, dehydra-
tion and hydrogenation proceed as consecutive reactions. Since the
234

acid sites were responsible for the former two reactions, IPA from
acetone hydrogenation predominated on the catalyst with fewer acid
sites.

Figure I Effect of AI/Si ratio on activity

of I%Pd/NaHZSM -5
Conditions :
Calcination temp.: 400'C i Calcination time :8hr.i reaciion
temp.:250'CjWHSV:2h~';timeonstream:4hr.; H2/
acetone mole r a t i o : I ; pressure : one atmosphere.

(2) Influence of the amount of Pd loading

The properties of supported Pd catalysts are shown in Table 2,
0
where is clear that the average Pd particle size raised from 14 A
to as large as 110 f while the Pd loading was increased from 0.1
wt% to 1.0 wt%. However, no appreciable change in the acidity of
the support was observed. It is therefore suggested that Pd
particles probably were formed on the external surface of the ZSM-5
and/or adjacent to the acid sites in the channels of ZSM-5. The
acid sites of ZSM-5 still remained active for condensation of the
acetone and dehydration of the diacetone alcohol to the interme-
diate product of mesityl oxide.
 235

Table 2. Effect of Pd content on properties of PdINaZSM-5 catalysts

Amount of Acidity(mnol/g cat.) W particles
Catalyst W laxling weak Strong ave. size metal dis.
wt. % (70-400°C) (400-60O0C) A %
O.l%ki/Na€ESM-5* 0.12 1.002 0.256 14 72.97
0.2%M/NaHZSM-5 0.21 0.703 0.225 25 39.88
0.546W/Na€ESM-5 0.45 0.828 0.204 49 20.53
0.74&w/NaHZSM-5 0.62 0.933 0.284 86 12.21
1.04&W/NaHZSM-5 0.94 0.705 0.184 106 9.55
. __ -

* SiO2 to A1203 ratio is 30.

The effect of Pd metal loading is shown in Fig. 2 . The conver-

sion of acetone increased from 33% to 46% initially. However, it
decreased to around 41% by further increasing the amount of Pd
loading. In addition to conversion, the yield of light hydrocar-
bons decreased with further increase in Pd metal loading. It is
very clear from Table 2 that the Pd metal dispersion decreased
rapidly regardless of increasing the amount of Pd loading. The
reason for the low conversion at higher Pd loading might be that
the large Pd particle was formed on the external surface of ZSM-5,
which inhibited the cracking reaction. Furthermore, the fact that
mesityl oxide was not observed until the amount of Pd loading was
higher than 0.3 wt% suggests that the lower conversion at the be-
ginning might be due to a scarcity of active metal sites so that
mesityl oxide could not undergo further reactions.

b*

;' Light hydrocarbons -.\

I
W
v,

AMOUNT OF LOADING , wt %

Figure 2 The effect of palladium loading on MlBK synthesis

( The reaction ccsditions are same as Fig. 1 )
236

( 3 ) Influence of reaction conditions

Fig. 3 illustrates the effect of temperature in the range 150-
300°C. The conversion and selectivity increased gradually with
temperature below 250°C; above 25OoC both dropped rapidly. This
might be because the rate of coking was enhanced above 2 5 0 ° C . The
retardation of acetone conversion might be due to a coverage of the
sites of the catalyst by coke.

50 - 100

h
o\o A Q -
-
U

v
E" 3c
'Light hydrocar<$'
-60 -
0
E

-
>
I-
2
z
l
n
E
W 2c-
L
/ b/ 'I\
-JO f
>
z /' M.I.B.K. -/h 0
W
-J
0
10-
d
k -20
W
"'

0 I I 0
100 150 200 250 3CO 350

Fig. 4 shows the effect of acetone space velocity on its conver-

sion at 2 5 0 ° C . Although the conversion decreased with increasin::
space velocity, the change in MIBK selectivity was less pronounced at
WHSV higher than 2 . 0 . Below this value, MIBK increased with in-
creasing WHSV. In contrast, the selectivity for DIBK decreased
when the WHSV was increased to 2; above this value, DIBK was no
longer detected. This finding indicated that acetone would con-
densate to trimeric species when the contact time was long enough.
The optimum range of WHSV is above 2.
 231

1 1 1 . Influence of various modified ZSM-5 supports

In order to obtain a good yield of MIBK, the ZSM-5 support was
modified by ion exchange with various al!tali metal ions and palla-
dium ions. The results are shown in Table 3. It is clear from
Table 4 that all modified Pd/ZSM-5 catalysts (except Pd/HZSM-5)
exhibited significantly higher activity, which might be due to a
partial replacement of strong acid sites by alkali metal ions.
Moreover, although the weak acid sites of Pd/CsHZSM-5 were reduced
to almost half of the other catalyst, the high conversion over Pd/
CsHZSM-5 as well as its high MIBK selectivity suggest that basicity
might promote the reaction. Further experiments are needed to
verify this point.
238

Table 3. Catalytic properties of modified ZSM-5 supported Pd

catalysts
-
&changed Acidity Aver. conv. of selectivity
CATALYST cations weak strong W 5ize acetone MIBK DIBK Others
(n:mle/g cat.) ( A ) (mole %) (mole $1

w
-
H
Z
S
M
-
5 w 0.558 0.360 256 22.6 82.3 5.2 12.6
1%M/HzsM-5 - 0.688 0.352 206 27.6 65.5 1.5 33.3
l%M/NaHZSM-5 Na 0.705 0.184 106 41.0 71.4 - 28.8
1W/KHZsM-5 K 0.719 0.069 136 45.3 6".7 1.4 33.4
1%Ri/CsHZSM-5 CS 0.343 0 250 41.9 82.4 2.2 15.2

CONCLUSIONS
The experimental data indicate that the one-step vapor phase
synthesis of MIBK from acetone and hydrogen proceeds via a three-
reaction mechanism, namely, condensation, dehydration, hydrogena-
tion. The proper catalyst may be described as follows:
1. The catalyst should have a weak acid strength and enough
active sites of metallic Pd to perform as a bifunctional
catalyst.
2. ZSM-5 zeolite, after modification of its acid strength by
exchange with alkali metal ions, especially C s ions, could
be a good support for MIBK synthesis.
3. The behavior of ZSM-5 supported palladium on thermal
stability and selectivity for MIBK is superior to that of a
Pd-resin catalyst.

REFERENCE
1. S . Kudo, "Formation of Higher Molecular Weight Ketones from
Acetone or Isopropanol", J. Chem. SOC. Japan, Ind. Chem.
Sect., 58, 1955, pp 785-7
2. JP 46-2009
3. French Patent 1,535
4. "New Solvent Process", Ind. Research, July 1968,PP. 25-6
5. German Patent 1,936,203
6. W.F. Hillebrand, C.E.F. Lundell, H.H. Bright and J.I. Hoff-
man in "Applied Inorganic Analysis", John Wiley and Sons,
New York, 1953.
7. J.C. Post and J.H.C. Van Hoff, Zeolites, 4, 1984, p . 9
8. K.J. Chao, B.H. Chu, C.C. Chu and S.Y. Jeng, Zeolites, 4,
1984. '?. 2
 239

9. R . K . Nand, R.K. D i t c h a , S . S . Wong, J . B . Iohen, R.L. Burwell

a n d J . B . B u t t , J. C a t a l . , 70, 1 9 8 1 , p . 2 9 8
10. R.J. P a r r a n t o , AIChE Symposium S e r i e s , No. 143, V o l . 7 0 ,
p . 9.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

ACETYLENE HYDRATION ON ZEOLITE CATALYSTS: AN I . R . SPECTROSCOPIC

STUDY OF THE SURFACE S P E C I E S

GY. ONYESTYAK, J . P A P P J r . a n d D . KALLO

C e n t r a l R e s e a r c h I n s t i t u t e f o r C h e m i s t r y o f t h e H u n g a r i a n Academy
o f S c i e n c e s , P.0.Box 1 7 , 1 5 2 5 B u d a p e s t ( H u n g a r y )

ABSTRACT
On l a t e t r a n s i t i o n m e t a l - f o r m s o f z e o l i t e s t h e f o r m a t i o n o f
adsorbed a c e t a l d e h y d e f r o m a c e t y l e n e and z e o l i t i c w a t e r has been
d e t e c t e d by i . r . s p e c t r o s c o p y f r o m 25°C on ( s t e a d y s t a t e c a t a l y t i c
r e a c t i o n p r o c e e d s a r o u n d 18OOC). On Cd-X a n d Cd-A t h e c r o t o n i c
condensation o f acetaldehyde takes place instantaneously r e s u l t i n q
i n t h e f o r m a t i o n o f c o k e r e s i d u e s . A d s o r p t i o n of T-bonded a c e t y -
l e n e i n c r e a s e s w i t h t h e d e h y d r a t i o n of z e o l i t e samples. F o r zeolites
c o n t a i n i n g r e d u c i b l e c a t i o n s a s Cu- a n d A g - c l i n o p t i l o l i t e s a c e t y -
l i d e formation i s observed. N e i t h e r s i d e r e a c t i o n s n o r a c e t y l i d e
f o r m a t i o n a r e d e t e c t a b l e on Cd- a n d Z n - c l i n o p t i l o l i t e s , w h i c h a r e
stable catalysts o f high s e l e c t i v i t y f o r acetylene hydration.

INTRODUCTION
L a t e t r a n s i t i o n m e t a l i o n s i n aqueous s o l u t i o n o r i n t h e f o r m
of o x i d e s , phosphates, tungstates, chromates e t c . a r e a c t i v e f o r
acetylene hydration ( r e f . 1). H i g h e r a c t i v i t y and b e t t e r s e l e c -
t i v i t y w e r e a t t a i n e d when Cu2+, Ag', Cd", Zn2+, Hg2+ i o n s wer
introduced i n X-zeolite (ref. 2). The f a s t d e a c t i v a t i o n o f t h e
c a t a l y s t s was s l o w e d down t o some e x t e n t b y a p p l y i n g m i l d e r
r e a c t i o n c o n d i t i o n s a n d b y p r e t r e a t m e n t w i t h ammonia ( r e f . 3 ) . A
l a r g e v a r i e t y o f l a t e t r a n s i t i o n metal forms o f d i f f e r e n t zeol t e s
was t e s t e d i n o r d e r t o e n l i g h t e n t h e s o u r c e ( s ) o f d e a c t i v a t i o n
and t o a r r i v e a t s t a b l e and s e l e c t i v e c a t a l y s t ( s ) . C o n c e r n i n g t h e
s t a b i l i t y t h r e e groups o f l a t e t r a n s i t i o n metal-forms o f z e o l i t e
c a t a l y s t s o f s a t i s f a c t o r y a c t i v i t y can be d i s t i n g u i s h e d ( r e f . 4 ) :
( i ) c a t a l y s t s as Cd-forms o f X - o r A - z e o l i t e s d e a c t i v a t e due
t o t h e f o r m a t i o n o f carbonaceous depos t s w i t h a C / H r a t i o o f
1/0.6; ( i i ) Cu-, Ag-, Hg-forms o f zeol t e s l o s e t h e i r a c t i v i t y
because t h e a c t i v e c a t i o n s a r e reduced under r e a c t i o n c o n d i t i o n s ;
( i i i ) c l i n o p t i l o l i t e d e r i v a t i v e s conta n i n g i r r e d u c i b l e
t r a n s i t i o n metal c a t i o n s , e.g. t h e Cd- o r Z n - f o r m s ( d e n o t e d as
242

Cd-CLI o r Zn-CLI), p r e s e r v e t h e a c t i v i t y , and no i r r e v e r s i b l e

changes a r e o b s e r v a b l e f o r s e v e r a l hundred h o u r s .
I d e n t i c a l r e a c t i o n m e c h a n i s m s w e r e f o u n d b o t h f o r Cd-X
s t a b i l i z e d b y ammonia p r e a d s o r p t i o n ( r e f . 5 ) a n d f o r Cd-CLI
( r e f . 6). Accordingly, weakly adsorbed a c e t y l e n e and s t r o n g l y
adsorbed water r e a c t i n a r a t e - d e t e r m i n i n g s u r f a c e r e a c t i o n , and
the e q u i l i b r i u m desorption o f acetaldehyde exerts a product
inhibition.
The a b o v e o b s e r v a t i o n o f t h e a c t i v i t y c h a n g e s a s w e l l a s
o f t h e c a t a l y t i c c o n v e r s i o n s h o u l d , however, be c o n f i r m e d and
some d e t a i l s e l u c i d a t e d . The a i m o f t h e p r e s e n t w o r k i s t o d e t e c t
surface species i n connection w i t h the c a t a l y t i c behaviour, i.e.
t o c l e a r up t h e mode o f a d s o r p t i o n o f t h e c o m p o n e n t s i n v o l v e d ,
t o s h e d l i g h t on t h e s u r f a c e i n t e r a c t i o n s a n d t o a t t e m p t t o
f o l l o w t h e h y d r a t i o n r e a c t i o n and t h e s i d e r e a c t i o n ( s 1 on t h e
surface. Typical representatives o f t h e t h r e e groups o f c a t a l y s t s
were chosen t o p e r m i t s u i t a b l e comparisons: f o r g r o u p ( i ) Cd-X
a n d Cd-A, f o r g r o u p ( i i ) Cu- a n d A g - C L I , f o r g r o u p ( i i i ) Cd- a n d
Zn-CLI.

EXPERIMENTAL
Materials
X-zeolite (Strem Chemicals, USA), A-zeolite (Serva, FRG) and
c l i n o p t i l o l i t e as c o n s t i t u e n t o f a r h y o l i t e t u f f f r o m T o k a j H i l l s
( H u n g a r y ) w e r e u s e d . The c o n c e n t r a t i o n o f c l i n o p t i l o l i t e i n t h e
r o c k i s 60%; t h e r e s t i s m a i n l y v o l c a n i c g l a s s , quartz,
c r i s t o b a l i t e a n d some p e r c e n t f e l d s p a r . C l i n o p t i l o l i t e was
p r e v i o u s l y t r a n s f e r r e d i n t o t h e pure sodium-form.
The t r a n s i t i o n m e t a l f o r m s w e r e p r e p a r e d f r o m t h e s e z e o l i t e s
b y i o n - e x c h a n g e w i t h 0.1 M s o l u t i o n o f t h e n i t r a t e s a t 70°C f o r
3 x 8 h o u r s . The i o n - e x c h a n g e f o r s i l v e r was c a r r i e d o u t i n d a r k n e s s
a t r o o m t e m p e r a t u r e . The d e g r e e o f i o n - e x c h a n g e was b e t w e e n 3 0
and 60 p e r c e n t .
The f r a c t i o n s o f l e s s t h a n 5 y m i n d i a m e t e r w e r e d r i e d a n d
p r e s s e d i n t o w a f e r s , w i t h o u t b i n d e r o f 5 - 8 mg/cm2 f o r i . r .
investigations.
A c e t y l e n e was a h i g h p u r i t y D i s s o u s gas ( O D V , H u n g a r y ) .
A c e t o n e was removed b y t r a p p i n g a t - 73°C. A c e t a l d e h y d e was a
Merck ( F R G ) p r o d u c t " z u r S y n t h e s e " grade. C r o t o n i c a l d e h y d e
was p r e p a r e d i n o u r l a b o r a t o r y .
 243

Methods
A P e r k i n - E l m e r 577 d o u b l e - g r a t i n g i .r. s p e c t r o m e t e r was u s e d .
The w a f e r s were i n s e r t e d i n t o a c e l l p r o v i d e d w i t h h e a t i n g f o r
p r e t r e a t m e n t . The c e l l was c o n n e c t e d t o a vacuum s y s t e m a n d a
gas d o s a g e a c c e s s o r y .
1.r. s p e c t r a were r e c o r d e d a f t e r a p r e t r e a t m e n t a t lo-' Pa
f o r 1 h o u r u s u a l l y a t 180"C, i.e. a t t h e average temperature o f
hydration reaction (curves 1 i n f i g u r e s ) , a f t e r t h e adsorption o f
a c e t y l e n e a t 1.3, 2.5 o r 13 kPa, o r a f t e r t h e a d s o r p t i o n o f
a c e t a l d e h y d e a t 0.13 kPa f o r 10 m i n u t e s a t 25°C (curves 2), after
evacuations a t lo-' Pa f o r 2 0 m i n u t e s a t 25°C ( c u r v e s 31, for 1
h o u r a t 100, 200 a n d 350°C ( c u r v e s 4, 5, 6, respectively). The
d i s c u s s e d bands o f t h e s p e c t r a a r e m a r k e d b y a r r o w s .

RESULTS A N D D I S C U S S I O N
C a t a l y s t s d e a c t i v a t i n g because o f coke f o r m a t i o n
A d s o r p t i o n o f a c e t y l e n e on Cd-X ( c u r v e 2 , F i g . 1) can be
d e t e c t e d b y t h e a p p e a r a n c e o f t h e b a n d s a t 3170 c m - l a s s i g n e d t o
t h e a s y m m e t r i c k C - H s t r e t c h i n g v i b r a t i o n a n d a t 1940 c m - l a s s i g n e d
t o t h e C=C s t r e t c h i n g v i b r a t i o n . L E C H Y a s y m i s 3287 c m - l i n the
gas p h a s e ( r e f . 8 ) a n d i t h a s been f o u n d t o d e c r e a s e a f t e r
a d s o r p t i o n on Cu-Y t o 3170 ( r e f . 7 ) . L)CrC c a n be c o r r e l a t e d w i t h
t h e R a m a n - a c t i v e f r e q u e n c y a t 1974 cm- ( r e f . 8 ) The J C - s y s t e m
o f a c e t y l e n e o v e r l a p s w i t h t h e c a t i o n o r b i t a l s and a " s i d e - o n "
a d s o r p t i o n t a k e s p l a c e r e s u l t i n g i n an i . r . a c t i v e c o n f i g u r a t i o n
o f l o w e r e d s y m m e t r y . F o r t h e same r e a s o n t h e v e r y weak b a n d o f
s y m m e t r i c r C - H s t r e t c h i n g v i b r a t i o n a r o u n d 3250 c m - l c a n b e
recognized, too.
A c e t y l e n e r e a c t s e v e n a t room t e m p e r a t u r e w i t h t h e z e o l i t i c
w a t e r bound t o Cd2+ i o n s , a n d a d s o r b e d a c e t a l d e h y d e i s f o r m e d , as
i t i s i n d i c a t e d b y t h e c a r b o n y l a b s o r p t i o n band a t 1 6 9 0 cm-'.
S i m u l t a n e o u s l y t h e r e a p p e a r s a n o t h e r b a n d a t 1635 cm-' assigned
t o a d s o r b e d c r o t o n i c a l d e h y d e . A t 1410 a n d 1360 c m - l t h e
a b s o r p t i o n bands o f a s y m m e t r i c a n d s y m m e t r i c C - H d e f o r m a t i o n
v i b r a t i o n s i n t h e methyl group o f aldehydes a r e seen ( r e f . 9 ) . The
a s s i g n a t i o n s were c o n f i r m e d by s e p a r a t e measurements c a r r i e d o u t
w i t h a c e t a l d e h y d e a n d c r o t o n i c a l d e h y d e . Qc0 f o r a d s o r b e d
a c e t a l d e h y d e i s l o w e r b y 3 0 cm-' a n d f o r a d s o r b e d c r o t o n i c aldehyde
l o w e r b y 45 cm-' t h a n i n t h e f r e e s t a t e ( r e f . 91, w h e r e a s t h e C-H
d e f o r m a t i o n f r e q u e n c i e s a r e t h e same i n g a s e o u s a n d a d s o r b e d
p h a s e s . The a l d e h y d e s a r e bound, most probably, by t h e i r carbonyl groups.
244

When t h e s a m p l e i s e v a c u a t e d a t 25'C, t h e a c e t y l e n e bands

disappear, w h i l e t h e i n t e n s i t y o f b o t h a l d e h y d e bands i n c r e a s e s

I . *--
4000 3500 3000 2000 1800 1600 1400
Wmvonurnber , crn"

F i g , 1. Cd-X a f t e r e v a c u a t i o n a t 180°C ( 1 1 , a f t e r a c e t y l e n e
a d s o r p t i o n a t 2.5 kPa, ( 2 ) f o l l o w e d b y e v a c u a t i o n a t 25'C ( 3 ) ,
1OO'C ( 4 ) , 200OC ( 5 ) , 35OCC ( 6 ) .

( c u r v e 3 ) . A f t e r e v a c u a t i o n a t 100cC t h e t r a n s f o r m a t i o n o f adsorbed
a c e t a l d e h y d e t o c r o t o n i c aldehyde can be observed ( c u r v e 4 ) . The
t r e a t m e n t a t 200'C r e s u l t s i n t h e disappearance o f acetaldehyde
( c u r v e 5 ) a n d a t 350'C i n s t e a d o f t h e c r o t o n i c a l d e h y d e b a n d new
bands emerge a t 1585, 1480, 1450 c m - l , w h i c h c a n b e a t t r i b u t e d t.o
c a r b o n a c e o u s d e p o s i t s ( r e f s . 9, 10).
The i n v e s t i g a t i o n o f t h e b e h a v i o u r o f a d s o r b e d a c e t a l d e h y d e
supports these observations.
I f Cd-X i s p r e t r e a t e d a t 5OOOC ( c u r v e 1 i n F i g . 2 ) , considerably
more a c e t y l e n e i s a d s o r b e d a t 25OC ( c u r v e 2 ) a n d r e m a i n s o n t h e
s a m p l e a f t e r e v a c u a t i o n ( c u r v e 3 ) . The a c c e s s i b i l i t y o f Cd2+
i o n s i s e n h a n c e d b y t h e more e x t e n s i v e d e h y d r a t i o n . Owing t o t h e
lower water content l e s s adsorbed acetaldehyde i s formed than
before (cf. t h e c o r r e s p o n d i n g b a n d i n t e n s i t i e s a t 1690 c m - ' ) . In
s p i t e o f t h e l a r g e r amount o f a d s o r b e d a c e t y l e n e i t s s i d e -
r e a c t i o n p r o d u c t s , e.g. o l i g o m e r s o r benzene c a n n o t be o b s e r v e d .
On c o n t a c t i n g a c e t y l e n e w i t h Cd-A t h e CEC stretching vibration
 245

band of "side-on" adsorbed acetylene at 1 9 4 0 cm-l is strong, EC-H

stretching vibrations are, however, not clearly detectable. The

Fig. 2. Cd-X after evacuation at 500'C ( 1 1 , after acetylene

adsorption at 1.3 kPa ( 2 ) , followed by evacuation at 25'C (3).

I . . . . , . . - - ' .
4MK) 3500 3000 2000 1000 1600 1400
-1
Wavrnumbr , em

Fig. 3 . Cd-A after evacuation at 18OOC ( 1 1 , after acetylene

adsorption at 13 kPa ( 2 1 , followed by evacuation a t 25°C ( 3 ) .
bands of adsorbed acetaldehyde at 1685 cm-' and of adsorbed
crotonic aldehyde at 1630 cm-' are very weak, while the dCH
246

bands a t 1450, 1360 cm-l a r e v e r y i n t e n s e ( c u r v e 2, Fig. 3). After

e v a c u a t i o n a t 25'C ( c u r v e 3 ) t h e a m o u n t o f a d s o r b e d c r o t o n i c aldehyde

1
1

4000 3500 3000 2000 1000 I600 MOO

Wavonumbor, Em-'

F i g . 4. C u - C L I a f t e r e v a c u a t i o n a t 180'C ( 1 1 , a f t e r a c e t y l e n e
a d s o r p t i o n a t 13 kPa ( 2 1 , f o l l o w e d b y e v a c u a t i o n a t 25°C ( 3 ) ,
100°C ( 4 1 , 200°C ( 5 ) .

i n c r e a s e d somewhat, while the JCH

bands diminish, and t h e band
a r o u n d 1580 cm-l a s s i g n e d t o c a r b o n a c e o u s d e p o s i t s ( r e f . 10)
appears; t h e s a m p l e becomes b l a c k .

Catalysts containing reducible active cations

When a c e t y l e n e i s a d s o r b e d o n C u - C L I a t 25OC, a weak s y m m e t r i c
and a s t r o n g asymmetric =C-H s t r e t c h i n g v i b r a t i o n bands a r e
d e t e c t e d a t 3305 a n d 3180 c m - l , respective1y.R-bonding of
a c e t y l e n e i s r e f l e c t e d b y t h e band a t 1950 c m - l ( c u r v e 2, Fig. 4).
The f o r m a t i o n o f a d s o r b e d a c e t a l d e h y d e i s i n d i c a t e d b y t h e
dco
band a t 1705 cm-l and by t h e OC-H s t r e t c h i n g v i b r a t i o n band a t
2 9 2 0 cm-' (ref. 9).
On p u m p i n g a t 25OC ( c u r v e 3 ) t h e a c e t a l d e h y d e b a n d i n t e n s i t y
increases, C-H bands o f a c e t y l e n e a r e s h i f t e d t o w a r d l o w e r
frequencies, t h e band a t 1950 cm-l d i s a p p e a r s a n d a new b a n d i s
o b s e r v a b l e a t 1810 cm-'. Instead o f "side-on" bound a c e t y l e n e ,
 241

a c e t y l i d e appears c h a r a c t e r i z e d by a Uc3 a t 1810 cm-l a n d b y

l o w e r rl, values ( r e f . 10).
=C-H
A f t e r e v a c u a t i o n a t 100°C ( c u r v e 4 ) t h e i n t e n s i t i e s o f

'-I -. __
4000 3500 3000 2000 1800 1600 1400
-1
Wavenumber, cm

F i g . 5. A g - C L I a f t e r e v a c u a t i o n a t 180'C ( l ) , a f t e r a c e t y l e n e
a d s o r p t i o n a t 13 kPa ( 2 ) , f o l l o w e d b y e v a c u a t i o n a t 25°C (31,
100°C ( 4 ) , 200°C ( 5 ) .

a c e t y l i d e b a n d s d e c r e a s e a n d a t 200°C ( c u r v e 5) t h e s e bands
d i s a p p e a r , w h i l e t h e c o n c e n t r a t i o n o f adsorbed a c e t a l d e h y d e does
n o t change. I t d e s o r b s c o m p l e t e l y a t 350°C o n l y .
On A g - C L I t h e a d s o r p t i o n o f a c e t y l e n e a t 25°C r e s u l t s i n t h e
appearance o f one symmetric and two a s y m m e t r i c rC-H stretching
v i b r a t i o n bands a t 3320 and a t 3260, 3 1 9 0 cm-', respectively
(ref. 7), a n d i n t h e f o r m a t i o n o f a d s o r b e d a c e t a l d e h y d e ( c u r v e 2,
F i g . 5 ) . A f t e r e v a c u a t i o n a t 25°C t h e b a n d s a t 3 3 2 0 , 3260 cm-l
d i s a p p e a r . A t 1OO'C t h e a d s o r b e d a c e t a l d e h y d e f o r m a t i o n i n c r e a s e s
a n d t h e i n t e n s i t y o f t h e b a n d a t 3 1 9 0 cm-' does n o t change
e s s e n t i a l l y . B o t h a c e t y l e n e and a c e t a l d e h y d e d e s o r b above 200°C.
No "side-on" adsorbed acetylene b u t some a c e t y l i d e have been detected.
248

C a t a l y s t s of h i g h s t a b i l i t y
O n C d - C L I p r e t r e a t e d i n vacuum a t 45OoC ( c u r v e 1 , F i g . 6 )
b o t h t h e a d s o r b e d a c e t y l e n e and t h e f o r m a t i o n of a d s o r b e d
a c e t a l d e h y d e a r e o b s e r v e d a f t e r a d m i s s i o n o f a c e t y l e n e a t 25*C
( c u r v e 2 ) and a f t e r e v a c u a t i o n a t 25’C ( c u r v e 3 ) . The p r e t r e a t m e n t
a t h i g h e r t e m p e r a t u r e (45OOC i n s t e a d of 180*C) r e s u l t s i n a more
i n t e n s e 9- band a t 3190 cm-’ and i n t h e a p p e a r e n c e of
.C-H,asyrf
a t 1930 cm a s a s h o u l d e r a s s i g n e d t o Tr-bonded a c e t y l e n e .
QCEC
The i n t e n s i t y of t h e O c 0 band a t 1705 cm-l a s s i g n e d t o a d s o r b e d
a c e t a l d e h y d e i n c r e a s e s a f t e r e v a c u a t i o n s a t 25°C ( c u r v e 3 ) , a t
100°C ( c u r v e 4 ) and a t 200°C ( c u r v e 5 ) . A t 350’C a c e t a l d e h y d e i s
c o m p l e t e l y d e s o r b e d , and n o r e s i d u e s a r e d e t e c t a b l e .
A f t e r i d e n t i c a l t r e a t m e n t s i . r . s p e c t r a a r e most s i m i l a r o f
Zn-CLI a s of C d - C L I .

. .
4000 3500 3000 2000 1000 moo 1400
Wavanumber , cm-’

F i g . 6 . Cd-CLI a f t e r e v a c u a t i o n a t 450°C ( 1 1 , a f t e r a c e t y l e n e
a d s o r p t i o n a t 1 . 3 k P a ( 2 ) , f o l l o w e d by e v a c u a t i o n s a t 25°C ( 3 ) ,
100°C ( 4 ) , 200°C ( 5 ) .
 249

CONCLUSIONS
The r e a c t i o n o f a c e t y l e n e w i t h z e o l i t i c w a t e r bound t o
t r a n s i t i o n metal ions r e s u l t s i n t h e formation o f adsorbed
a c e t a l d e h y d e which can be observed a t room t e m p e r a t u r e . Its
surface concentration increases w i t h increasing temperature u n t i l
i t d e s o r b s n e a r 200°C. On Cd-X a n d Cd-A t h e f o r m a t i o n o f a c e t -
a l d e h y d e i s i n e v i t a b l y accompanied by c r o t o n i c c o n d e n s a t i o n , the
p r o d u c t o f w h i c h c a n n o t b e d e s o r b e d a n d t r a n s f o r m s t o c o k e . No
c r o t o n i c c o n d e n s a t i o n t a k e s p l a c e o n Cu-, Ag-, Cd-, Zn-clino-
p t i l o l i t e s . The C O b o n d i n a d s o r b e d a c e t a l d e h y d e i s l e s s w e a k e n e d
on c l i n o p t i l o l i t e d e r i v a t i v e s t h a n on Cd-X o r Cd-A. T h e corresponding
f r e q u e n c i e s a r e 1705 a n d 1 6 9 0 cm-’, r e s p e c t i v e l y .
Since the degree o f c a t a l y s t dehydration i n f l u e n c e s e s s e n t i a l l y
the adsorption o f acetylene, i n accordance w i t h t h e k i n e t i c s
(ref. 5 1 , t h e a d s o r p t i o n o f a c e t y l e n e i s much w e a k e r t h a n t h e
adsorption o f water. On Cd- o r Z n - z e o l i t e s a c e t y l i d e f o r m a t i o n
c a n n o t b e d e t e c t e d , w h i l e o n Cu- a n d A g - z e o l i t e s i t h a s b e e n
r e v e a l e d ( r e f s . 7, 1 0 ) . P r e s u m a b l y t h i s i s t h e f i r s t s t e p o f t h e
reduction o f these cations found e a r l i e r ( r e f . 4).
1.r. measurements s u p p o r t e d a l s o t h e o u t s t a n d i n g b e h a v i o u r
o f Cd- a n d Z n - c l i n o p t i l o l i t e , on w h i c h none o f t h e u n d e s i r e d
transformations takes place.

REFERENCES
1 J.W. C o p p e n h o v e r a n d M.H. B i g e l o w , A c e t y l e n e a n d C a r b o n
M o n o x i d e C h e m i s t r y , R e i n h o l d , New Y o r k , 1 9 4 9 ;
2 G. G u t and K. A u f d e r e g g e n , H e l v . Chim. A c t a 57 ( 1 9 7 4 ) 441-452.
3 E . D e t r e k o y , Gy. O n y e s t y a k a n d 0 . K a l l o , R e a c t . K i n e t . C a t a l .
L e t t . 15 ( 1 9 8 0 ) 4 4 3 - 4 5 0 .
4 0 . K a l l o a n d Gy. O n y e s t y a k , i n B. D e l m o n a n d G.F. F r o m e n t
( E d i t o r s ) , C a t a l y s t D e a c t i v a t i o n , E l s e v i e r , Amsterdam, 1987,
pp. 605-612.
5 Gy. O n y e s t y a k a n d D. K a l l o , A c t a C h i m . Hung. 1 2 4 ( 1 9 8 7 ) 4 7 - 5 5 .
6 D. K a l l o a n d Gy. O n y e s t y a k , t o b e p u b l i s h e d .
7 P . P i c h a t , J . P h y s . Chem. 79 ( 1 9 7 5 ) 2 1 2 7 - 2 1 2 9 .
8 N . T . Tam, R . P . Cooney a n d G . C u r t h o y s , J . Chem. S O C . F a r a d a y
T r a n s . 72 ( 1 9 7 6 ) 2 5 7 7 - 2 5 9 1 ; i b i d . 7 2 ( 1 9 7 6 ) 2 5 9 2 - 2 5 9 7 .
9 W.W. Simons ( E d i t o r ) , The S a d t l e r Handbook o f I n f r a r e d S p e c t r a ,
S a d t l e r , Heyden, 1978.
10 J . H o w a r d a n d Z . A . K a d i r , Z e o l i t e s 4 ( 1 9 8 4 ) 4 5 - 5 0 .
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

P R E P A R A T I O N AND C H A R A C T E R I Z A T I O N OF M o - H Y ZEOLITES

A . M E S Z A R O S - K I S a n d J.VALYON
C e n t r a l R e s e a r c h I n s t i t u t e f o r C h e m i s t r y , H u n g a r i a n Academy o f
S c i e n c e s , P.O.Box 1 7 , 1525 B u d a p e s t ( H u n g a r y )

ABSTRACT
Mo-HY z e o l i t e s were p r e p a r e d by r e a c t i n g HY z e o l i t e s w i t h
t e t r a k i s - H - a l l y l m o l y b d e n u m . The maximum molybdenum l o a d i n g
a c h i e v e d was 1 . 3 % b y w e i g h t , i . e . , 1.6 Mo a t o m p e r u n i t c e l l .
I R s p e c t r o s c o p y was a p p l i e d t o s t u d y t h e s u r f a c e r e a c t i o n a n d
t h e d e c o m p o s i t i o n o f t h e s u r f a c e c o m p l e x upon h e a t i n g i n H o r
0 . Upon c o n t a c t i n g t h e z e o l i t e and t h e p e n t a n e s o l u t i o n
o 6 g a n o m e t a l l i c molybdenum compound t h e i n t e n s i t y o f t h e
03 the

h i g h - f r e q u e n c y OH-band a t 3 6 4 0 c m - l d e c r e a s e s a n d band s h i f t s
t o h i g h e r wavenumbers. The l o w - f r e q u e n c y OH-band r e m a i n s
p r a c t i c a l l y u n c h a n g e d . The e n t i r e o r g a n i c s u r f a c e c o m p l e x i s
decomposed on t r e a t m e n t a t 2OD.C. A b o u t 9 0 % o f t h e h y d r o x y l
g r o u p s o r i g i n a l l y p r e s e n t i n HY a r e r e c o v e r e d when t h e s a m p l e
i s h e a t e d t o 400’C i n H I f t h e sample i s h e a t e d i n 0 about
50% o f t h e p r o t o n s i n H f ’ i s r e p l a c e d b y Mo. A t 400’C M 6 l H Y
p r e p a r a t i o n s p r e s e r v e t h e i r c r y s t a l l i n i t y b o t h i n o x i d i z e d and
reduced s t a t e .

INTRODUCTION
I n r e c e n t y e a r s an i n c r e a s i n g i n t e r e s t i n molybdenumcontaining
z e o l i t e c a t a l y s t s has developed ( r e f s . 1-10). D i f f e r e n t techniques
h a v e been u s e d t o p r e p a r e a n d c h a r a c t e r i z e t h e M o - z e o l i t e s ;
however, i m p o r t a n t q u e s t i o n s , s u c h as d i s p e r s i o n and d i s t r i b u t i o n
o f Mo, the structural s t a b i l i t y o f the zeolite, etc., remained
unanswered.
I n t r o d u c t i o n o f molybdenum i n t o t h e z e o l i t e m a t r i x was attempted
b y t h e c o n v e n t i o n a l methods o f i o n - e x c h a n g e a n d i m p r e g n a t i o n f r o m
aqueous s o l u t i o n ( r e f s . 2,9,101. I t i s d i f f i c u l t t o exchange t h e
c a t i o n s o f a z e o l i t e f o r molybdenum i o n s d i r e c t l y b e c a u s e h i g h - v a -
l e n t c a t i o n i c molybdenum c a n o n l y e x i s t i n v e r y a c i d i c s o l u t i o n
where i o n - e x c h a n g e e q u i l i b r i a a r e u n f a v o u r a b l e a n d many z e o l i t e s
a r e u n s t a b l e . The a p p l i c a t i o n o f t h e c a t i o n i c d i n u c l e a r molybdenum-
e t h y l e n e d i a m i n e c o m p l e x f o r t h e i o n - e x c h a n g e o f Na-Y p r o d u c e s a
u n i f o r m d i s t r i b u t i o n o f t h e m e t a l ; however, a c o m p l e t e removal o f
t h e m e t a l f r o m t h e b u l k phase o c c u r s u p o n t r e a t m e n t w i t h O2 a t
300°C ( r e f . 3 ) . I m p r e g n a t i o n w i t h n e u t r a l and a n i o n i c s p e c i e s
r e s u l t s i n surface loading only. I n o r d e r t? overcome t h e
252

d i f f i c u l t i e s o f t h e aqueous i o n - e x c h a n g e , molybdenum was

introduced i n t o z e o l i t e s b y t h e s o l i d - s o l i d e x c h a n g e m e t h o d .
S o l i d s t a t e i o n - e x c h a n g e o f H - z e o l i t e s w i t h MoC15 r e s u l t s i n
M o - z e o l i t e a n d HC1 ( r e f s . 1,3). D a i e t a l . (ref. 1) reported
t h a t z e o l i t e Y l o s e s c r y s t a l l i n i t y i n t h e exchange process
p r o b a b l y due t o t h e a t t a c k o f HC1 on t h e z e o l i t e l a t t i c e .
T r e a t m e n t w i t h s o l i d o r v a p o u r p h a s e MoC15 c a n b e s u c c e s s f u l l y
a p p l i e d i n p r e p a r i n g t h e Mo-form o f t h e a c i d - r e s i s t a n t z e o l i t e s
( r e f . 5). A s p e c i a l p r o c e d u r e was d e v e l o p e d r e c e n t l y f o r
i n i t i a t i n g c o n t r o l l e d m i g r a t i o n o f M O O ~ ( O H )i ~n t o t h e z e o l i t i c
p o r e s f r o m t h e e x t e r n a l s u r f a c e o f M o - i m p r e g n a t e d NaY ( r e f . 10).
H i g h a n d homogeneous d i s p e r s i o n o f molybdenum c a n be a c h i e v e d
i n p r e p a r i n g M o - z e o l i t e s t h r o u g h a redox r e a c t i o n between M o ( C O ) ~
complex and t h e h y d r o x y l groups o f t h e z e o l i t e s ( r e f s . 3,4,6-8).
The a v e r a g e o x i d a t i o n number o f t h e molybdenum c a n be c o n t r o l l e d
by v a r y i n g t h e p r o t o n c o n c e n t r a t i o n o f t h e s u p p o r t . I n theabsence
o f o x i d i z i n g s i t e s ( p r o t o n s ) thermal decomposition o f adsorbed
M o ( C O ) ~ r e s u l t s i n z e r o - v a l e n t Mo d i s t r i b u t e d h o m o g e n e o u s l y
w i t h i n t h e p o r e s ( r e f s . 6,7).
I t i s w e l l known t h a t o r g a n o m e t a l l i c compounds c a n be a n c h o r e d
t o oxide surfaces (ref. 11). M o - f i x e d c a t a l y s t s o b t a i n e d f r o m t h e
r e a d y r e a c t i o n o f t h e OH-groups of s o l i d supports, such as s i l i c a
o r alumina, w i t h molybdenum-n-ally1 complexes have been s t u d i e d
extensively (refs. 11-17). These c a t a l y s t s w i t h w e l l d e f i n e d
s u r f a c e a r e v e r y s u i t a b l e f o r o b t a i n i n g more p r e c i s e i n f o r m a t i o n
a b o u t t h e a c t i v e s i t e s . The p r e p a r a t i o n o f m e t a l - z e o l i t e c a t a l y s t s
u s i n g t h e r e a c t i o n o f o r g a n o m e t a l l i c compounds a n d z e o l i t e s
c o n t a i n i n g r e a c t i v e OH-groups was c o n s i d e r e d ( r e f . 18); h o w e v e r ,
i t has n o t y e t been a t t e m p t e d t o o b t a i n m o l y b d e n u m - c o n t a i n i n g
z e o l i t e f r o m such r e a c t i o n . The p u r p o s e o f t h e p r e s e n t s t u d y was
t o examine t h e r e a c t i o n o f " t r u e " HY z e o l i t e s w i t h t e t r a k i s - r ( -
a l l y l m o l y b d e n u m and t o c h a r a c t e r i z e t h e p r e p a r e d M o - f i x e d HY
z e o l it e .

EXPERIMENTAL
The NaY z e o l i t e was o b t a i n e d f r o m EKA Kemi, Sweden, a n d c o n t a i n -
e d 56 A1 p e r u n i t c e l l . The ammonium-exchanged Y zeolite was p r e -
p a r e d by d o u b l e i o n - e x c h a n g e w i t h 1M NH4N03 a t 70°C. A " t r u e " H Y
f o r m o f t h e z e o l i t e was o b t a i n e d b y o u t g a s s i n g NH4Y z e o l i t e
[Na,(NH4),,(A102),,(SiD~) 1 3 J i n vacuum a t 400°C f o r 2 h, f o l l o w e d
by c a l c i n a t i o n f o r 2 h i n f l o w i n g 02 a n d p u r g i n g i n f l o w i n g He a t
 253

400°C f o r 1 h . Gases were p u r i f i e d by c o n v e n t i o n a l methods.

M O ( I I - C ~ H ~ was
) ~ p r e p a r e d a c c o r d i n g t o Wilke e t a l . ( r e f . 1 9 ) .
The s y n t h e s i s s t e p s a r e a s f o l l o w s :

C3H5C1tMg(large e x c e s s )
room t e m p e r a t u r e
diethyl ether - C3H5MgC,

4 C 3 H 5 M g C 1 M ° C 1 5 droom
+
temperature
iethyl e t h e r , pentang M0(a-C3H5I4. (2)

B e f o r e t h e i r u s e , s o l v e n t s and a l l y 1 c h l o r i d e were r e f l u x e d o n
Na w i r e a n d m o l e c u l a r s i e v e 5A, r e s p e c t i v e l y , t h e n d i s t i l l e d .
B o t h MoC15 a n d M o ( T C - C ~ H ~ )a~r e e x t r e m e l y s e n s i t i v e t o O 2 o r
m o i s t u r e , hence t h e complex was p r e p a r e d under p u r e n i t r o g e n
in a n a p p a r a t u s s i m i l a r t o t h a t d e s c r i b e d by Bonnemann ( r e f . 2 0 ) .
MoC15 was p r e p a r e d i n s i t u b y r e a c t i n g c h l o r i n e and Mo metal a t
400°C. S o l v e n t s were e v a p o r a t e d from t h e r e a c t i o n m i x t u r e
o b t a i n e d from r e a c t i o n ( 2 ) ; t h e n s o l i d r e s i d u e was e x t r a c t e d
with p e n t a n e . R e s u l t s of chemical a n a l y s i s c o n f i r m e d t h a t t h e
s t o i c h i o m e t r i c c o m p o s i t i o n of t h e e x t r a c t c o r r e s p o n d s t o f o r m u l a
Mo(n-C3H5)4.
The H Y z e o l i t e was c o n t a c t e d w i t h t h e d a r k g r e e n s o l u t i o n of
t h e Mo(X-C3H5l4 a t room t e m p e r a t u r e . I n o r d e r t o remove t h e
e x c e s s Mo complex t h e Mo-fixed z e o l i t e was washed w i t h a copious
amount of p e n t a n e . Both f i x i n g r e a c t i o n a n d w a s h i n g were carried
o u t under f l o w i n g pure h e l i u m . I n t h e f i x i n g r e a c t i o n t h e
e v o l u t i o n of p r o p y l e n e was examined. Gases l e a v i n g t h e r e a c t o r
c o n t a i n i n g a b o u t 1 g of z e o l i t e were p a s s e d t h r o u g h a t r a p
c o o l e d w i t h l i q u i d N 2 . The v e r y small amount of p r o p y l e n e trapped
was d e t e r m i n e d v o l u m e t r i c a l l y , w i t h g r e a t u n c e r t a i n t y ; l e s s
than one p r o p y l e n e molecule was e v o l v e d p e r Mo atom i n t r o d u c e d .
S e l f - s u p p o r t i n g w a f e r s w i t h a t h i c k n e s s of a b o u t 8 - 1 0 mg.cm-2
were p r e s s e d from t h e homogeneous d i s p e r s i o n of NH4Y powder.
Samples were p l a c e d i n a n I R c e l l e q u i p p e d w i t h KBr windows and
f u r n a c e r e g i o n i n t o which t h e z e o l i t e w a f e r c o u l d be r a i s e d
m a g n e t i c a l l y . The c o n s t r u c t i o n of t h e c e l l a l l o w e d both vacuum
a n d g a s - f l o w t r e a t m e n t of t h e w a f e r s .
A f t e r deammoniation t h e f i x i n g r e a c t i o n was c a r r i e d o u t by
immersing t h e wafer i n t o t h e p e n t a n e s o l u t i o n of M o ( R - C ~ H ~ ) ~
f o r 1 h a n d t h e n i n t o pure p e n t a n e f o r 30 min. The w a f e r was
r e p l a c e d i n t h e IR c e l l . The whole p r o c e d u r e was c a r r i e d o u t
i n i n e r t g a s t o p r e v e n t t h e c o n t a c t of t h e w a f e r w i t h a i r .
254

The I R s p e c t r o p h o t o m e t e r employed was a N i c o l e t 170 S X Fourier

t r a n s f o r m i n s t r u m e n . t . S p e c t r a r e c o r d e d a t room t e m p e r a t u r e were
t h e a v e r a g e of 3000 s c a n s a t 2 cm-l r e s o l u t i o n . They were routinely
s t o r e d o n f l o p p y d i s c s and computer-enhanced i f n e c e s s a r y .
Computer s u b t r a c t i o n of t h e s p e c t r a h e l p e d t o e v a l u a t e c h a n g e s
o f absorbance.
A b s o r p t i o n c a p a c i t i e s f o r N 2 were measured v o l u m e t r i c a l l y a t
-196'C.
Samples were r e n d e r e d s o l u b l e i n a m i x t u r e of c o n c e n t r a t e d
H F , HN03 and H2S04. The r h o d a n i d e complex o f t h e molybdenum was
formed a n d t h e molybdenum c o n t e n t was d e t e r m i n e d b y p h o t o m e t r y .

RESULTS
IR s p e c t r a o f H Y and Mo-HY z e o l i t e s a r e s h o w n i n t h e O H - a n d
C - H s t r e t c h i n g r e g i o n ( 4 0 0 0 - 2800 c m - ' ) i n F i g . 1 .
The c h a r a c t e r i s t i c v ( 0 H ) bands a p p e a r a t 3640 cm-l a n d a t
3540 cm-' ( F i g . 1 , s p e c t r a A and a ) . S p e c t r a B a n d b i n F i g 1
were recorded following the fixation reaction of HY with M o ( ~ T - C ~ H ~ ) ~ ,
t h e p e n t a n e washing and ( f o r e x p e l l i n g p e n t a n e ) a purge w i t h
h e l i u m a t 100°C f o r 1 h . The i n t e n s i t y of t h e h i g h - f r e q u e n c y
v(0H) band d e c r e a s e s s u b s t a n t i a l l y , and t h e b a n d s h i f t s w i t h
a b o u t 8 cm-' t o h i g h e r wavenumbers. The l o w - f r e q u e n c y b a n d
r e m a i n s p r a c t i c a l l y unchanged. New C - H s t r e t c h i n g v i b r a t i o n
bands a p p e a r between 3000 a n d 2800 cm-'. T r e a t m e n t of t h e w a f e r s
i n f l o w i n g H 2 o r O2 a t 200°C f o r 1 h c o m p l e t e l y removes t h e s e
bands ( F i g . 1 , s p e c t r a C and c ) . All t h e o t h e r s p e c t r a i n F i g . 1
were r e c o r d e d a f t e r s u b s e q u e n t 1 hour O 2 o r H 2 t r e a t m e n t s a t 300
and 400'C. I t was found t h a t u p o n h e a t i n g Mo-fixed H Y o f t h e
same Mo c o n t e n t ( 1 . 3 % by w e i g h t , i . e . , 1.6 Mo p e r u n i t c e l l )
i n H 2 o r 02, s i g n i f i c a n t l y d i f f e r e n t amounts of t h e OH-groups
become i n v o l v e d i n b i n d i n g molybdenum. I n t e n s i t y o f t h e v ( 0 H )
bands d e c r e a s e s by a b o u t 10% o n l y when wafer i s t r e a t e d i n
hydrogen ( c f . F i g . 1 , s p e c t r a A and E ) a n d a b o u t 50 % upon
t r e a t m e n t w i t h oxygen ( c f . F i g . 1 , s p e c t r a a and e l . A t 400'C
i n 02, t h e h i g h - f r e q u e n c y OH-band i s a l m o s t of t h e same
i n t e n s i t y , b u t t h e l o w - f r e q u e n c y band i s c o n s i d e r a b l y s m a l l e r
t h a n t h e c o r r e s p o n d i n g b a n d of H Y . H 2 - t r e a t e d s a m p l e s a r e b l a c k ,
i n d i c a t i n g t h e p r e s e n c e of r e d u c e d Mo. The w h i t e 0 2 - t r e a t e d
.
s a m p l e s p r o b a b l y c o n t a i n mainly Mo 6 + O x i d a t i o n o f t h e H2-reduced
sample a t 400'C r e s u l t s i n a s m a l l ( - 1 0 % ) d e c r e a s e of v ( 0 H ) b a n d s
 255

]---'I\
1-
I\ -
I00 3400 2800 4000 3400 2800
WAVENUMBERS WAVENUMBERS

F i g . 1 . I n f r a r e d s p e c t r a i n t h e v ( O H ) a n d t h e v ( C H ) r e g i o n : HY
( A a n d a ) ; c o n t a c t e d w i t h t h e p e n t a n e s o l u t i o n o f Mo(n-C3H514 a t
r o o m t e m p e r a t u r e f o r 1 h a n d p u r g e d w i t h He a t 1 O O " C f o r 1 h
( B a n d b ) ; a c t i v a t e d i n f l o w i n g H a t 2 0 0 (C), 3 0 0 ( 0 ) a n d 4 0 0 ' C
( E ) o r i n f l o w i n g 0 a t 2 0 0 ( c ) , 300 ( d ) a n d 4 0 0 ' C ( e ) f o r I h;
t h e sample a c t i v a t e $ i n f l o w i n g H2 a t 400'C a f t e r t r e a t m e n t w i t h
0 a t 4 0 0 ' C f o r 1 h ( F ) a n d H a t 400°C f o r 1 h ( G ) ; t h e s a m p l e
a s t i v a t e d i n f l o w i n g 0 a t 406.C a f t e r t r e a t m e n t w i t h H a t 4 0 0 ' C
f o r 1 h ( f ) . B o t h s a m p l z s c o n t a i n 1.6 Mo-atom p e r u n i t c e ? l .

(cf. Fig. 1 , s p e c t r a E a n d F ) , b u t d i s a p p e a r i n g OH g r o u p s c a n b e
r e g e n e r a t e d b y t r e a t m e n t w i t h H2 ( F i g . 1, s p e c t r u m G). No
s i g n i f i c a n t c h a n g e o c c u r r e d when we t r i e d t o r e d u c e t h e m o l y b d e -
num i n t h e s a m p l e w h i c h was h e a t e d u p i n O 2 ( c f . Fig. 1, spectra
e and f ) .
B E T a d s o r p t i o n i s o t h e r m s o f HY a n d Mo-HY z e o l i t e s f o r N 2 a t
-196'C were determined a f t e r d i f f e r e n t t r e a t m e n t s . Sorption
c a p a c i t y o f t h e HY s a m p l e p r e p a r e d b y i n s i t u d e c o m p o s i t i o n o f
t h e NH4Y i s c o m p a r a b l e t o t h e s o r p t i o n c a p a c i t y o f t h e M o - f i x e d
samples h e a t e d e i t h e r i n O2 o r i n H2. Similar sorption capacity
v a l u e s w e r e r e p o r t e d f o r NaY a n d HY e a r l i e r ( r e f . 4,21). A t 1OO'C
p e n t a n e c a n b e q u a n t i t a t i v e l y e x p e l l e d f r o m t h e p o r e s o f HY
256

w h i l e 60% o f t h e p o r e v o l u m e o f t h e M o - f i x e d HY r e m a i n s b l o c k e d
f o r a d s o r p t i o n o f N2 a f t e r t h e same t r e a t m e n t ( s e e T a b l e 1 ) .

TABLE 1
N i t r o g e n a d s o r p t i o n d a t a o f HY a n d M o - H Y ' ~ ) z e o l i t e s .

Sample a n d t r e a t m e n t Nitrogen uptake a t

13 kPa a n d -196"C, g/g
Sample 1: H Y z e o l i t e o b t a i n e d f r o m t h e d e - 0.28
a m m o n i a t i o n o f N H 4 Y a t 400°C
Sample 2 : Sample 1 was c o n t a c t e d w i t h 0.26
p e n t a n e a n d p u r g e d w i t h He a t 100°C f o r 1 h.
Sample 3 : Sample 1 was c o n t a c t e d w i t h t h e 0.12
p e n t a n e s o l u t i o n o f ( M o ( r - C H ) , washed i n
p e n t a n e a n d p u r g e d w i t h He h 5 1 6 0 0 C f o r 1 h .
Sample 4 : Sample 3 was t r e a t e d w i t h f l o w i n g 0.27
H 2 a t 400°C f o r 1 h .
Sample 5 : Sample 3 was t r e a t e d w i t h f l o w i n g 0.27
O 2 a t 4OOcC f o r 1 h .

( a ) M o c o n t e n t o f t h e s a m p l e i s 1 Mo p e r u n i t c e l l .

DISCUSSION
D e h y d r o x y l a t i o n o f z e o l i t e s o c c u r s when p r o t o n s o f t h e
z e o l i t e o x i d i z e l o w - v a l e n t m e t a l s . The o x i d a t i o n o f Mo i n t h e
Mo(r-C3H514 c o m p l e x by HY c a n b e d e s c r i b e d a s f o l l o w s :

where Z r e p r e s e n t s t h e z e o l i t e m a t r i x . S u p p o s i n g t h a t t h e c o m p l e x
w h i c h was n o t f i x e d c h e m i c a l l y was r e m o v e d b y w a s h i n g t h e z e o l i t e
w i t h p e n t a n e , one w o u l d e x p e c t a c c o r d i n g t o e q . 3 t h e f o r m a t i o n
o f minimum one p r o p y l e n e m o l e c u l e p e r molybdenum i n t r o d u c e d .
In fact, much l e s s p r o p y l e n e was d e t e r m i n e d . A possible expla-
n a t i o n i s t h a t p r o p y l e n e was s i m p l y t o o s t r o n g l y b o u n d w i t h i n
t h e p o r e s t o be e v o l v e d a t room t e m p e r a t u r e . Nevertheless, it
c a n n o t be e x c l u d e d t h a t a s u r f a c e o r g a n o m o l y b d e n u m compound
c o u l d be f o r m e d w i t h t h e p a r t i c i p a t i o n o f t h e T-0-T g r o u p s i n
the reaction. I t was shown b y Yermakov (ref. 11) f o r n o n - z e o l i t i c
s u p p o r t s t h a t =T-C3HS s p e c i e s a r e formed i n such a r e a c t i o n .
The maximum a c h i e v a b l e l o a d i n g i s a b o u t 1.3% Mo b y w e i g h t .
U n e x p e c t e d l y a l a r g e p o r t i o n o f t h e a c i d i c OH-groups w h i c h w e r e
supposed t o be a c t i v e d i d n o t p a r t i c i p a t e i n t h e f i x i n g r e a c t i o n .
 251

S t e r i c h i n d r a n c e may l i m i t t h e maximum M o - c o n t e n t a c h i e v a b l e i n
one s t e p . P r o b a b l y h i g h e r l o a d i n g s c o u l d b e o b t a i n e d i n repeated
reaction-and-decomposition cycles.
Pentane c a n be e a s i l y removed f r o m t h e p o r e s o f HY. A l l y 1 li-
g a n d s a r e much m o r e s t r o n g l y b o u n d t h a n p e n t a n e ( T a b l e 1 ) . v ( C H )
b a n d s o b s e r v e d i n t h e 3 0 0 0 - 2 8 0 0 cm-’ region a f t e r treatment a t
100°C c a n b e a t t r i b u t e d t o s u r f a c e a l l y l g r o u p s ( F i g . 1, spectra
B a n d b ) . No b a n d s a p p e a r a t a b o u t 3 1 0 0 c m - l , indicating that
surface-bound hydrocarbon has no d o u b l e bond c h a r a c t e r , i.e., in
t h e s u r f a c e complex a l l y l l i g a n d i s bound t o t h e molybdenum atom
by a 6-bond r a t h e r than by a TI-ally1 bond. The hydroxyl band of t h e
M o - f i x e d HY a t 3 6 4 8 c m - l (Fig. 1, s p e c t r a B a n d b ) i s o f much
l e s s i n t e n s i t y t h a n t h a t o f t h e HY ( F i g . 1, s p e c t r a A a n d a ) .
A d s o r p t i o n o f o l e f i n s on d e c a t i o n i z e d Y i n d u c e s s i m i l a r a change
i n t h e 3(OH) r e g i o n ( r e f . 2 2 ) . I t seems l i k e l y t h a t t h e i n t e n s i t y
o f t h e 3640 cm-l OH b a n d d e c r e a s e s p r i m a r i l y d u e t o i n t e r a c t i o n
o f t h e a l l y l l i g a n d s and t h e hydroxyl groups, and t h e sample i s
n o t d e h y d r o x y l a t e d t o s u c h a n e x t e n t t h r o u g h o x i d i z i n g Mo.
D i s a p p e a r a n c e o f t h e \)(CH) b a n d s i n d i c a t e s t h a t a l l o f t h e
o r g a n i c s u r f a c e c o m p l e x d e c o m p o s e s b e l o w 200°C ( F i g . 1, s p e c t r a
C a n d c ) . The s i m u l t a n e o u s a n d a l m o s t c o m p l e t e r e c o v e r y o f t h e
b a n d a t 3 6 4 0 cm-’ s u p p o r t s t h e c o n c l u s i o n t h a t t h e b a n d was
s h i f t e d and decreased i n i n t e n s i t y through t h e e f f e c t o f t h e
a l l y l ligands.
The 5 0 % d e c r e a s e o f v ( O H ) i n t e n s i t i e s u p o n t r e a t m e n t i n O 2 a t
400°C c a n p r o b a b l y a c c o u n t f o r a r e a c t i o n s i m i l a r t o t h a t d e -
s c r i b e d f o r t h e o x i d a t i o n o f r e d u c e d Ag-HY (ref. 23):

w h e r e Mont r e f e r s t o a s u r f a c e - b o u n d molybdenum atom and n i s

s m a l l e r t h a n 6. S u b s c r i p t ‘ s ’ d e s i g n a t e s a s u r f a c e oxygen atom.
I t i s g e n e r a l l y b e l i e v e d t h a t t h e b a n d a t 3 5 4 0 cm-’ represents
hydroxyl groups i n t h e hexagonal prisms.The i n t e n s i t y decrease
o f t h e b a n d a t 3 5 4 0 cm-’ shows t h a t t h e s e h y d r o x y l s a r e p r e f e r -
e n t i a l l y consumed i n t h e a b o v e p r o c e s s . The r e a c t i o n c a n t a k e
p l a c e o n l y i f l o w - v a l e n t molybdenum atoms m i g r a t e f r o m t h e
s u p e r c a g e s t o t h e more i n a c c e s s i b l e h e x a g o n a l p r i s m s a t h i g h e r
temperature.
M i g r a t i o n o f t h e Mo a t o m s c a n a l s o o c c u r when t h e s a m p l e i s
heated i n Hp. I n t h i s p r o c e s s p r o b a b l y l a r g e r molybdenum clusters
258

a r e formed w i t h i n t h e supercages o r on t h e e x t e r n a l s u r f a c e s o f
the c r y s t a l l i t e s . I n H2, therefore, Mo-fixing reaction results
i n o n l y a 10 % d e h y d r o x y l a t i o n . The m o l y b d e n u m c l u s t e r s c a n n o t
be d i s i n t e g r a t e d a n d r e d i s t r i b u t e d b y t r e a t m e n t w i t h O 2 a t 400°C.
F u r t h e r s t u d i e s on t h e p r e p a r a t i o n a n d c a t a l y t i c p r o p e r t i e s
o f Mo-fixed z e o l i t e s are i n progress.

We t h a n k D r . S . H o l l y (Central Res.Inst. f o r Chem. o f the

Hung. Acad. Sci., Hungary) f o r making t h e I R spectroscopic
m e a s u r e m e n t s . We a c k n o w l e d g e t h e f i n a n c i a l s u p p o r t o f t h e
N a t i o n a l S c i e n t i f i c R e s e a r c h F o u n d a t i o n (OTKA, P r o j e c t No. 782.).

REFERENCES

1 P . E . D a i a n d J.H. L u n s f o r d , J . C a t a l . , 64 ( 1 9 8 0 ) 1 7 3 - 1 8 3 .
2 E.L. Moorehead, U S P a t e n t 4,297,243 ( 1 9 8 1 ) .
3 M.B. Ward a n d J.H. L u n s f o r d , i n D.H. O l s o n a n d H . B i s i o
( E d i t o r s ) , P r o c . 6 t h I n t e r n . Z e o l . Conf., Reno, U S A J u l y 10-15,
1983, B u t t e r w o r t h , G u i l f o r d , 1984, pp. 4 0 5 - 4 1 6 .
4 S. Abdo a n d R.F. Howe, J. P h y s . Chem., 87 ( 1 9 8 3 ) 1 7 1 3 - 1 7 2 2 .
5 J.R. J o h n s a n d R.F. Howe, Z e o l i t e s , 5 ( 1 9 8 5 ) 2 5 1 - 2 5 6 .
6 Y.S. Yong a n d R.F. Howe, J . Chem. S O C . , F a r a d a y T r a n s . I . , 82
(1986) 2887-2896.
7 Y . S . Yong and R.F. Howe, i n Y . M u r a k a m i , A . I i j i m a a n d J.W.
Ward ( E d i t o r s ) , P r o c . 7 t h I n t e r n . Z e o l . C o n f . , Tokyo, Japan,
A u g u s t 1 7 - 2 2 , 1986, Kodansha L t d . , Tokyo, 1986. pp. 8 8 3 - 8 8 9 .
8 T . Komatsu a n d T . Yashima, J. M o l . C a t a l . , 4 0 ( 1 9 8 7 ) 8 3 - 9 2 .
9 R. C i d , F.J. G i l L l a m b i a s , J.L.G. F i e r r o , A.Lopez Agudo a n d
J . V i l l a s e n o r , J . C a t a l . , 89 ( 1 9 8 4 ) 4 7 8 - 4 8 8 .
10 J.L.G. F i e r r o , J.C. Conesa a n d A . L o p e z Agudo, J. C a t a l . , 108
(1987) 334-345.
11 Yu. I . Yermakov, C a t a l . R e v . - S c i . Eng., 13 ( 1 9 7 6 ) 7 7 - 1 2 0 .
12 Y . Iwasawa, Y . Nakano a n d S . Ogasawara, J . Chem. S O C . , F a r a d a y
T r a n s . I . . 74 ( 1 9 7 8 ) 2 9 6 8 - 2 9 8 1 .
13 Y . Iwasawa a n d ' S . Ogasawara, J . Chem. S O C . , F a r a d a y T r a n s . I.,
75 ( 1 9 7 9 ) 1 4 6 5 - 1 4 7 6 .
14 Y . Iwasawa, T . Nakamura, K . T a k a m a t s u a n d S . Ogasawara, J.Chem.
S O C . F a r a d a y T r a n s . I., 76 ( 1 9 8 0 ) 9 3 9 - 9 5 1 .
15 Y . Iwasawa, H . I c h i n o s e a n d S . Ogasawara, J . Chem. S O C . F a r a d a y
T r a n s . I., 77 ( 1 9 8 1 ) 1 7 6 3 - 1 7 7 7 .
16 Y . Iwasawa, Y . S a t 0 a n d H. K u r o d a , J . C a t a l . , 8 2 ( 1 9 8 3 ) 289-298.
17 Y . Iwasawa a n d M. Y a m a g i s h i , J . Catal., 8 2 ( 1 9 8 3 ) 3 7 3 - 3 8 1 .
18 Kh.M. M i n a c h e v a n d Ya. I s a k o v , i n J.A. Rabo ( E d i t o r ) , Z e o l i t e
C h e m i s t r y a n d C a t a l y s i s , A C S Monograph 1 7 1 , A m e r i c a n C h e m i c a l
S o c i e t y , W a s h i n g t o n , 1976, p p . 5 5 2 - 6 1 1 .
19 G . W i l k e , B . B o g d a n o v i c , P . H a r d t , P . Heimbach, W . Keim, M.
K r u n e r , W . O b e r k i r c h , K . Tanaka, E . S t e i n r u c k e , 0. W a t e r a n d
H . Zimmermann, Angew. Chem. I n t . Edn., 5 ( 1 9 6 6 ) 1 5 1 - 1 5 2 .
20 H . Bonnen ' i , Angew. Chem., 8 5 ( 1 9 7 3 ) 1 0 2 4 - 1 0 3 5 .
21 W . B r e c k , Z e o l i t e M o l e c u l a r S i e v e s , W i l e y - I n t e r s c i e n c e , New
York, 1974.
22 B . V . L i e n g m e a n d W.K. H a l l , T r a n s . F a r a d a y S o t . , 62 ( 1 9 6 6 )
3229-3243.
23 H . B e y e r , P . A . J a c o b s a n d 3.8. U y t t e r h o e v e n , J. Chem. S O C . ,
F a r a d a y , I. 72 ( 1 9 7 6 ) 6 7 4 - 6 8 5 .
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

P R OP Y L E NE ME T A T HE S IS RE A C T I 0N 0V ER Mo/ Y - ZE 0 L IT E S

M. tANIECKI
Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznafi
Poland

ABSTRACT
The Mo(C0) loaded Y-zeolites differing in Si/Al ratio and
surface acidity have been used to study the activity in propylene
metathesis. Both sodium and hydrogen forms of Y-zeolites were
applied as supports. Oecom7osition of adsorbed Mo(C0) , during
heating,produces a variety of surface Mo species diffgrbng in $ k e
degree of decarbonylation and oxidation number (from Mo to Mo 1.
The catalytic activity decreased with increasing protonic acidity
of the support and oxidation number of molybdenum. U V / V I S tran-
smission spectroscopy was applied to study the influence of the
support acidity on the formation of surface species during
adsorption and decomposition of MO(CO)~.

INTRODUCTION
It is well known that one of the most difficult transition met-
als to ion exchange into the zeolites has been molybdenum, due to
the absence of simple salts of this element which are stable under
solution-ion-exchange conditions. F o r this reason, the different
techniques of Mo implantation into the zeolite framework,including
solid-state exchange with MoC15 (1) and M ~ ~ ( e n ) ~ C (2)
l ~ has been
applied. However, the less direct but m o r e efficient method of
molybdenum loading into HY zeolites is based on the saturation of
activated zeolite with volatile molybdenum carbonyl. Gallezot et
a1.(3) and Ward and Lunsford (2), applying mainly IR spectroscopy,
established that Mo(CO)~, initially adsorbed within the supercage
of HY zeolite, become oxidized by zeolite protons during thermal
activation. The IR and EPR studies by Abdo and Howe (4) cornplemen-
ted results reported earlier and indicated that i n the case of
Mo(C0)6/NaY the formation o f supported zero-valent Mo is possible.
Ward and Lunsford (2),studying normal and ultrastable HY zeolites,
found that Mo ions are probably located at SII positions within
the large cavities.
Although the results presented by the groups of Howe (4), Luns-
260

ford(2) and Yashima(5-7) disclosed some chemistry of the Mo/Y-zeo-

lites, there are few papers concerning the catalytic properties of
these systems. Komatsu et al.(6),studying the propylene metathesis
over Mo-loaded zeolites as a function of oxidation number, found
that molybdenum species responsible for catalytic activity have an
oxidation number lower than +4. They also stressed the importance
of Mo dispersion on catalytic activity. It was established(7) that
atomically dispersed ivlo with oxidation number close to zero is
responsible for polymerization and hydrogenation of ethylene. Yong
and Howe(8) reported recently the activity of molybdenum zeolites
in the Fisher-Tropsch reaction. They established that application
of Nay, KY and KL zeolites as supports leads to the formation of
active centers in the Fisher-Tropsch process, namely zero-valent
molybdenum. The propylene epoxidation reaction has also been
studied with Mo-loaded zeolites ( 9 ) .
The present paper seeks to contribute to an understanding of
the surface chemistry and catalytic activity of molybdenum zeol-
ites.The influence of zeolite composition and thermal pretreatment
on the catalytic activity in propylene disproportionation reaction
has been studied.

EXPERIMENT
NaY faujasites with Si/A1 ratio 2.0 and 2.7 were obtained ac-
cording to the procedure described by Kacirek and Lechert(lO).The
equivalent ammonium forms were obtained by triple exchange with
1M solution of NH4C1 at 345 K (for details s e e Table 1).
The dehydration of sodium forms as well a s the dehydration and de-
ammoniation of ammonium forms of Y-zeolites was carried out in a
stream of purified helium inside the U-shaped quartz reactor at
675, 775 o r 875 K, for two hours. The amount of the support used
was always adjusted to 0.25 g o f activated zeolite (for weight
losses see Table l).After cooling and one-minute evacuation, the
desired amount of doubly sublimed Mo(C016 was transferred at room
temperature under vacuum onto the support and kept in a closed
reactor for 1 2 hours. A similar procedure for alumina support has
been described earlier(l1). The activation o f supported Mo(CO)~
was carried out in helium in 50 K intervals up to 675 K for 60
minutes. The evolved gases were trapped at liq. N2 temperature
(for a H2 trap with molecular sieves 5A was used) and, after
warming, analyzed with a thermal conductivity detector and 2.5 m
 261

column of activated carbon (Mcrck, 25-35 mesh).

The propylenc metathesis reaction was studied by a pulse me-
thod. The propylone pulses were injected from the gas-sampling
vale (1.21 cm3) into the carrier gas (He o r H2) flowing at a
rate of 3 0 cm3- n1in-l and carried through the catalyst bed at
335 K . Reaction products were collected in a trap and, after each
injection, analyzed with gas chromatography.
The average oxidation number ( O . N . ) of Mo was calculated on
the basis of oxygen titrations performed at 575 I( with a well
calibrated sampling valve.
The U V / V I S experiments were carried out in the high vacuum sys-
tem. The details of the cell, high-vacuum and gas-dosing system
have been described elsewhere (12). The self-supporting wafers of
zeolite with a thickness of 2 - 3 m g + c m - 2 were employed.
The U V / V I S spectra were recorded at room temperature in transmis-
sion mode with a Perkin-Elmer U V / V I S spectrometer (Model 556)
equipped with baseline corrector. Similarily t o the catalytic
experiments, in the spectroscopic studies the zeolite wafers were
dehydroxylated under vacuum in the U V / V I S cell at elevated tempera-
tures prior to the Mo(CO)~ admission. In the spectroscopic studies
the amount of supported Mo(CO)~ was calculated from the pressure
drop of carbonyl vapours, whereas in the catalytic experiments
the Mo content was analyzed with atomic absorption spectrometry.

TABLE 1
Characterization of zeolites used.

Unit cell Pretr. Weight IR absorbance**(a.u.)

temp. loss* OH vibrations BPy LPy
(K) (%) 3640 3550 1545 1455

(NH4)48Na7A162Si1320384 675 30.1 2.52 1.65 0.88 0.43

Si/Al=2.11 775 30.4 - - 0.04 1.35

(NH4)35Na14A152Si1420384 6 7 5 28.3 2.52 1.30 1.00 0.30

Si/A1=2.72 775 28.5 0.08 - 0.13 1.46
875 30.0 - - 0.03 1.58
~ ~~~

*after 2 hours at indicated temperature in N

**after 2 hours activation under vacuum follo8ed by interaction
with pyridine at 475 K (2h adsorption, lh desorption).
8Py and LPy represent the density o f the Brunsted and Lewis
centers, respectively.
262

RESULTS AND DISCUSSION

The application of tIY zeolites with different S i / A 1 ratio
shows that the initial composition (and consequently also the ini-
tial acidity) influences the decomposition of supported Mo(CO)(,.
Figure 1 shows the amount of CI1 and H2 cvolvcd upon heating the
Mo(CO16 loaded zaolites, pretreated at 6 7 5 K. In the case of
zeolite with higher A 1 content the decomposition of Mo(CO)~ pro-
ceeds at lower temperatures than with the sample where Si/A1=2.7.
The complete decarbonylation for these samples was achieved at
520 and 6 5 0 K , respectively.

6 3 F i g . 1 . CO and H evolution
during decomposftion of
0
1
supported Mo(CO) .
I HY-1 and HY-2 refiresent
\L 2 P
rn supports with Si/A1=2.11
0 and 2.72 respectively.
0
I Pretreatment temperature
w N
\ of the support - 6 7 5 K.
62 1 I
I 0

0
300 LOO 500 600
TEMPERATURE K 1

The quantities of hydrogen released in the reaction of Mo(C0l6

with surface hydroxyl groups are smaller than those found
previously ( 2 ) . These amounts, however, can serve a s well as
titrations for the estimation of an average oxidation nurnber(0.N.)
of molybdenum, because for the samples activated at 575 K a good
agreement has been found. The evaluation o f the O . N . was based on
the assumption that during oxygen titrations all Mo species are
oxidized to Mo'~. It was found for the applied HY zeolites pretrea-
ted at 675 K that in every step o f thermal decomposition the 0.11.
is always lower f o r the zeolite with lower Si/A1 ratio. F o r exam-
ple, samples activated at 675 K show the O.N. close to + 4 f o r
those with Si/Al=2.1, whereas +6 is shown f o r those with Si/A1=2.7.
Similar behaviour has been observed f o r HY supports when pre-
treated at 775 K. The values of O.N. ( s e e Table 2) for the Mo s p e -
cies were very much lowered in comparison with pretreatment at
675 K.The decarbonylation process had been also completed at lower
temperatures in both cases. As previously, the hydrogen evolution
was observed, but only f o r the sample with lower A1 content.
 263

When HY zeolite with Si/Al 2.1 was pretreated at 875 K only

carbon monoxide was found in the decomposition products.
Comparing the influence o f the initial acidity, expressed a s
the average density of Ertlnsted and Lewis centers (Table 11, with
the average oxidation number (Table 2 ) one can conclude that the
surface hydroxyl groups are essentialy responsible for the oxidat-
ion process of supported molybdenum carbonyl. Abdo and Howe (4),
applying IR spectroscopy, found that adsorbed Mo(C016 interacts
with surface hydroxyls even at r o o m temperature and thermal
activation causes the complete disappearance of IR bands origin-
ating from OH vibrations.
In o u r case, while the support is practically dehydroxylated,
the molybdenum carbonyl decomposes instantly, releasing only car-
bon monoxide with parallel formation of Mo species with O.N.close
to zero. Such a situation exists when the HY zeolite is pretreated
at high temperatures o r when the parent NaY zeolites are applied
as supports.
I n the absence of an oxidizing agent such a s a hydrogen from OH
groups, as well as in the presence of the basic sites present in
NaY zeolites, the decomposition of Mo(C0l6 started immediately
after deposition onto the support. After one hour of the contact
a t room temperature,the species with the average formula M o ( C O ) ~
were formed. Only the activation at elevated temperatures caused
the complete decarbonylation of supported Mo(C016. F o r the sample
with Si/A1=2.11 the complete decarbonylation was observed above
455 I ( , and above 400 I( for the sample with Si/A1=2.72. The oxygen
titrations indicated that application of NaY zeolites a s supports,
pretreated at 6 7 5 I ( , leads to the fornation o € zerovalent 140
particles.

TABLE 2
Average oxidation number of Mo supported on hydrogen Y-zeolites.

Support Average oxidation number of 110 after

pretreatment activation at indicated temperature ( K )
temperature Si/Al=2.11 Si/A1=2.72
( I( ) 415 575 675 475 515 615
675 +0.0 +2.4 +4.0 +1.1 + 3 . 3 +6.0
775 - +0.3 +0.3 +0.4 +0.7 +1.5
075 - - - +0.1 +0.3 +0.3
264

Samples differing i n Mo oxidation state and containing two Mo

atoms per supercage of Y zeolite were tested i n propylene metathe-
sis reaction. Catalyst activities were determined by passing
pulses of propylene over the catalyst kept at 335 K in a stream
of helium. Assuming pure disproportionation and equilibrium
between the 2-butene isomers, the equilibrium conversion i s 42.8%
( 1 3 ) . Pure disproportionation will yield only 2-butenes and
ethylene in equimolar amounts. Analysis up through the hexenes
revealed only tiny amounts of 1-butene as an additional product
f o r any of the studied samples, showing a selectivity higher than
99.5%. The ratio of ethylene/Z-butenes was usually higher than
1.4, suggesting higher adsorption of 2-butenes on the catalyst.
It was also dependent on the pulse number. The ratio of trans-
2-butene to cis-2-butene was close to the equilibrium value of 2.8.

-
,s 20
I - HY-1 I
Fig.2. Variation of ac-
tivity with the pulse
number for catalysts
activated at 575 K .
Support pretreatment
8
U
temperature - 675 K .
H Y - 1 , Si/Al=2.11
K? H Y - 2 , Si/A1=2.72
L$ 10 Nay-1, Si/A1=2.00
5 Nay-2, Si/A1=2.70
Open triangles represent
activity obtained after
0 6 pulses o f ethylene
5 10 15 20 followed by propylene
pulses over HY-1.
PULSE NUMBER
The results o f catalytic activity measurements,expressed as propy-
lene conversion, for catalysts pretreated at 675 K are shown in
Fig.2. F o r both hydrogen forms of Y-zeolites a low activity after
first pulses of propylene was observed. The effect is the reverse
of that with the alumina as a support ( 1 4 ) . The maximum activity
usually was reachod with 15 p u l s s s , and n z x t a sln1.i ;!::cr>az:? l i a s
n:?:;-svzC. ?rli,iy:-.nc conv~rsiari ov?c th-: c a t a l y s t : ; ,.:it:i:ii:1:i::r
: < i n t s , i t as in all studied c3s05 always higher than f o r those
tdhcro Si/A1=2.7. For iblo-loadcd ;!aY zeolites the activity bias
cJnstant f r o m t h c first pulse, however, very much lowered in
comparison with HY supports.
Very similar results have been obtained €or the catalysts where
t l i o sup7orts uere pretreated at 775 o r 875 I<. The initial activity
after the first pulses of propylane was at 775 K twice as high and
 265

'act.
3ob a - 475 K
- 575 K

Fig.3. Activity versus

average oxidation number
(O.N. 1.
HY-1 , Si/Al=2.11
HY-2 , Si/A1=2.72

0 2 4
OXIDATION NUMBER
at 875 I( over three times as high as for those pretreated at 6 7 5 K.
The increase of pretreatment temperature for NaY zeolites above
675 K did not influence the changes in the catalytic activity.
In order to establish the influence of the reaction products
on the catalytic activity, pulses of ethylene and trans-2-butene
were passed over the fresh catalyst before propylene injections.
Preadsorption of butene did not change the activity very much, but
significant changes were observed for the samples originating
from the HY supports pretreated with ethylene. I n a l l cases when
ethylene was applied before propylene admission the initial acti-
vity increased at least six times that expected for fresh catalyst
( s e e Fig.2.). The explanation for such behaviour can be based on
the assumption that carbene-Mo complexes are formed much faster
with ethylene than with propylene and butene. This would also e x -
plain thc presence of an induction period during the first pulses
of propylene. It i s known that carbene complexes, which themselves
can undergo disproportionation, can be isolated from homogencous
olefin metathesis systems(l5,ld). According to the mechanism pro-
posed by Casey and Rurkhardt (15), a carbene complex is initially
required in order ts catalyze disproportionation.
Figure 3 shows the influence of the value of oxidation number
on the catalytic activity, measured after 15 pulses. Similar to
the results presented by Komatsu et a1.(6), the activity decreases
266

with increasing oxidation number for HY supports. The low activity

o f catalysts originating from NaY zeolites i s due probably to
the low dispersion of Moo particles ( 7 ) .
In the present paper U V / V I S transmission spectroscopy has been
applied to study the adsorption and decomposition o f supported
M o ( C 0 l 6 . Figure 4 shows the U V / V I S spectra of molybdenum carbonyl
supported over HY zeolite, pretreated at 6 7 3 K . The band positions
at 230, 285 and 3 2 5 n m , characteristic for Mo(C016 (171, indicate
that at room temperature only physisorption occurs. The changes in
V."

Fig.4. U V / V I S spectra of Mo(C016

supported at r o o m temperature over
hydrogen form o f Y-zeolite recorded
0.6 after :
a - 5 min.; b - 20 min.; c - 1 hr;
d - 2 h r ; e - 4 hr.
The amount of Y O ( C O ) ~ introduced -

1
2
0.2
0.0127 mmo1-g- .

the absorbance after M o ( C O ) ~ admission

suggest a very slow migration of carb-
onyl particles inside the zeolite
cavities.
0.0 The decrease of the BrMnsted site
population (Table 1 ) with increased
200 300 400
WAVELENGTH Inm 1 pretreatment temperature to 7 7 5 :<
causes the reaction of introduced
W O ( C O ) ~ with the zeolite framework already at room temperature.
This was observed a s changes in the main band intensities as well
as the ayp:'arance o f th:: ahou1dL.r b a n d s 3 t 7 5 0 a n d 2 7 3 nn.
I n a C L i l i o n , t.volutioii ~ i n s ~ : :;i i z <?:is2rv2r:. T : E ;,PI'Jct o f cir3cr-
cnszd Zrbnstzrl acidity was cven inorc pronounczd 1,ihen the zeolite

'Fig.5. uv/vIs s!JC?CtrJ Of

supported at room
:40( 30) I

a - after
mmo1.g '
temperYturc over Nay zeolites.
mission of 0.0091
and recorded
after 1 min.
b - recordod after 30 min.
c - after adnissior another
0.0091 mno1.g- , recorded
after 1 min.
1 I 1 d - recorded after 1 hr.
200 300 wx) 500
WAVELENGTH Inm 1
 267

was almost completely dehydroxylated at 875 K. The band at 230 nm

was present only at the initial stage of adsorption, whereas the
bands at 250, 270 and 340 nm increased their intensity.App1ication
of the support with Si/Al=2.11 produced the same tendency as in
the previous case; however, the decomposition of Mo(C016 started
already at room temperature, even if the support was pretreated
at 675 K .
The instant decomposition of molybdenum carbonyl at room tem-
perature was observed for NaY zeolites. Figure 5 shows spectra
after adsorption of Mo(C0)6 over these supports. The prolonged
contact of molybdenum carbonyl with NaY caused the appearance of
new bands at 260, 320 and 390 nm. Concomitantly,a strong evolution

-300 K Fig.6. U V / V I S spectra of Mo(C0)

- _ _ _ 375 K adsorbed at room temperature ovgr
175 K HY-zeolite and activated at different
temperatures.
Support pretreatment temp. -675 K
Si/Al = 2.72
Amount-pf Mo(CO)~ adsorbed - 0.0138
mmol-g .

of CO was observed. The amount of

-1 released CO, both under static and
200 300 Loo 500
WAVELENGTH Inm 1 dynamic (He flow) conditions suggests
the formation of Mo(CO)~ ads.species.
On the other hand, the bands at 320 and 3 9 0 nm can originate from
dimolybdenum-like species (18). The appearance of the same bands
has been also noticed for HY supports however, only after activ-
ation up to 425 K ( s e e fig.6). Activation at higher temperatures
was always associated with the decrease of band quantity and
intensity.
The results presented suggest that mainly basic sites are
involved in the decomposition of supported MO(CO)~. In both cases,
of NaY and HY zeolites, the oxygen anions act as basic sites.
However, f o r NaY the oxygen ion carries a much higher negative
charge than the corresponding oxygen in the H-form of the zeolite.
Additional U V / V I S experiments with olefins and Mo-loaded zeolit-
e s indicated the interaction of propylene and butenes with the
acidic supports (both protonic and non-protonic) with fast format-
ion o f r - a l l y 1 carbocations (19). Contrary to that, the interact-
ion of ethylene and the zeolite acidic centers was much slower,
268

and formation of r - a l l y l i c structures was very much delayed. Such

behaviour can explain the increased activity in propylene metathes-
is after ethylene pulses, as well as the existence of an induction
period at the initial stage of the reaction. In the case of propyl-
ene the competition reaction of j-r-ally1 complexe formation proceeds
first, and next the carbene-Mo complexes are formed. With ethylene
the reverse sequence is probably involved, and 7 - a l l y 1 carbocat-
ions can be developed after the formation of carbene complexe.

CONCLUSIONS
1. The decomposition of Mo(C016 over NaY and HY zeolites occurs
on the basic sites. Surface hydroxyl groups of HY zeolites are
responsible for the oxidation of supported molybdenum hexacar-
bony1 at elevated temperatures.
2. In the absence of hydroxyl groups in NaY zeolites the supported
metallic Mo can be formed.
3 . The catalytic activity in propylene metathesis is strongly in-
fluenced by the value of the oxidation number of supported Mo
species. The lower the O.N. of Mo, the higher i s the catalytic
activity.
Application o f NaY supports leads to the formation of a catal-
yst with low activity due to the poor dispersion of Moo particl
es.
4. Carbene-metal complexes are probably involved in the mechanism
of propylene disproportionation over these catalyts.
The mechanism via metallocyclobutane intermediate has to be
questioned because of its validity on a thermodynamic basis.
Besides, no cyclopropane has been observed from propylene, as
would be the case if a metallocyclobutane were a n intermediate.

ACKNOWLEDGEMENT
The author is indebted to Or. H.G.Karge f o r the critical re-
vision o f the manuscript and the provision of the UV/VIS facility
which made this work possible.

REFERENCES
1 P.E.Dai, J.H.Lunsford, J.Cata1. 6 4 (1980) 173-184
2 M.B.Ward, J.H.Lunsford, Proceed.6th 1nter.Zeolite Conf.
July 1983, Reno (D.Olson,A.Bisio Eds.), Butterworth 1984,
pp. 405
3 P.Galezot, G.Courdier, M.Primet, B.Imelik, ACS Symposium Ser.
40 (1977) 144-155
 269

Ir S.Abdo, R.F.Howe, J.Phys.Chem. 07 (1983) 1713-1722 and 1722-

1730
5 T.Komatsu, S.lJamba, T.Yashima, Proceed.Int.Symp.on Zeolite
Catalysis, Siofok, blay 13-16, 1985, pp.251
T.Komatsu, S.Namba, T.Yashima, K.Domen, T.Onishi, J.Mol.Cata1.
3 3 ( 1 9 ~ 5 ) 345-356
T.Komatsu, T.Yashima, J.Mo1.Catal. 40 (1987) 83-92
Y.S.Yong, R.F.Howe, Proceed. 7th Inter.Conf.Zeolites, August
17-22, Tokyo 1986 (Y.Murakami et al. Eds.), Kodansha Ltd.,
1936, pp.833
9 t 4 . B . Nard, X .Mizuno, J. H. Lunsford, J. M o l . Catal. 2 7 (1904) 1-10
10 H.Kacirek,H.Lechert, J.Phys.Chem. 79 ( 1 9 7 5 ) 1587-1593
11 M.tanieclci, R.L.8urwell Jr.,J.Coll.Interface.Sci. 7 5 (1980)
95-104
12 H.G.Karge, M.Zidlek, M.taniecki, Zeolites, 7 (1907) 197-202
13 Selected Values of Properties o f Hydrocarbons and Related
Compounds, API Research Project 4 4 , Texas A and M University,
College Station, Texas.
14 A.Brenner, R.L.Burwel1 J r . , J.Cata1. 5 2 (1970) 364-374
15 C.P.Casey, T.J.Burkhardt, J.Am.Chem.50~. 76 (1974) 7000-7810
16 D.J.Cardin, M.J.Doyle, M.F.Lappert, Chem. Comm. (1972)
927-923
17 ll.Strohmeier, K.Gerlach, Z.Phys.Chemie, Neue Folge, 27 (1961)
439-442
13 M.L.Carson, F.W.Moore, 1norg.Chem. 2 (1963) 881-884
19 M.taniecki, H.G.Karge, in preparation
This Page Intentionally Left Blank
H.G.Karge,J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science PublishersB.V., Amsterdam - Printed in The Netherlands

I. M. Harris,' J. Dwyer,' A.A. Garforth,' C.H. McAteer2 and W.J. Ball2

' Chemistry Department, UMIST, P.O. Box 88, Manchester M60 lQD, U.K.
BP International Plc, Research Centre, Sunbury-on-Thames,Middlesex, U.K.

ABSTRACT
Mo oxide is incorporated into H-ZSM-5. At low loadings, up to 8%
oxide, molybdenum is highly dispersed on both internal and external
crystalline surfaces. Tetrahedral dioxomolybdenum species are formed by
reaction with zeolitic hydroxyls. Molybdenum-oxide-loadedH-ZSM-5 catalysts
are evaluated using several reactions and some comparisons are made with
gallium counterparts. Catalytic conversion of n-butane over H-ZSM-5 and
over zeolites with low loadings of Mo can be explained by an initial
activation which involves direct protonation at both C-C and C-H bonds. At
higher loadings of Mo oxide and in the presence of Ga oxide an initial
dehydrogenation can be involved. As conversion of butane increases secon-
dary products including aromatics are produced. Conversion of butane,
butene and 1,7 octadiene demonstrate an order for aromatisation H-<Mo-<Ga-.
Equilibrium amounts of aromatics are obtained with relatively small loading
of Ga.

IWRODUCTION
The incorporation of transition-metaloxides into zeolite catalysts
permits modification of both acidity and diffusivity and can introduce a
hydrogen transfer function. Although molybdenum-containing zeolite
catalysts have been developed for hydroprocessing there are few reports on
the activation of small hydrocarbons by molybdenum - containing pentasil
zeolites. This work considers the incorporation and dispersion of
molybdenum oxides in H-ZSM-5 and the catalytic consequences particularly in
the conversion of n-butane. Results for conversion of butene, 1.7 octadiene
and trimethylbenzene are also examined with a view to understanding
mechanisms and site location. Experimental results for molybdenum-
containing H-ZSM-5 are compared with results for a gallium-loaded catalyst
which has commercial significance (1).

4
lmEm
l
Zeolite ZSM-5 (Si/Al = 14) was synthesised using a patented procedure
( 2 ) . It was modified in the ammonium form either by impregnation or by
direct mixing. The impregnation procedure involved addition of NH4-ZSM-5 to
a solution of ammonium heptamolybdate stirred at 80 "C. The resulting thick
paste (pH 5 ) was dried at room temperature and calcined in air at 500 O C
(16 hours). Direct mixing involved gentle grinding of NH4-ZSM-5 and Moog to
212

produce an intimate mixture which was then calcined as above.

A Philips PW 1400 instrument was used for XRF chemical analysis and a
Philips PW1380 diffractometer for powder diffraction. Mid-infrared spectra
were obtained using KBr discs and a Mattson Cygnus 100 FT-IR instrument and
the hydroxyl region was investigated using self-supporting discs and a
Nicolet 7199B FT-IR spectrometer. TEM and HRTEM images were obtained using
a JEOL 2000 EX instrument with point resolution of 2.1 1 and EDS analyses
were made with a JEOL 2000 PX TEM equipped with a link system analyser. XPS
results were obtained using a VG ESCALAB Mk 1 instrument and 27Al and 29Si
MASNMR spectra of fully hydrated samples were produced using a JEOL GNM
GX400 FT NMR spectrometer (27Al) or a JEOL FX 200 spectrometer (29Si). For
temperature-programmeddesorption of ammonia (TPDA) a VG micromass 6 mass
spectrometer was used to monitor desorbed ammonia.

RESULTS AND DISCUSSION

Powder XRD of uncalcined mixtures of Moo3 and H-ZSM-5 shows a peak at
d = 3.26 8, due to Moo3, which increases linearly with the MOO3 content.
However, after calcination this peak cannot be detected in the powder
pattern at oxide loadings less than 8% (Fig 1). Since XRF analysis (3)
shows that MOO is not lost, on calcination, these results imply that Mo is
3
very finely dispersed by calcination. A similar spreading of MOO over
3
alumina and magnesia is reported (4) (5). The excellent dispersion of
molybdenum oxide can also be seen by TEM. At 22 oxide loading Mo can be
detected analytically but no separate phase is evident. At lo%, and higher
loading, surface agglomeration of Mo oxide is observed (Fig 2). Sorption
results are consistent with XRD and TEM. A fine dispersion in the pore
system of H-ZSM-5 should reduce micropore volume and this is observed.
Sorption capacity of p-xylene decreases up to a loading of around 8% oxide
and, as expected, the rate of ingress of o-xylene is reduced by
incorporation of the oxide ( 3 ) .
Fig 3 shows 27Al MASNMR spectra. In NH4-ZSM-5 the single peak, with
spinning side bands, at 56 ppm is due to tetrahedral framework aluminium.
On calcination to produce H-ZSM-5 a proportion of this is dislodged as
shown by the peak at 3 ppm due to octahedral extraframework aluminium. More
severe calcination in the presence of molybdenum salts or oxide results in
more extensive dislodgement of aluminium as evidenced by an increased
signal at 3 ppm and the development of a broad signal associated with
extraframework aluminium species of lower symmetry. At a given loading of
Mo the amount of dislodged A1 depends on the calcination procedures (3).
FT-IR spectra of the hydroxyl region are shown in Fig 4a. The extensive
 273
1

i
J mix I .
.w

/
I.W
mid-crystal

I
'0 4 6 12 16 !=I,
1.960 WJ
MO OXIDE (%I b-rich &e
Fig.1. Intensity of major (XRD) EM%~v=b!s

peak for MoO3. Fig.2.Dispersh of Mo oxide (EM).

la1
lbl i
!&
i
E
,-zsns 1
-
HQSH5
o -m
IS m 10
-CMMICU
o -S
IW
S H I ~won IN IH,OI,I*/PP.
Fig 3 nAI MASNHR laJNH,/H-ZSM-5
-
100

(bl Mo oxde/H-ZSM-5, calcined

/lO%Mo

20

10

1
0
0 2 4 6 8 10
r I I I I
Mo oxide (%I
3900 3340 ml wo
WVENUPBER I c i l l WAVENUMBER Ici'l Fig5 Effect of molybdenum oxide
Fig.b.Effect of calcination with Mo oxide. content on conversion of
1a)hydruxyl region. iblmid I R . n-butane (SOOOC).
274

reduction in the band around 3601 cm-l (%70X), on incorporation of2X Moo3.
is due to loss of framework aluminium by calcination (Fig 3) and
interaction of bridged hydroxyls with molybdenum oxide. The reduced
intensity of the band at 3740 cm-l reflects the interaction of terminal
silanols with Moo3. Confirmation of this is seen in the mid-infrared
spectra (Pig 4b). A band at 870 cm-l is indicative of bulk Moo3 but bands
at 915 and 950 cm-' are assigned to molybdenum species in the zeolite. A
band at 915 cm-l is previously ( 6 ) assigned to the M=O stretch in
tetrahedral Mo species on silica or alumina

and bands at 890 cm-l (7) and 900 cm-l (8) are reported for Mo-modified
zeolite Y. Consequently we assign the band at 915 cm-l to the M=O stretch
in tetrahedral dioxomolybdenum species and the band at 950 cm-l to T-0-Mo
vibration (T = A1 or Si). The absence of absorption at 915 and 950 cm-l in
the catalyst prepared by calcining a mixture of MOO and Na-ZSM-5 supports
3
the role of zeolitic hydroxyls in generating these tetrahedral Mo species.
Thus, at lower loadings of Moog in H-ZSM-5 a dispersed layer of
dioxomolybdenum species is generated on both internal and external surfaces
of the crystals. XPS results show a largely symmetric doublet due to
ejection of Mo3dgI2 and M 0 3 d ~ /electrons
~ with binding energies typical of
Mo(V1) species (3). However, ESR spectra reveal the presence of some Mo(V)
centres after calcination and these increase following reaction with
n-butane at 500 OC (3).
Relative rates of reaction of n-pentene and 4,4-dimethylpenteneS using
a pulsed reactor and a hydrogen stream, show the presence of a
hydrogenation function in the presence of Mo oxide (3). Discrimination
against 4,4-dimethylpenteneat low loadings of Mo show that Mo in internal
sites also possesses a hydrogenation/dehydrogenation function. At higher
Mo loadings (10%) and on Moo3 no discrimination is observed (3).
The accumulation of Mo oxide on outer crystalline surfaces (Figs 1 and
2) reduces the effectiveness of outer-surface acid sites. The rate of
isomerisation of the bulky 1.3,s-trimethylbenzene at 500 "C decreases as Mo
loading increases up to about 8% (3) consistent with the formation of a
monolayer of dioxomolybdenum species (Pig 4b) by utilising internal and
external hydroxyls (Fig 4a). At higher loadings there is build-up of an
external phase of MOO with no further decrease in rate.
3
Of interest in this work is the conversion of n-butane which is used here
 275

to assess the potential of Mo/H-ZSM-5 in dehydrocyclodimerisation

reactions. Continuous-flow experiments using butane in nitrogen (10%) show
that small quantities of Mo oxide enhance the rate of conversion at 500 "C,
but also lead to increased rates of deactivation ( 3 ) . Over H-ZSM-5 the
activation energy is 125 kJ mol
-1
. A pulsed microreactor is used to
estimate activation energies for the Mo/H-ZSM-5 catalysts which deactivate
in the continuous mode. Activation energies decrease and then increase as
the Mo oxide level is increased ( 3 ) . Consequently, as with the continuous
reactor, enhanced activity is observed at lower loadings of Mo.(Pig 5).
Changes in activation energy suggest that active sites may be modified by
incorporation of Mo oxide or that new sites are produced, perhaps leading
to a change in mechanism.
In the multistage aromatisation of n-butane over H-ZSM-5 ( 9 ) the rate-
determining step involves the initial activation of the alkane. It is also
known that the conversion of olefins over acid zeolites is facile compared
with alkane conversion. Consequently, rates of alkane conversion can be
enhanced by addition of dehydrogenation centres such as Ni or Zn (10) to
the zeolite. Since the Mo/H-ZSM-5 catalysts shows activity in
hydrogenation of olefins ( 3 ) it is possible that enhanced activity at low
loadings of Mo could result from generation of olefins by dehydrogenation.
Reduced rates at higher Mo loadings might then be explained by both a
reduction in dehydrogenation sites, resulting from a poorer dispersion of
Mo, and a loss of Bronsted sites to capture olefins produced initially.
Separate experiments (3)(11) show that conversion of butene and 1.7
octadiene is facile at the temperatures used, even with higher loadings of
Mo oxide, which emphasises the importance of the initial alkane activation
in rate factors.
To examine this aspect further an intermittent-flowreactor is used,
at 450 "C, to investigate product distributions at low levels of
conversion. Some typical results are given in Table 1.
scheme 1
276

TABLE 1 Conversion of n-Butane at 450 'C.

Typical results using an intermittent-flow reactor

H-ZSM-5 Mo/H-ZSM-5 Ga/H-ZSM-5

Conversion 0.40 1.08 10.31 5.97
Products (mo1/100 mol/C4H10)
44.9 24.7 5.5 48.8
26.5 26.9 7.7 18.2
28.3 32.2 9.8 12.3
30.3 38.4 14.3 18.8
12.2 76.3 43.4
26.9 34.5 10.6 17.8
i -C 1.9 6.8 13.7
4
C; 45.5 22.1 6.3 10.4
3.6 1.7
c5
0.3
6'
B+T 1.5 5.3
Product H/C 2.49 2.48 2.51 2.59

Results at low conversion are similar for both H-ZSM-5 and for low loadings
of Mo oxides, and this is emphasised by Fig 6. This suggests that
mechanisms over H-ZSM-5 and low-loaded Mo/H-ZSM-5 may be similar, in which
case an additional dehydrogenation function does not appear to be necessary
to explain initial product distributions over Mo/H-ZSM-5 (2%). A mechanism
which can account for these results may be proposed, based on direct
protonation of butane according to scheme 1 (a), (b), (c) with minimal
contribution from (d). Reactions (b) and (d) cannot be distinguished on the
basis of products but (d) is presumed to occur on dehydrogenation centres
or via radicallradical ion processes (11).

If the carbenium ions formed by the primary reactions (a) -+ (c) are
desorbed largely as olefins. at very low conversion, then scheme 1 (a),(b)
-
(c) suggests that initial yields of Ca, H2; C;, C2; C;, C1 should be
similar and experimental results at low conversion are in reasonable
agreement with this (Table 1). Desorbed butenes are found to be in
thermodynamic equilibrium (3). in agreement with carbenium ion precursors.
Consequently, any olefin produced by dehydrogenation (d) or by other
processes such as radical reactions (111, or by Lewis site hydride
abstraction, is captured by acid sites prior to desorption. A contribution
from processes associated with reaction (d), however, cannot be excluded.
Over H-ZSM-5 it is proposed, on the basis of product distributions,
 277

that reaction (d) is not extensive and that primary reactions involve
direct protonation of C-C or C-H bonds. At low conversion (x = 0.28) over
H-ZSM-5 at 450 'C, results (3) suggest that, for conversion of 100 mol
n-C4HI0, 48 mol are converted via reaction (b), 25 mol via (c) and 27 mol
via reaction (a). At a conversion (x = 0.4) good agreement with
experimental results(Tab1e 1) is found if 45 mol react via (b), 26 via (c)
and 29 via reaction (a). These results suggest that protonation of C-C is
slightly favoured, over protonation of C-H, over H-ZSM-5 but separate
results (12) on H-ZSM-5 activated at higher temperatures suggested more
extensive protonation of C-C bonds in n-C4 H10'
The initial activation of hydrocarbons by acid zeolites has been a
subject of considerable discussion and only recently has direct protonation
of C-H (13) or C-C (14) bonds been proposed. The present work, and related
studies (12), suggest that, in the case of n-butane, protonation can occur
at both centres, the relative extent of these processes depending on
catalyst pretreatment and reaction conditions.
If, on the basis of similarity in product distribution at low
conversion, we accept that n-butane is initially activated over Mo/H-ZSM-5
(2%) by the same major processes (a), (b), (c) in scheme 1, then we require
an explanation for the enhanced activity observed with low loadings of Mo
oxide. An explanation, without recourse to reaction (d), can be provided by
considering changes in acidity as reflected in ammonia retention at higher
temperatures (Pig 8 ) . Similar results (15) have been obtained for n-hexane
conversion over steamed H-ZSM-5 where increased acidity is attributed to
the presence of limited amounts of non-framework aluminium which can
produce sites of enhanced activity (15)(16)(17). The 27Al NMR results (Pig
4) show that calcination with Mo oxide does dislodge aluminium from the
framework and, as suggested previously (15). an optimal balance between
framework and non-framework aluminium may give optimal catalytic activity.
However, in the present work the picture is complicated by the presence of
molybdenum species which may be involved in active site modification ( 3 ) .
At low conversion the carbenium ions produced by primary reactions (scheme
1) are largely in equilibrium with olefinic products, but at higher
conversions there is increased reaction of alkanes and olefins with
carbenium ions which cover more of the reaction surface. Consequently,
oligomerisation and bimolecular hydride transfer occur to give products
which may be desorbed or cyclised to give aromatics depending on the
product, the catalyst and the process conditions. As a result the products
from the primary processes tend to decrease with increased conversion (Figs
6,7).
278

wO 2 4 6 6 1 0
conversion 1%)
CONVERSION I%)
Fig.6.Hydrogen and butenes at low Fig.7. Propane and methane from butane
conversion of n-butane (45OOC). (intermittant flow reactor,450Oc).

/'
f 2%Mo
/
/
/

{21i/ /L:
c
, , ;./Mo

0 10 20 30 w)
ammonia desorbed at 4OOT [units) CONTACT TIME Is)
Fig.8. Catalytic activit and acidity
of Mo oxide/H- SM-5. r Fig.9.Relative activity of H-ZSM-5
and oxide modified H-ZSM-5.

El
e 40
8 f Ga
H-ZSK5
Mo/H-ZSM-S
Ga/H-ZSM-5
0
0 6
I

0 20 40 60 80 100
conversion (%I
Ga lMo1oxide imprmated in H-ZSM-5
Figlo. Aromatics selectivity (BTX)
from conversion of n-butane Fig.11. Ammatics selectivity (BTX) at 40@C,
over H-ZSM-5; 0.5% oxide 100% conversion (pulse reactor1,from
loading (SOO'C). butene or 1.7 octadiene.
 279

The Ga/H-ZSM-5 catalysts are much more active than H-ZSM-5 or

Mo/H-ZSM-5 (Fig 9) and products at similar conversion also differ. In
particular there is much more molecular hydrogen and increased amounts of
aromatics and isobutane. These preliminary and limited results for
Ga/H-ZSM-5 are probably best explained by dual-function catalysis where
both dehydrogenation/hydrogenation and acid catalysis can play a
significant role. Initial activation of the alkane is presumably enhanced,
in Ga/H-ZSM-5 by effective dehydrogenation [reaction (d) in scheme 11, to
-
provide Ci which is then protonated. The increased amounts of i-C4 and
aromatics, in secondary products observed at higher conversion ( 2 to lo%),
with Ga as opposed to Mo-loaded catalysts (Table 1) is in keeping with a
more effective role for Ga in hydrogen transfer and in olefin cyclisation.
Selectivity to aromatics is increased as intermediates are cyclised at the
expense of cracking (Fig 10). However, Mo does show some capacity for
increased aromatics yield (Fig 10).
These aspects are seen more clearly when postulated intermediates are
used as reactants. At 400 "C quite low loadings of Ga oxide produce
aromatic yields (BTX) close to calculated equilibrium values for the
conversion of 1-butene or 1,7-octadiene (Pig 11). Higher loadings of Mo are
needed to give significant increases in aromatics. Increased yields of
aromatics presumably reflect increased cyclisation, at the expense of
cracking, when Ga and Mo centres are present in H-ZSM-5. In addition, at
very high loadings, when there is a separate bulk MOO phase, there is
3
possibility of cyclisation of olefins produced by dehydrogenation on
coordinatively unsaturated Mo centres which can stabilise aromatic species
(18) .
- A
We thank BP International Plc, Research Centre, Sunbury-on-Thames, for an
ENRA and BP and SERC for a case award to IMH. We thank D. White and L.
Hayes (B.P. Research Centre) for TEM.

REFmmlcEs
1 J.A. Johnson and G. K. Hilder, Proc. Nat.Petrol.Refines Assoc. Annual
Meeting, Texas (1984).
2 W.J. Ball and D. G. Stewart, USP 4, 452, 907 (1984)
3 I.M. Harris, PhD Thesis, UMIST (1987)
4 S.R. Stample, Y. Chen, J.A. Dumesic, C. Niu. G.G. Hill, J.Cataly., 105
(1987) 445
5 T.F. Hayden, J.A. Dumesic, R.D. Sherwood. R.T.K. Baker, J.Cataly., 105
(1987) 299
6 Y. Iwasawa, Y.Nakono, S.Ogasawara. J.Chem.Soc.Faraday Trans 1,
74(1978) 2968; Ibid, 1, 75 (1979) 1465
280

7 R.Cid, F.J. Gil Llambias, J.L.G.Fierro, A. Lopez Agudo, J. Villasenor,

J.Catal., 89 (1984) 478
8 P.E. Dai, J.H. Lunsford, J.Catal., 64 (1980) 173
9 R.F. Batchelder, H.W. Pennline, R.R. Schehl, D.H. Finseth, Energy
Res.Abst., 10 (4) Abst. No.6549 (1985)
10 M.G. Riley and R.G. Anthony, J.Catal., 100 (1986) 322
11 G.B. McVicker, G.M. Kramer and J.J. Ziemak, J.Catal., 83 (1983) 286
12 J. Dwyer, R.A. Shigeisi, unpublished work.
13 W. 0. Haag and R.M. Dessau, Proc. 8th 1nt.Cong. on Catalysis, Berlin
(1984) Vol 2, p.305, Dechema, Frankfurt-am-Main (1984)
14 A. Corma, J. Planelles, J.Sanchez-Marin and F. Tomas, J.Catal., 93
(1985) 30
15 A.G. Ashton, S. Batmanian, D.M. Clark, J. Dwyer. F.R. Fitch, A.
Hinchliffe and F.J. Machado, in B.Imelik et al. (Editors), Catalysis
by Acids and Bases, Elsevier (1985) 101.
16 C. Mirodatos and D. Barthomeuf, J.C.S. Chem Comun. (1981) 39
17 R.M. Lago, W. 0. Haag, R.J. Mikowsky, D.H. Olson, S.D. Hellring, K.D.
Schmitt and G.T. Kerr, in Y. Murokami, A. Iiijima and J. W. Ward
(Editors), New Developments in Zeolite Science and Technology,
Kodansha-Elsevier (1986) 101
18 O.V. Krylov, Catalysis by Non-Metals, (1970).
H.G.Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

SURFACE AND WALYTIC PR3PERPIEs OF THE NEW Z W L I T E TYPE LZ 132

z. TVARUZKOVA~, M. WA', P. JI&, A. NASIRI~, G. GIORDNW~ and F. TRIFIRO~

'J. HeymvsW I n s t i t u t e of Physical Chenistry and Electrocknistry, Czechoslovak
A c a d q of Sciences, -182 23 Prague 8 (Czechoslovakia)
2
D
t- of chenistry, university, co~enza( ~ t a l y )
3
Departrru3nt of Idustrial chemistry and Materials, U n i v e r s i t y of ~ologna,
1-40136 Bolcqna (Italy)

ABSTRACT
The " s n a l l pore" zeolite LZ 1 3 2 exhibits, in ccmparison with other zeolites,
an increased selectivity for the tpnsfonnation of qthanol to ethylene i n the
reaction temperature range 35Ck.500 C. A t WEV = 2 h , the weight ratio of C2H4+
tC H to C H i n the reaction products ranges between 1 and 4. Besides the
ef2&t of &-4 reactant s ~ p selectivity,
s this fact may be interpreted as the
participation of the asynetrical methoxy groups i n surface and as the presence
of protordonor centres of lower acidity. They do not oligamerize ehtylene
although they have this effect on the more basic molecule of ppylene. Coke of
the type of polyenes is fonned both on the electrowacceptor and protol-rdonor
cetres .
I ~ I O N
The n w type of zeolite, LZ 132 (ref. 1), belongs to the group of "anall pore"
zeolites (its effective pore radius is 4.3 8) which fran the point of view of
their selectivity are attractive for the catalytic transfonmtion of methanol to
lwer olefins. The aim of this paper is therefore to characterize the surface and
catalytic properties of HLZ 132, inclUaing the mechanism of ethylene and propylene
oligcnnerizatim and that of the methanol transformation to ethylene and propylene.

EXP-
The LZ 132 z e o l i t e was prepared by hyzlrothennal synthesis (ref. 1).The raw
product (Na+-fm, Si/Al = 33, 0.2 w t . % Na) was activated by decQnposing the
stmzture-direct- agent either i n air or successively in N2 and 02, then by
performing the ion exchange in 0.5 M NH4N03,ad finally by transforming the
agent into the H+-fonn by heating it a t either 350 or 5OO0C i n vacuo (Table 1).
order to canpre the surface and catalytic praperties of the new zeolite
with the HZSM-5 zeolite, canparative measuranents were also perfarmeed with a
sanple of the latter (Si/Al = 13.6, Ar sorption capacity 5.9 m l e / g zeolite,
ratio of the absorbancies OA(549 an-') / OA(454 an-') = 0.69 for skeletal vib-
rations bands i n question).
The crystallinity of HLZ 132 was characterized by determining the Ar and H20
TABLE 1 N
W
N

Surface and catalytic properties of the LZ 132 zeolite

Qlm 1 2 3 4 5 6 7 8 9 10 11

LZ 132 Ian sarption capacity Activation

ro4
S'D'A.
sanple form deoanp. -le/g zeol. ) O A ~ P A ~ invacuo "b "b ".OM
Of Na form Ar(-195OC) HqO(230C) (18 h) 1 2 3 4 (Inin-5

0.47 0.40 - 0.32

in& 35OoC
3720 36l5 3555
N
a
' 6OO0C 6.34 7.72 0.12 -
6 h 5OO0C 0.28
3740
- - -
inair 35OoC 0.46 0.62 0.59 o*61 24.4
3720 3615 3608sh 3555
H+ 6OO0C 7.8 8.6 0.15
6 h 5OO0C 0.27
3740
0.22
3615
- 0.18
3555
1) in N2 0.48 0.64 0.60
35OoC 3720 3615 3600sh 28.2
H+ 2) in o2
7.9 9.7 0.16
55OoC
5OO0C 0.28
3740
0.21
3620
- :$:23.8
(5) (5,6)

S.D.A. = structure-directixq agent ("tenplate")

$,A2 = mrmalized a b d a n c i e s of the bands at 565 and 460 a
n
-'
, resp.
initial rate ro of C3H6 oliqanerization at 8OoC and p = 20 torr
 283

sorpticn capacities as well as absorban~yratios o% / O.2 in the range of s ~ e

t a l vibrations. The experimenbl details are given in the publications (refs.1-4)
quoted in Table 1.
The acidobasic properties were characterized by mesurhq IR spectra, i.e. by
de- the absorbancies of the bands of the structural OH groups of the zeo-
lite as w e l l as the abmrbamies of the bands of adsorts3 d3-acetanitrile, the
adsorption of which was performed a t 25OC wi t h a pressure of 0.27 kPa for 15 m i -
nutes on sanples which had been previously evacuated d kept a t 35OoC ovanight.
The desorption toak place a t 25OC for 15 minutes.
?he measurmmts were carried out i n a high-vacuum IR cwette d with self-
sqqortirg pellets (with the tkickness of 10 q / m 2 ); for details see (ref. 5) i n
Table 1. The I R spectra were registered with a E F I R spectraneter Nicolet MX 1.
The sane type of IR cwett&was used in measurements of the IR spectra of
methanol adsorw in quantities ammting to 10m l e / g a t 2 0 ' ~ on self-support-
tirq pellets (with thickness of 10 q / m 2 1; the tenperature of activation of the
sanple in vacuo before the methanol adsorption was 35OOC. The IR spectra were re-
gistered after tempering the plate of the zeolite rapidly to a certain tarcpera-
ture i n the range 20-400°C, maintaining the sample a t t h i s tenperature for 30 mi-
nutes d then cooling it qui&ly d a ~ nto 20'~.
The i n i t i a l ethylene a d promlene oligomerization rates a t 8OoC and polefin=
= 2.66 kPa w e r e calculated fran the e x p r i m n t a l l y determined (with a McBain bal-
ance) t h e course of the mass increase of the HLZ 132 s q l e s . For experimental
details see (refs. 5,6).
The transformation of methanol was performed in a catalytic minoreactor a t
4OO0C and MEW = 2 h-' over a catalyst w i t h 0.4 -
0.6mngrain size. The f e d con-
tained 17 vol.% CH30H, 68 m1.%H20 and 15 vol.% N2 under the total pressure of
101 &a. The reaction products were analyzed with a gas &anatogra& (Chmpre
jekt MCH 112).

RESULTS AND DISCUSSION

Preparation and activation of H U 132
The X-ray diffractcgra&ic data of the NaU 132 zeolite correqmrded to those
given i n the literature (ref. 1).
~ 0 t hthe ~r and H ~ Osorption capacities and the a b s o r a ratio o ~ /lin
the range of skeletal vibrations shaw - when canpard with the NaLZ 132 - that
the crystallinity of the HLZ 132 zeolite is preserved also in the H+-form. Differ-
ent corditions of deccmposition of the tenplate (either mare drastic directly by
air or m e gentle in N2 and then in a h (Table 1, column 2) have no effect on
the crystallinity of the NaLz 132 zeolite and thus indicate the good thennal sta-
bility of the LZ 132 zeolite (Table 1, colunns 3-5, 7-9). Increased tenprature
+
of the activation of the H -form of LZ 132 causes the decrease of the absorbancies
284

of the carresponding to three types of OH groups only (Table 1, calm 7-10).

These are probably protordonor sites and electmn-acceptor sites created by par-
t i a l dehydmxylaticm, as follaws fran measurerents of I R spectra resulting fran
the interactions of HLZ 132 w i t h d3-acetanitrile (see below).

Oliganerization of ethylene and prow1-

A t 8OoC, HLZ 132 is inactive i n ethylene oliganerization ( r o e 0.2 m i n - l ) .
Frun the decrease of the oliganerization i n i t i a l rate (ro) of the more basic pro-
pylene (Table 1, column 11) with increasirq degree of dehydroxylation and frat?
the resulting changes i n the nunber of both types of acid centres, it f o l l m
that prcpylene is oligcmerized on both types of centres. Fran the experbentally
determined (fran their man aksorbancies) decrease of the concentration of OH
groups and increase of the concentration of Lewis centres with increasing tape-
rature of activation, a decrease of the i n i t i a l oliganerization r a t e fran
(ro)3000 = 24.4 to (ro)sooo = 16.3 may be p r d c t e d (since accoIcLing to (ref. 6)
i n the course of dehyamxylatian fran tsm OH p u p one nw Lewis site is formed).
This is i n good agreement w i t h the e x p d m n t a l l y founl (ro)5ooo = 15.6 min-1
(sample H in Table 1).
he i n i t i a l o l i q m a i z a t i o n rate of ethylene ro-= 0.2 min'l is by orders
of magnitude lacrR1: than t h a t of prcpylene (ro = 28.2 min-l) vhich is mre basic.
The different behaviour of HLZ 132 i n the oliganerization of C2H4 and C3H6 irdi-
cates that the proton-donor centres (and probably also the electron-acceptor cen-
tres) of the zeolite which take p a r t in the oliganerization on zeolites (ref. 6)
are less acidic (or weaker) than,e.g., on HZSM-5, wkre the ethylene oligoaneriza-
tion rate u d e r the smne conditions was ro = 45.1 m i n . -1

z+ztivity and. selectivity

The distribution of the prcducts of methanol transformation as a function of
the on strean is given in T a b l e 2. The r a t i o of (C2-)/T a f t e r 60 minutes on
strean a s a function of the reachon temperature is given in Fig. 1. The depen-
dence observed shaws that with increasing tanperature of the reactor the a n a n t
of ethylene in the products increases too. With a feed containing no w a t e r w p u r
a similar anposition of prcducts of methanol transformation was found, the pres-
ence of H20 having only a positive effect on the lifetime of the catalysts (Figs.
2,3). The results presented in Figs. 3 and 4 s h w that HLZ 132 is theunally sta-
ble in the course of the catalytic transformation and m y be easily regenerated.
The I R spectra registered before and after the catalytic test in the range of
skeletal vibrations (Fig. 4) did not charge and have shown that during the cata-
lytic reaction the r a t i o 0 0
A56w-l / A460m-l of the n o d i z e d a b d a m i e s of
the bards i n question (and also the c r y s t a l l i n i t y of the zeolitic catalysts) un-
dement no charqes.
 285

TABLE 2
Catalytic transformation of CH30H over LZ 132 zeolite
(Grain size 0.4-0.6 mf reaction terrperature 4OO0Cf WHSV (H20 + cH30H) = 6.5 h-lf
input mixture 17 vol.% CH30H + 68 m1.%H20 + 15 vol.%N2. integral microreaCtor)

time on total conv. % mnv. of cH30H to hydrocarbons

S+XW of m3OH related to total conv. of CH30H to C1 - C5
onin. 1 (%I c2+5 c3 5 15 zc4 EG P 5

15 99.4 40.5 7.8 31.8 0.0 1.2 11.0 7.6

60 96.1 51.0 3.5 34.5 0.0 1.2 9.6 3.7
120 49.1 52.8 1.7 37.0 0.0 0.0 8.6 0.0
In the products no aranates w e r e found

Fig. 1. The hydrocarbon r a t i o C2CdTafter 60 min. on strean as a function of

the reaction tgnperature.

Catalytic tests over the HZSM-5 zeolite (Si/Al = 1 7 ) , performed under the same
reaction conditions, led to a pmduct with a significantly 1- content of C2 +
c3 olefins. The produd contained in t h i s case 22 wt.% C2 + 5
(1 wt.%CZf 8.3wt.%
C3f 26.5 wt.% Csf 37.5 wt.% C4 + C5 hydrocarbons; the rest mre higher hydrocar-
bons and amnatics.
286

Fig. 2. The total mnversion of

CH (wt.%) deperdirrg on
thd time on stream a t 400°C and
WlISv = 2 h-'.
w i t h water
A feed without water

I I I
0 2 4 6 number of cycles

Fig. 3. The conversion of CH OH (wt.%) to C

n u b r of working cycles a t aOO°C and WJSV 2-3 Ey' -
ocarbns as a function of the
, time on stream 1 hour,
E a r 5 mrkiq cycle is mnposed f m n the CH OH tgmsfolmaticm for 120 min. and.
fran the regeneraticm of HLZ 132 z e o l i t e a s 450 C i n the flaw of O2 f o r 4 hours:
feed with w a t e r
feed without water
 Fig. 4. I R spectra of the HLZ 132
zeolite in the frequency range of
skeletal vibrations:
1) i n the original state
2) aftgr the catalytic t e s t a t
400 C, 6 working cycles

1 I I I

3800 cni’ 1200

Fig. 5. Sorption of d3-ace&trile on HLZ 132 zeolite after the tramsfomtion

of CH OH (6 mrkiq cycles) without regeneration:
1) b e h e the adsorption of d3-acebni.trile
2) after the adsorption of d3-acetonitrile.
288

The results shaw that the yields of C2 + C3 olefins over HLZ 132 zeolite are
significantly higher than h e cbtained w i t h FWM-5. The weight r a t i o R =
(C2+Cj / -
in the products a t t a i n s a t the reaction tanperatwe of 350 5OO0C
values of 1 to 4; namely R = 1.6 qt 4OO0C (Fig. 1), i.e. nearly 100 % higher
than over HZSI-5 d e r the same reaction conditions, namely R 0.83. Analogious
values of R obtained by chang (ref. 7) over " s ~ l l - p o r e "zeolites (erionite, cha-
basite, ZK-5) are also lawer than thme obtained over HLZ 132 a t the sane reaction
tanperature. Both values of R and the conversion sums to 5 + Cj hydrocarbons over
HLZ 132 are higher than over Nu-3 zeolite (ref. 8 ) which belongs also to the group
of zeolites similar to levynite. A t 45OoC after 84 min. on stream the value of R
obtained over HLZ 132 is 2.1, whereas for MI-3 it is 0.92. Supposing that the dif-
ference between the oliganerization rates of C2H4 and C3H6 on the HLZ 132 zeolite
is preserved d s o at higher reaction tanperatures, we m y interpret the high value
of R i n the CH30H transformation products a s resulting fram the formation of coke
fran the greatest p a r t of the C 3 ~ 6formed. man the IR spectra Fig. 5) it f o l l m
that this coke on HLZ 132 corresponds only to polyens, as expected. This w a s cow
finned by the presence of a strong band a t 1600 an-' (ref. 9 ) , whereas on HZ-5
the cake formed exhibits the structure of both polyenes ard polyarorrratics.

Acidobasic praperties and their changes

In the murse of the adsorption of acetonitrile the formation of a coordi7a-
tion ccrqlex with el&xon-acceptor mlecules takes place, accarpanied by t h e
s h i f t of the fundmental vibration UCCrN) tnwards higher values when canpared
with the vibration fresuency of liquid acetonitrile. This e f f e c t is caused by
charges i n the coordination i n the nitrogen 2 s l o n e p a i r o r b i t a l , which are re-
sponsible for the strergthenim~of the CN band (ref. 1 0 ) . With regard to the f a c t
that the spectnm of liquid acetonitrile exhibits tv.u bands i n the frequency re-
gion of the CN bod stretcking vibrations, i.e. the fundamntal band a t 2254 an-'
as w e l l as the bard a t 2293 an-' caused by the Ferrni resonaxe between the wobi-
nation vibration u3 + u4 and the fundamental vibration u2, it is m e convenient
to use d3-ac&nitrile which exhibits anly a single CN vibration. This is especial-
l y advantqaus i n the case of d3-acetonitrile sorption on zeolites, as i n this
case the CW) h o d vibration is affected by the f0llmi.q factors:
i) the Lewis centres of electron-acceptor type,
ii) the electrostatic f i e l d of the cations,
iii) the interaction w i t h the OH g r c u ~ 6of the zeolite which causes the freqency
s h i f t of the CN b w l as d l as the appearance of a hydmgen b a d i n the frequency
range of the structural OH group Cref. 10).
The use of d3-acebnitrile in the sorption f a c i l i t a t e s very mch the interpreta-
tion of the spectrum. In Figs. 6,7 are present the I R spectra in the (CrNl bond
s t r e k h h q vibrations range obtained w i t h d3-acetmnitrile sorption an HZW-5 a d
 I

I A B

I I I I ............. I t I 1

2600 2000 2600 2000

c m-1

Fig. 6. Sorption of d -acetonitrile on HLZ 132 z e o l i t e before (A) and a f t e r (B)

the reaction w i t h Ol$H: 1) evacuation a t 35OoC overnight and the subsequent sorp-
tion of d -acetonitrile a t rcun tgnperature, 15 min.; 2) desorption of d3-aceto-
n i t r i l e a2 roam t e n p r a t u r e , 15 m i n .

.........
2600 2000
C l d

Fig. 7. Sorption of d -acetonitrile on €:ZsE2-5 zeglite before (A) and after (B)
the interaction w i t h &+31: 1) evacuation a t 350 C overnight and the subsequent
sorption of dj-acetonit2ile a t roan temperature, 15 min. ?, 2) desorption of d
acetonitrile a t rccnn temperature, 15 min. 3-
290

HLZ 132 both b e f o r e and a f t e r methanol adsorption. Table 3 presents the n o d -

ized absorbancies of the a x r e s p o n d i n g a b s o r p t i o n bards.

TABLE 3
Sorption of d 3 - a c e t o n i t r i l e o n HLZ 132 and HZSM-5 before and a f t e r the i n t e r -
a c t i o n w i t h CH30H

0 0 0
sample %425 ’2321 OA2294 OA2266 “2113
(2500) (2273)

HZ.9ul-5 0.32 1.04 1.00 0.67 0.19

HLZ 132 0.24 0.45 0.54 0.52 0.10
HZSM-SOCH 0.24 0.66 0 -82 0.46 0.13
HLZ 132-CCd3 0.18 0.33 0.54 0.55 0.09

0
Am-1 - nomlited absorbancies a t the given frequency

Ps follows fran Figs. 6,7, a f t e r the s o r p t i o n i n the range of ( C a ) v i b r a t i o n s

three bands a t 2323, 2294 and 2266 an-’, may be found. I n the case of the LZ 132
z e o l i t e t h e l a s t b a d is s h i f t e d towards the frequency 2273-6 an-’. Fran these
bands may be a t t r i b u t e d ( r e f s . 10,111: the k a x l a t 2323 an-’ may be attributed to
the interaction w i t h the Lewis centre and t h e band a t 2294 cn-’ to the i n t e r a c -
t i o n of t h e electrostatic f i e l d of the Na+ c a t i o n w i t h d3-acetonitrile. The band
a t 2266 an-’ ( w i t h HZm-5) or 2276-3 an-’ ( w i t h IILZ 132) appears i n the spectrum
only when d3-acetonitrile is adsorbed; a l r e a d y a f t e r 1 5 minutes of d e s a r p t i o n a t
roan tarperatwe it either disappears ccrrrpletely or i t s i n t e n s i t y d e c r e a s e s to an
i n s i g n i f i c a n t shoulder. T h i s Lard m y be ascrited ( r e f . 10) to the e f f e c t of the
OH group of the z e o l i t e on the CN group of d3-acetonitrile. I n the r e g i o n of OH
groups s t r e t c h v i b r a t i o n s this e f f e c t is indicate2 by a broad band s h i f t e d t o
3420 an-’ ( w i t h HLZ 132) or 2970 an-’ (with SZSU-5). The bands a t 2425 an-’
(HZSM-5) and 2500 cat-’ are p r o w l y Cwertones of the OH berding v i b r a t i o n ( r e f .lo).
As follows fran Table 3 and fran Figs. 6 and 7, after t h e s o r p t i o n d 3 - a c e b
nitrile in the I R spectrum a l l three types of the bards mentioned above may be
found o n b t h zeolites (i.e. E Z S - 5 and HLZ 132). T h i s w a s the case b o t h w i t h
pure sanples previously evacuated and kept a t 35OoC overnight and w i t h samples
after their i n t e r a c t i o n w i t h m e t h a n o l a t 40OoC. Differences appear o n l y in the
i n t e n s i t i e s of the i n d i v i d u a l bands. When canparing the normalized absorbancies
given in Tab. 3 for t h e pure z e o l i t e s , we m y cane to the conclusion that the
nlrmber o f Lewis c e n t r e s on LZ 132 mounts to about a half o f that p r e s e n t on
!!ZEN-5, t h e n u h e r of Eiqdnsted centres on both z e o l i t e s being a p r o x i m a t e l y the
sane.
After the s o r p t i o n o f d3-acetonitrile on z e o l i t e sanples after their interac-
t i o n w i t h m e t h a n o l a t 400°C (see Iselow) t h e intensity of the bards a t 2321 and
 29 1

2666 an-' decreases by 35% on the average i n the case of the HZW5 z e o l i t e ,
whereas w i t h the HLZ 132 z e o l i t e only the i n t e n s i t y of t h e bard a t 2321 cn-l
(corresponding to t h e Lewis c e n t r e s ) decreases by approximately 30%.
I n Fig.5 the I R spectra of the HLZ 132 z e o l i t e a f t e r the c a t a l y t i c test of
methanol transformation are given. The coke formed is characterized. by bani% i n
the region 3000-2800 crr-l, 1610-1590 an-' and 1450-1350 a!!'.Fran t h e i r observed
i n t e n s i t i e s w e may conclude t h a t the coke is of the p l y e n e s type a d more probab-
l y w i t h hydrogen-saturated c h a r a c t e r ( r e f . 9 ) . The band a t 1540 m-', which is
typical f o r t h e a r a n a t i c s , is absent. After d 3 - a c e t o n i t r i l e has been sorbed on
this sanple, t h e very w e a k banis a t 2323 and 2269 cm-' appear, t h e band a t
2293 6'(corresponding to the i n t e r a c t i o n w i t h the N
a
' c a t i o n ) i s absent. The
absence of the band a t 2293 mV1and the presence of t h e hrrls a t 1590 and
1610 an-' ( r e f . 9 ) indicate that n o t only have t h e a c i d i c c e n t r e s been blocked
but a l s o the pores of the z e o l i t e have been f i l l e d .
The i n t e r p r e t a t i o n of t h e I R s p e c t r a of d 3 - a c e t o n i t r i l e adsorbed on the HLZ 132
z e o l i t e may be summrized i n the following way:
1) I n the EL2 132 z e o l i t e both types of acidobasic centres (i.e. proton-donor and
electron-acceptor c e n t r e s ) are present.
2) I n c m p r i s o n to HzSG5, t h e n W r of t h e proton-donor centres is approximate-
l y the sane, whereas the n w b e r of electron-acceptor c e n t r e s on HLZ 132 m u n t s
to h u t a half o f that on HZB1-5.
3 ) Methanol strongly bound on HLZ 132 a f t e r the i n t e r a c t i o n a t 4OO0C i s a l s o
blocking the electron-acceptor c e n t r e s , whereas the m u n t of proton-clonor
c e n t r e s is approximately the same as on the original HLZ 1 3 2 before its i n t e r -
a c t i o n w i t h CH30H. The latter c e n t r e Sean t h e r e f o r e to be e a s i l y regenerated
a f t e r the i n t e r a c t i o n w i t h methanol a t 4OO0C as w e l l as to be a c t i v e i n t h e
methanol t r a n s f o m t i o n . The coke, which is of the polyenes type, is i n t h e
i n i t i a l phase of t h e i n t e r a c t i o n formed f i r s t on t h e electron-acceptor c e n t r e s
and only later also on the proton-donor c e n t r e s .
4 ) Spectra of HLZ 132 f u l l y covered Ly coke shm that t h e latter is localized. not
only on both types of acidobasic c e n t r e s b u t also in the pores of t h e z e o l i t e .

Surface canplexes w i t h
I n order to g e t an i n s i g h t i n t o t h e causes o f the higher selectivities of t h e
HLZ 132 z e o l i t e i n the formation o f l m e r o l e f i n s C2 - C3, the I R spectra of the
c a t a l y s t i n the frequency range of s t r u c t u r a l OH groups and methanol s u r f a c e com-
plexes i n t h e temperature range 20 - 4OO0C of the i n t e r a c t i o n w e r e registered.
Such r e a c t i o n conditions simulate the i n i t i a l steps of the c a t a l y t i c t r a n s f o m -
t i o n of methanol.
Fig. 8 s h m s t h e I R spectra of the HLZ 132 z e o l i t e i n the frequency range cor-
292

I I . . - - - . -...-
3800
I I I
3400
crn-’
. 3050
1 I I
2800

Fig. 8. I R spectra of the HLZ 132 zeolite evacuated a t 4OO0C overnight:

1) before the interaction with methanol,
2) a f t e r the interaction with methanol a t 2Oog f o r 30 min. ,
3) a f t e r the interaction with methanol a t 150 C f o r 30 min. ,
4) a f t e r the interaction with methanol a t 4OO0C f o r 30 min.

responding to the structural OH groups as w e l l a s i n the range correspanding to

the stretching vibrations u(C-H) before and a f t e r the interaction w i t h methanol.
f i e corresponding absorbancies are given in Table 4. In the original I R spec-
of the HLZ 132 zeolite four OH barids are present, namely a t 3720, 3615, 3600 and
3555 an-’. After the adsorption of methanol at 2OoC, follwed by a short desorp-

TABLE 4
Interaction of CH30H with HLZ 132 zeolite a t temperatures 20 - 4OO0C
(in normalized absorbancies - OAm-l)
temperature 0 0 0 0 0
C0C, A2987 A2972 A2957 %925 A2855
25 0.09 - 0.23 0.03 0.16
100 0.06 0.11 0.15 0.02 0.12
150 0.05 0.10 0.12 - 0.09
200 0.04 0.09 0.11 0.02 0.10
300 0.04 0.08 0.10 0.02 0.09
400 0.03 0.06 0.06 - 0.06
 293

tion of the gaseous phase a t the sane tgrlperature, the spectrum exhibits two broad
bands a t 3710 and 3500 an-' which inclicate the strong interaction of cIi30H w i t h
the OH groups (the proton-eonor centres of the zeolite) anzl overlap the band a t
3740 an-'. In the region of the U(C-I;) vibrations two strong bands a t 2957 and
2855 an-' are formed, accompanied by shoulders a t 2987 and. 2925 an-', respective-
ly. When the taperatwe of the interaction is l5OoC, a l l four bands appear i n the
spectrum again. The reduction of their intensity i d c a t e s that a part of methanol
has desorbd. whereas another part of it has remined solidly bound to the zeolite.
I n the region of the u(C-3) vibrations both bands and their shoulders formed a t
~ O O Cw e r e preserved; only their intensity decreased. In u t i o n , another intense

band appeared a t 2972 at-'. M.th the interaction taking place a t 4OO0C a l l four
original ban& of OH groups are preserved, their intensity being hi- than
a f t e r the interaction with n&haml a t 15OoC. A t the latter tanperature of inter-
action the intensity of a l l four bands i n the range of u (C-E) vibrations (includ-
ing the shou1ders)is reduced so that even the shoulder a t 2925 cn-' could not be
registered distinctly.
The decrease of the intensities of the bands i n the frequency range of U(C-3)
vibrations (as w e l l as that of the calculated absorbancies), acwnpanied by the
increase of the intensities of the OH bards, indicates the cccurence of a reaction
between the surface group fonned previously where gaseous hydrocarbon products
are formed and the OH groups (the proton-donor centres)are regenerated sirrolltane
ously.
The coordination of the four above m t i o n e d absorption bands i n the I R spec-
trum w i t h the respective vibration groups provided the possibility of a better
understanding of the processes which take part i n the interaction of methanol w i t h
HLZ 132 a t higher t a p e r a w e s , i.e. a t 300-400°C i n this case. The bands i n the
range of the structural OH groups vibrations as w e l l as their changes clearly cor-
respond to OH groups w i t h prokudonor properties, as follanls also f r a n the I R
spectra of HLZ 132 cbtained a f t e r the interaction with acetonitrile. The bands i n
-
the range of the u(C-H) vibration may be - w i t h high prcbability ascribed to
two types of surface methoxy canplexes zeolite-ocHj (designated A and El) which
are farmed a f t e r the interaction of methanol with the protan-donor centres of the
zeolite, similarly as has been described in previous publications (refs. 12-16]
i n the case of HX, HY wl E m - 5 zeolites. The bards a t 2955 and 2855 cm" as w e l l
as t k shoulder a t 2925 would correspard to the symnetrical zeoliteOCH3 species
B. The aqmnetrical ccmplex A i s - -
acrording to I b r r o w (ref. u) characterized
by one s t r o q a d two weak C-H bonds. We may adopt the idea t h a t these weak C-I!
bonds, when in two neighbowing surface canplexes, f a c i l i t a t e the elimination of
water a d the formation of ethylene.
Chr results are i n agrement with the suggestions made by Casci and whittam
(ref. 8 ) about the role of "shape selectivity" of the zeolite carU=erning the
294

transformation of mthanol to lwer olefins over a similar "small pore" z e o l i t e

Nu-3 ard they canplete the suggestions i n the following p i n t s . Over HLZ 132,
e t h y l e n e m y be formed as a product of the reaction between either ha reactive
surface woplexes of type A or one surface c q l e x of type A and gaseous methanol.
T h i s model is i n agreement w i t h the mechan'sm of methanol transformation over
ZS4-5 z e o l i t e w i t h dimethyl ether i n t e n n d i a t e , as has been suggested by Derouane
( r e f . 1 7 ) . The experimentally fourd. me- groups i n HLZ 132 could s e r v e as a
p r e c u r s o r to the formation of d h e t h y l ether or p l a y the role of the latter "in
s t a t u M S C ~ "T .h i s would be in agregnent w i t h the mechanism of t r a n s f o r m a t i o n
as quoted above. The subsequent transformation of ethylene t o higher o l e f i n s
proceeds then to a reduced extent owing to the laver a c i d i t y of the HLZ 132 zeo-
lite. For its h i g h e r a c i d i t y e t h y l e n e is not activate2 by the proton-donor centres
a c t i q i n the f o l l w i n g r e a c t i o n , i.e. either the o l i g a n e r i z a t i o n or the r e a c t i o n
with another molecule of CH30H. This leads to the lw y i e l d of higher olefins.
The content of propylene and further higher olefins (with molecules more basic
than that of ethylene) i n the reaction products is f u r t h e r reduced by o l i g a n e r i z a -
t i o n which leads to the prcgressive covering o f the zeolite by coke of the p l y -
enes type.

1 Eurcpsn P a t e n t Application, EP 91.048.

2 V. Bosdcek, V. Patzelovd, C. Wbl and Z. Tvaruzkovd, J. C a t a l . 36 (1975) 371.
3 G. Coudurier, C. Naccache ard J. V e d r h , J. Chen. Soc., Chan. Camun. 1982,
p. 1413.
4 D.W. Eire&, i n Z e o l i t e Molecular Sieves Pbrqraph, J. W i l e y , N.Y. 1974, pp.
81, 415.
5 Z. Tvaruzkovd, G. C e n t i , P. J h and F. Trifiro, Awl. C a t a l . 1 9 (1985) 307.
6 L. Kubelkavd, J. Novdkovd, V. Bosdcek, V. Patzelovd and. 2. Tvmzkovd, Acta
Phys. et Chen. 24 (1978) 189.
7 C.D. Qlarg, Rev. S c i . Erg., 26 (1984) 325.
8 J.L. Casci and T.V. Whittan, Zeolites, B. Drzaj et a l . (rntors), 1985 E l s e v i e r
Sci. -1. B.V. 623.
9 L. Kubelkovd, J. Nov&ovd, V. Tupd and Z. T v m z h v a , Prcc. Inter. Symp. on
Z e o l . Catal. Siofok 1985, H u q a q , p. 649.
10 C.L. Angel1 and Y.V. Haell, J. Phys. Chen. 73 (1977) 1153.
11 R.E. Sempels ard P.G. Rouxhet, Prcc. of the 49th N a t i o n a l Colloid Symp.,
Postdam, N.Y. 1975.
12 L. Kubelkova, J. Nwdkovd ard P. J h , Structure and R e a c t i v i t y Of Modified
Zeolites, P.A. Jaaobs e t al. (Editors) 1984 Elsevier Sci. Publ. B.V., 217.
13 B.H. fibrrow, JCS, Faraday !trans. 1, 70 (1974) 1527.
14 P. Salvador and W. Kladnig, JCS, Faraday Trans. 1, 73 (1977) 1153.
1 5 V. Bosdcek and 2. T v m b A , Coll. Czech Chem. Cannun. 36 (1971) 551.
16 T.E. F o r e s t e r and R.F. Hawe, J. Am. chgn. SOC. 109 (1987) 5076.
17 E.G. Derouane, J.B. Nagy, P. Dejaifve, J.H.C. van Hooff, B.P. Spekman,
J.C. V e d r i n e and C. Naccach, J. Caw. 53 (1978) 40.
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

PtRh-DOPED ZEOLITES AS THREE-WAY-CATALYSTS: SIMS ANALYSIS AS A

TOOL FOR THE SELECTION O F SUITABLE ZEOLITE TYPES

C. PLOG, J . HAAS and J. STEINWANDEL

Dornier S y s t e m G m b H , P. 0. Box 1360, D-7990 F r i e d r i c h s h a f e n (FRG)

ABSTRACT

Principal q u e s t i o n s i n t h e d e v e l o p m e n t of e x h a u s t c a t a l y s t s a r e r e l a t e d to a n
i n c r e a s e of t h e 1 - w i n d o w and a r e d u c t i o n of t h e n o b l e m e t a l c o n t e n t . In t h e s e
a r e a s t h e u s e of n o b l e - m e t a l - d o p e d z e o l i t e s i s a d v a n t a g e o u s . T h e s e l e c t i o n of
PtRh-doped Y-zeolite and m o r d e n i t e a s t h r e e - w a y - c a t a l y s t s by t h e a d d i t i o n a l
use of t h e s u r f a c e a n a l y t i c a l m e t h o d SIMS is p r e s e n t e d . Depth p r o f i l e s s h o w e d
t h a t t h e r e e x i s t s a c l e a r c o r r e l a t i o n f o r t h e r e a c t i o n s of t h e c a t a l y t i c c o n v e r -
s i o n of t h e e m i s s i o n of O t t o - c y c l e e n g i n e e x h a u s t s b e t w e e n c a t a l y s t a c t i v i t y
and t h e chemical c o m p o s i t i o n of t h e s u r f a c e of t h e z e o l i t e c r y s t a l s .

INTRODUCTION

The r e d u c t i o n of a i r p o l l u t a n t s is of c e n t r a l i m p o r t a n c e t o e n v i r o n m e n t
p r o t e c t i o n . C o n s e q u e n t l y , a l l c o m b u s t i o n p r o c e s s e s , p a r t i c u l a r l y of a u t o m o -
bile e n g i n e s , a r e of c o n s i d e r a b l e i n t e r e s t . F o r e x a m p l e , t h e i n c r e a s e of t o t a l
e m i s s i o n of n i t r i c o x i d e s f r o m 2.8 million t o n s p e r year t o 3 . 0 million t o n s p e r
y e a r b e t w e e n 1982 and I986 is r e l a t e d e x c l u s i v e l y t o t h e i n c r e a s e of a u t o m o b i l e
t r a f f i c . The e m i s s i o n of n i t r i c o x i d e s is t h e c a u s e of a c o n s i d e r a b l e a m o u n t of
damage t o trees (Waldsterben).

Besides n i t r i c o x i d e s , t h e c o m b u s t i o n p r o c e s s e s i n a n O t t o - c y c l e e n g i n e
p r o d u c e h y d r o c a r b o n s ( H C ) a n d c a r b o n m o n o x i d e ( C O ) . w h i c h have a l s o to b e
c o n s i d e r e d a s p o l l u t a n t s of i m p o r t a n c e . A s i g n i f i c a n t r e d u c t i o n of t h e e m i s s i -
on of a l l t h r e e t y p e s of p o l l u t a n t s , a t t h e p r e s e n t s t a t e of t h e a r t , is n o t pos-
s i b l e t h r o u g h e n g i n e d e s i g n a n d ignition m o d i f i c a t i o n s . T h e r e f o r e , in t h e FRG
( a n d i n E u r o p e ) t h e t e c h n i q u e of c a t a l y t i c p o l l u t i o n c o n t r o l h a s b e c o m e im-
p o r t a n t s i n c e 1986. Before t h a t , t h e t e c h n i q u e of c a t a l y t i c p o l l u t i o n c o n t r o l
w a s used s u c c e s s f u l l y i n t h e USA and J a p a n .

A f t e r a t e s t p h a s e of o x i d a t i o n - . e d u c t i o n a n d d o u b l e - b e d catalysts
( w h i c h , in p a r t i c u l a r , w a s p e r f o r m e d i n t h e USA), t h e t h r e e - w a y - c a t a l y s t i s now
e s t a b l i s h e d w o r l d - w i d e . The t e c h n i q u e is t h e only p o s s i b i l i t y f o r c a t a l y z i n g t h e
o x i d a t i o n and r e d u c t i o n r e a c t i o n s s i m u l t a n e o u s l y . T h e r e a c t i o n s a r e l i s t e d in
t a b l e 1. C o n c e r n i n g a n a l m o s t c o m p l e t e r e m o v a l of a l l p o l l u t a n t c o m p o n e n t s ,
however, i t is n e c e s s a r y t o o p e r a t e a t X =1 , e . g. a s t o i c h i o r n e t r i c r a t i o of oxidi-
296

zing a n d r e d u c i n g c o m p o n e n t s in t h e e x h a u s t ga s. T h i s is a c hie ve d in t h e a u t o -
m o b i l e by using c o m p l i c a t e d m e a s u r e m e n t a n d c o n t r o l p r o c e s s e s ( 1 - p r o b e a n d
electronic fuel injection).

TABLE 1
S c h e m a t i c s of m o s t t h e i m p o r t a n t r e a c t i o n s in t h e c a t a l y t i c c o n v e r t e r .

C,H, + ( m + n / 4 ) 0, ---0 m CO, + n / 2 H,O

C,H, + m/2 0, ---0 m C O + n H,O
co + 1/2 0, --Q CO,
H, + 1/2 0, --0 H,O
C O + NO --0 1/2 N, + CO,
C,H, + 2 ( m + n / 4 ) NO ---0 ( r n + n / 4 ) N, + n/2 H,O) + m CO,
H, + NO ---0 112 N, + H,O

W i t h i n c r e a s i n g o x y g en c o n t e n t ( X > 1 , l ean b u r n r e g i o n ) t h e ve loc ity of pol-

l u t a n t r e d u c t i o n r e a c t i o n s ( n i t r i c o x i d e r e d u c t i o n ) d e c r e a s e s , w hile t h e re a c -
t i o n velocity o f t h e o x i d at i o n r e a c t i o n s ( C O a n d HC o x i d a t i o n ) i n c r e a s e s . T h e
c o n d i t i o n s a r e r e v er s ed in t h e rich b u r n i n g r e gion ( X < l ) . Fig. 1. i l l u s t r a t e s t h e
very n a r r o w r e g i o n f o r o p t i n r a m r emo v al of a l l t h r e e p o l l u t a n t c o m p o n e n t s a s
a f u n c t i o n of t h e X-value, wh i ch , c o n s e q u e n t l y , is know n a s t h e X-window.

A-window

loo

n
x
U
60

h
U
C
.-
al 60

.-U
ry
w 40

0.w 0.06 *so 1.06 1.10

A-value

Fig. 1. Efficiency o f a t h r ee- way - cat al y s t a s a f u n c t i o n of t h e X-value f o r a l l

t h r e e p o l l u t a n t c o m p o n e n t s2) .
 297

N o t o n l ? t h e e f f i c i e n c j of a t h r e e - w a ) - c a t a l l s t ( X = l - t e c h t i i q u e ) , b u t a l s o
f u e l c o n s u m p t i o n a n d engine p o l l u t a n t e m i s s i o n d e p e n d o n t h e X-value. T h i s
is s h o w n i n Fig. 1. From Fig. 2 . i t f o l l o w s t h a t f o r e c o n o m i c a l r e a s o n s ( f u e l
c o n s u m p t i o n ) and a l s o with r e s p e c t t o r e d u c e d p o l l u t a n t e m i s s i o n , t h e o p e r a -
t i o n of O t t o - c j c l e e n g i n e s i n t h e lean burn r e g i o n (X a b o u t 1.2) w o u l d b e d e s i -
r a b l e . However. a t t h i s 1 - v a l u e t h e efficiency of a three-way c a t a l y s t a s t o t h e
n i t r i c o \ i d e r e d u c t i o n is e \ t r e r n e l ) u n s a t i s f a c t o r y .

Fig. 2 . I n f l u e n c e of t h e A-value on e \ h a u s t g a s e m i s s i o n a n d f u e l c o n s u m p t i o n
of a n O t t o - c j c l e engine').

A l t h o u g h l o n g e \ p e r i e n c e with t h e o p e r a t i o n of t h r e e - w a ) c a t a l j s t s e x i s t s
i n t h e U S A a n d J a p a n ( a n d , a l s o i n Europe b e c a u s e of i t s i n t r o d u c t i o n t o mar-
k e t m e a n w h i l e ) . s o m e s i g n i f i c a n t p r o b l e m s remain u n r e s o l v e d . Basic q u e s t i o n s
i n r e s e a r c h and d e v e l o p m e n t c o n c e r n i n g e x h a u s t c a t a l ? s t s a r e r e l a t e d t o a n
i n c r e a s e of t h e A-window ( l e a n b u r n r e g i o n ) . a r e d u c t i o n of t h e n o b l e m e t a l
c o n t e n t ( a t p r e s e n t a b o u t 1.S g n o b l e m e t a l per l i t e r c a t a l y s t v o l u m e ) . and
f i n a 1 1 j t he d e v e I o p me tit of h i g h - t e m p e ra t u r e - r e s i s t e n t c a t a 1y s t s .

Besides t h e l a s t p o i n t . t h e u s e of n o b l e - m e t a l - d o p e d z e o l i t e s is of advan-
t a g e . I n t h e p r e s e n t p a p e r . t h e s e l e c t i o n of s u i t a b l e z e o l i t e s by t h e a d d i t i o n a l
use of t h e s u r f a c e anal).tical m e t h o d S l M S is p r e s e n t e d . By using s e c o n d a r y
ion m a s s s p e c t r o m e t r j ( S I M S ) it is p o s s i b l e t o a n a l y s e t h e n o b l e m e t a l d i s t r i -
b u t i o n i n near s u r f a c e r e g i o n s of t h e z e o l i t e c r y s t a l l i t e s .
298

EXPERIMENT

As starting materials for t h e preparation of t h e catalysts, commercially

available z e o l i t e s o f mordenite type and Y-zeolites were used (Bayer AG a n d
Norton Comp.). The doping o f t h e zeo l i t es with noble m e ta ls w a s p e rfo rm e d
by t h e m e t h o d o f ion e x c h a n g e c i t e d i n t h e l i t e r a t u r e .

A f t e r p r e p a r a t i o n o f t h e c a t a l y t i c a c t i v e p o w d e r s by ion e x c h a n g e a n d s u b -
s e q u e n t thermal t r e a t m e n t o r reduction, cordierite honeycombs were c o a t e d
w i t h t h e p o w d e r s by a specially d e v e l o p e d p r o c e s s . T h e g e o m e t r y o f t h e c o r -
dierite honeycombs corresponded t o t h a t usually used i n t h e automobile indu-
s t r y ( t e s t m o n o l i t e s . 3.15 inch l o n g , I inch d i a m e t e r , 400 c e l l s p e r i n c h ) .

T h r e e - w a y - c a t a l y s t s p r e p a r e d by t h e m e t h o d d . a . w e r e t e s t e d in a l a b o r a -
tory p l a n t t o d e t e r m i n e t h e e f f i c i e n c y o f t h e r e d u c t i o n o f t h e t h r e e r e l e v a n t
p o l l u t a n t s N O x , CO a n d HC. A s y n t h e t i c e x h a u s t g a s c o n s i s t i n g o f NO ( f o r
N O x ) a n d p r o p a n e ( f o r HC) a n d CO w a s u s e d . T h e l a b o r a t o r y p l a n t c o n s i s t s o f
a gas-mixing s t a t i o n , a gas-heating s y s t e m . a reaction chamber containing t h e
c a t a l y s t , and finally a gas-analysis s y s t e m . The s t a n d a r d composition of t h e
s y n t h e t i c e x h a u s t g a s is s h o w n i n t a b l e 2.

TABLE 2
Standard composition o f exhaust g a s for t h e present experiments.

Gas c o m p o n e n t Fraction (Val.-"/.)

----
NZ 75.08
CO, 14.0
H2O 8.0
0 2 0.84
co 1 .o
"2 0.33
NO 0.1
C3H8 0.05

By using a g a s c y l i n d e r b a t t e r y a n d e l e c t r o n i c m e a s u r e m e n t a n d control
c o m p o n e n t s it is p o s s i b l e t o vary t h e e x h a u s t g a s c o m p o s i t i o n o v e r a w i d e
r a n g e . The s y s t e m p e r m i t s s t a t i c and d y n a m i c m e a s u r e m e n t s , w h e r e t h e s y n -
t h e t i c e x h a u s t g a s c o n t a i n s a maximum o f 9 d i f f e r e n t c o m p o n e n t s . T h e t e s t
p l a n t a l l o w s a maximum g a s v o l u m e s t r e a m u p t o 5 0 I / m i n .
 299

The g a s - h e a t i n g s y s t e m a l l o w s e x h a u s t t e m p e r a t u r e s up to 700 OC. Pro-

g a m m a b l e h e a t i n g using s t a n d a r d i z e d t e m p e r a t u r e p r o g r a m s p e r m i t s m e a s u -
r e m e n t s of t h e s t a r t i n g behaviour of t h e c a t a l y s t s w i t h r e l a t i o n t o t h e d i f f e -
rent pollutants.

The g a s c o m p o s i t i o n d o w n s t r e a m a n d u p s t r e a m in t h e c a t a l y t i c c o n v e r t e r
is c o n t r o l l e d by t h e g a s a n a l y s i s s y s t e m . T h e s y s t e m c o n s i s t s o f a GC w i t h FID
a n d HCD d e t e c t o r , and a c h e m i l u m i n e s c e n c e NOx a n a l y z e r .

The chemical c o m p o s i t i o n of t h e c a t a l y t i c a c t i v e p o w d e r s w a s a n a l y z e d by
EDX, a n d f o r n e a r - s u r f a c e r e g i o n s by SIMS. The i n f o r m a t i o n d e p t h of EDX is
a b o u t 1 t o 2 pm. A t a c r y s t a l l i t e s i z e of t h e z e o l i t e s of 1 t o 4 ym, t h e v o l u m e
c o m p o s i t i o n is a l s o d e t e r m i n e d by t h e E D X m e t h o d .

The SIMS m e t h o d is c h a r a c t e r i z e d by a n i n f o r m a t i o n d e p t h of 1 a t o m i c lay-

e r , t h u s e x a c t i n f o r m a t i o n a b o u t t h e c h e m i c a l c o m p o s i t i o n of t h e s u r f a c e c a n
be o b t a i n e d . A s i m u l t a n e o u s s p u t t e r i n g by ion b o m b a r d m e n t a l l o w s a n a l y s i s
of d e e p e r a t o m i c l a y e r s and c o n s e q u e n t l y t h e r e c o r d i n g of a d e p t h p r o f i l e .
C o n c e r n i n g t h e a n a l y s i s of c a t a l y s t s u n d e r i n v e s t i g a t i o n SIMS m a s s s p e c t r a a t
d e p t h s of 0.1, 0.2, 0 . 4 , 1, 2, 4 , 10 nm w e r e r e c o r d e d .

RESULTS A N D DISCUSSION

The p o s s i b i l i t i e s f o r u s i n g Y z e o l i t e a n d m o r d e n i t e a s t h r e e - w a y - c a t a -
l y s t s will b e c o m p a r e d in t h e f o l l o w i n g , w h e r e t h e z e o l i t e s have b e e n d o p e d
w i t h p l a t i n u m a n d rhodium in t h e r a t i o S:1. C o m p a r i s o n c r i t e r i a w e r e t h e c o n -
version c h a r a c t e r i s t i c of t h e p o l l u t a n t s NO, CO a n d p r o p a n e of a new a n d a
used c a t a l y s t . T h e new c a t a l y s t s w e r e analyzed by SIMS c o n c e r n i n g t h e d i s t r i -
b u t i o n of t h e n o b l e m e t a l s .

With t h e aim of c h a r a c t e r i z i n g t h e a c t i v i t y of a u t o m o b i l e e x h a u s t c a t a -
l y s t s it is i m p o r t a n t t o m e a s u r e t h e d e p e n d e n c e of t h e p o l l u t a n t c o n v e r s i o n
on t h e 1 - v a l u e a s well a s its d e p e n d e n c e o n t e m p e r a t u r e . I t is p o s s i b l e t o p e r -
f o r m m e a s u r e m e n t s e i t h e r s t a t i s t i c a l l y o r dynamically ( 1 - p u l s e ) . I n t h e f o l -
l o w i n g , t h e s t a t i c c o n v e r s i o n c h a r a c t e r i s t i c s a s a f u n c t i o n of t h e e x h a u s t g a s
temperature w i l l be presented.

Fig. 3. s h o w s a typical c o n v e r s i o n c h a r a c t e r i s t i c of P t R h H - m o r d e n i t e .
A s can be s e e n , c o n v e r s i o n o n s e t f o r a l l t h r e e p o l l u t a n t s is a t a b o u t
2 2 0 OC. Besides t h e HC c o n v e r s i o n a s t e e p i n c r e a s e of t h e c o n v e r s i o n w i t h
i n c r e a s e d e x h a u s t t e m p e r a t u r e is f o u n d . At a b o u t 300 OC, nearly 100 % c o n v e r -
300

s i o n f o r a l l t h r e e p o l l u t a n t s is f o u n d . The s o m e w h a t f l a t t e r i n c r e a s e of HC
c o n v e r s i o n is r e l a t e d t o t h e k i n e t i c i n e r t h y d r o c a r b o n p r o p a n e . C o n s i d e r i n g a
real e x h a u s t g a s a s t e e p e r i n c r e a s e of H C c o n v e r s i o n d u e to u n s a t u r a t e d h y d r o -
c arbons would be expected.

A c o m p l e t e c h a r a c t e r i z a t i o n of a t h r e e - w a y - c a t a l y s t is p o s s i b l e o n l y by
s i m u l t a n e o u s p l o t t i n g o f t h e c o n v e r s i o n o f a l l t h r e e r e l e v a n t p o l l u t a n t s . In
c o m p a r i n g d i f f e r e n t c a t a l y s t s , h o w e v e r , a g r a p h i c view w o u l d l e a d t o con-
f u s i o n . T h e r e f o r e , t h e e x p e r i m e n t s will be p r e s e n t e d i n t a b u l a t e d f o r m . A s
c h a r a c t e r i s t i c t e m p e r a t u r e s , t h o s e c o r r e s p o n d i n g to 50 % c o n v e r s i o n ( s t a r t i n g
r e g i o n ) and YO X c o n v e r s i o n ( t y p i c a l o p e r a t i o n r e g i o n of t h e c a t a l y s t ) a r e
listed.

'
loo

00 '

60 '

40 '

20

I 200 220 240 260 ZOO 300

Temperature [ "C ]

Fig. 3. Typical c o n v e r s i o n c h a r a c t e r i s t i c of a new t h r e e - w a y - c a t a l y s t of type

PtRhH-mordenite f o r t h e p o l l u t a n t s N O , CO and propane.

TABLE 3
C o m p a r i s o n of p o l l u t a n t c o n v e r s i o n o f new PtRh-doped z e o l i t e s .

Ty Pe SO % c o n v e r s i o n 00 X c o n v e r s i o n
NO co HC NO co HC

PtRhH-M 289OC 201°C 294OC 290 OC 297 OC 3 0 8 OC

PtRhH-Y 292 OC 3 0 8 OC 341 OC 314OC 321 OC 4OO0C
 301

A c o m p a r i s o n of t h e c o n v e r s i o n b e h a v i o u r of t h e t w o PtRh-doped z e o l i t e s
m o r d e n i t e a n d Y-zeolite is s h o w n i n t a b l e 3 , w h e r e i t is s e e n t h a t t h e m o r d e -
n i t e is c h a r a c t e r i z e d by a s i g n i f i c a n t l y h i g h e r a c t i v i t y c o m p a r e d to t h e Y-zeo-
l i t e . T h i s f o l l o w s f o r t h e r e d u c t i o n of n i t r i c o x i d e a s well a s f o r t h e o x i d a t i o n
of c a r b o n m o n o x i d e . In p a r t i c u l a r , t h e high a c t i v i t y of t h e m o r d e n i t e c o n c e r -
ning t h e o x i d a t i o n of t h e k i n e t i c i n e r t h y d r o c a r b o n p r o p a n e is a n i m p o r t a n t
r e s u l t . Y O % c o n v e r s i o n o c c u r s a t a t e m p e r a t u r e 100 OC l o w e r t h a n for t h e Y-
zeolite.

A f t e r t h e e x p e r i m e n t s w e r e p e r f o r m e d , b o t h c a t a l y s t s w e r e a g e d in a t u b e
oven a t 800 OC in o x y g e n - and w a t e r - v a p o u r - c o n t a i n i n g a t m o s p h e r e . T h e c o n -
version c h a r a c t e r i s t i c of t h e aged c a t a l y s t s is s h o w n i n t a b l e 4 . Again t h e
h i g h e r a c t i v i t y o f t h e m o r d e n i t e c a t a l y s t c a n be s e e n . W h i l e t h e n o b l e - m e t a l -
d o p e d m o r d e n i t e s h o w s conversion of t h e p o l l u t a n t s ( b e s i d e s NO) a t t e m p e r a -
t u r e s s i g n i f i c a n t l y l o w e r t h a n 4 0 0 OC ( 9 0 % c o n v e r s i o n ) , t h e Y - z e o l i t e o n l y
c o n v e r t s CO. P r o p a n e c o n v e r s i o n in t h e t e m p e r a t u r e r a n g e u n d e r i n v e s t i g a t i o n
( u p t o 5 0 0 OC) is f a r b e l o w 5 0 %.

TABLE 4
C o m p a r i s o n of c o n v e r s i o n of PtRh-doped z e o l i t e s a f t e r o p e r a t i o n .

Ty pe 50 % c o n v e r s i o n 9 0 % conversion
NO co HC NO co HC

PtRhH-M 3 4 4 OC 342 OC 359 OC -*) 356 OC 3 8 4 OC

PtRhH-Y 375 OC 401 OC -*) -*) 4 4 0 OC -*)

*) c o n v e r s i o n b e l o w 5 0 % and 90 % over in t h e t e m p e r a t u r e r a n g e of t h e e x p e -
riments.

The very d i f f e r e n t behaviour of t h e t w o z e o l i t e s c o n c e r n i n g t h e c o n v e r s i o n

o f t h e t h r e e p o l l u t a n t s i n t h e e x h a u s t g a s of O t t o - c y c l e e n g i n e s s e e m s s u r -
p r i s i n g , t h e m o r e so when t a k i n g i n t o a c o u n t t h a t t h e Y - z e o l i t e a d o p t e d m o r e
n o b l e m e t a l t h a n t h e m o r d e n i t e , a l t h o u g h c o n d i t i o n s f o r ion e x c h a n g e w e r e
i d e n t i c a l . While t h e Y-zeolite c o n t a i n s 0 . 3 3 m a s s - % of Rh. t h e R h - c o n t e n t of
t h e m o r d e n i t e is b e l o w t h e d e t e c t i o n c a p a b i l i t y of EDX. T h e c o n t e n t o f p l a t i -
num is of t h e o r d e r of 0 . 5 4 mass-% f o r t h e Y-zeolite and of 0.16 m a s s - % f o r t h e
mordeni t e .

Because of t h e higher c o n t e n t of n o b l e m e t a l , t h e Y-zeolite s h o u l d b e e x -

p e c t e d t o be m o r e a c t i v e t h a n t h e m o r d e n i t e . The z e o l i t e c a n n o t b e r e g a r d e d
a s a n inert carrier f o r t h e noble metal, b u t s o m e synergy e f f e c t b e t w e e n noble
302

m e t a l sites a n d acid s i t e s of t h e z e o l i t e t a k e s p l a c e . T h i s e f f e c t p l a y s a n p a r -
t i c u l a r l y i m p o r t a n t r o l e c o n c e r n i n g t h e c o n v e r s i o n of s a t u r a t e d h y d r o c a r b o n s .
However, b e s i d e s t h e s y n e r g y e f f e c t , p l a t i n u m is t h e m o s t i m p o r t a n t c o m p o -
n e n t in t h e a c t i v i t y of t h e z e o l i t e c a t a l y s t .

A s w a s d e m o n s t r a t e d in e a r l i e r w o r k , t h e c o n v e r s i o n of g a s e o u s r e a c t a n t s
is f a v o r e d in n e a r - s u r f a c e r e g i o n s of t h e z e o l i t e c r y ~ t a l l i t e s ~ ’ ~a l’ t~h )o ,u g h
t h e o p e n c h a n n e l s y s t e m of t h e z e o l i t e s c o u l d , i n p r i n c i p l e , a l s o i n d u c e t h e
reactions. Therefore i t was necessary to investigate w h e t h e r t h e d i f f e r e n c e s
in a c t i v i t y of t h e t w o z e o l i t e s can b e r e l a t e d t o a s u r f a c e e f f e c t . Z e o l i t e pow-
d e r s w e r e i n v e s t i g a t e d by u s i n g SIMS, in p a r t i c u l a r c o n s i d e r i n g t h e n o b l e me-
t a l d i s t r i b u t i o n in t h e c r y s t a l l i t e .

In Fig. 4. a P t d e p t h p r o f i l e ( Y - z e o l i t e , o p e n s q u a r e s : m o r d e n i t e , f i l l e d
s q u a r e s ) t o a d e p t h of 10 nm is p r e s e n t e d . I n c o n t r a s t t o t h e b u l k v a l u e s t h e
mordenite s h o w s a significantly higher Pt c o n t e n t i n near-surface regions.
T h i s c o n t e n t is a b o u t t w i c e a s high a s f o r t h e Y-zeolite, a l t h o u g h t h e Y-zeoli-
t e c o n t a i n s a b o u t 3 t i m e s m o r e Pt t h a n t h e m o r d e n i t e in t h e b u l k . M o r e o v e r ,
t h e P t d e p t h p r o f i l e of t h e m o r d e n i t e s h o w s a p l a t i n u m e n r i c h m e n t a t t h e ou-
t e r m o s t s u r f a c e of t h e c r y s t a l l i t e s . In c o n t r a s t t o t h a t , t h e Y - z e o l i t e s h o w s
a l m o s t no p l a t i n u m a t t h e o u t e r m o s t s u r f a c e .

T h e d i f f e r e n t d e p t h p r o f i l e s of t h e t w o z e o l i t e s c a n b e e x p l a i n e d by t h e
very d i f f e r e n t c h a n n e l s t r u c t u r e . The m o r d e n i t e is c h a r a c t e r i z e d by a o n e - d i -
m e n s i o n a l p o r e s y s t e m . The Y - z e o l i t e , h o w e v e r , is c h a r a c t e r i z e d by a t h r e e -
dimensional pore s y s t e m with additional cages. The comparably l a r g e plati-
num c o m p l e x , which w a s used for ion e x c h a n g e , is a b l e t o d i f f u s e a t h i g h e r
r a t e s i n t o t h e c h a n n e l s y s t e m of t h e Y - z e o l i t e , r e s u l t i n g i n a h i g h e r p l a t i n u m
c o n t e n t . P l a t i n u m c l u s t e r s p r o d u c e d by r e d u c t i o n of t h e c o m p l e x a r e e x p e c t e d
t o b e l o c a l i z e d in t h e b i g c a g e s m o r e i n s i d e t h e c r y s t a l l i t e .

Due t o t h e n a r r o w m o r d e n i t e p o r e s y s t e m , d i f f u s i o n of t h e p l a t i n u m c o m -
p l e x is s l o w . T h i s r e s u l t s i n a low P t c o n t e n t . H o w e v e r , t h e p l a t i n u m c o n t e n t
in n e a r - s u r f a c e r e g i o n s will b e e n h a n c e d . I t c a n t h e r e f o r e b e a s s u m e d t h a t by
r e d u c t i o n P t c l u s t e r s a p p e a r in t h e very o u t e r m o s t s u r f a c e l a y e r s . C o n c e r n i n g
t h e m o r d e n i t e , t h e a c t i v e m e t a l is l o c a l i z e d a t t h e l o c a t i o n of t h e r e a c t i o n .
T h i s e x p l a i n s t h e c o n s i d e r a b l y h i g h e r c a t a l y t i c a c t i v i t y of t h e m o r d e n i t e c o m -
pared w i t h t h e Y-zeolite.
 303

I\
I
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L
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S
a
0
C
0
0
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v
a

,
0 10
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Fig. 4. SIMS Pt d e p t h p r o f i l e o f PtRhH-M ( f u l l s q u a r e s ) a n d PtRhH-Y ( o p e n

squares).

A
I
C
U
.C

4J

L
iJ
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...............................................................................................................................
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d e p t h C n m l -->

Fig. 5. SIMS Rh d e p t h p r o f i l e of PtRhH-M ( f u l l s q u a r e s ) a n d PtRhH-Y ( o p e n

squares).
304

T h e r h o d i u m d e p t h p r o f i l e o f t h e t w o z e o l i t e s s h o w n i n Fig. 5. i l l u s t r a t e s
t h e r e v e r s e c o n d i t i o n s a s t h e p l a t i n u m d e p t h p r o f i l e of Fig. 4. T h e Y - z e o l i t e
c o n t a i n s m o r e r h o d i u m i n n e a r s u r f a c e r e g i o n s a s t h e m o r d e n i t e . T h i s , in a d d i -
t i o n . c o r r e s p o n d s t o t h e r a t i o s i n t h e t o t a l v o l u m e a n d c a n b e e x p l a i n e d by a
f a s t e r ion e x c h a n g e o f r h o d i u m c o m p a r e d t o p l a t i n u m . T h i s f o l l o w s f r o m t h e
a l m o s t i d e n t i c b u l k c o m p o s i t i o n of p l a t i n u m a n d r h o d i u m i n t h e Y - z e o l i t e ,
a l t h o u g h t h e ion e x c h a n g e s o l u t i o n c o n t a i n e d a five f o l d e x c e s s of p l a t i n u m .

T h e i n f l u e n c e of t h e r h o d i u m c o n t e n t in n e a r s u r f a c e r e g i o n s of t h e z e o l i t e
c r J s t a l l i t e s is of m i n o r i m p o r t a n c e a s t h a t of t h e p l a t i n u m f o r t h e t w o f o l l o -
wing r e a s o n s . F i r s t . t h e m e t a l l i c p l a t i n u m p l a y s a much m o r e i m p o r t a n t r o l e
c o n c e r n i n g t h e c o n v e r s i o n of t h e p o l l u t a n t s a s a t o t a l t h a n t h e r h o d i u m . S e -
c o n d . c o m p a r e d t o t h e u s u a l Pt:Rh r a t i o of 5: l t h e r h o d i u m is e n r i c h e d in t h e
near s u r f a c e r e g i o n s o f t h e t w o nobel m e t a l d o p e d z e o l i t e s . From t h a t , i t f o l -
l o w s t h a t an a d d i t i o n a l i n c r e a s e of t h e r h o d i u m c o n t e n t c a n n o t lead t o a f u r -
t h e r i n c r e a s e of t h e c a t a l y t i c a l a c t i v i t y . T h i s f o l l o w s f r o m a c o m p a r i s o n o f
Fig. 4. and Fig. 5.

T h e a n a l y s i s of t h e SlMS d e p t h p r o f i l e s s h o w e d t h a t t h e r e e x i s t s a c l e a r
c o r r e l a t i o n f o r t h e r e a c t i o n s o f t h e c a t a l y t i c c o n v e r s i o n of t h e e m i s s i o n of
O t t o cycle engine e x h a u s t s between c a t a l y s t a c t i v i t j and t h e chemical compo-
s i t i o n o f t h e s u r f a c e of t h e z e o l i t e c r y s t a l l i t e s . I n p a r t i c u l a r t h e e n r i c h m e n t
of p l a t i n u m c l u s t e r s f o u n d in near s u r f a c e r e g i o n s o f t h e m o r d e n i t e c r y s t a l l i -
t e s significantly increases t h e a c t i v i t j , e. g . concerning t h e oxidation o f hydro-
carbons.

C o n c e r n i n g p l a t i n u m e n r i c h m e n t and d i s p e r s i o n a t t h e m o r d e n i t e s u r f a c e
t h e d e m a n d of a r e d u c t i o n of t h e nobel m e t a l c o n t e n t a t c o m p a r a b l e a c t i v i t y
w a s p o s s i b l e . While c o n v e n t i o n a l t h r e e - w a y - c a t a l y s t s c o n t a i n a b o u t 1.5 g
n o b l e m e t a l p e r l i t e r , a m o n o l i t e having a z e o l i t e c o a t i n g is c h a r a c t e r i z e d by a
nobel m e t a l c o n t e n t b e t w e e n 0.1 and 0.5 g / l .

REFERENCES

1 C h e m i s c h e R u n d s c h a u 22, 03.06.1988, S. 3 8 .
2 O b l a n d e r , K . a n d A . B. Nagel, VDI B e r i c h t e 531 ( 1 9 8 4 ) , S. 39.
3 H e r r m a n n . C . , J . Haas a n d F. F e t t i n g , A p p l . C a t a l . 35, 299 ( 1 9 8 7 ) .
4 H a a s , J . , F. F e t t i n g , C . Plog, W. Kerfin, W. G e r h a r d a n d G. R o t h
Appl. C a t a l . 3.5, 311 (1987).
5 H e r r m a n n . C., F. F e t t i n g a n d C . Plog, Appl. C a t a l . 39, 213 ( 1 9 8 8 ) .
H.C. Karge,.J, Weitkamp (Editors1, Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Else& Science Publishers B.V., Amsterdam - Printed in The Netherlands

TRANSFORMATION OF ETHANETHIOL OVER ZEOLITES

M. ZIdtEKl, P. DECYK1, M. 0EREWIdSKI2 and J. HABER2

'Faculty of Chemistry, A . Mickiewicz University, Poznah, Poland
21nstitute of Catalysis and Surface Chemistry, Polish Academy of
Sciences, Krakow, Poland.

ABSTRACT
The hydrogen sulphide elimination reaction of ethanethiol and
further transformations of alkyl radicals were studied on sodium
and hydrogen forms of X, Y and ZSM-5 type zeolites. BrMnsted acid
sites are catalytic active centres in elimination, whereas sodium
ions play the role of sites active in transformations of alkyl
radicals. The activity of zeolites in elimination increases with
the increase of the strength of the zeolite acidity,poisoning with
pyridine thus favours the further transformations of alkyl radi-
cals. Adsorption of hydrogen sulphide strongly enhances the tran-
sformations to aromatics due to generation of new active sites.

INTROOUCTION
In hydroprocessing operations petroleum components react cataly-
tically with hydrogen. The most important reaction is hydrodesul-
phurization leading to the conversion of organic si~lphur compounds
into H 2 S and hydrocarbon products (1). The aim of our present study
is to investigate the possibility of the application of zeolites to
convert thiols vithout the use of hydrogen and to disclose the
nature of active sites of these catalysts responsible for the acti-
vity and selectivity in the transformations of ethanethiol (Et-SH).

EXPERIMENT
Catalysts
The following catalysts were used: Na-XI Linde Lot N o . 2 5 6 5 3 3 0 ,
with Si/Al = 1.13; Na-Y, Leuna, with Si/A1 = 2.56; Na-ZSM-5,
Ultraset T - l O f l O / J , synthesized in the Institute of Industrial
Chemistry Warsaw, with Si/Al = 3 8 and hydrogen forms of these
zeolites. Modified forms were prepared by an ion exchange with
0.25M solution of NH4C1. Hydrogen zeolites were obtained by the
calcination of ammonium forms in a shallow bed at 673K for 4hr in
a flow of pure, dried He. The following catalysts were obtained
306

(degree of exchange in parentheses): H,Na-X (50%); H,Na-Y (70%)

and H-ZSM-5 (100%).

Acidity measurements
The acidity of zeolites was estimated from the Temperature-Pro-
grammed Desorption (TPD) of pyridine. The sample of 50 mg of zeoli-
te was activated a t 773K for 1 hr at a pressure o f ~ x I O -Torr.
~
After cooling to room temperature the sample was exposed to 2 0 yl
of pyridine for 15 min. and outgassed for 45 min. at R.T. The TPD
experiment was carried out in the temperature range 303-1073K a t
a heating rate of 10 K/min. Desorbing pyridine w a s analyzed with
a Balzers 311 mass-spectrometer.

Reaction conditions
The conversion of Et-SH was determined in a pulse microreactor,
8 mm in diameter, filled with 0.2 g of the dehydrated form of the
zeolite. Zeolite crystallites were pelleted without binder,
ground, sieved to a 0.5-1.0 mm diameter range and activated for
4hr at 673K in He flow.
The H2S elimination of Et-SH was carried out a t 573, 6 2 3 and
673K. The flow rate of He as the carrier gas was 40 cm 3 /min at
atmospheric pressure. Pulses of 1 p1 of Et-SH (Fluka) were intro-
duced at the reaction temperature. Products were analyzed using an
on-line gas chromatograph with flame ionization detector and a 4 m
column filled with Chromosorb W (60-80 mesh) and silicon oil D C
with 5% addition of stearic acid a s the active phase.
Catalytic experiments at 623K were also conducted after poiso-
ning the acid centres with pyridine (40 p l ) and after adsorption
o f hydrogen sulphide on the activated samples from the flow of
hydrogen sulphide ( 1 cm 3 /min) in helium through the catalyst bed
at 623K for 1 hr.

RESULTS
Characterization of the zeolite acidity
TPD spectra obtained after pyridine adsorption at R.T. over
sodium and hydrogen forms of zeolites are presented in Figures 1
and 2. In the case of sodium forms of faujasite-type zeolites two
maxima are observed on the desorption curves. On Fla-Y zeolite the
iirst maximum appears a s a shoulder. he spectra have the s a n e
characteristics a s those shown in Ref 2.The first maximum origina-
tes from physisorbed pyridine and the second from pyridine chemi-
 307

Fig.1. TPO s p e c t r a
obtained a f t e r
a d s o r p t i o n of
p y r i d i n e on
sodium forms
of zeolites.
TEMPERATURE IK 1

s o r b e d o n s o d i u m c a t i o n s . The T P D s p e c t r u m of Na-ZSM-5 a f t e r a d s o r -
p t i o n o f p y r i d i n e ( F i g . 1 ) s h o w s t h r e e maxima: t h e f i r s t , a t t h e
l o w e s t t e m p e r a t u r e , i s d u e t o p h y s i s o r b e d p y r i d i n c or p y r i d i n e
a d s o r b e d o n t e r m i n a l s i l a n o l g r o u p s ( 3 ) ; t h e s e c o n d i s d u e t o py-
r i d i n e chdmisorbed on sodium c a t i o n s ; and t h e t h i r d t o p y r i d i n e
c h e m i s o r b e d on t h e f e w Brtlnsted a c i d s i t e s which a r e formed a s
a r e s u l t o f t h e t e m p e r a t u r e d e c o m p o s i t i o n of t h e o r g a n i c compounds
u s e d i n t h e z e o l i t e s y n t h e s i s . On t h e b a s i s o f t h e p r e s e n t e d

- H,No-X
---- H.No -Y
........ H-ZSM-5

Fig.2. TPD s p e c t r a
obtained a f t e r
a d s o r p t i o n of
p y r i d i n e on
273 473 673 873 1073 hydrogen forms
TEMPERATURE IK ]
of z e o l i t e s .

TPD s p e c t r a t h e f o l l o w i n g s e q u e n c e o f t h e a c i d i c s t r e n g t h o f s o -
dium c a t i o n s may b e c o n c l u d e d :
Na-X> Na-ZSM-5 >
Na-Y
H y d r o g e n f o r m s o f z e o l i t e s show t w o TPD maxima ( F i g . Z ) . T h e f i r s t
maximum a t t h e l o w e r t e m p e r a t u r e may b e a s s i g n e d t o p h y s i s o r b e d
p y r i d i n e a n d t h e s e c o n d t o p y r i d i n e c h e m i s o r b c d o n t h e a c i d i c si-
t e s . H-ZSM-5 a n d H,Na-Y z e o l i t e s d o n o t s h o w a n y maxima f r o m p y r i -
308

d i n e a d s o r b e d on sodium c a t i o n s . H,Na-X z e o l i t e i n which the

exchange o f sodium c a t i o n s was o n l y 50% (because of t h e d e s t r u c t i o n
o f t h e framework a t h i g h e r d e g r e e s of exchange) shows a b r o a d band
a t a b o u t 63QK w h i c h o v e r l a p s w i t h t h e maximum o r i g i n a t i n g f r o m
p y r i d i n e a d s o r b e d o n sodium c a t i o n s ( a t 5 8 8 K - c . f . F i g . 1 ) . I n the
case o f h y d r o g e n f o r m s of z e o l i t e s t h e f o l l o w i n g sequence o f t h e
a c i d s t r e n g t h can t h u s be d e r i v e d :
H-ZSM-5 > H,Na-Y > H,Na-X
E f f e c t o f temperature
F i g . 3A.shows t h e c o n v e r s i o n o f E t - S H o n Na-ZSM-5 zeolite at
d i f f e r e n t temperatures. The same sequence was o b t a i n e d i n t h e c a s e
o f a l l i n v e s t i g a t e d samples, i . e . w i t h t h e i n c r e a s e of t h e r e a c t i o n
t e m p e r a t u r e , t h e c o n v e r s i o n o f Et-SH i n c r e a s e s . The m a i n r e a c t i o n
p r o d u c t s a r e : H 2 S , e t h y l e n e , d i e t h y l s u l p h i d e and p r o d u c t s of
o l i g o m e r i z a t i o n and a r o m a t i z a t i o n . The h i g h e s t amount of E t 2 S i s
o b s e r v e d o n Na-X z e o l i t e .
F i g . 36 p r e s e n t s t h e a c t i v i t y o f d i f f e r e n t z e o l i t e s a t 573K.
F o r sodium f o r m s o f z e o l i t e s t h e f o l l o w i n g sequence o f c o n v e r s i o n
i n t h e f i r s t p u l s e o f E t - S H i s observed:
Na-X > Na-ZSM-5 > Na-Y
and f o r h y d r o g e n f o r m s
H-ZSM-5 > H,Na-Y > H,Na-X

,
TIME [ M I N I
, * 1qo 2!0* . 31I0 100 200 300
1- A No-ZSM-5 oNa-X
-&? A H-ZSM-5 OH,Na-X
0 NO-Y

NUMBER OF P U L S E S

F i g . 3. E t - S H c o n v e r s i o n on z e o l i t e s : ( A ) Na-ZSM-5 a t d i f f e r e n t
t e m p e r a t u r e s , (€I) on d i f f e r e n t z e o l i t e s a t 573K.
 309

As seen from Fig. 38 in the case of Na-X zeolite the conversion

rapidly decreases with the number of pulses, whereas for other ze-
olites it decreases only to a small extent o r remains constant,
Thus it may be concluded that rapid deactivation of Na-X zeolite
takes place in the course of the reaction.

Reaction products
Tables 1 and 2 represent the initial conversions of Et-SH and
the yields of products obtained over sodium and hydrogen forms of
zeolites at 623K. The product distributions on sodium forms of
faujasites and Na-ZSM-5 are different. The main reaction products
over Na-X and Na-Y zeolites are ethylene as the result of elimina-
tion, and diethyl sulphide, olefins and aromatics resulting from
further transformations of ethyl groups. At variance, Na-ZSM-5
zeolite favours only the elimination reaction, yielding predomi-
nantly ethylene.

TABLE 1
Conversion of ethanethiol over sodium forms of zeolites at 623K
~ ~~~

Catalyst Na-X Na-Y Na-ZSM-5

Conversion ( % ) 89.8 19.7 74.7
Yield of products ( % )
Ethylene 67.0 10.1 73.4
Butane, butenes 1.0 0.7 0.2
0.6 1.2 0.2
Cc5 (olefins,paraffins) 0.5 1.2 -
Abomat ics 7.0 2.2 0.1
Diethyl sulphide 12.9 4.3 0.6

The exchange of sodium cations for protons causes the increase

of the Et-SH conversion in the case of Y and ZSM-5 zeolites
(Table 2). A change in the product distribution is also observed.
The yield of ethylene becomes higher and that of other products
lower. H,Na-X zeolite differs in its behaviour, showing lower ini-
tial activity than Na-X; but after exposure to a higher number of
Et-SH pulses the activity of both catalysts becomes similar, a s
shown in Fig. 36. This may be easily understood if i t i s remembered
that the hydrogen-exchanged Na-X zeolite is partially dealurninated
and in the acidic atmosphere of reactants slowly decomposes.Indeed,
the ir spectra obtained after reaction indicate partial decomposi-
tion o f the faujasite framework.
310

TABLE 2
Conversion of ethanethiol over hydrogen forms of zeolites at 623K

Catalyst H,Na-X H,Na-Y H-ZSM-5

Conversion ( % ) 31.2 30.1 87.8

~~ ~

Yield of products ( 9 6 )
Ethylene 22.6 21.3 86.3
Butane, butenes 0.7 0.4 0.3
1.1 0.2 -
cc5 (olefins,paraffins) - 0.1 0.1
Agomatics 2.8 1.3 1.0
Oiethyl sulphide 4.0 0.8 0.1

Influence of pyridine adsorption

After pyridine adsorption at reaction temperature the total
activity of catalysts distinctly decreases. This is accompanied by
considerable changes in the product distribution, as shown in
Table 3, in which the selectivity to different products is summa-
rized. The selectivity of Et-SH conversion towards ethylene decre-
ases after adsorption of pyridine,whereas that of the rest o f pro-
ducts - increases. The most distinct effect of the pyridine poiso-
ning is observed on 2 3 4 - 5 type zeolites.

TABLE 3
Influence of pyridine poisoning on the activity and selectivity of
hydrogen forms of zeolites (TR = 62310 in ethanethiol conversion.

Catalyst H,Na-X H, Na-Y H-ZSM-5

pure poisoned pure poisoned pure poisoned
Conversion ( % ) 31.2 13.4 30.0 14.2 87.8 21.2
Selectivity to
different products (5):
Ethylene 72.5 61.9 91.0 81.0 98.3 64.2
Butanes,butenes 2.2 4.5 1.3 2.8 0.3 5.2
3.5 12.1 0.7 8.5 - 7.5
c5
C (olefins,paraffins) - 0.7 0.1 0.7 0.1 1.4
Agomatics 9.0 4.5 4.3 3.5 1.2 10.4
Oiethyl sulphide 12.8 15.7 2.6 3.5 0.1 11.3

Influence of hydronen sulphide preadsorption

After preadsorption of H2S the conversion of ethanethiol incre-
ases. This effect is most spectacular in the case of Na-X and
H,Na-X zeolites. This is understandable in view of the fact that
 311

the amounts of H2S adsorbed on Na-Y, H,Na-Y and Na-ZSM-5 are low
(Table 4) in comparison to those adsorbed on Na-X and H,Na-X.
Table 5 shows the results of catalytic tests on Na-X, H,Na-X and
Na-ZSM-5 zeolites before and after H2S adsorption. It can be seen
that adsorption of H2S increases the yield of C6 hydrocarbons
(olefins and paraffins) and aromatics and results i n a decrease or
complete disappearance of Et2S from the reaction products.

TABLE 4
H2S adsorption at 623K

Catalyst Na-X H,Na-X Na-Y H,Na-Y Na-ZSM-5 H-ZSM-5

H2S ads.(mmol.g-’) 4.2 2.0 0.4 0.3 0.1 -

TABLE 5
Comparison of activity of pure zeolites with activity after H2S
adsorption (TR=623K)

Catalyst Na-X H ,Na-X Na-ZSM-5

pure H,S ads. pure H,S ads. pure H,S ads.
Et-SH conversion ( % ) 89.8 100 31.2 66.1 14.1 81.4
Yield of products,%
Ethylene 67.0 54.5 22.6 56.2 13.4 77.1
Eutane,butenes 1.0 - 0.1 . 1.6 0.2 0.9
0.6 - 1.1 3.0 0.2 0.1
c5
C (olefins,paraffins) 0 . 5 10.9 - 0.2 - 0.6
Agomatics 7.0 34.6 2.0 3.5 0.1 2.3
Oiethyl sulphide 12.9 - 4.0 2.2 0.6 0.4

DISCUSSION
Some of the first information concerning the conversion of
thiols over zeolites was noted in Ref.4. The similarity in the
mechanism of the H20-elimination from Et-OH and H2S-elimination
from Et-SH over alumina was discussed by Sugioka e t al.(5).Results
of our present study confirm that also in the case of zeolites the
same mechanism operates in these two elimination reactions, but
further transformations of the resulting hydrocarbon radicals
proceed along different pathways.
A series of studies (6,7) of the catalytic activity of zeolites
poisoned by pyridine showed that in the transformations of alcohols
312

consecutive steps in the reaction sequence, viz. alcohol -olefins-

oligomers - cyclopolyenes- aronatics/paraffins, are catalyzed by
Brtlnsted acid centres of increasing strength, according to the
following scheme:
very \$leak weak
acid centres acid centres
alcohol _____f olefins _____j oligomers

aromatics strong
centres
acid cyclopolyenes/\
strong acid
centres
strong acid
centres
paraffins

Analysis of the data summarized in Tables 1 and 2 indicates that

on Z S M - 5 zeolites, both sodium and hydrogen exchanged, mainly eli-
mination of H2S takes place, whereas higher yields of the diethyl
sulphide and of products of further hydrocarbon transformations are
observed on Na-X and Na-Y zeolites. After activation at 673K these
zeolites do not contain any acid hydroxyl group (9) and it is the
sodium ions which operate as active sites for the reaction of
Et-SH. This suggests that two parallel reaction pathways exist,one
consisting of simple elimination of H2S on acid hydroxyl groups of
the zeolite and the second, in which diethyl sulphide is formed as
the first intermediate of the series of consecutive transformations
of hydrocarbon radicals, resulting in the formation of higher ole-
fins, paraffins and in particular aromatics. It seems that the f o r -
mation of diethyl sulphide takes place on sodium cations whose p r e -
sence in the zeolite framework generates the appearance of Lewis
acid-base pairs. Indeed, it is known (8) that in the presence of
pairs of Lewis acid-base centres ethanol in an analogous reaction
forms diethylether. Na-X becomes rapidly deactivated in the course
of Et-SH conversion (c.f.Fig.3). The reason f o r this deactivation
could be coke formation. The yield of aromatics was highest over
Na-X (Tables 1 and 2). It is known (10) that aromatic and coke have
a common precursor and that in the large cavities of faujasite-type
zeolites coke i s very easily formed.
These conclusions are confirmed by studies of zeolite activity
after adsorption of pyridine and HgS. Pyridine adsorbed at 623K
poisons mainly Brtlnsted acid sites, and sodium cations are poisoned
only partially. TPO o f pyridine has shown the maxima of sodium
cations below 623K, but some cations may still retain pyridine
molecules even at higher temperatures (Fig.1). Thus, after
 313

adsorption of pyridine the simple H2S elimination i s suppressed,

and s o is the total activity, whereas the relative importance of
the pathway to diethyl sulphide and further transformations of
hydrocarbon radicals is enhanced. This effect i s most significant
in the case of ZSM-5 zeolites which have the strongest Brtlnsted
acid sites.
The experiments with the adsorption of H2S provided further
support to the postulated r o l e of the sodium cations and acid OH
groups in the reaction of Et-SH. On adsorption of H2S on Na-X
dissociation of H 2 S occurs, and HS- and H+ ions are formed (11).
The dissociative adsorption of H2S decreases with the increase of
the Si/Al ratio, and hence the effect of H2S adsorption is most
pronounced on X zeolites. HS- ions are adsorbed on sodium cations
and generate a dense network of active sites for adsorption o f
Et-SH through the formation of a 5-5 bond known to be readily
formed and fairly strong. On such "quasi-sulphidic" surface of much
lower polarity than the oxide surface, the reactivity of C2H5 ra-
dicals may be high, oligomerization and aromatization thus procee-
ding readily. On the other hand one should note that, in the first
step of the dissociative adsorption of H 2 S , hydroxyl groups are
formed at sites with a very high electrostatic potential and
exhibit a band at 3635 cm-l ( 1 2 ) . Such OH groups are absent in the
H,Na-X activated at 673K, but may form upon H2S adsorption and be
involved in the aromatization process which takes place on strong
acid sites.

CONCLUSIONS
Reaction of Et-SH over faujasites and ZSM-5 zeolites proceeds
along two parallel pathways: (i) simple elimination of H 2 S on
Brdnsted acid sites, resulting in the formation of ethylene, and
(ii) generation of diethyl sulphide as the intermediate in further
transformations of ethyl radicals to form higher olefins, paraffins
and aromatics. Formation of diethyl sulphide takes place on sodium
cations which in the zeolite framework play the role of L e w i s
acid-base pairs. Preadsorption of H 2 S o n Na-X zeolite generates
sulphide sites, which strongly enhance the formation of aromatics.

ACK N OWL E 0 G E ME N T
The authors are greatly indebted to Dr. H.G. Karge for helpful
discussion and the critical revision of the manuscript.
314

REFERENCES
1. 8.C. Gates, J.R. Katzer and G.C.A. Schuit, "Chemistry of cata-
lytic p r o c e s s e s " , Mc Graw-Hill Book Company, 1979 p . 390.
2. N. Pesl, Thesis, Technische Universityt Wien, 1978.
3. Nan-Yu Topsoe, K. Pedersen and E.G. Derouane, J . Catal. 70
(1981) 41.
4. C.D. Chang and A.J. Silvestri, J.Cata1. 47 (1977) 249.
5. Masatoshi Sugioka, Takayoshi Kamanaka and Kazuo Aomura,
J. Catal. 52 (1978) 531.
6 . S. Dzwigaj, J. Haber and T. Romotowski, Zeolites 4 (1984) 147.
7. M. Derewihski, S. Dzwigaj, J . Haber and G. Ritter, Proc.
Intern. Symp. on Zeolite Catalysis, Siofok 1985, Acta Phys.
Chem. Szegediensis, Szeged 1985, p. 535.
8. J. Haber and U. Szybalska, Disc. Faraday SOC. 7 2 (1981) 263.
9. M . Zi6lek, I. Bresihska and H.G. Karge, Proc.Intern.Symp. o n
Zeolite Catalysis, Siofok 1985, Acta Phys. Chem. Szegediensis,
Szeged 1985, p. 551.
10. J.C. Vedrine, P. Dejaifve and E.O. Garbowski, "Catalysis by
Zeolites", ed. 8. Imelik e t al., Elsevier 1980, p. 29.
11. H.G. Karge and J . Rask6, J.Colloid Interface Sci. 64 (1978)
522.
12. H.G. Karge, M . Zi6lek and M . taniecki, Zeolites, 7 (1987) 197.
H G. Karge, d. Weitkamp (Editors), Zeolites as Cakdyn$ts,Sorbents and Detergent Rudders
0 1989 Elsevier Science Puhlishers R.V., Amsterdam - Printed in The Netherlands

STUDY OF THE STRUCTURE AND THE REDOX REACTIVITY OF NaX

ENCAPSULATED Co(I1)-PHTHALOCYANINE
G. Schulz-Ekloff', D. Wbhrlez, V. Iliev3, E. Ignatzek' and
A. Andreev3
'Institut fiir Angewandte und Physikalische Chemie,
Universitht Bremen, D-2800 Bremen 3 3 , FRG

21nstitut fiir Organische und Makromolekulare Chemie,

Universitgt Bremen, D-2800 Bremen 3 3 , FRG
31nstitute of Kinetics and Catalysis, Bulgarian Academy of
Sciences, BG-1040 Sofia, Bulgaria

ABSTRACT
The preparation of NaX-encaged cobalt phthalocyanine by
thermally activated tetramerization of l,2-dicyanobenzene in
cobalt ion-exchanged zeolite results in average loadings < 1
complex per unit cell and some lattice fragmentation. The encaged
molecule exhibits restricted CH vibrations and a protonated state
in the IR and a twofold symmetry in the EPR spectrum. The encaged
chelates catalyze the oxidation of mercaptans and ethylbenzene as
well as the valence isomerization of quadricyclane to
norbornadiene. The results are compared with those of cobalt
phthalocyanine on silicagel and unsupported cobalt phthalocyanine.

INTRODUCTION
Zeolite-encapsulated organometallic complexes represent a
unique class of immobilized and heterogenized coordination
compounds. An especially stable inclusion can be expected for the
in-situ prepared metal phthalocyanine molecule accommodated in the
supercage of the faujasite structure Crefs.1-31. In the following,
new results on the structure of cobalt(I1)-phthalocyanine (Copc,
Fig. 3(1)) entrapped inside faujasite X (Copc/X) and its
reactivity in the oxidation of ethanethiol, ethylbenzene and in
the valence isomerization of quadricyclane to norbornadiene are
presented and discussed. In addition, unsupported Copc and Copc on
silicagel (Copc/SiOz) was studied to interpret the results.

EXPERIMENT
Preparation
Self-prepared zeolite NaX (Si/Al = 1.2) was cobalt ion-
exchanged (cobalt acetate, 0 . 0 2 5 mol dm-3) to a cobalt content of
316

the water-free samples of about 4 wt.t (E 1841 degree of exchange).

The COX samples were partially dehydrated (24 h at 513 K, argon),
mixed with 1,2-dicyanobenzene (dcb/Co = 4) in a glove box (dry
nitrogen), filled in a pressure tube (Duran glass, 100 x 12 mm),
sealed at 1 Pa, heated to 573 R (20 I[ min-1) and held at this
temperature for 16 h. The reaction product was extracted in a
Soxhlet with acetone (4 h) and pyridine until it was color-free to
remove excess Copc formed at the external surface of the zeolite
crystals [ref. 21. The chosen parameters guaranteed a minimum of
unreacted dcb or of the side-product phthalimid. The formation of
triazine (Fig. 3, (2)) can occur by special variation of the
synthesis parameters [ref -41.
Large-pore silicagel (Riedel-de Haen, 300 mzg-1 ) was loaded
with cobalt by suspending in cobalt chloride solution and
saturating with ammonia. The adsorbed cobalt tetra-ammine complex
was decomposed by calcination. The cobalt loaded silicagel was
reacted with dcb (dcb/Co = 4) as described above resulting in
products (Copc/SiOn ) uniformly dispersed on the carrier [ref -51.

Characterization
The quantitative loadings with Copc were determined
photometrically following the destruction of the faujasite X
lattice in concentrated acid solution or dissolving the chelate
from the surface of the silicagel with sulfuric acid. The samples
were characterized by X-ray powder diffraction, light microscopy,
scanning electron microscopy, FT-IR spectroscopy (in KBr),
electron paramagnetic resonance (Bruker ER 200-SRC, X-band, 130 K)
and nitrogen physisorption capacities at 77 K.

Catalysis
The oxidation of ethanethiol (CzHaSH) was carried out in a
continuously stirred batch reactor (250 ml. 298 K) containing the
dispersed solid Copc/X catalyst (0.12 pmol Copc) and the dissolved
thiol (2.7 ymol) in 100 ml heptane as well as air (=1 mmol 02).

The conversion of the thiol was followed by potentiometric

titration with silver nitrate using an ion-selective electrode
(Ag' / S a - 1.
The oxidation of ethylbenzene was studied in a continuously
stirred batch reactor (30 ml, 409 K) containing the dispersed
solid Copc/X catalyst (8 pmol Copc) in 12 ml ethylbenzene (~0.1
mol). Oxygen was bubbling (25 ml min-l) through the liquid phase
via a glass frit. The products were analyzed by gas chromatography
 317

(PE F 22, capillary column, cyano-methyl-phenyl-silicon as

stationary phase).
The valence isomerization of quadricyclane to norbornadiene was
studied in a glass ampoule (10 ml, room temperature) shaken to get
a uniform dispersion of the solid Copc/X catalyst (0.1 w o l Copc)
in the solvent (CC14). Quadricyclane (0.3 mmol) was added by a
syringe through a rubber septum to the oxygen-free three-phase
mixture. The rate of conversion was followed by sampling and gas
chromatography.

RESULTS
Infrared spectra
The infrared spectra of the Copc/X following to the removal of
external excess Copc and of the Copc/SiOz (Fig. 1) were evaluated
by subtracting the corresponding spectra of the metal-loaded
carriers. The band at 850 cm-1 (Pig. lc) is an artefact.

T
R
A
N
S
M
I
S
5
I

!I
0
N

0 450
L

Ffg. 1. FT-IR spectra of cobalt phthalocyanine pure (a), on

silicagel (b) and encaged in faujaaite X (c).
318

The band around 2250 cm-I is assigned to cyano end groups of

either unreacted dcb or of formed impurities, e.g. triazine. The
spectra of both samples exhibit a new broad band at 1020 cm-1. For
Copc/X the intensities of the C-H bands (1050- 1200 cra-l) and of
the C-C bands (1200 -1600 cm $ 1 are strongly decreased.

Electron paramagnetic resonance spectra

The EPR spectra of extracted Copc/X were obtained in air (Pig.
2 a,c) and in vacuo (Fig. 2 b) and were reproduced repeatedly by

i
g=2
1 I 1 1 1
1 I I
1 1

Fig. 2. X-band EPR spectra of Copc/X at 130 K and 1 mPa (b) and at normal
pressure in air (a,c). The identified features are inserted. The arrows indicate
the increase of the magnetic field A(G) and the abscissa extensions.
 319

cycles of removal and addition of air. The vacuum spectrum shows a

strong narrow signal at g = 2, i-e. close to the free electron
value, and a broad signal g = 2.4. The addition of air generates a
broad signal at g J 4 and a complex hyperfine structure having
spacings around 90 G. Two quintets centered around g = 2 and an
octet centered around g = 2.05 are identified.

Copc loading and physisorption of nitrogen

The obtained average Copc loadings of the zeolite samples were
around 1 wt.4, i.e. about one Copc molecule per three unit cells.
The X-ray powder diffraction, giving global informations about
the crystallinity of the zeolite samples, did not show a
significant loss of the overall crystallinity or a marked change
of the lattice dimensions.
The nitrogen physisorption capacity is strongly decreased, i.e.
often more than 50%, following to the synthesis of Copc/X and to
the removal of the external excess Copc. In general, an increase
of the nitrogen adsorption is obtained after shaking the samples
in sodium acetate solution. Further increase of the nitrogen
adsorption is obtained by burning off the organic material in air
(773 K, 6 h), resulting in BET values ranging from 50 - 80% of the
initial value of NaX (ca. 700 m'g-').

Catalysis
With respect to the missing information about the diffusion
coefficients and the mass transfer coefficients influencing the
kinetics, semi-quantitative comparisons of catalytic activities r
(initial rates of conversion, percent per h) are made, aiguing
with orders of magnitude only.
The ethanethiol oxidation experiments yielded negligible blank
values for the conversion on NaX (140 mg) and Copc (0.12 pmol),
i.e. r < 14 h-1. Relatively high conversions were obtained on
cobalt ion-exchanged NaX (140 mg), i.e. r z 104 h-1. A significant
increase of the catalytic activity was observed using the Copc/X
samples resulting in initial rates of conversion ranging from 10 -
10% h-1 for Copc/X from different charges of preparation.
Comparable activities were obtained for the Copc/SiOn catalysts
(Table 1). The supported Copc samples are 2 - 3 orders of
magnitude more active than the unsupported complex. Repeated use
of a catalyst produced no significant loss of activity.
320

TABLE 1
Initial rates of ethanethiol conversion ( & h-l) on Copc/SiOz (0.3
lo-” mol Copc) as a function of the Copc dispersion.

wt.% Copc on SiOz 12 6 0.4 0.06

conversion (Ib h-1) 7 11 12 95

Decreasing loading of the support with Copc gave increasing

dispersion of the complex, i.e. decreasing thickness of the Copc
layers from W-VIS analysis. This eatplains the increase of the
rate of conversion (normalized to 0.12 pmol Copc) with decreasing
loading -
The ethylbenzene oxidation tests show no significant
conversions on NaX and CoNaX in the blank experiments. The
efficiencies of the active samples are in the order

Copc < Copc/SiOz (6 wt.% Pc) < Copc/X

having the relative values

Ccpc/Si& : Copc a 10 and Copc/X : Copc = 100.

Maximum conversions for Copc/X of 20% h-’ were found. The

higher conversions on Copc/X are accompanied by much lower values
of the selectivity ratio methylphenylcarbinol/acetophenone. All
catalytic samples exhibited rapid and irreversible deactivation.
The experiments with the valence isomerization of quadricyclane
to norbornadiene give no activities for NaX, CoNaX or unsupported
Copc in the blank experiments and an activity ratio for the active
catalysts Copc/SiOr : Copc/X = 100. The catalysts Copc/SiOz giving
maximum conversions of 40% h-1 usually show deactivation
accompanied by changes in the colour, i.e. from blue to green.
This colour change was not observed for the Copc/X sample which
did not exhibit any significant deactivation, even after contact
times of several days.

DISCUSSION
Structure
The diameter of the square planar cobalt phthalocyanine
molecule along the metal nitrogen bond axis amounts to 1.25 nm and
exceeds the openings of (0.75 nm) of the
the 12-ring windows
faujasite structure, but can fit into the zeolite supercage of
1.3 nm size rref.61. This means that the zeolite-encaged complex
can be obtained only by in-situ synthesis with molecules small
enough to diffuse into the zeolite matrix.
 32 1

The preparation of Copc/X from CoNaX and dcb leads to

phthalocyanine molecules which can be either encaged or deposited
at the external surface of the zeolite crystals. The external
excess Copc is identified by scanning electron microscopy and X-
ray powder diffraction [ref.2] and can be removed completely by
the applied extraction procedures. Shpiro and coworkers [ref. 71
have applied X-ray photoelectron spectroscopy to distinguish
between internal and external Copc.
The Copc located within the zeolite matrix reduces the nitrogen
physisorption capacity. The strong decrease of these values which
are found in spite of the relatively low loadings led to the
proposal of a fractal distribution of the complex molecules in the
zeolite framework [ref. 81. However, the authors did not take into
account the contribution of zeolite fragments to the decrease of
the nitrogen adsorption. It is highly probable that the material
which reduces the nitrogen adsorption following to the removal of
the organic compounds by burning off consists of zeolite
fragments. The molecule dcb, which has a high tendency to form
complexes, might remove aluminum from zeolite framework positions
resulting in some subsequent lattice fragmentation. The assumption
that this process occurs preferentially in a shell close to the
external surface of a zeolite crystal would explain the increase
of the adsorption capacity after shaking in sodium acetate
solution which might remove some pore plugging material.
The FT-IR spectrum shows that the structure of the incorporated
Copc has changed significantly. The decrease of intensities of the
CH vibration bands might be related to the spatial constraints for
the encaged molecule. A band at 1020 cm-1 is found in the metal-
free phthalocyanine and is interpreted as NH vibration
[refs.9,101. The corresponding band of the Copc/X spectrum
indicates a protonation of the inner nitrogen atoms. Protons are
formed in the tetramerization of the dcb and take over the charge
compensation for the chelated cobalt cations. The hydrogen form of
phthalocyanine (Hzpc) has never been identified as a reaction
product from zeolite and dcb.
The interpretation of the IR spectrum of Copc/X can be
supported by comparison with the spectrum of Copc/SiOz. The SiOn
support, also containing protons from the tetramerization of dcb,
protonates the complex, as is revealed by the generation of a new
322

band at 1020 cm-1 , but does not affect the CH vibrations to such
an extent as for the Copc/X.
The EPR spectra of the encaged Copc show similarities to the
spectra of the solid crystalline material Iref.111 and the
dissolved complexes iref.121. The appearance of a free radical
signal at g = 2 is observed frequently [refs.ll,l2]. Presumably,
the conjugated dianionic macrocycle can generate paramagnetism by
electron transfer to an electron accepting impurity or site. Lewis
sites in zeolites are known to act as electron acceptors towards
organic molecules [ref.l3]. Therefore the prediction can be made
that the free radical signal will be an inherent constituent of
the spectrum of the zeolite-encaged chelate. The broad signal at g
a 2.4 (Fig. 2b) can be related to the unpaired 3d electron
associated with the cobalt atom [ref.l2]. The addition of air
will, presumably, lead to the chemisorption of dioxygen in axial
coordination at the cobalt atom, as is found for many cobalt
complexes [refs.14-17]. A signal at g = 4. indicating a high-spin
state, can be related to zeolite-coordinated cobalt ions [ref.l8].
The octet centered at g = 2.05 results from the hyperfine
interaction of the unpaired electron with the S9Co nuclear spin I
= 7/2 [ref .11].
Interesting new structural information can be gleaned from the
existence of the quintets centered at g z 2. A five-component
spectrum can be expected if a one-spin system couples with two
equivalent nuclear spins I = 1 (S = 1/2; ms = 1/2; ml = 0 , f 1;
f 2; M. = 1; MI = 0 ) . This means, however, that the four
nitrogen atoms surrounding the cobalt central ion are not
equivalent, and that the fourfold symmetry of the complex is
lowered to a twofold symmetry for the encaged chelate. The
lowering of the symmetry of Copc/X was also concluded from the
analysis of its W - V I S spectrum [ref -191- Non-equivalent nitrogen
atoms for the encaged phthalocyanine, in contrast to the external
excess complex, are also identified by X.P.S. [ref. 71.

Catalysis
Cobalt phthalocyanines are used as catalysts in the Merox-
Sweetening process [ref.201 .
It is proposed that the mercaptans
are converted to disulfides via internal redox processes at the
cobalt ion [ref.21]. The assumption that the monomer complexes are
the active species in the reaction iref.221 is supported by the
observed increase of activity with increasing dispersion of Copc
 323

on SiOz (Table 1) or in the zeolite. The fact that the oxidation

of the thiols proceeds already on cobalt ion-exchanged zeolites
supports the above-mentioned idea about the decisive role of the
cobalt ion as the active center of the catalyst.
The zeolite-encaged Copc exhibits the highest activity in the
oxidation of ethylbenzene. This can be related to the high
dispersion of the catalytically active cobalt complex in the
faujasite matrix. Presumably, the oxidation of ethylbenzene to
methylphenylcarbinol (0-CHOH-CHs) and acetophenone (O-CO-CH3
proceeds autocatalytically via hydroperoxide intermediates
[ref.22]. The usually observed induction periods and irreversible
deactivation of the catalysts are also found for Copc/X.

Fig. 3. Structures of metal phthalocyanine (1) and triazine ( 2 )

and scheme of the valence isomerization of quadricyclane to
norbornadiene ( 3 .

The valence isomerization of quadricyclane to norbornadiene

(Fig. 3) plays a role in concepts of solar energy storage
[ref.24]. Metal phthalocyanines are found to be active catalysts
for this reaction [ref.25]. The finding that this isomerization is
also catalyzed by zeolite-encaged Copc indicates reaction pathways
via transition states fitting into the supercage dimensions.
Presumably, the usually observed deactivation processes require
more bulky intermediate states, which cannot be realized for
Copc/X, resulting in the maintenance of the catalytic activity.
324

CONCLUSIONS
Cobalt phthalocyanine molecules which are irreversibly encaged
in the cavities of the faujasite lattice are obtained by in-situ
preparation. The thermally activated reaction results in
relatively low loadings and undesired side-reactions such as local
lattice fragmentation. The chelate is located inside the zeolite
matrix, as can be concluded from structural changes revealed by
IR, W-VIS, EPR and XPS, and from its contribution to the decrease
in the gas adsorption. The encaged complexes are active in various
catalytic reactions, i.e. they are accessible for reacting
molecules. The high catalytic activities for the oxidation of the
smaller molecules (ethanethiol, ethylbenzene) support a high
dispersion of Copc in the faujasite matrix.

ACKNOWLEDGEMENT
The authors gratefully acknowledge financial support by the
Deutsche Forschungagemeinschaft. This work is part of a
cooperation between the Institute of Kinetics and Catalysis of the
Bulgarian Academy of Science and the Department of Chemistry of
the University of Bremen. We are indebted to Dr. U. Hiindorf for
preparing and characterizing various samples.

REFERENCES
1 a) V.Yu. Zakharov and B.V. Romanovsky, Moscow University
Chemistry Bulletin 32,2 (1977) 16, Engl. transl., Allerton
Press, New York 1977.
b) ibid., 32.2 (1977) 74.
2 G. Meyer, D. Wehrle, M. Mohl and G. Schulz-Ekloff, Zeolites 4
(1984) 30.
3 N. Herron, G.D. Stucky and C.A. Tolman, J.C.S., Chem. Commun.
(1986) 1521.
4. E. Ignatzek, Thesis, University of Bremen 1987.
5 D. W6hrle, U. Hiindorf, G. Schulz-Ekloff and E. Ignatzek, Z.
Naturforsch. 41b (1986) 179.
6 D. Breck, Zeolite Molecular Sieves, Wiley, New York 1974.
7 E.S. Shpiro, G.V. Antoshin, O.P. Tkachenko, S.V. Gudkov, B.V.
Romanovsky and Kh.M. Minachev, in "Structure and Reactivity of
Modified Zeolites" (P.A. Jacobs et al., Eds.), Elsevier,
Amsterdam 1984; Stud. Surf. Sci. Catal., vol. 18, p. 31.
8 E. Ignatzek, P.J. Plath and U. Hiindorf, 2. physik. Chem.
(Leipzig) 268 (1987) 859.
9 H . F . Shurvell and L. Pinzuti, Can. J. Chem. 44 (1966) 125.
10 T. Kobayashi, F. Kurokava, N. Uyeda and E. Suito, Spectrochim.
Acta 26A (1970) 1305.
11 J.M. Assour and W.K. Kahn, J. Amer. Chem. SOC. 87 (1965) 207.
12 J.A. debolfo, T.D. Smith, J.F. Boas and J.R. Pilbrow, J.C.S.
Faraday Trans. I1 72 (1976) 481.
 325

13 J.C. Vedrine, A. Auroux, V. Bolls, P. Dejaifve, C. Naccache, P.

Wierzchowski, E.G. Derouane, J.B. Nagy, J.-P. Gilson, J.H.C.
van Hooff, J.P. van den Berg and J. Wolthuizen, J. Catal. 59
(1979) 248.
14 T.D. Smith and J.R. Pilbrow. Coord. Chem. Rev. 39 (1981) 295.
15 J.H. Lunsford, Catal. Rev.-Sci.Eng. 12 (1975) 137.
16 N. Herron, Inorg. Chem. 25 (1986) 4714.
17 W. Lubitz, C.J. Winscom, H . Diegruber and R. Meseler, Z.
Naturforsch. 42a (1987) 970.
18 I.D. Mikheikin, 0.1. Brotikowski, G.M. Zhidomirov and V.B.
Kazanskii, Kinetika i Kataliz 12 (1971) 1442.
19 H. Diegruber and P.J. Plath, Z. phys. Chem. (Leipzig) 266
(1985) 641.
20 R.A. Meyers (Editor), "Handbook of Petroleum Refining
Processes", McGraw-Hill, New York 1986.
21 J. Zwart, H.C. van der Weide, N. Brbker, C. Rummens, G.C.A.
Schuit and A.L. German, J. Mol. Catal. 3 (1977/78) 151.
22 T.P.M. Beelen, C.O. da Costa Gomez and M. Kuijer, J. Royal
Netherl. Chem. SOC. 98,lO (1979) 521.
23 A . Kropf, Lieb. Anal. Chem. 637 (1960) 73.
24 H.D. Scharf, J. Fleischhauer, H . Leismann, J. Ressler, W.
Schleker and R. Weitz, Angew. Chem. 91 (1979) 696.
25 J. Manassen, J. Catal. 18 (1970) 38.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

SELECTIVE REDUCTION OF NITRIC OXIDE OVER ZEOLITE-SUPPORTED I R I D I U M CATALYST

--
ROAR MYRDALa) and STEIN KOLBOE
Department of Chemistry, U n i v e r s i t y o f Oslo, P.O. Box 1033, B l i n d e r n ,
N-0315 Oslo 3, Norway

ABSTRACT
W i t h t h e goal o f f i n d i n g s u i t a b l e c a t a l y s t s f o r r e d u c i n g NOx b y CO i n
oxygen-containing atmosphere, t h e NaX z e o l i t e ( L i n d e 13-X) was i m p r e g n a t e d w i t h
i r i d i u m b y i o n exchanging w i t h (Ir(NH3)5C1)C1 2. The c a t a l y s t d i s p l a y e d h i g h
c a t a l y t i c a c t i v i t y and s e l e c t i v i t y f o r r e d u c i n g NO a l s o i n t h e presence of
oxygen w i t h f pronounced optimum t e m p e r a t u r e c l o s e t o 29OoC a t a space v e l o c i t y
GHSV=40000h- where 85% NO c o n v e r s i o n was o b t a i n e d u s i n g a f e e d gas c o n t a i n i n g
200 ppm NO, 1%C O and 3.6 % 02. W i t h o x y g e w f r e e f e e d gas 1 0 0 % NO r e d u c t i o n
was o b t a i n e d f r o m 230 OC on. A d s o r p t i o n / d e s o r p t i o n s t u d i e s o f NO, CO and 02
have a l s o been c a r r i e d out.

INTRODUCTION
The e q u i l i b r i u m c o n c e n t r a t i o n o f n i t r o g e n o x i d e s NO and NO2 (= NO,) in air
i s e x t r e m e l y l o w a t o r d i n a r y temperatures. B u t t h e e q u i l i b r i u m c o n s t a n t f o r t h e
r e a c t i o n N2 + O2 = 2N0 i n c r e a s e s s t r o n g l y w i t h i n c r e a s i n g t e m p e r a t u r e and a t
2000 K i t i s a l r e a d y 4 ~ 1 0 - ~NO
. i s t h u s b e i n g formed d u r i n g a l l h i g h
temperature combustion processes. Besides i t s f o r m a t i o n b y n a t u r a l processes,
t h e anthropogenic component has i n c r e a s e d m a r k e d l y d u r i n g t h e l a s t years, due
m a i n l y t o i n d u s t r y and t h e widespread use o f cars.
It has become i n c r e a s i n g l y c l e a r t h a t NO, e i t h e r d i r e c t l y o r through
p r o d u c t s due t o NO, has d e l e t e r i o u s e f f e c t s on p l a n t as w e l l as a n i m a l l i f e
and i s one o f t h e most i m p o r t a n t p o l l u t a n t s ( r e f . 1).
The c o n t r o l o f NOx i n t h e atmosphere i s m o s t e f f i c i e n t l y c a r r i e d o u t a t i t s
source. Since NOx i s u n s t a b l e one m i g h t l o o k f o r a c a t a l y s t f o r i t s decomposi-
t i o n i n t o N2 and 02, b u t a t p r e s e n t i t appears more p r o f i t a b l e t o l o o k f o r
c a t a l y s t s f o r r e d u c t i o n o f NOx b y a r e d u c i n g agent l i k e CO and/or r e s i d u a l
hydrocarbons w h i c h a r e a l r e a d y p r e s e n t i n m o t o r exhausts. I n l a r g e i n d u s t r i a l
p l a n t s , such as power s t a t i o n s , ammonia i s a t p r e s e n t t h e p r e f e r r e d r e d u c i n g
agent, p a r t l y because t h e f l u e gas i s u s u a l l y q u i t e r i c h i n oxygen and p o o r i n

a) On l e a v e o f absence f r o m The Norwegian Defence Research Establishment.

328

reducing material, making reduction d i f f i c u l t ; and p a r t l y because t h e addition

of ammonia t o f l u e gas i s f a i r l y straightforward (ref. 2).
I n motor c a r s , ammonia addition i s impracticable and t h e r e a r e already
reducing agents present. The oxygen excess i s smaller, thus d i r e c t treatment of
the exhaust gases i s t h e preferred method i f oxygen excess can be k e p t small
enough. T h u s a main objective in pollution control and the study of c a t a l y t i c
reduction of NO by CO i s t o find a c a t a l y s t a b l e t o operate in an oxidizing
atmosphere. The two competing r e a c t i o n s a r e (refs. 3-5):
2CO t 2NO + 2C02 t N 2 and 2CO t 02--2C02.
I t has been reported t h a t I r supported on alumina o r s i l i c a c a t a l y z e t h e NO-
CO reaction in the presence of oxygen (refs. 3-6). I t i s known t h a t i n some
cases metals supported in z e o l i t e pores acquire enhanced c a t a l y t i c p r o p e r t i e s ,
hence i t was decided t o i n v e s t i g a t e t h e p r o p e r t i e s o f zeolite-supported I r -
c a t a l y s t s . This c a t a l y s t system has not been t e s t e d on t h e NO reduction and i s
l i t t l e studied in general, a p a r t from t h e works of Gelin e t a l . ( r e f s . 7,8).

EXPERIMENTAL
Catalyst preparation
The c a t a l y s t s were made according t o t h e procedure given by Gelin e t a l .
( r e f . 7) by ion exchanging batches of 2.0 g Linde-13X with (Ir(NH3)5C1)C12
(Johnson Mattheys Co) dissolved in 200 ml d i s t i l l e d water. Three d i f f e r e n t
batches were made using I r - s a l t m o l a r i t i e s 0.026, 0.005 and 0.001.
The ion exchange was c a r r i e d out under stirring (1 h) a t 75OC. The ion-
exchanged z e o l i t e was then recovered by f i l t e r i n g and f i n a l l y washed with
d i s t i l l e d water u n t i l chloride free. Before use t h e c a t a l y s t was a c t i v a t e d by
c a l c i n a t i o n in a i r and reduction in hydrogen a t 250 OC.

Characterization
The elemental composition of the c a t a l y s t s was analyzed (by AAS and ICP)
before and a f t e r ion exchange. 100 mg z e o l i t e was dissolved i n 2.5 ml conc. HF.
Saturated boric acid (25 ml) was t h e r e a f t e r added t o bind surplus HF and
prevent possible l o s s of v o l a t i l e s i l i c o n fluoride. D i s t i l l e d water was then
added t o 100 ml. Stoppered p l a s t i c f l a s k s were used throughout.
The i d e n t i t y and c r y s t a l l i n i t y of t h e z e o l i t i c material were checked by X-
ray d i f f r a c t i o n .
Nitrogen adsorption capacity and equivalent surface areas were determined in
an ordinary BET type instrument. Crystal morphology and s i z e , before and a f t e r
ion exchanging and use a s c a t a l y s t , were studied i n a P h i l i p s SEM 515 scanning
e l e c t r o n microscope.
Metal dispersion was estimated by H2, COY NO and O2 adsorption and X-ray
 329

diffraction line broadening.

Adsorption and reaction studies
Reaction. The reactants were taken from compressed gas cylinders containing
dilute mixtures with main component being nitrogen - supplied and analyzed by
Norsk Hydro. Reactant composition and feed rate were controlled by mixing gases
from two or three gas cylinders using flow controllers and meters.
The experiments were standardized to use about 300 m g catalyst with a feed
rate ( reactants t nitrogen carrier gas ) of 200 ml(STP)/min. Prior t o use the
catalysts were reduced in flowing hydrogen ( 8 % in He) at 250 OC. Conver-
sions and rates were obtained from differences in entrance and exit gas streams
which were continuously analyzed.
Adsorption. Adsorption properties for NO, CO, and O2 of the Ir catalyst
was studied by several instruments. Temperature-programmed desorption (TPD)
were studied using the flow reactor system. Gravimetric adsorption studies were
performed in a Stanton Redcroft STA 785 thermal analysis instrument on 30 m g
samples, and in a vacuum balance on 200 m g samples.
-
Gas analysis. The gas (entering and) leaving the reactor w a s analyzed
continuously utilizing the following methods and instruments.
CO and COP; IR: Leybold-Heraeus Binos 1. (CO; 0-5 % : COP; 0-20%)
NO and (NO+N02); Chemiluminiscence: Bendix 8102 NO/NOx analyzer. (0-500 ppm)
02; paramagnetism: Sybron/Taylor Servomex O2 analyzer OA 570. (0-100%)
The instruments were periodically checked for drift and possible need for
recalibration. Ample time was a1 lowed for stabilization before measurements.

RESULTS
Ca ta 1 ys ts
The main analytical data of the original X-zeolite and the three catalysts
which were obtained after carrying out ion exchange are given in Table 1.

TABLE 1
Elemental composition (weight percent) o f the 13-X zeolite and
the Ir-exchanaed catalystsa).
Ca ta 1 ys t
desiqnation Ir Si A1 Na Ca Fe
Na-X 0 18.8 12.9 10.8 0.065 0.012
Ir-1.36 1.36 17.6 12.1 9.6 - -
Ir-6.41 6.41 16.5 11.3 7.7 - -
Ir-14.4 14.4 15.5 10.6 5.2 - -
a) The analyses are based on zeolites exposed to humid air,
i.e. they contain about 23% water.
330

N i t r o g e n a d s o r p t i o n a c c o r d i n g t o t h e BET p r o c e d u r e on t h e Na-X and t h e I r -

14.4 ( c a l c i n e d a t 50OoC) gave t h e e q u i v a l e n t s u r f a c e areas 788 and 651 m2/g.
Renewed measurements on t h e Ir-14.4 a f t e r use i n a r e a c t o r t e s t a t up t o 500 OC

f o r 100 h gave 645 m2/g. A c o n s i d e r a b l e p a r t o f t h e area r e d u c t i o n a f t e r m e t a l

l o a d i n g i n s i d e t h e p o r e s i s a consequence o f t h e i n c r e a s e d mass o f t h e u n i t
c e l l . I t may t h u s be c o n c l u d e d t h a t t h e s u r f a c e a r e a o f t h e z e o l i t e r e m a i n s
e s s e n t i a l l y u n p e r t u r b e d b y t h e t r e a t m e n t t o w h i c h i t i s subjected.
One purpose o f c a r r y i n g o u t c a t a l y t i c r e a c t i o n s w i t h m e t a l s i m p r e g n a t e d i n
z e o l i t e s i s t o o b t a i n a b e t t e r metal dispersion than m i g h t be obtained w i t h
o t h e r m e t a l c a r r i e r s . T h i s h i g h d i s p e r s i o n i s b y no means assured, however,
and much e f f o r t has been devoted t o f i n d t e c h n i q u e s l e a d i n g t o h i g h m e t a l
d i s p e r s i o n s and t o f i n d methods t o c h a r a c t e r i z e i t ( r e f . 9).
I t i s n o t t h e o b j e c t i v e o f t h i s work t o go d e e p l y i n t o t h i s problem, b u t i t
was deemed i m p o r t a n t t o g a i n a p p r o x i m a t e knowledge a b o u t i n i t i a l m e t a l
d i s p e r s i o n s i n t h e c a t a l y s t s and t h e e v o l u t i o n o f t h i s d i s p e r s i o n ( p o s s i b l e
a g g l o m e r a t i o n ) as t h e c a t a l y s t underwent t h e v a r i o u s t r e a t m e n t s .
The most e x t e n s i v e s e t o f measurements was o b t a i n e d b y a d s o r p t i o n o f H2, O2
and CO a t room temperature. The r e s u l t s a r e g i v e n i n T a b l e 2 w h i c h shows H-
atom, 0-atom and CO m o l e c u l e p e r I r - a t o m f o r t h e t h r e e c a t a l y s t s . A n c i l l a r y
a d s o r p t i o n e x p e r i m e n t s on Na-X showed z e r o a d s o r p t i o n o f t h e t h r e e gases, t h u s
t h e a d s o r p t i o n w h i c h t a k e s p l a c e i s caused b y t h e presence o f i r i d i u m .

TABLE 2
A d s o r p t i o n o f H2, O2 and CO a t room t e m p e r a t u r e on
ir i d i um-zeol it e c a t a l y s t s .
Calcinati n -H -O C J
Catalyst temp. /OCa 9 Ir Ir Ir
Ir-1.36 250 1.0 0.43 0.59
Ir-6.41 250 1.1 0.42 0.50
I1
500 - 0.49 0.33
Ir-14.4 500 - 0.39 0.18
a ) C a l c i n a t i o n i n a i r o v e r n i g h t a t i n d i c a t e d temperature. R e d u c t i o n
t o m e t a l l i c s t a t e b y f l o w i n g hydrogen (8 % i n He) a t 250 OC
f o r 1 h.

I t has been p o i n t e d o u t t h a t t h e e s t i m a t e s o f m e t a l d i s p e r s i o n b y gas

a d s o r p t i o n easurements have a l a r g e i n h e r e n t u n c e r t a i n t y ( r e f . 10). The e x a c t
s t o i c h i o m e t r y o f t h e r e a c t i o n i s n o t known, and m e t a l atoms w i t h i n t h e z e o l i t e
 331

cage may n o t be a c c e s s i b l e t o t h e a d s o r b i n g gas. Furthermore, m e t a l c l u s t e r s

w i t h u p t o about 23 atoms may have 22 o f them on t h e surface, so t h e a d s o r p t i o n
method i s n o t a b l e t o d i s t i n g u i s h c l u s t e r s o f t h i s s i z e and s m a l l e r .
L e a v i n g these f i n e r p o i n t s aside, t h e i n f o r m a t i o n o b t a i n e d b y t h e a d s o r p t i o n
measurements r e p o r t e d i n Table 2 i s t h a t t h e m a j o r i t y o f t h e i r i d i u m atoms have
n o t agglomerated and a r e a c c e s s i b l e t o gas phase molecules.
I n f o r m a t i o n a b o u t p a r t i c l e s i z e may a l s o be o b t a i n e d f r o m measurements o f l i n e
broadening o f X-ray d i f f r a c t i o n l i n e s b y means o f t h e S c h e r r e r e q u a t i o n
( r e f . 11). The t w o f o r m s o f Ir-6.41 i n Table 2 d i s p l a y e d weak, broad Ir-
d i f f r a c t i o n l i n e s . The broadening l e d t o p a r t i c l e d i a m e t e r e s t i m a t e s o f 4 and
10 nm r e s p e c t i v e l y f o r t h e t w o f o r m s w h i c h had been c a l c i n e d a t 250 and 50OoC.
These e s t i m a t e s a r e h i g h e r t h a n t h e r e s u l t s o b t a i n e d f r o m a d s o r p t i o n
experiments. Such a d i s c r e p a n c y i s n o t unexpected, however, i f t h e r e i s a
pronounced spread i n p a r t i c l e sizes. The m a i n p a r t o f t h e d i f f r a c t i o n l i n e s
w i l l b e dominated b y t h e l a r g e s t p a r t i c l e s . The small p a r t i c l e s w i l l c o n t r i b u t e
m a i n l y t o t h e base o f t h e d i f f r a c t i o n l i n e - i f a t a l l - and t h e i r contribution
t o t h e l i n e broadening i s u n d e r e s t i m a t e d u n l e s s a f u l l l i n e p r o f i l e a n a l y s i s i s
c a r r i e d out ( r e f . 11).

The NO/CO
-- reaction
The main o b j e c t i v e i n t h i s work i s t o f i n d p o s s i b l y a c t i v e c a t a l y s t s f o r
NOx c o n t r o l . I t was t h e r e f o r e decided t h a t t h e r e a c t o r f e e d s h o u l d have a NO
c o n t e n t s i m i l a r t o exhaust gases f r o m c o m b u s t i o n processes. Feeds c o n t a i n i n g
0.02 % 200 ppm on a volume (i.e. m o l a r ) b a s i s were t a k e n t o r e p r e s e n t a
t y p i c a l combustion gas.
Although most r u n s were c a r r i e d o u t w i t h about 1 % CO as r e d u c i n g a g e n t and
w i t h oxygen present, i t was t h o u g h t t o be o f i n t e r e s t t o c a r r y o u t a r e a c t i o n
s e r i e s w i t h o u t added oxygen and u s i n g a much s m a l l e r c o n c e n t r a t i o n o f CO (500
ppm) t h a n i s u s u a l l y met i n combustion gases. The c o n v e r s i o n s o f NO vs.
temperature f o r t h i s r e a c t i o n system and a r e p r e s e n t a t i v e c u r v e f o r a f e e d
c o n s i s t i n g o f N O / C 0 / O 2 a r e shown i n F i g . 1.
c
0
4
+,
u
a
U
m
L

0
z
x
Fig. 1. E f f i c i e n c y o f c a t a l y s t (Ir-1.36)
f o r r e d u c i n g NO a t v a r i o u s temperatures.
NO i n f e e d 200 ppm. C u r v e A: 500 ppm C O Y 100 140 180 220 260 300
No oxygen. C u r v e B: 1.05 % C O Y 3.65 % 02. Temperature/ O C
332

I t i s seen t h a t i n the oxygen-free system (curve A) a much h i g h e r NO

conversion i s obtained than when oxygen (curve B) i s present. NO i s 100 %
reduced t o n i t r o g e n a t 230 OC i n absence o f oxygen, b u t o n l y 15 % when oxygen
i s present. Furthermore, i n t h e l a t t e r case conversion never exceeds 85 %.
Since 100 % conversion i s e a s i l y obtained i n the oxygen-free case i t i s
c l e a r t h a t the r e a c t i o n system i s e s s e n t i a l l y f r e e o f d i f f u s i o n e f f e c t s , and
the 85 % conversion l i m i t i n the presence o f oxygen i s n o t caused b y d i f f u s i o n
1i m i t a t i o n s .
An Arrhenius p l o t based on the low-conversion p a r t o f curve A gives an
apparent a c t i v a t i o n energy o f 130 kJ/mol.
The m a j o r i t y o f the measurements were - . I

:
~

c a r r i e d out i n NO/C0/O2 systems. The 1.oc- .200

n
\
C
r e s u l t s o f a s e r i e s o f such measurements
w i t h feed gas composition NO;C0;02 = 200 -150
ppm; 1.05 %; 3.65 %; ( b a l a n c e N2) a r e
given i n Fig. 2. The d i r e c t l y measured
e x i t concentrations o f CO, NO, and NO2 Q50 .
z
from 18 runs a t various temperatures i n
0 z
the range 200 t o 500 OC are shown. Care
425 -
was taken t h a t t h e measurements should 'j
¶
r e f l e c t a steady state. This could f o r O

low temperatures r e q u i r e more than 30 h, Y , , , ,

200 250 300 350 400 450 500
although a f t e r the f i r s t few hours t h e Temperature/ OC

system changed o n l y slowly. A f t e r each

Fig. 2. Composition o f e x i t gases from
change i n r e a c t i o n temperatures 10 '0 20 r e a c t o r i n the temperature range 200-
h was t y p i c a l l y allowed before making 50OoC. C a t a l y s t Ir-1.36. Feed: 200
ml/min c a r r i e r gas (N ) c o n t a i n i n g
f i n a l measurements. The sequence o f 200 ppm NO; 1.05 % &and 3.65 % 0,. L
temperatures was taken a t random t o
ensure t h a t a slow e v o l u t i o n o f c a t a l y s t a c t i v i t y w i t h t i m e d i d n o t v i t i a t e the
results. This procedure a t the same t i m e showed t h a t t h e c a t a l y s t a c t i v i t y i s
highly stable.
It i s worth n o t i n g t h a t CO and NO decreases i n a very p a r a l l e l manner w i t h
increasing temperature u n t i l a l l CO i s o x i d i z e d t o CO2 a t about 275 OC. A t this
temperature t h e r e i s s t i l l some unconverted NO, and t h e f i r s t traces o f NO2
appears. As t h e temperature increases f u r t h e r the NO l e v e l continues t o f a l l
slightly before an increase s t a r t s . NO2, however, increases s t r o n g l y w i t h
increasing temperature, and a t 300 OC t h e r e i s 40 ppm i n the e x i t gas. Total
NOx reduction t h e r e f o r e shows a very sharp maximum a t 275-280 OC.

The NO2 concentration has a very broad maximum from 300 t o 400 OC. Above
35OoC t h e components NO/N02/02 are i n v i r t u a l e q u i l i b r i u m . The decreasing NO2
 333

c o n c e n t r a t i o n above 400 OC i s t h e r e f o r e n o t due t o a k i n e t i c process r e l a t e d t o

c a t a l y t i c a c t i v i t y . It s h o u l d be emphasized t h a t NO2 was n o t formed w i t h o u t
c a t a l y s t . We b e l i e v e t h a t i t i s no c o i n c i d e n c e t h a t NO2 appears simultaneously
w i t h t h e complete o x i d a t i o n o f CO.
F u r t h e r measurements w i t h o t h e r oxygen c o n c e n t r a t i o n s i n t h e f e e d
i n d i c a t e d t h a t i n a l l cases 275-300 OC were optimum t e m p e r a t u r e s f o r NO,
r e d u c t i o n . A p o s s i b l e dependence upon space v e l o c i t y was n o t i n v e s t i g a t e d .
The c a t a l y s t s a b i l i t y t o s e l e c t i v e l y
reduce NO b y CO i n t h e presence o f an excess
o f oxygen was i n v e s t i g a t e d b y a s e r i e s o f
experiments w i t h d i f f e r e n t oxygen c o n t e n t
i n t h e feed. A l l t h e s e e x p e r i m e n t s were
based on 200 ppm NO and 0.5-1 % CO a t t h e
e s t a b l i s h e d optimum temperature, 285 OC. The 0 40
z
r e s u l t i s d i s p l a y e d i n Fig. 3. I n agreement x 20
with established practice, the r a t i o
R=(202+NO)/C0 ( = o x i d a n t / r e d u c t a n t r a t i o ) i s
I I I I
0 12
4 8
16 20
used t o i n d i c a t e t h e e x t e n t o f oxygen excess OxidarWRaductant r a t i o R
( r e f . 12). The f i g u r e shows c l e a r l y t h e v e r y Fig. 3. C a t a l y s t e f f i c i e n c y
f o r r e d u c i n g NO; dependence
high s e l e c t i v i t y o f the I r / z e o l i t e cataiyst. on o x i d a n t / r e d u c t a n t r a t i o
Even f o r a t w e n t y f o l d excess o f o x i d a n t o v e r R=(202 t NO)/CO. C a t a l y s t : I r -
1.36. R e a c t i o n temperature:
r e d u c t a n t 60 % c o n v e r s i o n i s obtained, and 285 OC. Feed: 200 m l / m i n N2
f o r R = 4 85 % c o n v e r s i o n i s o b t a i n e d . c o n t a i n i n g 200 ppm NO, 0.5-1%
CO and v a r i a b l e c o n c e n t r a t i o n s
o f 02.
A d s o r p t i o n / d e s o r p t i on on c a t a l y s t
I n an e f f o r t t o g a i n f u r t h e r u n d e r s t a n d i n g o f t h e c a t a l y t i c process more
d e t a i l e d experiments on t h e a d s o r p t i o n and d e s o r p t i o n have been c a r r i e d o u t .
Rate o f a d s o r p t i o n . These e x p e r i m e n t s were c a r r i e d o u t i n a vacuum b a l a n c e
--
u s i n g ZOO mg o f adsorbent b y r e c o r d i n g t h e w e i g h t change upon i n j e c t i o n o f a
small q u a n t i t y o f a d s o r b i n g gas (3 m l STP) l e a d i n g t o a p r e s s u r e o f 2 mbar i n
t h e p r e v i o u s l y evacuated w e i g h t chamber. The a d s o r p t i o n t o o k p l a c e a t room
temperature under f a i r l y c o n s t a n t p r e s s u r e (COY NO o r 02), a b o u t 2 mbar. The
main r e s u l t s are: The a d s o r p t i o n i s f a s t . I n a l l cases 50 % o r more o f t h e
q u a n t i t y adsorbed a f t e r 100 - 200 s i s a l r e a d y adsorbed a f t e r 10 s. Our
p r e v i o u s e x p e r i e n c e w i t h a d s o r p t i o n i n z e o l i t e s t e l l s us t h a t t h e u p t a k e o f
adsorbate i n these e x p e r i m e n t s i s a t l e a s t i n p a r t d e t e r m i n e d b y d i f f u s i o n
r e s i s t a n c e , so t h e i n t r i n s i c a d s o r p t i o n r a t e i s a c t u a l l y s t i l l higher. A t a l l
temperatures where t h e NO/CO r e a c t i o n s were a c t u a l l y m o n i t o r e d (200-5OO0C), t h e
a d s o r p t i o n r a t e p e r se was n o t l i m i t i n g . I n t h e case o f CO o r 02, e q u i l i b r i u m
a d s o r p t i o n was reached i n 100 s ; NO on t h e o t h e r hand d i s p l a y e d a v e r y s l o w
334

adsorption continuing f o r a v e r y long t i m e a f t e r t h e i n i t i a l f a s t adsorption.

The e q u i l i b r i u m uptakes a r e r e p o r t e d i n T a b l e 2. The gases CO, NO and O2 a r e
a l l s t r o n g l y adsorbed. A t room t e m p e r a t u r e o n l y a s m a l l p a r t w i l l d e s o r b even
a f t e r p r o l o n g e d evacuation.
A d s o r p t i o n e x p e r i m e n t s a t h i g h e r t e m p e r a t u r e s (250-300°C) were c a r r i e d o u t
i n t h e thermal a n a l y s i s instrument b y i n j e c t i n g small q u a n t i t i e s o f t h e
a d s o r b i n g gas i n t o a c a r r i e r gas s t r e a m (N2). These e x p e r i m e n t s were p e r f o r m e d
on t h e Ir-6.41 ( c a l c i n e d and reduced i n s i t u ) .
The u p t a k e o f oxygen a t 25OoC
was c o n s i d e r a b l y h i g h e r t h a n a t
room temperature. A p r e v i o u s l y
reduced sample was f o u n d t o adsorb
oxygen c o r r e s p o n d i n g t o an a t o m i c
i 0.1 o . o ~ ~ m , c
r a t i o O/Ir=1.5 a f t e r a few m i n u t e s
exposure t o oxygen, a n d t o E

2 0.1
O/Ir=1.8 a f t e r a more p r o l o n g e d
exposure. Due t o e x p e r i m e n t a l d i f - -
Y
6 0.2
g o 25 50 75 100
ficulties a final equilibrium Tlns/nln

v a l u e was n o t e s t a b l i s h e d , b u t
a p p a r e n t l y t h e r a t i o 2 correspon-
Fig. 4. Weight changes ( l o w e r c u r v e ) o f
d i n g t o I r 0 2 would r e s u l t . c a t a l y s t (Ir-6.41; 30 mg; p r e v i o u s l y
Fig. 4 shows t h a t a t 250 OC o x i d i z e d ) upon a d d i t i o n o f hydrogen and
oxygen t o c a r r i e r gas a t 250 OC. Upper
o x i d a t i o n / r e d u c t i o n o f t h e Ir curve d i s p l a y s t h e simultaneous heat
p a r t i c l e s was a process t a k i n g e v o l u t i o n i n t h e c a t a l y s t bed.
p l a c e r a t h e r e a s i l y . I t shows
t h e w e i g h t o f a c a t a l y s t sample (30 mg, o x i d i z e d s t a t e ) , and h e a t e v o l u t i o n i n
t h e sample as f u n c t i o n s of t i m e . A t 12 min a b o u t 2 m l H2 i s added t o t h e
c a r r i e r gas. The h e a t c u r v e shows t h a t a f a s t e x o t h e r m i c p r o c e s s i s t a k i n g
place, and a decrease i n w e i g h t i s observed due t o f o r m a t i o n o f w a t e r w h i c h i s
desorbed a t t h i s temperature. The s m a l l e n d o t h e r m i c d i p i s caused b y d e s o r p t i o n
o f water. One s i n g l e p u l s e o f hydrogen w h i c h g i v e s a hydrogen ambiance f o r a
few m i n u t e s i s s u f f i c i e n t f o r a l m o s t c o m p l e t e r e d u c t i o n . F u r t h e r p u l s e s have
been found t o have a l m o s t no e f f e c t , t h e e x o t h e r m i c peak becoming q u i t e s m a l l .
One s i n g l e p u l s e o f oxygen ( a t 45 min) l e a d s t o a l m o s t c o m p l e t e r e o x i d a t i o n .
The oxygen i s s t r o n g l y bound; no decrease i n w e i g h t was observed i n f l o w i n g
n i t r o g e n . Hydrogen appears l e s s s t r o n g l y bound. Weighing c o u l d n o t b e done w i t h
s u f f i c i e n t p r e c i s i o n , b u t i t was observed t h a t i f a s m a l l p u l s e o f oxygen was
added o n l y a few m i n u t e s a f t e r a hydrogen pulse, t h e u s u a l w e i g h t i n c r e a s e was
i m m e d i a t e l y observed. B u t i n t h i s case a w e i g h t decrease f o l l o w e d , s i m i l a r t o
t h e one observed a f t e r hydrogen a d d i t i o n t o t h e o x i d i z e d system, b r i n g i n g t h e
 335

we ight back t o t h e pre-oxygen value. F u r t h e r work showed t h a t t h e r e a c t i o n

2H2 t O2 -2H20 t o o k p l a c e a l r e a d y a t room temperature.

TPD experiments. I n many cases TPD i s a method which g i v e s f a r b e t t e r

i n s i g h t i n t o a d s o r p t i o n / d e s o r p t i o n b e h a v i o u r than i s o b t a i n e d f r o m a d s o r p t i o n
isotherms i f these measurements a r e c a r r i e d o u t w i t h o n l y moderate accuracy.
The equipment used f o r s t u d y o f t h e CO/NO r e a c t i o n was w e l l s u i t e d f o r TPD
experiments. A summary o f some r e s u l t s on NO adsorption/TPD a r e g i v e n i n
Fig. 5. I t i s seen t h a t t h e r e a r e a t
l e a s t t h r e e adsorbed s t a t e s which, w i t h
t h e chosen e x p e r i m e n t a l set-up, show
peaks a t ca. 100, 1 8 0 a n d 400 OC. The
d i f f e r e n c e between t h e t h r e e curves i s
t h a t c u r v e A was o b t a i n e d a f t e r 1 h
a d s o r p t i o n f r o m a 200 ppm NO stream, B
was o b t a i n e d a f t e r 2 h a n d C a f t e r 4 h.
Curves A and B were o b t a i n e d w i t h o n l y
10 m i n N2 f l u s h i n g b e f o r e t h e s t a r t o f
Temperature/'C t h e TPD run, whereas C was s t a r t e d a f t e r
Fig. 5. Thermal d e s o r p t i o n s p e c t r a of 1 h f l u s h i n g . A more d e t a i l e d t r e a t m e n t
No adsorbed (from ppm No in N2) o f t h e above and o t h e r r e s u l t s on TPD
a t room t emp era t u r e on Ir-1.36.
Curves A, B and C r e l a t e t o adsorp- w i l l b e g i v e n l a t e r ( r e f . 13).
t i o n t i m e s 1, 2 a n d 4 h.

DISCUSSI O N
I ridium-bas ed c a t a l y s t s have been s u r p r i s i n g l y l i t t l e s t u d i e d f o r NO
r e d u c t i o n b y CO. Reported s t u d i e s have used a lumina (ref s. 3-5) and s i l i c a
support s ( r e f . 6).
P re v ious a ut h o r s m o s t l y worked a t h i g h t e mperat ures and a l o w oxygen excess.
The NO r e d u c t i o n s e l e c t i v i t y was discussed i n t e r m s o f t h e p a r t i t i o n i n g o f CO
between NO and O2 ( r e f . 3,5). The r e a s o n i n g went along t h e f o l l o w i n g l i n e s :
Based on t h e assumption t h a t NO and D2 r e a c t s w i t h CO a c c o r d i n g t o t h e eqns.
d(NO)/dt = -kl(NO)(CO) (1)
d(Op)/dt = -k2(Op)(CO) (2)
i t i s seen t h a t
d l n(NO)/dl n(0 2)= kl/k2 (3)
T h i s r a t i o t he n d e t e r m i n e s t h e p a r t i t i o n o f CO between NO and 02. Eqn. 3 i s
integrated t o .
1n((NO)/(NO),) = (kl/k2)ln((o,)/(o,),) (4)
( S u b s c r i p t o r e f e r s t o i n l e t concentrations.) By v a r y i n g t h e space v e l o c i t y
eqn. 4 can be used t o d e t e r m i n e t h e r a t i o k l / k 2, and a v a l u e o f about 3 was
336

r e p o r t e d ( r e f . 3,5). I n o u r case t h e space v e l o c i t y was n o t v a r i e d , b u t an

e s t i m a t e f o r t h e p a r t i t i o n i n g r a t i o can s t i l l be obtained.
I n a case l i k e t h e one p r e s e n t e d i n F i g . 2 (02)i s much h i g h e r t h a n (NO),
and a l s o much h i g h e r than (CO). Consequently (02) remains e s s e n t i a l l y constant
and t h e major r e a c t i o n r o u t e o f CO i s o x i d a t i o n b y 02. Taking t h i s and t h e
s t o i c h i o m e t r i c f a c t o r 2 i n t o account, eqn. 2 i s r e w r i t t e n
-
d(CO)/dt = 2k2(02)(CO) (5)
Combination o f eqns. 1 and 5 g i v e s
d(CO)/d(NO) = ( 2 k 2 / k l ) ( ( 0 2 ) / ( N O ) ) (6)
T h i s eqn. i n t e g r a t e s t o
XCO = -
( 2 k 2 / k l ) ( ( 8 2 ) / ( c o ) o ) l n(l-xNO) - (7)
where x represents f r a c t i o n a l conversion, and (02) t h e mean c o n c e n t r a t i o n
through t h e bed - i n this case m a r g i n a l l y s m a l l e r than ( 0 ~ ) ~ .
Varying conversions were o b t a i n e d by changing t h e r e a c t i o n temperature. By
u t i l i z i n g eqn. 7 and t h e CO and NO conversion p o i n t s i n t h e range 200-270°C as
given i n Fig. 2, e s t i m a t e s of t h e p a r t i t i o n i n g r a t i o , which increased r e g u l a r l y
from 3.9 a t 200' t o 6.3 a t 27OoC, were obtained. T h i s i n d i c a t e s t h a t t h e
i r i d i u m / z e o l i t e system i s a more s e l e c t i v e c a t a l y s t than t h e Ir/A1203 system.
The same a p p l i e s t o a comparison w i t h Knight's r e s u l t s ( r e f . 6). He worked w i t h
Ir/Si02 and obtained 20 % removal f o r R = 8, where t h e I r / z e o l i t e c a t a l y s t
removed more t h a n 75 % o f NO.

REFERENCES
1 W. Strauss and S. J. Mainwaring, A i r P o l l u t i o n ,
E. Arnold. London. 1984. DD 38-49.
2 A. G. Clarke and A. Wiliiams, I n s t . Chem. Enq. - Smp. - . Series
No 96 (1986) 261.
3 S . J. Tauster and L. L. M u r r e l l , J. C a t a l y s i s 41 (1976) 192.
4 S. J. Tauster and L. L. M u r r e l l . J. C a t a l v s i s 53 (19781 260.
5 K.C. T a y l o r and J.C. S c h l a t t e r , - J . C a t a l y i i s 63 (i980)'53.
6 S.J. Knight, B r i t i s h P a t e n t s p e c i f i c a t i o n 1 581 628 (1980).
7 M. Dufaux, P. G e l i n and C. Naccache, i n B. I.I m e l i k , C. Naccache, Y. Ben
T a a r i t , J. C. Vedrine, G. Coudurier and H. P r a l i a u d ( E d i t o r s ) ,
C a t a l y s i s b y Z e o l i t e s , E l s e v i e r , Amsterdam, 1980, pp. 261-271.
8 P. Gelin, G.Coudurier, Y. Ben T a a r i t and C. Naccache,
J. C a t a l y s i s 70 (1981) 32.
9 Lemaitre, P. G. Menon and F. Delannay, i n F. Delannay (Editor),
C h a r a c t e r i z a t i o n o f heterogeneous c a t a l y s t s , Marcel Dekker, New York,
1984, pp 299-365.
10 P. G a l l e z o t and G. Bergeret, i n P. A. Jacobs, N. I . Jaeger, P. J i r u t and
G. S c h u l t z - E k l o f f ( E d i t o r s ) , Metal m i c r o s t r u c t u r e i n z e o l i t e s ,
E l s e v i e r , Amsterdam, 1982, pp 167-177.
11 P. G a l l e z o t , i n J. R. Anderson and M. Boudart ( E d i t o r s ) , C a t a l y s i s -
Science and~Technology, Springer, B e r l i n , v o l . ' 5 , 1984; ~ p p2211273.
12 L. L. Hegedus, R. K. Herz, S. H. Oh and R. Aris, J. Catal. 57 (1979) 513.
13 S. Kolboe and R. Myrdal, i n p r e p a r a t i o n .
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

METAL-DOPED ZEOLITES FOR SELECTIVE CATALYTIC REDUCTION O F

NITROGEN O X I D E S I N COMBUSTION GASES

J . HAAS. J . STEINWANDEL and C. PLOG

Dornier S y s t e m GmbH, P. 0. Box 1360, D-7990 F r i e d r i c h s h a f e n (FRG)

ABSTRACT

In t h e p r e s e n t work i t is d e m o n s t r a t e d t h a t t h e a c t i v i t y of z e o l i t e s c o n c e r n i n g
t h e S C R - p r o c e s s can be i n c r e a s e d s i g n i f i c a n t l y by m e t a l d o p i n g . T h e SCR
c a t a l y s t s p r e p a r e d by m e t a l ion e x c h a n g e o f m o r d e n i t e a n d Y-zeolite w e r e
t e s t e d i n a l a b o r a t o r y p l a n t t o d e t e r m i n e t h e efficiency of t h e c o n v e r s i o n of
n i t r i c o x i d e s w i t h ammonia. C o p p e r - d o p e d Y - z e o l i t e c a n b e u s e d a s a SCR
c a t a l y s t i n a wide t e m p e r a t u r e r a n g e . T h e r e f o r e , t h e o p e r a t i o n is p o s s i b l e a s
well in a l o w - d u s t region, s u c h a s behind a d e s u l p h u r i z a t i o n p l a n t . A c o m p l i -
c a t e d t e m p e r a t u r e c o n t r o l f o r o p t i m u m c o n v e r s i o n is not n e c e s s a r y . A l s o t h e
e x c e l l e n t a m m o n i a s t o r a g e c a p a c i t i e s of t h e z e o l i t e c a t a l y s t s c a n be d e m o n -
s t r a t e d . T h e r e f o r e , c h a n g e s i n t h e ammonia f e e d o r t h e NO c o n t e n t in t h e ex-
h a u s t g a s c a n be c o m p e n s a t e d .

1NTRODUCTlON

Due to t h e p u b l i c d i s c u s s i o n c o n c e r n i n g new t y p e s of e n v i r o n m e n t d a m a g e
( W a l d s t e r b e n ) , a r a p i d d e v e l o p m e n t of t e c h n o l o g i e s h a s s t a r t e d i n t h e FRG
c o n c e r n i n g t h e r e d u c t i o n of p o l l u t a n t s f r o m e x h a u s t g a s e s . M e a n w h i l e , p r o -
c e s s e s c o n c e r n i n g d e s u l p h u r i s a t i o n have b e e n i n t r o d u c e d w i d e l y . In c o n t r a s t ,
t h e various t e c h n o l o g i e s f o r n i t r i c o x i d e r e d u c t i o n a r e s t i l l u n d e r i n v e s t i -
gation.

In t h e USA a s well a s t h e FRG, n o t only t h e w e l l - e s t a b l i s h e d ( s i n c e 1970)

J a p a n e s e p r o c e s s e s a r e t a k e n i n t o a c c o u n t . T h e J a p a n e s e t e c h n o l o g y o f NO
r e d u c t i o n by u s i n g modified TiO, c a t a l y s t s s h o u l d b e r e p l a c e d by a l t e r n a t i v e
s o l u t i o n s . C o n c e r n i n g t h e maximum e m i s s i o n v a l u e s ( N O x ) given by g o v e r n -
m e n t a u t h o r i t y a n d mainly r e l a t e d to l a r g e h e a t i n g p l a n t s (e.g. b l o c k h e a t i n g
p o w e r p l a n t s ) , primary p r o c e s s e s d o not lead t o s a t i s f y i n g r e s u l t s . I t is in-
s t e a d n e c e s s a r y t o d e v e l o p new p r o c e s s e s f o r r e d u c i n g NOx e m i s s i o n s : f o r
example wet p r o c e s s e s and reductive processes (using ammonia) m u s t be
t a k e n i n t o a c c o u n t . T a b l e 1 s h o w s a s e l e c t i o n of s u c h p r o c e s s e s a l r e a d y u n d e r
investigation.
338

TABLE 1

Selection o f secondary t r e a t m e n t s for NOx reduction.

__________

* Selective noncatalytic reduction (SNCR)

* Selective catalytic reduction (SCR)
.: Active carbon process
* Oxidation/Absorption process
* Electron beam process
* Dry sorption
* Sulphonic a c i d l n i t r i c acid process
* Complex s a l t process
________----__--------------------------------------

Oxidative methods produce nitrates or nitric acid, and problems arise con-
cerning the back-transfer of t h e products into t h e product cycle. Therefore,
t h e m o s t practicable methods consist of reductive processes, which finally
produce nitrogen. For t h e selective reduction of nitric oxides by ammonia a t
acceptable temperatures and conversion r a t e s , the use of catalytic processes
(SCR) i s essential. A possible reaction scheme is shown i n table 2.

TABLE 2
Selection of possible partial reactions, SCR process

Selective Reduction:
4 N H 3 + 6 N 0 ---D 5 N, +6 H,O
4 NH, + 4 NO + 0, --* 4 N, + 6 H,O

Production o f N,O:
2 NH, + 2 0, ----0 N,O + 3 H,O
8 NH, + 12 N O + S 0, --+ 10 N,O + 12 H,O

Oxidation of ammonia:
4 NH, + 7 0, --+ 4 NO, + 6 H,O
4NH,+50, --0 4NO+6H20
4NH,+30, -- 2N2+6H,O
 339

In view of t h e h e t e r o g e n e o u s l y c a t a l y z e d r e a c t i o n s , v a r i o u s t y p e s o f c a t a -
l y s t s have a l r e a d y been d e v e l o p e d . The c a t a l y s t t y p e is mainly r e l a t e d t o t h e
r e q u i r e d l o c a t i o n in t h e p r o c e s s . In p r i n c i p l e , t h r e e p o s s i b l e c a t a l y s t l o c a t i o n s
m u s t be t a k e n i n t o a c c o u n t , a s s h o w n in Fig. 1. F o r e x a m p l e , p r o c e s s e s a r e
k n o w n , whereby nitric o x i d e s a r e r e d u c e d by a n o b l e - m e t a l - c o n t a i n i n g c a t a l y s t
a t c o m p a r a b l y l o w t e m p e r a t u r e s , producing n i t r o g e n . H o w e v e r , r e l a t i v e l y high
n o b l e - m e t a l c o s t s p o s e s o m e r e s t r i c t i o n s f o r t h e p r o c e s s . In a d d i t i o n , t h e
c a t a l y s t s a r e s u b j e c t t o p o i s o n i n g by s u l p h u r d i o x i d e in t h e e x h a u s t g a s .

T h e r e a r e c h e a p e r a n d m o r e s t a b l e c a t a l y s t s b a s e d on j a p a n e s e t e c h n o -
mainly c o n s i s t i n g of vanadium and t i t a n i u m o x i d e s . A g e n e r a l d i s a d -
v a n t a g e of t h e s e c a t a l y s t s , however, is t h e heavy-metal c o n t e n t of u s e d c a t a -
l y s t s . P r o c e s s e s a r e known which employ z e o l i t e c a t a l y s t s . A n a d v a n t a g e of
m o l e c u l a r sieve c a t a l y s t s is t h e s t o r a g e c a p a b i l i t y of a m m o n i a . By t a k i n g ad-
v a n t a g e of t h i s e f f e c t , s h o r t t i m e v a r i a t i o n s of t h e a m m o n i a c o n c e n t r a t i o n c a n
be c o m p e n s a t e d . The p r o c e s s e s , however, r e q u i r e r e l a t i v e l y high o p e r a t i o n
t e m p e r a t u r e s ( u p t o 48OoC), a n d t h e r e is no c o m p l e t e n i t r i c o x i d e c o n v e r s i o n
due t o t h e comparatively reaction-inactive z e o l i t e c a t a l y s t s .

In t h e p r e s e n t work it is d e m o n s t r a t e d t h a t t h e a c t i v i t y of z e o l i t e s c o n -
c e r n i n g t h e S C R p r o c e s s c a n b e i n c r e a s e d s i g n i f i c a n t l y by m e t a l d o p i n g . T h e r e -
f o r e , t h e u s e of t h e c a t a l y s t a t l o w e r t e m p e r a t u r e s will b e p o s s i b l e .

1 Dust 2 Desulph. 3
Vessel plant 8 - Flue
removal -'

1 High-Dust catalyst
2 Low-Dust catalyst
3 LT catalyst

Fig. 1. P o s s i b l e l o c a t i o n s of SCR c a t a l y s t s .
340

EXPERIMENTAL

A s s t a r t i n g m a t e r i a l s f o r t h e p r e p a r a t i o n of t h e S C R - c a t a l y s t s , c o m m e r c i a l -
ly a v a i l a b l e z e o l i t e s of m o r d e n i t e t y p e a n d Y - z e o l i t e s w e r e u s e d ( B a y e r A C
a n d N o r t o n C o m p . ) . T h e d o p i n g of t h e z e o l i t e s w i t h m e t a l s w a s p e r f o r m e d by
t h e m e t h o d of i o n e x c h a n g e c i t e d i n t h e l i t e r a t u r e .

S C R c a t a l y s t s can b e used a s b u l k - c o n t a c t honeycomb c a t a l y s t s o r a s c o a t -

ed h o n e y c o m b c a t a l y s t s . From t h e p o i n t of v i e w of p r o c e s s d e v e l o p m e n t , w e
d e c i d e d t o use t h e c o a t e d h o n e y c o m b t y p e . A f t e r t h e p r e p a r a t i o n of t h e c a t a -
lytic a c t i v e p o w d e r s by ion e x c h a n g e a n d s u b s e q u e n t t h e r m a l t r e a t m e n t o r r e -
d u c t i o n , c o r d i e r i t e h o n e y c o m b s w e r e c o a t e d w i t h t h e z e o l i t e p o w d e r s by a
s p e c i a l d e v e l o p e d p r o c e s s . The g e o m e t r y of t h e c o r d i e r i t e h o n e y c o m b s c o r r e s -
ponded t o t h a t u s u a l l y used i n t h e a u t o m o b i l e i n d u s t r y ( t e s t m o n o l i t e s ,
3.15 inch l o n g , 1 inch d i a m e t e r , 400 S q . c e l l s p e r S q . i n c h ) .

The SCR c a t a l y s t s p r e p a r e d by t h e m e t h o d d e s c r i b e d a b o v e w e r e t e s t e d in a
l a b o r a t o r y p l a n t t o d e t e r m i n e t h e e f f i c i e n c y of t h e c o n v e r s i o n of n i t r i c o x i d e s
w i t h ammonia. A s a m o d e l s u b s t a n c e f o r t h e g r o u p of n i t r i c o x i d e s , NO w a s
used. T h i s can b e j u s t i f i e d b e c a u s e t h e NO c o n t e n t of n o r m a l e x h a u s t g a s is
a b o u t 9 0 %of t h e N O x . The l a b o r a t o r y p l a n t c o n s i s t s of a g a s - m i x i n g s t a t i o n , a
g a s - h e a t i n g s y s t e m , a r e a c t i o n c h a m b e r c o n t a i n i n g t h e c a t a l y s t , and f i n a l l y a
gas-analysis system.

By u s i n g a g a s c y l i n d e r b a t t e r y a n d e l e c t r o n i c m e a s u r e m e n t a n d c o n t r o l
c o m p o n e n t s i t is p o s s i b l e to vary t h e e x h a u s t g a s c o m p o s i t i o n o v e r a w i d e
r a n g e . T h e s y n t h e t i c e x h a u s t g a s c o n t a i n s a m a x i m u m of 9 d i f f e r e n t c o m p o -
n e n t s . The t e s t p l a n t a l l o w s f o r a maximum gas v o l u m e s t r e a m u p t o SO I / m i n .
The s t a n d a r d c o m p o s i t i o n of t h e s y n t h e t i c e x h a u s t g a s is s h o w n i n t a b l e 3.

TABLE 3
S t a n d a r d c o m p o s i t i o n of e x h a u s t g a s f o r t h e p r e s e n t e x p e r i m e n t s .

79.86
10.0
4.0
6.0
0.07
0.07
 341

T h e g a s h e a t i n g s y s t e m p e r m i t s e x h a u s t t e m p e r a t u r e s b e t w e e n 150 a n d
450 OC. P r o g r a m m a b l e h e a t i n g using s t a n d a r d i z e d t e m p e r a t u r e p r o g r a m s
a l l o w s f o r m e a s u r e m e n t s o f t h e c a t a l y s t behaviour w i t h r e l a t i o n t o t h e
d i f f e r e n t e x h a u s t - g a s t e m p e r a t u r e s . T h e g a s c o m p o s i t i o n d o w n s t r e a m a n d up-
s t r e a m of t h e c a t a l y t i c c o n v e r t e r is c o n t r o l l e d by t h e g a s - a n a l y s i s s y s t e m .
The s y s t e m c o n s i s t s o f a GC w i t h FID a n d HCD d e t e c t o r s , a n d a c h e m i l u m i -
n e s c e n c e NOx a n a l y z e r .

T h e chemical c o m p o s i t i o n of t h e c a t a l y t i c a c t i v e p o w d e r s w a s a n a l y z e d by
EDX. The i n f o r m a t i o n d e p t h o f EDX is a b o u t 1 t o 2 pm. W i t h a c r y s t a l l i t e s i z e
of t h e z e o l i t e s o f 1 t o 4 pm, t h e volume c o m p o s i t i o n is a l s o given by t h e EDX
method.

RESULTS A N D DISCUSSION

A s a l r e a d y s t a t e d i n t h e i n t r o d u c t i o n , t h e s t a t e of t h e a r t c o n c e r n i n g n o b l e
m e t a l c a t a l y s t s a l l o w s f o r a c c e p t a b l e n i t r i c o x i d e c o n v e r s i o n a t low t e m p e r a -
t u r e s . A s is a l r e a d y known f r o m work o n t h r e e - w a y c a t a l y s t s ’), i t is p o s s i b l e ,
by f i n e d i s p e r s i o n of p l a t i n u m i n n e a r - s u r f a c e r e g i o n s of m o r d e n i t e c r y s -
t a l l i t e s , t o p r o d u c e a c a t a l y s t c h a r a c t e r i z e d by high a c t i v i t y w i t h low n o b l e -
m e t a l c o n t e n t . I n a d d i t i o n , d u e t o t h e a d s o r p t i o n of a m m o n i a m o l e c u l e s a t t h e
acid z e o l i t e s i t e s , t h e r e e x i s t s t h e a d d i t i o n a l e f f e c t of s y n e r g y .

T h e r e f o r e , we s t a r t e d t h e i n v e s t i g a t i o n by using P t - d o p e d m o r d e n i t e a s
SCR c a t a l y s t , b e c a u s e a r a t h e r low o p e r a t i o n t e m p e r a t u r e in c o n j u n c t i o n w i t h
high c o n v e r s i o n r a t e s s h o u l d t h u s be e x p e c t e d . Fig. 2. s h o w s t h e n i t r i c o x i d e
c o n v e r s i o n a s a f u n c t i o n o f t h e g a s t e m p e r a t u r e f o r t w o d i f f e r e n t c a t a l y s t s of
t y p e P t H - m o r d e n i t e . C a t a l y s t s w e r e p r e p a r e d f o r i d e n t i c a l Pt c o n t e n t of a b o u t
0.2 g/l.

From Fig. 2. it is s e e n , t h a t f o r b o t h c a t a l y s t s a l m o s t 100%n i t r i c o x i d e c o n -

version o c c u r s . H o w e v e r , t h e t e m p e r a t u r e r a n g e f o r o p t i m u m c o n v e r s i o n , b u t
a l s o i n c r e a s e a n d d e c r e a s e of t h e conversion s l o p e a r e q u i t e d i f f e r e n t . T h i s is
d u e t o t h e d i f f e r e n t S i / A l - r a t i o of t h e t w o m o r d e n i t e c a t a l y s t s . T h e m o r d e n i t e
o f c a t a l y s t (11) w a s d e a l u m i n a t e d by acid t r e a t m e n t b e f o r e P t - d o p i n g . T h i s
r e s u l t e d i n a m o d u l u s ( m o l a r r a t i o SiO,/AI,O,) of a b o u t 2 0 . T h e m o r d e n i t e of
c a t a l y s t ( 1 ) w a s n o t modified ( m o d u l u s o f a b o u t 12).

By t h e dealumiiiatioii of t h e anionic l a t t i c e of t h e moi-denite in conji:::cti:,-

with a s i n i u l t a n e o u s c h a n g e o f t h e s t e r i c c o n d i t i o n s in t h e p o r e s y s t e m . a
c h a n g e i n a c i d i t ) r e s u l t s . C h a n g e s i n s p e c i f i c s u r f a c e w e r e d e t e r m i n e d b)
342

using BET. T h e l o w e r c o n t e n t of n e g a t i v e p a r t i a l c h a r g e s o f t h e l a t t i c e a f t e r
d i s s o l v i n g t h e a l u m i n u m r e s u l t s i n a d e c r e a s e in n u m b e r o f acid s i t e s . T h e i r
s t r e n g t h , h o w e v e r , i n c r e a s e s . Both e f f e c t s i n f l u e n c e t h e n u m b e r of a d s o r p t i o n
c e n t r e s f o r a m m o n i a a s well a s t h e d i f f u s i o n i n t o t h e p o r e s y s t e m . T h i s r e s u l t s
i n a much b e t t e r c o n v e r s i o n c h a r a c t e r i s t i c f o r t h e d e a l u m i n a t e d P t H - m o r d e n i t e .

0 1I I
i
150 200 250 300
Temperature ["Cl

Fig. 2. Activity b e h a v i o u r of P t H - m o r d e n i t e o f d i f f e r e n t m o d u l i a s a f u n c t i o n
of g a s t e m p e r a t u r e .

C a t a l y s t (1) s h o w s 90%c o n v e r s i o n o v e r o n l y a r e l a t i v e l y n a r r o w t e m p e r a t u r e
r a n g e , a n d t h e a c t i v i t y s t r o n g l y d e c r e a s e s a t l o w e r o r h i g h e r t e m p e r a t u r e s . In
c o n t r a s t , t h e d e a l u m i n a t e d c a t a l y s t s (11) s h o w s a l m o s t 100%c o n v e r s i o n b e t -
ween 170 and 200 O C . I n a d d i t i o n , t h e maximum c o n v e r s i o n i s m a i n t a i n e d a l s o
a t h i g h e r g a s t e m p e r a t u r e s . T h e d e c r e a s e in c o n v e r s i o n f o r b o t h c a t a l y s t s a t
h i g h e r t e m p e r a t u r e s is r e l a t e d t o t h e onset of t h e N O - p r o d u c i n g a m m o n i a o x i -
d a t i o n . T h i s r e s u l t s in a s i g n i f i c a n t d e c r e a s e of t o t a l NO c o n v e r s i o n . C a t a l y s t
(11) s h o w s a h i g h e r SCR a c t i v i t y a t l o w e r t e m p e r a t u r e s a n d a l o w e r a c t i v i t y
(desired) concerning ammonia oxidation a t higher t e m p e r a t u r e s .

A s an a l t e r n a t i v e t o noble metal containing z e o l i t e c a t a l y s t s f o r selective

r e d u c t i o n of n i t r i c o x i d e , z e o l i t e c a t a l y s t s d o p e d w i t h t r a n s i t i o n m e t a l s o f t h e
 343

p e r i o d i c s y s t e m w e r e p r o d u c e d . A s b a s i s m a t e r i a l s , Y-zeolite a n d m o r d e n i t e
w e r e u s e d . Z e o l i t e s w e r e d o p e d w i t h e i t h e r vanadium o r c o p p e r . F i r s t , vanadi-
um is known a s a c t i v e c o m p o n e n t of t h e T i 0 2 - b a s e d S C R - c a t a l y s t of J a p a n e s e
t e c h n o l o g y . C o p p e r , o n t h e o t h e r h a n d , is k n o w n to a c t a s c e n t r a l ion in a m -
monia c o m p l e x e s , r e s u l t i n g i n a d d i t i o n a l s t o r a g e o f a m m o n i a in t h e z e o l i t e .

n
P
Y

!
'C

i
Y
i
3

Fig. 3. C o n v e r s i o n c h a r a c t e r i s t i c of d i f f e r e n t d o p e d z e o l i t e s a s a f u n c t i o n o f
t h e gas temperature.

Fig. 3. s h o w s a s i g n i f i c a n t d i f f e r e n c e in t h e a c t i v i t y b e h a v i o u r o f t h e t h r e e
m e t a l - d o p e d z e o l i t e s a s a f u n c t i o n of e x h a u s t t e m p e r a t u r e . I t c a n b e s e e n t h a t
t h e H-mordenite (vanadium-doped) d o e s n o t show significant activity in con-
t r a s t t o t h e Pt-doped f o r m . Over t h e e n t i r e t e m p e r a t u r e r a n g e 200 t o 400 OC,
o n l y NO-conversion r a t e s of 10 X a r e r e a c h e d . Vanadium is p r e s e n t in t h e z e o -
lite in a c o m p l e t e l y d i f f e r e n t f o r m , a s is t h e c a s e f o r t h e TiO, c a t a l y s t . T h e r e -
f o r e , vanadium c a n n o t play t h e identical role. In a d d i t i o n , i t is o b v i o u s t h a t
t h e H - m o r d e n i t e a l o n e e x h i b i t s e x t r e m e l y l o w a c t i v i t y a s a n SCR c a t a l y s t .
344

I n c o n t r a s t t o vanadium, c o p p e r a s doping metal s h o w s a positive e f f e c t f o r

t h e H - m o r d e n i t e . A t t e m p e r a t u r e s up t o 300 OC, t h e r e is n o d i f f e r e n c e b e t w e e n
t h e t w o c a t a l y s t s . A t t e m p e r a t u r e s a b o v e 300 OC, h o w e v e r , a s i g n i f i c a n t in-
c r e a s e i n t h e s e l e c t i v e r e d u c t i o n of n i t r o g e n o x i d e is f o u n d f o r t h e CuH-
m o r d e n i t e . A t 380 OC a maximum c o n v e r s i o n o f a b o u t 50 % is r e a c h e d . A f u r t h e r
i n c r e a s e i n t e m p e r a t u r e , however, r e s u l t s in a s t r o n g d e c r e a s e of NO c o n -
version. T h i s is d u e t o t h e r a p i d i n c r e a s e o f NH, o x i d a t i o n . Above 400 OC,
more ammonia molecules a r e reacting with oxygen t h a n with nitrogen oxide,
f i n a l l y r e s u l t i n g in a n i n c r e a s e of NO e m i s s i o n in t h e t o t a l mass b a l a n c e .

T h e p a r a l l e l r e a c t i o n o f a m m o n i a o x i d a t i o n c a n b e r e d u c e d by u s i n g a c o p -
p e r - d o p e d Y - z e o l i t e . a s s h o w n in f i g . 3. T h i s p a r t i c u l a r c a t a l y s t c o m b i n e s t h e
c a p a b i l i t y of r e d u c i n g ammonia o x i d a t i o n w i t h a high a c t i v e NO r e d u c t i o n .
T h i s l e a d s t o a r e l a t i v e l y high c o n v e r s i o n p l a t e a u o v e r a w i d e t e m p e r a t u r e
r a n g e . Between 250 a n d 400 OC NO c o n v e r s i o n is b e t t e r t h a n 80 %.

1 I I

Fig. 4 . C o m p a r i s o n of c o n v e r s i o n c h a r a c t e r i s t i c f o r d i f f e r e n t l y p r e p a r e d c o p -
per-doped Y-zeolites.
 345

?., I
i
'k; i
9,? - \ I
\ I
1
\
I
n
I k !
Y 6n -
\ i
I
\\

1:

Time iminl

Fig. 5. C o n v e r s i o n r a t e of t h e r e a c t i o n NO + NH, v e r s u s t i m e ( m i n ) a f t e r i n t e r -
r u p t i o n o f t h e ammonia f e e d .

T h i s h i g h e r p o t e n t i a l o f t h e c o p p e r - d o p e d Y-zeolite a s SCR c a t a l y s t c a n
a l s o b e s e e n f r o m fig. 4 . H e r e , NO c o n v e r s i o n i s p l o t t e d a g a i n v e r s u s g a s t e m -
p e r a t u r e , and t w o d i f f e r e n t l y p r e p a r e d CuNaY-zeolites a r e c o m p a r e d . I t c a n
b e s e e n t h a t by o p t i m i z i n g t h e p r e p a r a t i o n t e c h n i q u e a f u r t h e r i n c r e a s e in c o n -
v e r s i o n c h a r a c t e r i s t i c s is p o s s i b l e . T h e c a t a l y s t CuNaY(2) s h o w s m o r e t h a n
80 % c o n v e r s i o n over a t e m p e r a t u r e r a n g e 2 0 0 - 400 OC. Between 250 a n d 390 OC
a n a l m o s t 100 % c o n v e r s i o n of n i t r i c o x i d e is f o u n d .

T h e r e f o r e , t h e c o p p e r - d o p e d Y-zeolite c a n b e o p e r a t e d a s SCR c a t a l y s t a t -
l e a s t o n a l a b o r a t o r y s c a l e - t o b e u s e d o v e r a wide t e m p e r a t u r e r a n g e . O p e r a -
t i o n is p o s s i b l e a s w e l l in a l o w - d u s t r e g i o n s u c h a s b e h i n d t h e d e s u l p h u r i z a -
t i o n p l a n t , w h e r e t h e g a s t e m p e r a t u r e is a l r e a d y r e d u c e d s i g n i f i c a n t l y . A c o m -
p l i c a t e d t e m p e r a t u r e c o n t r o l f o r o p t i m u m c o n v e r s i o n is n o t n e c e s s a r y d u e t o
t h e wide t e m p e r a t u r e w i n d o w of t h e c a t a l y s t .
346

An a d d i t i o n a l i m p o r t a n t c h a r a c t e r i s t i c of t h e z e o l i t e SCR c a t a l y s t s is s h o w n
in f i g . 5. H e r e , T h e o p t i m i z e d C u N a Y - z e o l i t e w a s u s e d . During a l o n g - t e r m
o p e r a t i o n a t a n e x h a u s t g a s t e m p e r a t u r e of 300 OC, t h e a m m o n i a f e e d w a s
i n t e r r u p t e d , w h i l e t h e NO f e e d w a s m a i n t a i n e d c o n s t a n t . Fig. 5 s h o w s NO c o n -
v e r s i o n v e r s u s t i m e ( m i n ) a f t e r i n t e r r u p t i o n of t h e a m m o n i a f e e d .

T h e e x c e l l e n t a m m o n i a s t o r a g e c a p a b i l i t y of t h e z e o l i t e , in p a r t i c u l a r t h e
c o p p e r - d o p e d Y - z e o l i t e , c a n b e d e m o n s t r a t e d . Even u p t o 3 min a f t e r a m m o n i a
f e e d i n t e r u p t i o n , a 100 % c o n v e r s i o n o f NO is m a i n t a i n e d . A f t e r t h i s t i m e t h e
r e a c t i o n e f f i c i e n c y d e c r e a s e s . H o w e v e r , even a f t e r 10 m i n , t h e r e is still 2 0 %
NO c o n v e r s i o n . A f t e r 2 0 min, t h e r e a c t i o n e f f i c i e n c y is z e r o . By u s i n g t h e e x -
c e l l e n t s t o r a g e c a p a b i l i t y , c h a n g e s in t h e a m m o n i a f e e d o r t h e NO c o n t e n t in
t h e e x h a u s t g a s c a n be c o m p e n s a t e d . This h o l d s a l s o f o r s h o r t - t i m e c e s s a t i o n
of t h e a m m o n i a f e e d .

T h e d i f f e r e n t l y modified z e o l i t e SCR c a t a l y s t s d e s c r i b e d i n t h i s w o r k c a n
be u s e d f o r d i f f e r e n t o p e r a t i n g c o n d i t i o n s . S u c h a d v a n t a g e s a s e c o n o m i c a l
basis s u b s t a n c e , excellent activity behaviour ( i n p a r t over wide t e m p e r a t u r e
r a n g e s ) a n d , i n p a r t i c u l a r , t h e unique s t o r a g e c a p a b i l i t y f o r t h e r e a c t i o n c o m -
p o n e n t a m m o n i a have been d e m o n s t r a t e d . I n a d d i t i o n , d u e t o t h e c o m p o s i t i o n
of t h e z e o l i t e s , t h e d i s p o s a l of used c a t a l y s t s is l e s s t r o u b l e s o m e c o m p a r e d
w i t h heavy-metal-containing TiO, c a t a l y s t s .

ACKNOWLEDGEMENTS

The a u t h o r s g r a t e f u l l y a c k n o w l e d g e financial s u p p o r t by t h e B u n d e s -
m i n i s t e r f u r F o r s c h u n g und T e c h n o l o g i e .

REFERENCES

1 DE-OS 26 17 744.
2 US.-PS 3,279,884.
3 U.S.-PS 4,010,238.
4 EPA-A1 0 161 743
5 H a a s . J . . C. Plog a n d J . S t e i n w a n d e l , S t u d . S u r f . Sci. C a t a l . . i n p r e s s
H.G. Karge, J. Weitkamp (Editors ), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

PREPARATION OF NiHZSM-5 CATALYST FUR ISOMERIZATION OF C8 ARaMATICS.

SOLIE-STATE INCORFORATION OF NICKEL

B. WICHTEELOV$. S. BERANI. L. KUBELKOVL1, J. NOVhVAl, A . SMI&OVfl. and

R .&~Ikz
J . Heyrovsw Institute of Physical Chemistry and Electrochemistry,
Czechoslovak Academy of Sciences, 182 23 Prague 8 (Czechoslovakia)

Research Institute for Oil and Hydrocarbon Gases, 823 17 Bratislava

(Czechoslovakia)

A high temperature interaction between ?US?d-5 and solid NiC12. NiS04,

Ni(CH3COO)z and NiO was investigated. For NiC12. disaggregation of the salt is
complete at 7'70 K with evolution of gaseous hydrochlorid acid, resulting in
solid-solid ion exchange of Ni ions into the zeolite cationic sites at the ex-
pense of the strong acid skeletal OH groups. The heat treatment of the zeolite
with NiS04 above 670 K leads to a decrease in the number of skeletal OH groups
to approximately half the original number. Moreover, no evolution of acid or its
decomposition products is observed. Ni(CH3COO)2 behaves differently. No ion-
change (even in a wet paste) occurs up to the salt decomposition temperature
(520K). NiO formed at higher temperatures also does not interact with the
skeletal OH groups. The described high-temperature solid-solid ion exchange
between HZSM-5 and NiC12 was used successfully for the incorporation of Ni2+
into the zeolite cationic sites. Subsequent reduction of these ions by hydrogen
yields well-dispersed metallic nickel, which is active in the isomerization of
c8 aromatic hydrocarbons.

Catalysts based on HZSM-5 zeolite with metallic nickel finelly dispersed

within the zeolite channels have been found to have excellent hydrogenation
activity in isomerization of hydrocarbons, which prevents olefin polymeri-
zation and, consequently, zeolite coking. The usual procedure for obtaining well
dispersed metallic nickel in the zeolite catalyst involves ion exchange of the
Ni2+ ions into the zeolite cationic sites, followed by reduction with hydro-
gen. According to the patent literature (ref. l), this exchange can be carried
out from Ni salt solutions. A further possibility for incorporation of Ni ions
into the zeolite cationic sites appears to be solid-solid ion exchange between
Ni salts and an H form of the zeolite.
Solid-solid ion exchange between metal halides and the H forms of A, X . Y ty-
pes of zeolites above 570 K was first described by Rabo et al. (refs. 2. 3) and
Clearfield et al. (ref.4). Recently, several papers have been devoted to solid-
state reactions with the catalytically important H forms of mordenites and ZSM-5
zeolites (ref. 5-8). Evidence based on the B R spectra of the metal cations, IR
spectra of OH groups and detection of evolved acids has been given for the dis-
aggregation of the solid salts of Cu, Mn, Ca, Mg, Cr and oxides of Cu. Fe, V and
Cr mixed with zeolites; in some cases metal cation exchange with the zeolite
protons has been detected.
348

This paper deals with the high-temperature interaction of the solid Ni2+
salts or oxide with the HZSh4-5 zeolite, considering possible use for the prepa-
ration of the isomerization catalyst for Cg aromatic transformation. A compa-
rison with NilUSM-5 prepared via Ni2+ ion exchange in aqueous medium is made.

The HzsM-5 zeolites (Si/Al = 13.6 (a) and 22.5 (b)) were synthesized using
tetrapropylammonium base according to a procedure given in ref. 9 and then heat-
ed to 820 K in an oxygen stream and decationized by 0 . 5 HN%. The NiHZSM-5(b)-w
was prepared by the ion exchange of a Ni(NH3)6(CH3C00)2 solution with H'ZSM+5(b)
at 298 K and @ 10.8l(Table 1). Ni(CH3C00)2.M+$ and Ni(Q)2.6H@ salts (Merck
p.a.) were used for estimation of the level of the ion exchange in an aqueous
medium and the amount of Ni salt remaining in solution. HZSM+(a) and HZSM-B(b)
and NiC12.6 H20. NiS04.7HS and Ni(CH3C00)2.4HZO and NiO (Merck p.a.) were
employed for solid-state interactions between the H Z M zeolites and Ni2+ solid
salts or an oxide. The zeolite with a particular salt or oxide (the amounts are
given in Table 2) was stirred in an agate mortar to obtain well-powdered and
mixed mechanical mixture. This mixture was heated (temperature increase of 5
K/min) to the temperature indicated in Table 2 and then held at this temperature
for 6 hours in an oxygen stream. After this treatment, the mixture was equi-
librated with atmospheric moisture at ambient temperature (zeolite abbr.
NiHZSM-S(a) or (b)-s). In s o m e cases heat-treated mixtures were reduced by hy-
drogen at 720 K for 4 hours or treated with 1 N NH@% solution at 330 K for 10
hours.
The following characteristics were investigated for the heat-treated solid
mixtures (modified zeolites) and for the parent zeolites:
i) The OH groups were monitored by recording the IR spectra (
spectrometer) of the sample in the form of a pellet (thickness of
which was evacuated at 670 K for 1 hour.
-
ITNicolet MX-1E
7 mg/c&)

ii) The number of strong acid skeletal OH groups was estimated from the
high-temperature peak of the tempetarureprograd desorption of ammonia
(TPDA). carried out in the temperature interval from 373 to 670 K (20 K/min) in
a stream of dry helium on samples equilibrated with dry ammonia at 373 K. The
evolved ammonia was detected by a heat conductivity cell (ref. 10).
iii) Mass spectrometric detection (MCH 1302 USSR) was used for determination
of gases evolved from the zeolite mixture during its programmed heating in vacuo
( 5 K/min, 1 0 4 Pa).
iv) The amount of acid evolved from the zeolite mixture into an oxygen stream
was detected by the absorption of the eluent gas in an alkaline solution (0.1 N
NaOH) and its back titration with 0.1 N HC1.
v) The catalytic activity of zeolites in isomerization of Cg aromatic hydre
carbons was tested using a model mixture consisting of 80.0vol.% of 0-xylene
and 20.0 vol.% of ethylbenzene in hydrogen (H/M molar ratio 5 . 0 ) . The investi-
gated catalysts in the form of pelletes ( 0 . 5 nnn in diameter, 5 . 0 g) contain
30 w t . % of the zeolite sample and 70 wt.% of alumina (Lachema p.a.). The cata-
lyst was pretreated in a hydrogen stream at 720 K for 4 hours and then in a
stream of the model mixture mentioned above (W 3.4h-l) for 100 hours.
During the following 5 hours, the conversion and selectivity data (presented in
Fig. 2) were found to be constant. Conversion of the initial hydrocarbons and
composition of the products were determined by owline chromatographic analysis
of gaseous products and off-line analysis of the liquid products, collected for
5 hours in a trap at 273 K.
 349

TABLE 1
Chemical composition of -5 and NiHZ'3&6 prepared by ion exchange in an
aqueous medium

SiO, A1A Nag CaO NiO skeletal OH groups

zeolite wt.% wt.% wt.% wt.% wt.% (mmol/g)
chem,anal. Tm3A

-5(a) 93.68 5.90 0.117 0.30 - 1.06 0.91=

m ( b ) 96.04 3.75 0.046 0.30 - 0.62 0.5W xx+

NiHZSM-5(b)-w 95.36 3.72 0.046 0.30 0.76a 0.39 0.29

&.
0. x xx
I

Chemical composition is based on a dry zeolite, a0.102 mmol/g of Ni,

reduction in hydrogen at 720 K; Xisomerization activity is presented in Fig. 2;
=IR spectra of OH groups are depicted in Fig. 1.

Incorporation of Ni into the HZShf-5 zeolite using an aqueous medium

Metal-ion exchange from solutions into the zeolites is a method that is wide-
ly used for preparation of their cationic forms. In introducing Ni cations from
salt solutions, only a limited degree of ion exchange is achieved, while a
considerable amount of Ni remains in solution. For instance. with a suspension

,
of the HZSM-5 (Si/Al = 13.6) in Ni(NH3)6(CH3COO)2 solutions (concentrations 1 -
7 g Ni/l) for which the Ni/Al molar ratio ranges from 0 . 5 to 0.12 (pH 10.8), a
m w i w of 12 % Ni ion exchange is attained at 298 K. Similarly, with the same

3745 36\3 36i2cm-1

"0

B
Q

-.

Fig. 1. IR spectra of OH groups of the parent HZSd-5 and NiHiSM-5 zeolites

prepared by ion exchange in aqueous medium and in solid-state with NiClZ at
770 K

1- HZSM+(a). 2- HZSM-.5(a) + NiCl2 (0.30mmol Ni/g), 3- HZSM-5(a) +

NiCl2 (0.45mmol Ni/g), cf. Table 2, 4- HZSM-5(b), 5- NiHZSd4(b)-w (0.102mmol
Ni/g) + reduced in hydrogen at 720 K, & HZSd4(b) + NiC12 (0.102 mmol Ni/g) +
reduced in hydrogen at 720 K. cf. Tables 1. 2.
BZsnS(a) 0.91 Nia2 0.30 0.33 0.50 -
0.6dM 0.58

-5 (a) 0.91 NiCl2.6Et20 0.45 nF o.oP 0.0P 0.90

-5 (a) 0.91 N m 4 . 7E20 0.45 670 0.64 0.27 -
770 0.35 0.56 -
mSM-5m, 0.50 Nm2. m20 0.102

0.00 -
0.00 -
0.00 -
HZS4-5 0) 0.50 Ni((cI13ax))2.4€i20 0.102 no 0 . d 0.oOx -
ESM-Sb) 0.50 Nio 0.40 no 0.50 0.00 -
concentrations and Ni/A1 ratios the use of solutions of Ni(CH3COO)z or Ni(N03)~
leads, as a consequence of lower pH (5.2and 2.4.resp.) to 8 and 4 % Ni ion ex-
change, respectively. It is obvious that with N i ( ~ 3 ) 6 ( ~ 3 C ~ ) 2 .Ni(CH$OO)2 and
Ni(N%)2 solutions mentioned above, and ion exchange performed at 298 K, at
least 5 0 , 70 and 85 %. respectively, of Ni remains in solution. This remaining
salt represents a considerable problem in the waste water from preparation of
the NiHZWS zeolite.

Ni ion incorporation using solid mixture of a zeolite and Ni salt

Heating of the mixture of the solid NiCl2 and HZSM-5 in an oxygen stream
above 570 K leads to the evolution of gaseous hydrochlorid acid. The amount of
evolved HC1 (for mixtures treated at 770 K for 6 hours) corresponds to the
amount of Ni in the mixture (Table 2). Simultaneously, a decrease in the number
of skeletal OH groups, corresponding also to the amount of Ni in the mixture. is
observed by TPDA and IR spectra of OH groups (Table 2, and Fig. 1, band at 3612
cm-l). Moreover. the IR spectra do not detect substantial change in the
intensity of the band of the Si4H groups (3745 cm-l); note that the Ni/A1 molar
ratios do not exceeds a value of 0.5.
Therefore. the above data indicate that the process of solid-solid ion ex-
change described by the following reaction is complete at 770 K:

H Si - 0 - A1
I t
2 Si - 0 - A 1 + NiCl2 -> Ni + 2 HC1
1
Si - 0 - A1

This conclusion is further supported by the fact that the incorporated charge-
balancing Ni ions in NiHZSM-5(b)+iC12 can be re-exchanged with a WQ solu-
tion, yielding the H form of the zeolite with practically the same number of
skeletal OH groups as the original zeolite (Table 2). Moreover. the reduction of
NiHZSd+(b)+iC12 with hydrogen at 720 K again leads to the restoration of
nearly all (95 W ) of the skeletal OH roups.
f
The low-intensity band at 3663 cm- observed in the spectra of the heat-
treated mixture of HZSM-5 and NiCl2 can indicate the presence of a low number of
OH groups located on extra-lattice A1 species (ref. 11). These A 1 species should
be formed as a result of a leaching of A1 from the zeolite skeleton under the
action of hydrochloric acid. However, the low intensity at 3663 cm-l. together
with the fact that practically all the skeletal OH groups can be restored by re-
exchanging or by reduction of Ni2+ ions, indicates that only negligible, if any.
zeolite dealumination occurs during solid-solid ion exchange with NiC12.
Heating of the mixture of NiS04 with HZSM-5 causes a decrease in the number
of structural OH groups. This decrease (increasing with temperature, cf. Table
2) is only roughly h a l f of a possible value given by the amount of Ni ions
present in the mixture. In contrast to NiC12. no evolution into the gaseous
phase of the corresponding acid or its decomposition products occurs. This
indicates that one NiS04 is probably coordinated to one skeletal OH group.
Temperatureprograd heating of the physical mixture of HZSM-5 and
Ni(CH3COO)z in vacuo. with mass spectrometric detection of the evolved gases.
reveals decomposition of the salt above 520 K accompanied by the evolution of
CO. q. H2, acetic acid and acetone (as a result of a subsequent reaction
occurring on the zeolite). Therefore, formation of NiO can be expected when
heating this mixture in a stream of oxygen above 520 K. For physical mixture of
NiO and HZSM-5 heated up to 820 K, no incorporation of the Ni ions into the
zeolite cationic sites takes place (Table 2). This is most likely due to the low
volatility of NiO (melting point, 2173 K). Similarly, ion exchange does not
proceed at temperature below 520 K. when urdecomposed Ni(acetate) is present in
the mixture; no decrease in the number of structural OBI groups was observed
either on heating the mixture in an oxygen stream for 8 hours or on leaving the
352

mixture to stand (even in the form of a wet paste) at ambient temperature for
several days.
Sclllrmarizing, it can be stated that true high-temperature, solid-solid ion
exchange occurs quantitatively between HZSM-5 and solid nickel chloride at 770
K. This is not a result of the possible presence of water in the zeolite or in
the salt at a temperature below 570 K.

HydroRenation, isomerization and dealkylation activity of Ni-modified zeolites

Isomerization and dealkylation activity of the original HZSM-5(b) zeolite,
depending on the reaction temperature and relative content of ethylene in the C2
fraction of hydrocarbons in the gaseous products. is shown in Fig. 2.

-I I I I

401 ethylbenzene /I
p-xy lcnc

xylenes
I
570 590 610 630 570 590 610 T(K)

Fig. 2. Isomerization of the 0-xylene - ethylbenzene mixture on zeolites

depending on temperature (WHSV 3 . 4 h-l. H/cH molar ratio 5.0. pressure 1 m a ) .

A) Conversion (wt.%) of o-xylene and ethylbenzene based on fed o-xylene and

ethylbenzene, respectively, loss (wt.%) of xylenes based on fed o-xylene+ethyl-
benzene, respectively, and conversion of o-xylen-thylbenzene to pxylene on
w ( b ) I

B) Ethylene to C2 hydrocarbons molar ratio in gaseous products (conversion oi

o-xylenetethylbenzene to gaseous products reached a value from 0.1 to 2.8 w t . %
depending on temperature).

1- HZSM-5(b), 2- NiHZEU-5 (b)-w, 3- HZSM-5(b) + NiC12, 4- HZSM-5(b) +

Ni(ClI3W)z ; content of Ni is 0.102 nmol Ni/g for all samples, cf. Tables 1. 2.

To test the possibility of using the solid-solid ion exchange for preparation
of isomerization catalyst, NiHZSM-5 samples containing the s e u ~amount of Ni
(Tables 1, 2) prepared by 1) solid-solid ion exchange with NiC12. ii) decoiw
position of Ni(acetate), and iii) standard ion exchange in aqueous medium were
compared for their effectiveness in isomerization of the model cg aromatic mix-
ture.
It has been folud that isomerization and dealkylation activity of all these
NiHZSM-6 catalysts (after their reduction in a hydrogen stream at 720 K) is c o w
parable to that of the parent H7S-5 zeolite (Fig. 2). It is in line with the
same number of strong acid sites present in the zeolites after reduction of Ni2+
to Nio (Tables 1, 2, Fig. 1). In contrast, the hydrogenation activity of these
zeolites , which is important for zeolite coking, differs cansiderably.
NiHZSbi+(b)-Ni(acetate), most likely containing Nio outside the zeolite chan-
 353

nels, does not exhibit any hydrogenation activity as follows from a content of
ethylene in the gaseous products similar to that of the parent zeolite. On the
other hand, the hydrogenation activity of NiHZSLM(b)+iClz (solid-ion exchange)
is much higher than that of parent zeolite and close to that of NiHZW5(b)w,
prepared by standard Ni ion exchange in aqueous medium (Fig. 2B. cf. Tables 1.
2).

It can be stated that the high-temperature solid-solid Ni ion exchange, using

the solid nickel chloride and H form of 2 S 5 , proceeds quantitatively without
dealumination of the zeolite skeleton and with preservation of the zeolite
structure. Metallic nickel formed by subsequent treatment of the zeolite in hy-
drogen exhibits high hydrogenation activity during isomerization of Cg arom-
tics. Moreover, the solid-state incorporation of nickel into the zeolite c h a n
nels in comparison with ion exchange in aqueous medium has the following advan-
tages :
i) The degree of ion exchange can be controlled directly by varying the
amount of NiCl2 added to the zeolite.
ii) Practically complete Ni ion exchange into the zeolite cationic sites
(higher than 90 %) can be achieved. Such high degree of exchange is reached only
with difficulty when using solutions of Ni salts.
iii) Generally, this pathway of metal ion exchange is especially important for
incorporation of metal cations that tend to hydrolyze in aqueous solutions into
the zeolite cationic sites.
iv) From a technological point of view, the preparation of the cationic forms
of zeolites by ion exchange between solids does not produce a large amount of
waste water containing metal salts, with detrimental effect on natural envirow
ment .
However, the solid-solid ion exchange must be carried out with caution to
exclude the following:
i) the presence of residues of the original salt, by using sufficiently long
treatment of the system at temperatures above 670 K;
ii) some dealumination or even damage of the zeolite structure by evolved
gaseous acid by applying a high velocity of the eluent gas (for this reason,
this method can be used only with structurally stable high-silica zeolites like
mordenites. ZSd-5 etc.).

REFERENCES

1 F.G. Dwyer (Mobil Oil Co.) US patent 4 100 214.

2 J.A. Rabo, M . L . Poustma and G.W. Skeels, Proc. 5th Int. Congr. Catal.. Miami
Beach 1972, J.W. Hightower ed.. North Holland Publ. Co. N.Y. 1973, p.1353.
3 J.A. Rabo. Zeolite Chemistry and Catalysis, J.A. Rabo ed., ACS Monograph 171,
Washington D.C.. 1976. p. 332.
4 A. Clearfield, C.H.Saldarriaga and R.C. Wlckley, F'roc. 3rd Int. Conf. Mol.
Sieves, Zurich, 1973, Hecent Progress Reports, J.B. Uytterhoeven ed.. Univ.
Leuven Press. p. 241.
5 A.V. Kucherov and A.A. Slinkin. Zeolites 6 (1986) 175, 7 (1987) 38. 7 (1987)
6 B. Wichterlova. S . Beran. S . Bednarova. K. Nedomova. L. W i k o v a and P. Jiru.
Stud. Surf. Sci. Catal. 37 (1988) 199.
7 H.K.Beyer. H.K.Karge and C. Borbely, Zeolites 8 (1988) 79.
8 H.K.Karge. H.K.Beyer and C. Borbely. Catal. Today, 3 (1988) 41.
9 US patent 3 702886 (1972).
10 G.I. Kapustin. T.R. Brueva. A.L. Klyachko. S. Beran and B . Wichterlova. Appl.
Catal.. 42 (1988) 239.
11 L . M . Kustov, V.B. Knzansky, S. Beran, L. Kubelkova and P. Jiru. J. Phys.
Chem. 91 (1987) 5247.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

FORMATION OF CARBOCATIONS FROM C, COMPOUNDS I N ZEOLITES

Imre K i r i c s i ' , H o r s t F o r s t e r 2 and Gyula T a s i '

' A p p l i e d Chemistry Department, J o z s e f A t t i l a U n i v e r s i t y , R e r r i c h

B. t e r 1, H-6720 Szeged, Hungary

' I n s t i t u t e o f P h y s i c a l Chemistry, U n i v e r s i t y o f Hamburg,

Bundesstr. 45, 0-2000 Hamburg 13, Federal R e p u b l i c o f Germany

ABSTRACT
Formation o f u n s a t u r a t e d carbenium i o n s f r o m 1-hexene, cyclohexane, c y c l o -
hexene, cyclohexadiene and benzene upon i n t e r a c t i o n w i t h t h e H-forms o f
z e o l i t e s ZSM-5 and Y was p r o v e d by U V - V I S and I R spectroscopy. W i t h t h e
e x c e p t i o n o f benzene, which forms d i e n y l i o n s a t t h e b e g i n n i n g , c a r b o c a t i o n
f o r m a t i o n from t h e o t h e r C, compounds s t a r t s w i t h monoenylic species, which
t r a n s f o r m i n t o o l i g o e n y l i c i o n s w i t h t i m e o f c o n t a c t . From the c y c l i c
hydrocarbons c y c l i c i o n s as w e l l as open-chain a l k e n y l i o n s a r e formed. The
i o n f o r m a t i o n c a p a b i l i t y decreases i n t h e sequence c y c l o h e x a d i e n e > c y c l o h e x -
ene > 1-hexene > cyclohexane > benzene. F o r t h e f i r s t stages o f carbenium i o n
development t h e f o r m a t i o n o f a r o m a t i c s u r f a c e species may be excluded.

INTRODUCTION
Formation o f a r o m a t i c s i n t h e MTG process i s supposed t o proceed v i a alkyl
and alkenyl carbenium i o n s formed f r o m o l e f i n s as p r i m a r y intermediates of
t h i s process ( r e f . 1 ) . R e c e n t l y some papers have been p u b l i s h e d d e a l i n g w i t h
g e n e r a t i o n and t r a n s f o r m a t i o n o f a l k y l carbenium i o n s f r o m ethene and propene
i n zeolites (ref. 2 ) . Formation o f a l k e n y l carbenium i o n s f r o m l o w e r olefins
in zeolites mordenite, f a u j a s i t e and ZSM-5 has been p r o v e n a l s o by UV-VIS
spectroscopy ( r e f . 3 ) .
The o b j e c t i v e o f t h i s paper was t o i n v e s t i g a t e i n d e t a i l t h e i d e n t i f i c a t i o n
of unsaturated s u r f a c e i n t e r m e d i a t e s d e r i v e d f r o m some C, hydrocarbons in
zeolites. S p e c i a l a t t e n t i o n was d i r e c t e d t o t h e t r a n s f o r m a t i o n cyclohexene +

cyclohexadiene + benzene, assumed t o be one o f t h e pathways for yielding

a r o m a t i c s i n t h e MTG process ( r e f . 4), although the formation o f unsaturated
carbenium ions f r o m these c y c l i c compounds has n o t y e t been experimentally
proved.

EXPERIMENTAL
Starting m a t e r i a l s were z e o l i t e NaY f r o m Union Carbide and z e o l i t e ZSM-5,
synthesized i n the laboratory o f Prof. L e c h e r t . D e t a i l s o f sample p r e p a r a t i o n
356

and f u r t h e r t r e a t m e n t a r e g i v e n by K i r i c s i and F o r s t e r ( s e e r e f . 5 ) . The u n i t

cell compositions determined by neutron activation analysis and atomic
a b s o r p t i o n spectroscopy were
HNaY: H, ,Na, ,A1 ,Si ,03
HNaZSM-5 : .O Z N a O . 0 6 A 1 1 . O ESi 9 4 . go, 9 2 .

T r a n s f o r m a t i o n o f C, hydrocarbons was more t h o r o u g h l y s t u d i e d w i t h t h e l a t t e r .

1-Hexene, cyclohexane, cyclohexene, c y c l o h e x a d i e n e - 1 . 4 and benzene, p u r -
chased f r o m Merck, Darmstadt, i n a q u a l i t y b e t t e r t h a n 99%, were used as
adsorbates.
For the spectroscopic i n v e s t i g a t i o n s s e l f - s u p p o r t i n g wafers o f 5-7 mg/cm2
thickness were pressed and outgassed a t 770 K o v e r n i g h t under high vacuum
c o n d i t i o n s i n t h e o p t i c a l c e l l , made f r o m f u s e d q u a r t z f o r t h e U V - V I S and f r o m
g l a s s w i t h S i l v a c a - g l u e d KBr windows f o r t h e I R e x p e r i m e n t s .
The UV-VIS spectra were r u n i n t r a n s m i s s i o n on a Cary 17 spectrometer
c o n t r o l l e d by a B a s i s 108 computer. The d i g i t i z e d s p e c t r a were smoothed a f t e r
background correction. A n o n l i n e a r l e a s t squares p r o c e d u r e was used f o r the
deconvolution of the e l e c t r o n i c spectra, fitting Gaussian peaks to the
measured d a t a . I R s p e c t r a were r e c o r d e d on a P e r k i n - E l m e r 225 s p e c t r o m e t e r .
The a c i d i t y o f t h e samples was determined a p p l y i n g p y r i d i n e as a p r o b e . The
r a t i o o f B r o n s t e d t o Lewis a c i d s i t e s Bpy/Lpy was f o u n d t o be 0.19 and 2 . 2 1 i n
case o f HNaY and HNaZSM-5, r e s p e c t i v e l y .

RESULTS
U n s a t u r a t e d carbenium i o n s have been formed f r o m a l l C 6 compounds investi-
gated. Similarities as w e l l as d i f f e r e n c e s were f o u n d i n t h e s p e c t r a o f the
v a r i o u s hydrocarbons a f t e r a d s o r p t i o n . While a f t e r cyclohexane admission o n l y
a weak band near 310 nm appeared a t room temperature, two bands o f v e r y low
i n t e n s i t i e s a t 373 and 495 nm were f o u n d a f t e r a d s o r p t i o n o f benzene.
Generation and t r a n s f o r m a t i o n o f a l k e n y l carbenium i o n s f r o m 1-hexene were
v e r y s i m i l a r t o those o b t a i n e d f r o m propene i n b o t h z e o l i t e s HNaY and HNaZSM-
5. After a d s o r p t i o n and r e a c t i o n o f 1-hexene bands a t 325, 380 and 450 nm
developed, which can be assigned t o t h e mono-, d i - and t r i e n y l i c carbenium
ions, respectively. Details o f 1-hexene a d s o r p t i o n and c o n v e r s i o n and the
comparison o f these U V - V I S r e s u l t s w i t h those o f Maixner e t a l . , obtained by
NMR spectroscopy a r e g i v e n elsewhere ( r e f . 5 ) .
Cyclohexene adsorbed i n HNaZSM-5 gave r i s e t o a b s o r p t i o n s a t 298, 310, 340
and 391 nm, as can be seen i n F i g . 1. W i t h c o n t a c t t i m e t h e 310 and 340 nm
bands i n c r e a s e d and two new a b s o r p t i o n s near 420 and 530 nm became d e t e c t a b l e .
Upon e v a c u a t i o n a t 370 K t h e i n t e n s i t y o f t h e 310 nm band was enhanced and an
additional band a t 380 nm developed and became d o m i n a t i n g i n t h e whole spec-
 357

aI
U

aJ n
m
U
c 0
v)
n
m n
4
m
0
n
4

3
300 400 500 300 400 500
X/nm X/nm
Fig. 1. Transmission electronic Fig. 2. U V - V I S spectra o f z e o l i t e
s p e c t r a o f z e o l i t e HNaZSM-5 loaded HNaZSM-5 exposed t o 133 Pa cyclo-
w i t h 666 P a cyclohexene. ( a ) A t hexadiene. ( a ) A t room temperature,
room temperature, immediately a f t e r s h o r t l y a f t e r admission, ( b ) 30
admission, ( b ) 1. ( c ) 2, ( d ) 3 h min, ( c ) 1 h l a t e r . A f t e r evacua-
l a t e r . A f t e r evacuation f o r 1 h a t t i o n f o r 1 h a t ( d ) room tempera-
(e) room temperature, ( f ) 370 K, ture, ( e ) 370 K, ( f ! 470 K and ( 9 )
(9) 470 K and (h) 570 K. 570 K.

trum. A f t e r vacuum t r e a t m e n t a t 470 K a b s o r p t i o n s a t 270 ( s h o u l d e r ) , 295 ( t h e

most i n t e n s e band), 340, 380, 420 and 530 nm were observed, w h i l e a t 570 K a
broad a b s o r p t i o n o f o v e r l a p p i n g bands remained.
S h o r t l y a f t e r admission o f 133 Pa cyclohexadiene v e r y i n t e n s e bands a t 320
(shoulder), 410, 460, 520 and 570 nm c o u l d be d i s t i n g u i s h e d even by t h e naked
eye (see F i g . 2); t h e i n t e n s i t y o f each i n c r e a s e d w i t h t i m e . Upon e v a c u a t i o n
at room temperature t h e i n t e n s i t y o f t h e l o w frequency bands decreased (see
spectrum d), while at 370 K a new band arose a t 590 nm. At 470 K the
a b s o r p t i o n s a t l o n g e r wavelengths almost c o m p l e t e l y disappeared. The spectrum
after e v a c u a t i o n a t 570 K was s i m i l a r t o those o f cyclohexene under t h e same
c o n d i t i o n s (compare s p e c t r a h and g i n F i g . 1 and 2 ) .
I t was a general observation t h a t w i t h exception o f benzene carbocation
f o r m a t i o n s t a r t s w i t h t h e monoenylic species f o l l o w e d by t h e o l i g o e n y l i c i o n s .
In t h e case o f benzene o n l y t h e development o f t h e d i - and t r i e n y l i c i o n s is
observed.
As i n f o r m a t i o n about t h e s t r u c t u r e o f t h e s u r f a c e s p e c i e s can be obtained
from the i n f r a r e d region, supplementary I R s p e c t r a o f t h e two most impor-
t a n t compounds cyclohexene and cyclohexadiene were r u n upon a d s o r p t i o n i n the
358

zeolites. The IR s t u d y o f benzene a d s o r p t i o n i n t h e z e o l i t e s was omitted,

because t h i s has a l r e a d y been conducted i n d e t a i l b y Karge and Datka (ref.
6).
The s p e c t r a o f cyclohexene adsorbed i n z e o l i t e HNaZSM-5 a r e shown i n Fig.
3. The s p e c t r a l changes a r e s i m i l a r t o t h o s e observed by Haber e t al. (ref.
7 ) . Bands a t 1653 and 3025 CN’ a r e c h a r a c t e r i s t i c o f t h e C=C i n t e r n a l c y c l i c
double bond and =C-H bond s t r e t c h i n g v i b r a t i o n s , b o t h d e c r e a s i n g w i t h t i m e .
The f a s t e v o l u t i o n o f an a b s o r p t i o n near 1510 cm-’ r e f l e c t s t h e formation of
u n s a t u r a t e d carbenium i o n s . No band a t 1478 cm-I, c h a r a c t e r i s t i c f o r the r i n g
stretching vibration o f benzene was d e t e c t a b l e . A f t e r evacuation a t 470 K
almost a l l bands disappeared.
I

al
U
c
m
Y
CI
.r
E
VI
C
a
L
I-

1
3100 2900 2700 1700 1600 I 500 1400
Wavenumber/cm-’
F i g . 3 . IR s p e c t r a o f cyclohexene adsorbed i n z e o l i t e HNaZSM-5.
( a ) Z e o l i t e background spectrum. A t beam temperature ( b ) 2 min
a f t e r admission o f 666 Pa o f cyclohexene, ( c ) 1 h, ( d ) 3 h l a t e r .
A f t e r e v a c u a t i o n a t ( e ) beam temperature, ( f ) 370 K and ( 9 ) 470 K
f o r 1 h.
Spectra obtained from c y c l o h e x a d i e n e i n z e o l i t e HNaZSM-5 proved to be
r a t h e r complex (see F i g . 4 ) . The band a t 3032 cm-’ due t o i n t a c t c y c l o h e x a d i e n e
decreased with t i m e o f c o n t a c t a t beam t e m p e r a t u r e as a result of surface
t r a n s f o r m a t i o n o f t h i s compound. Bands d e v e l o p i n g a t 1505 and 1535 cm-’ can be
assigned t o u n s a t u r a t e d carbenium i o n s formed on t h e zeolite surface. Here
again t h e band c h a r a c t e r i s t i c o f adsorbed benzene a t 1478 c d i s absent. S i n c e
t h i s band i s u s u a l l y v e r y sharp and i n t e n s e and we c a n n o t f i n d any indication
 359

I ..
31 00 2900 2700 1600 1500 1400
Wavenumber/cm-’

F i g . 4 . IR s p e c t r a o f cyclohexadiene adsorbed i n z e o l i t e HNaZSM-

5. ( a ) Z e o l i t e background spectrum. ( b ) A t beam t e m p e r a t u r e , 3 min
a f t e r admission o f 213 P a o f cyclohexadiene, ( c ) 1 h, ( d ) 2 h,
( e ) 4 h l a t e r . ( f ) A t 370 K a f t e r 1 h. ( 9 ) A f t e r 1 h e v a c u a t i o n
a t beam temperature.

of it in our spectra, the formation of benzene from cyclohexene and

cyclohexadiene upon admission t o z e o l i t e s a t low temperatures does n o t occur
t o any a p p r e c i a b l e e x t e n t .

DISCUSSION
Electronic spectra usually appear as broad absorptions due to their
unresolved rovibrational f i n e structure, rendering t h e i r complete analysis
extremely d i f f i c u l t . Consequently, a d j a c e n t e l e c t r o n i c t r a n s i t i o n s merge i n t o
broad o v e r l a p p i n g bands, which can be deconvoluted a p p l y i n g a d a t a manipula-
t i o n program (see F i g . 5), d e t a i l s o f which and a p p l i c a t i o n t o quantitative
analysis o f U V - V I S s p e c t r a w i l l be p u b l i s h e d elsewhere ( r e f . 8). Using the
bands r e s o l v e d by t h i s procedure q u a n t i t a t i v e c o n c l u s i o n s c o n c e r n i n g c a r b o c a t -
i o n f o r m a t i o n can be drawn.
UV-VIS bands of hydrocarbons adsorbed on s o l i d surfaces are generally
360

compared t o t h e s p e c t r a o f u n s a t u r a t e d carbenium i o n s observed in superacid

s o l u t i o n s . T h i s i s t h e most advantageous way f o r a t t r i b u t i n g bands t o d i s t i n c t
i o n i c species, as c a r b o c a t i o n f o r m a t i o n has been v e r y e x t e n s i v e l y s t u d i e d in
superacids ( r e f . 9 ) .

10.2 Absorbance u n i t s

F i g . 5. Deconvoluted s p e c t r a o f
( a ) benzene, ( b ) c y c l o h e x e n e and
( c ) c y c l o h e x a d i e n e adsorbed i n
z e o l i t e s . The s p e c t r a were r e -
c o r d e d a f t e r e x p o s i n g t h e zeo-
300 400 500 l i t e s t o t h e adsorbates f o r 1 h
X/nm a t room t e m p e r a t u r e .

I n some cases, e.g. f o r t h e appearance o f c e r t a i n carbenium i o n s and t h e i r

rate of formation, good correlations or similarities between superacid
solution and the z e o l i t e surface could be ascertained, even though the
environments o f t h e c a r b o c a t i o n s i n b o t h systems a r e d i f f e r e n t and influence
not only the r a t e o f formation b u t also the s t a b i l i t y of the unsaturated
species ( r e f . l o ) .
In other cases, l a r g e r d i f f e r e n c e s i n t h e band maxima of carbocations
formed i n s u p e r a c i d s and i n z e o l i t e s were found. T h i s i s demonstrated by Table
1, in which the wavelengths o f maximum absorbance o f the carbenium ions
i d e n t i f i e d i n a c i d i c s o l u t i o n s a r e compared t o t h o s e observed upon adsorption
o f hydrocarbons i n z e o l it e s .
I n t h e case o f benzene t h e two bands observed a t 373 and 495 nm do n o t a-
gree w i t h t h e f i n d i n g s o f p r e v i o u s a u t h o r s ( r e f . 1 2 ) , w h i c h means t h a t f u r t h e r
i n v e s t i g a t i o n s are required. The absence o f monoenylic species, p r o v e d by us,
 361

is quite understandable s i n c e p r o t o n a t i o n o f t h e a r o m a t i c ring immediately

y i e l d s d i e n y l i c s p e c i e s and,furthermore, r i n g - o p e n i n g seems t o be u n f a v o u r a b l e
a t low temperatures.
Comparing t h e s p e c t r a o f benzene, cyclohexene and c y c l o h e x a d i e n e ( s e e F i g .

TABLE 1
A b s o r p t i o n maxima o f c a r b o c a t i o n s formed in zeolites, compared to
superacids.

Carbocations i n s u p e r a c i d s * Hydrocarbons adsorbed i n z e o l i t e s Ref

max'nm maxi''
325 **
CH,\ +
C-CH-CH, 305 CH, =CH-CH, -CH, -CH, -CH, 380
CH( - - - - - - - CH, 450

298
310 **
0 340
0 315 391

284
324
414 **
464
517
5 74
-
0 325 440, 550
373, 495
12
**
0 310 **
-
0 330
0~
470 13

450
315 cb 530
--
12

325
408 357 14
377
392
** 415
From r e f . 11; T h i s work

5 ) i t becomes e v i d e n t t h a t those o f t h e . l a t t e r two resemble each o t h e r . I t i s

a l s o obvious t h a t t h e c a p a b i l i t y o f cyclohexadiene f o r i o n f o r m a t i o n exceeds
that o f cyclohexene. B u t i n t h e i r s p e c t r a t h e r e i s no e v i d e n c e f o r bands at
373 and 495 nm c h a r a c t e r i s t i c f o r adsorbed benzene. I t must be mentioned t h a t
a correct and unambiguous assignment o f t h e UV-VIS bands obtained upon
362

a d s o r p t i o n o f c y c l i c hydrocarbons has n o t y e t been p u b l i s h e d .

As far as the f o r m a t i o n o f benzene is concerned, Gibbs energies of
formation i n t h e sequence o f t h e r e a c t i o n m e t h y l c y c l o p e n t a n e + cyclohexane +

cyclohexene + cyclohexadiene + benzene were c a l c u l a t e d f o r d i f f e r e n t tempera-

t u r e s u s i n g t h e thermodynamic d a t a g i v e n i n r e f . 15 (see Table 2 ) . Herefrom i t
becomes e v i d e n t t h a t f o r m a t i o n o f benzene and c y c l o h e x a d i e n e i s u n f a v o u r e d at
low temperatures. This is in good agreement with experimental results
according t o which t h e f o r m a t i o n o f a r o m a t i c s f r o m l o w e r o l e f i n s on zeolite
HZSM-5 proceeds a t temperatures above 570 K ( r e f . 4 ) . From o u r s p e c t r o s c o p i c
r e s u l t s t h e same c o n c l u s i o n s can be drawn.

TABLE 2
Gibbs f r e e energy o f f o r m a t i o n o f m e t h y l c y c l o -
pentane, cyclohexane, cyclohexene, c y c l o h e x a -
diene, benzene and 1-hexene i n t h e t e m p e r a t u r e
range 298-673 K (see r e f . 15).

AGf/kJ mol-'
T'K I MCP CHAN CHEN CHOEN BENZ 1-HEXENE
-
298 35.6 31.6 106.7 186.5 129.6 87.4
323 36.6 44.7 116.3 193.0 133.6 98.3
373 72.4 71.6 135.7 206.4 141.8 120.6
473 123.8 127.2 176.1 234.6 159.3 166.8
573 176.8 184.4 217.8 264.0 177.6 214.5
673 231.1 242.8 260.3 294.2 196.5 263.2

As t h e z e o l i t e s used i n t h i s s t u d y c o n t a i n e d b o t h B r o n s t e d und Lewis acid

s i t e s , t h e f o r m a t i o n o f t h e f o l l o w i n g s u r f a c e s p e c i e s may be assumed:

b
0 0
0
uv-vis active *
* ) means a b s o r p t i o n a t h>200 nm

This v e r y s i m p l i f i e d r e a c t i o n scheme shows t h a t f o r m a t i o n of unsaturated

carbenium i o n s can be e x p e c t e d f r o m each compound, i n c l u d i n g cyclohexane, in
 363

t h i s case by secondary t r a n s f o r m a t i o n v i a t h e c y c l o h e x y l carbonium ion. This

may be the reason f o r the observation that cyclohexane is only slowly
converted i n t o UV-VIS a c t i v e s u r f a c e compounds.
Interconversion o f carbenium ions can also take place in zeolites.
T h e r e f o r e t h e bands observed w i t h cyclohexene and cyclohexadiene can be a t t r i -
buted to different intermediates formed upon transformation of primary
generated i o n s .

CONLCUSIONS
From o u r i n v e s t i g a t i o n s t h e f o l l o w i n g c o n c l u s i o n s must be drawn:
- From a l l C, compounds under i n v e s t i g a t i o n u n s a t u r a t e d carbenium i o n s could
be generated.
- The c a r b o c a t i o n f o r m a t i o n s t a r t s w i t h t h e monoenyl species, i n t h e case o f
benzene w i t h t h e d i e n y l i c carbenium i o n .
- Carbocations formed from cyclohexene and cyclohexadiene may be either
cyclohexyl and cyclohexenyl or cyclohexenyl and cyclohexadienyl ions
depending on whether i n t e r a c t i o n t a k e s p l a c e w i t h B r o n s t e d o r Lewis acid
sites. These species undergo r i n g - o p e n i n g t o open-chain a l k e n y l carbenium
ions .
- Cyclohexane transforms in the f i r s t step into saturated carbocations,
a b s o r b i n g i n t h e FUV range, y i e l d i n g e n y l i c carbenium i o n s o n l y a f t e r r i n g -
opening .
- From the spectroscopic i n v e s t i g a t i o n s i t can be inferred that the ion
formation capability of t h e hydrocarbons i n v e s t i g a t e d decreases in the
sequence cyclohexadiene > cyclohexene > 1-hexene > cyclohexane > benzene.
- At the f i r s t stages o f c a r b o c a t i o n development f r o m C, hydrocarbons the
f o r m a t i o n o f a r o m a t i c s u r f a c e species may be excluded.

ACKNOWLEDGEMENT
One o f t h e a u t h o r s ( I . K . ) i s g r a t e f u l t o t h e Alexander von Humboldt Founda-
t i o n f o r a r e s e a r c h f e l l o w s h i p . We thank D r . J . t e n Pas f o r t h e s y n t h e s i s o f
z e o l i t e ZSM-5.

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H.G. Karge,J. Weitkamp (Editors),Zeolites 0s Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science PublishersB.V., Amsterdam - Printed in The Netherlands

AN INFRARED AND CATALYTIC STUDY OF ISOMORPHOUS SUBSTITUTION IN PENTASIL

ZEOLITES

M.F.M. Post, T. Huizinga, C.A. Emeis, J.M. Nanne and W.H.J. Stork
Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B.V.), Badhuisweg 3 ,
1031 CM Amsterdam (The Netherlands)

ABSTRACT
The catalytic sites associated with aluminium-, iron- and gallium-containing
silicates of MFI structure have been characterized by infrared (IR) spectro-
scopy and in catalytic experiments in which n-hexane conversion served as a
test reaction. The protonic forms of the metal silicates exhibit characteristic
absorptions in the u(0H) region which are assigned to M(0H)Si bridging
hydroxyls: Fe, Ga, A1 in order of decreasing frequency. Rate constants for
n-hexane conversion were found to increase linearly with the concentration of a
particular trivalent metal ion in the silicate material, and this observation,
together with the IR studies, provides direct evidence that Al, Ga and Fe can
be incorporated in the MFI framework, giving rise to Brplnsted acidity. The
catalytic activity expressed per M(0H)Si site decreases in the order Al, Ga,
Fe, which is in agreement with the direction of change in IR frequency of the
absorption associated'withthe bridging hydroxyl group. A simple but straight-
forward model is offered to account for the variation in acidity observed.

INTRODUCTION
Zeolites play an important role in catalysis today, in particular in oil
refining. Use is made of their high acidity which, for instance, renders them
hundreds of degrees more active than amorphous mixed oxides (ref. 1). Particu-
larly successful has been the use of zeolite Y in catalytic cracking and also
the use of mordenite in paraffin isomerization (Shell Hysomer Process, ref. 2).
In the late '60s and '70s attention shifted towards the high-silica zeo-
lites. This was triggered partly by the possibilities offered by steam dealumi-
nation ("ultrastabilization";for a recent review see ref. 3 ) , but even more by
the increasing number of high-silica zeolites that could be synthesized direct
using organic templates. Here, of course, the synthesis and application of
ZSM-5 (ref. 4 ) was a landmark. From further work it emerged that the all-silica
analogues of many zeolites could be synthesized, silicalite being a prime
example.
This situation allows one to consider zeolites from the point of view of the
solid-state chemist and to consider the aluminium sites - though responsible
for activity - as lattice "defects" that can be introduced up to a certain
concentration (isomorphous substitution). In this concept the possibility of
366

introducing a different type of lattice "defect" becomes of interest. Of course

one then primarily considers in the first instance other trivalent cations that
fit well into a tetrahedral oxygen environment, such as Fe, Ga, and possibly
also B. In principle, however, this reasoning can be applied to any lattice
"defect",including trivalent ions that prefer octahedral coordination (Cr3+,
ref. 5), bivalent ions (Be2+, ref. 6) and tetravalent ions (Ge4+, Ti4+, ref.
7), some of which have been known for some time (ref. 8 ) . Obviously, one
expects the best stability - or the highest attainable concentration - for
those ions that fit best.
High-silica zeolites are generally synthesized hydrothermally from alkaline
mixtures, from which ultimately the zeolite is recovered as the solid phase.
Since many of the "hetero atoms" such as Fe and Ga will form precipitates of
oxides and hydroxides under such circumstances, the first question to be
addressed is whether such elements have indeed been incorporated as "defects"
in the "zeolite" lattice, or whether they are present as a separate impurity.
In the last five years much attention has been devoted to this question, the
zeolite phase being studied by a wide variety of techniques, such as X-ray
diffraction (ref. 6 ) , infrared (IR) spectroscopy (ref. 9), ion-exchange capaci-
ty (ref. 10) , temperature-programmed ammonia desorption ( e .g. ref. 9), and 57Fe
Mossbauer spectroscopy (refs. 11 and 12). In many cases it has indeed been con-
cluded that, up to a certain concentration, incorporation into the zeolite
lattice had occurred.
The next question is the characterization of this "hetero atom" site from a
catalytic point of view, since the catalytic activity of the system is general-
ly connected with it, through the charge-compensating bridging hydroxyl. The
-
nature of this hydroxyl group (Si-OH-X, X Al, Fe, Ga, B, . . . ) will depend on
X, as has been reported already (ref. 9 ) . In this study we aim to present
results from both IR and catalytic studies on the Al, Fe and Ga MFI silicates
to arrive at a consistent description. n-Hexane conversion was chosen as a test
reaction.

EXPERIMENTAL PART
Zeolite syntheses
MFI metal silicates with Fe, Ga and A1 were synthesized hydrothermally with
tetrapropylammonium hydroxide or n-butylamine as the organic component in the
zeolite synthesis mixture. Detailed experimental procedures have been outlined
elsewhere (ref. 10): in general, the syntheses were carried out at 423 K for
24 h, with stirring, using teflon-lined autoclaves. In the case of iron and
gallium silicates, care was taken to carefully monitor A1 contamination in the
product, and also in some experiments to reduce it, e.g. by acid leaching of
 367

the amorphous silica base material, or by starting from ultra-pure silica

sources.
The materials were converted into the hydrogen forms by standard methods:
ion exchange with NH4N03 solution (three steps, 10 ml 1 M solution per gram
silicate under reflux conditions for 1 h with intermediate washing), followed
by drying and calcining at 773 K. All samples were white or almost white (high
iron concentration). Details of the composition of the crystalline metal sili-
cates thus prepared are given in Table 1.

TABLE 1
Preparation and composition of the crystalline metal ailicataa studied

A. Preparation

Starting materials:
Amorphous ailica:
LO -
D = Davinon (jrade 952
Daviaon grade 952 leachod with HCl
H = ex Hallinckrodt
"3 = obtained by hydrolysis of tetramethoxyailme
NaAlO
Fe(N0')
Ga (NO31'
NaOH
Aqueous tetrapropylammonium hydroxide solution (T)
n-Butylamine ( 8 )
Molar composition of synthesin mixture:
25 SiO ; p A1 0 ; q Fez03; r GaZ03; n NaZO; t organica; 450 H20
2 2 3
Synthesis conditions:
In general: 24 h at 423 K. stirred autoclave
Silicates 86, B10: 113 h at 423 K. stirred autoclave
Activation procedure:
Calcination at 773 K
Anmonium exchange at 373 K with 1 M aqueous NE4N03 solution
Washing. drying
Calcination at 773 K (1 h)

B. Chemical composition of activated (H') catalysts

Abbreviations defined in Part A

A1 D O 0 n 3 9 T 0.039 0.43
A2 D 0.012 n n 3 Q T n.129 1.44
A3 D 0.039 o 0 1 Q T 0.165 1.84
A4 D 0.063 n n 1 9 T 0.315 3.52
A5 H O n 0 1 9 T o.on9 0.10
A6 LD 0.2 n 0 1 3 T 0.680 7.7

B1 M O 0.063 n 1 Q T 0.004 0.72 3.91

B2 D O n.w o 1 9 T 0.027 0.88 4.79
~3 TMS n 0.063 0 3 9 T 0.015 1.00 5.46
B4 M O n.nm n 3 Q T n.nn9 1.02 5.57
85 M O 0,125 0 1 Q T 0.007 1.24 6.79
86 H O 0.20 n 2.5 in B n.nm 1.72 9.48
87 H O 0.20 n 1 9 T 0.024 1.8~ 10.0
BB D O n.167 o 3 9 T 0.048 2.60 14.5
B9 LD n 0.03 n 2.3 9 T n.nn8 0.28 1.51
Bin ID o 0.20 n 2.5 in B n.ni4 1.77 9.8

c1 D O D 0.063 1 8 T n.ns8 1.02 4.46

c2 D O n n.125 i 9 T 0.047 1.32 5.79
c3 LD n n 0.2 1 9 T n.nw 1.60 7.04
c4 LO 0 n 0.33 1 o T n.nn8 3.23 14.6
368

Infrared sDectroscoDp
Thin self-supporting wafers of the hydrogen forms of various samples were
heated for 0 . 5 h at 723 K in vacuo. Infrared spectra were recorded at room
temperature (293 K) with a Digilab FTS-15 Fourier transform spectrometer.

Catalytic activitv testine Drocedures

Rates of conversion of n-hexane were measured in a stainless-steel downflow
microreactor containing 2 g catalyst, sized to a fraction having an average
diameter of 0 . 4 nun and diluted with silicon carbide particles (diameter 0.2 mm)
in a volume ratio of 1/2. To eliminate the possibility of thermal cracking con-
tributing to the overall conversion of n-hexane, we carried out the tests at
723 K (rather than 7 7 3 K, at which the a-test is normally performed; ref. 1)
and at a total pressure of 0 . 5 MPa (helium/n-hexane - 4/1 mol/mol).
The n-hexane was introduced with a high-precision displacement pump. Helium
was mixed with the hydrocarbon stream in the preheater. The conversion was
determined by gas chromatographic analysis of the reactor effluent.
Conversion of n-hexane (x) was found to obey first-order kinetics; hence the
reaction rate constant (k) can be obtained with the aid of the familiar
expression for an integral tube reactor: kr - -ln(l-x), where r denotes the
space time of the reactant, which is a function of its initial concentration,
molecular weight, zeolite density and weight hourly space velocity (WHSV).
Since in the present study the performance of the various catalysts is compared
at equal space velocity (WHSV - 1 kg/(kg.h)), it was considered appropriate to
express catalyst activities by the quantity -ln(l-x).

RESULTS
Catalytic activitv testing
For investigation of the effect of isomorphous replacement in crystalline
metal silicates of MFI structure on their catalytic activity, many reactions
may be considered. Studies reported in the literature include n-decane hydro-
conversion (ref. 1 3 ) , butane cracking (ref. ll), isomerization of alkyl
aromatics (refs. 14 and 15), alkylation of toluene with methanol (ref. 16),
conversion of methanol to hydrocarbons (refs. 17 and 18) and catalytic dewaxing
(ref. 14). In this work we have confined ourselves to a study of the BrZnsted
acidity in the catalytic conversion of n-hexane. This particular hydrocarbon
was selected since it is the standard probe molecule in the a-test (ref. 1).
Moreover, rates of n-hexane conversion are not disguised by diffusion limita-
tions (refs. 20 and 21) inside coarse-crystalline materials, properly reflec-
ting intrinsic acidity in a series of ZSM-5 materials with different A1 con-
tents (refs. 21 and 2 2 ) .
 369

The activities of crystalline aluminosilicates with the MFI structure in the

conversion of n-hexane as measured in this study are given in the upper part of
Table 2 . As expected, catalyst activity, expressed as -ln(l-x), increases
linearly with increasing A1 content, which was varied in the range 0.039 -
0.315 %w (see Fig. l), and these results are fully in line with previous
reports (refs. 21 and 22). Apparently, a ZSM-5 material without any aluminium
would be completely inactive in the conversion of n-hexane under the reaction
conditions chosen.

TABLE 2

Conversion of n-hexane over various crystalline metal silicates

with the MFI structure
Reaction conditions: Feed : n-C /He, 114 mollmol
T : 723%
p(overal1): 0 . 5 MPa
WHSV : 1 kg n-C,l(kg cat.h)

Silicate Al. Fe, Ga, -ln(l-x)

no. xw xw xw
overall" Arb FeC GaC

A1 0.039 0.35
A2 0.129 1.60
A3 0,165 1.79
A4 0.315 3.50

81 0.004 0.72 0.1s 0.04 0.15

82 0.027 0.88 0.50 0.30 0.20
83 0.015 1.00 0.37 0.17 0.20
84 0,009 1.02 0.31 0.10 0.21
85 0.007 1.24 0.33 0.08 0.25
86 0.018 1.72 0.56 0.20 0.35
87 0.024 1.82 0.78 0.27 0.51
88 0.048 2.60 1.02 0.54 0.48

c1 0.058 1.02 1.70 0.65 1.05

c2 0.047 1.32 2.15 0.53 1.62

'Overall catalytic activity taken at run hour 1 (expressed as

-ln(l-convsrsion); explained in text). The rates of deactivation
bware of the order of 2-3 X per h. or less.
Contribution of contaminating A 1 to catalyst activity.
'Resulting contribution of Fe or Ga to catalyst activity.

The results obtained with a series of crystalline iron silicates having the
MFI structure (samples B1 - B8) are given in the middle part of Table 2 . Owing
to the different silica sources used in the synthesis, the level of aluminium
contamination in the samples varies significantly (from 0.048 down to 0.004 %w).
As minor amounts of A1 may contribute to the overall activity of the iron sili-
cate, we first quantified the effect of contaminating aluminium by comparing
the activities of samples having similar iron contents but very different
levels of A1 contamination (samples B1 - 84). The results, plotted in Fig. 2 ,
show that a highly pure iron silicate material has significant activity, while
incorporation of aluminium results in a further gain in activity. The experi-
mental values lie on a straight line which runs parallel to the relation
between activity and A1 content for zeolite ZSM-5. Apparently the difference in
activity between an Al-contaminated iron silicate and a ZSM-5 material having
370

the same A1 content is independent of aluminium content and reflects the con-
tribution of the iron to overall activity. In other words, the presence of
residual A1 in iron silicates does not lead to synergistic effects in the con-
version of n-hexane: the contributions of the iron and aluminium in the MFI
structure are additive. Hence, the net contribution of the iron to catalytic
activity (Table 2 ) was obtained by linearly correcting the overall activities
for the contribution of residual A1 by interpolation of the data from Fig. 1.
The results, shown in Fig. 3 , indicate the existence of a linear relation
between the extent of isomorphous substitution of iron (at least in the range
0.7 - 2 . 6 %w Fe) and catalytic activity. It is also worth while mentioning that
this holds for all the iron silicates tested, which were prepared via different
routes.
Figure 4 compares the first-order rate constants for n-hexane conversion
over materials with MFI structure as a function of concentration and type of
trivalent metal ion in the silicate materials. In the figure we have also
included data on crystalline gallium silicates (lower part of Table 2 ) . The
activities of gallium and iron are net values, i.e., corrected for the contri-
bution of contaminating aluminium.

-tn ( I - x ) - tn(1-x)
0.6r

0 0.1 0.2 0.3 0.4 0 0.01 0.02 003 004 0.05

A t content of ZSM-5, %w AL content, % w

Fig. 1. Conversion of n-hexane over Fig. 2 . Effect of aluminium contamina-

ZSM-5: effect of A 1 content on rate tion on the activity of crystalline
constant. For reaction conditions iron silicates (MFI structure, -1 %w
see Table 2 . Fe) in the conversion of n-hexane. For
reaction conditions see Table 2 .
 371

- Ln(l-x)F,
0.51 0 .

I I 1 I I J
0 0.5 1 1.5 2 2.5 3
Fe,%w

Fig. 3 . Effect of iron content on the activity of crystal-

line iron silicates (MFI structure) in the conversion of
n-hexane. Rate constant is corrected for the contribution
of contaminating aluminium to activity. For reaction con-
ditions see Table 2 .

- tn (1- x ) ~

M=AL

M = Go

M: Fe
Fig. 4 . Conversion of n-hexane over
crystalline metal silicates. Effect of
trivalent metal content of the silicate
on reaction rate constant. Rate constant
of iron and gallium silicates is correc-
ted for the contribution of contamina-
0 5 I0 15 ting aluminium to activity. For reaction
M,03/Si02, mmoL/mol conditions see Table 2 .
372

IABLE 3
Absorbonce, log ( l 0 / l )
E f f e c t o f composition o f metal s i l i c a t e s
having MFI structur. on tha s t r e t c h i n 5
frequency of H(OR)Si hrid8ing hydroxyl
groups

Sample Al, Fe, Ga. H(OA)Si

no. xw Xw Xw I4 l"OR],
cm

A5 0,009 3740'
A6 0.680 A1 3610
BQ 0.008 0.28 Fe 3830
B10 0,014 1.77 Fe 3630
c3 0.008 1 . 6 0 Ga 3615
c4 0.008 3 . 2 3 Ga 3615

'Terminal SiOR hydroxyl groups.

Fig. 5. Infrared spectra of

crystalline metal silicates.
Bar indicates 0.1 absorbance
unit. Sample: a: A 5 ; b: A 6 : 3800 3700 3600 3500 3400
c: C4; d: B9. Wove number, cm-'

Infra-red measurements
It has been demonstrated in the past (e.g. ref. 9) that IR spectroscopy is a
powerful technique to monitor differences between various crystalline metal
silicates. In our work we used it to investigate the effect of isomorphous
replacement. The previous studies have shown that shifts in hydroxyl stretching
frequencies exist going from ZSM-5 to crystalline gallium, iron or boron
silicate. Our results confirm these findings, as indicated in Table 3 and Fig.
5. In this case the aluminium metal silicate has the lowest stretching frequen-
cy, followed by the gallium and the iron silicate.

DISCUSSION
The linear relations observed between the rate constant for n-hexane conver-
sion and the concentration of trivalent metal in the MFI structure provide
direct evidence for the fact that the reaction is associated with the trivalent
metal ion present in the crystalline metal silicate. This does not necessarily
imply that the ions are incorporated into the "zeolite" structure during the
synthesis and/or under the conditions prevailing during the catalytic test. It
does indicate, though, that the catalytic nature of the sites associated with
the trivalent metals in the MFI silicates is independent of the concentration
of these sites, at least in the ranges studied in the present work. For it to
be proved unequivocally that trivalent metal is incorporated into the zeolite
lattice separate studies are required. A magic-angle-spinning nuclear magnetic
resonance (MASNMR) study in which n-hexane cracking activities measured for A1
silicates of MFI structure have been correlated with tetrahedral A 1 signal
intensities (ref. 23) is a straightforward example of such a proof for alumi-
nium incorporation.
Incorporation of gallium in zeolite structures using Ga MASNMR techniques
has been recently demonstrated (ref. 24) and this technique has proved very
useful in providing evidence for the incorporation of Ga in MFI structures
(ref. 25). Incorporation of iron in the MFI structure to a certain level has
been recently demonstrated by means of 57Fe Mossbauer studies combined with
electron spin resonance (refs.11 and 1 2 ) and these results are in good agree-
ment with our observations (ref. 2 6 ) . In addition, the IR studies reported here
also lend firm support to the idea that A l , Ga and Fe are incorporated in the
MFI structure as lattice "defects", giving rise to Br$nsted acidities
associated with bridging hydroxyls whose IR frequencies decrease in the order
Fe(0H)Si > Ga(0H)Si > Al(0H)Si.
It is evident from Fig. 4 that there is a marked difference in activity as
far as the type of "defect" is concerned. In terms of first-order rate constant
the activities of the catalytic sites associated with the Fe, Ga and A 1 ions
incorporated are roughly in the proportion 1 : 6 : 25, respectively. It should
be mentioned that these results refer to a particular test reaction (i.e.,
n-hexane conversion) under specific reaction conditions and cannot be general-
ized in a quantitative way. The activity sequence, i.e., A 1 > Ga > Fe, however,
is expected to be encountered generally in Br$nsted acid catalysis.
Having established both IR and catalytic measurements it is convenient to
plot the relative cracking activity per trivalent metal ion site as a function
of the observed hydroxyl stretching frequency, as is done in Fig. 6 . Though the
relationship between IR frequency and acid strength in various zeolites and
related materials is not unambiguous, there are indications that, in a homo-
logous series of zeolites, the IR frequency shifts systematically to higher
wave numbers if the acidic strength decreases (ref. 27). From Fig. 6 we con-
clude that the bridging hydroxyl groups with the lower wave numbers, associated
with the more loosely bonded protons, have the higher catalytic activity per
trivalent metal ion. The fact that in this series of IR measurements the
zeolite structure is kept constant precludes possible IR shifts due to changes
in lattice (refs. 28 and 2 9 ) . A link reported earlier (ref. 9) between IR
hydroxyl frequency and NH3 desorption temperature has been established. In ref.
9 the lower IR frequencies correspond to the higher NH3 desorption tempera-
tures, which is in agreement with our findings.
374

R a t e constant, r e l a t i v e units

I
I
I
\
06 \
\
\
04 \

"1 'y-
0
,
3610 3620 3630
Fig. 6. Relative rate constants for n-hexane
conversion over crystalline aluminium, gallium
and iron silicates of MFI structure (based on
unit concentration of trivalent ion) as a
i-iydroxyl stretching frequency, cm-' function of hydroxyl stretching frequency.

It is tempting to speculate about the origin of these differences in acidi-

ty. In our opinion only quantum-mechanical calculations (such as presently in
progress at several locations) will ultimately be able to yield a full under-
standing of these effects. Meanwhile, though, it is attractive to try and
interpret the results with a simple electrostatic model. Thus, it is assumed
that all ions have their formal valencies and have their well-known ionic radii
- - -
(rGa3+ 0.62 , rA13+ 0.51 and rFe3+ 0.64 A; ref. 30). Thus, when we con-
sider the bridging hydroxyl group Si-OH-X, the proton-X distance, at comparable
bond angle, will decrease in the order Fe, Ga, Al. In our model this means that
the electrostatic repulsion between the proton and X increases in the same way,
and that we expect the acidity to increase in the same order. Interestingly,
though this model is obviously a gross oversimplification, it does predict the
correct acidity ranking.

REFERENCES

1 P.B. Weisz and J.N. Miale. J.Cata1... 4 (1965)

. 527-529.
2 H.W. Kouwenhoven and W. van Zyll Langhout, Chem. Eng. Prog., 67 (1971)
65-70.
3 J. Scherzer, in T.E. Whyte, R.A. Dalla Betta, E.G. Derouane and R.T.K.
Baker (Editors), Catalytic Materials: Relationship between Structure and
Reactivity, ACS Symposium Series No. 248, 1984, pp. 157-200.
4 US patent 3 702 886 to Mobil.
5 Patent EP 0 021 475 to Shell Internationale Research Maatschappij B.V.
6 J.C. Jansen, E. Biron and H. van Bekkum, in P.J. Grobet, W.J. Mortier,
E.F. Vansant, G. Schulz-Ekloff, B. Delmon and J.T. Yates (Editors), Innova-
tion in Zeolite Materials Science: Proc. Int. Symposium, Nieuwpoort,
Belgium, 1987, Studies in Surface Science and Catalysis 37, Elsevier,
Amsterdam etc., 1988, pp. 133-141.
7 B. Notari, ibid., pp. 413-425.
8 D.W. Breck, Zeolite Molecular Sieves; Structure, Chemistry and Use, Wiley
Interscience, New York etc., 1974.
9 C.T.W. Chu and C.D. Chang, J . Phys. Chem., 89 (1985) 1569-1571.
10 Patents GB 1 555 928, GB 2 055 357 and EP 0 030 751, all to Shell Interna-
tionale Research Maatschappij B.V.
 375

11 R. Szostak, V. Nair and T.L. Thomas, J. Chem. SOC., Faraday Trans. I, 83

(1987) 487-494.
12 G. Calis, P. Frenken, E. de Boer, A. Swolfs and M.A. Hefni, Zeolites, 7
(1987) 319-326.
13 M. Thielen, M. Geelen and P.A. Jacobs, in Proc. Int. Symposium on Zeolite
Catalysis, Siofok, Hungary, 1985, pp. 1-18.
14 B.S. Rao, G.P. Babu, V.P. Shiralkar, A.N. Kotasthane and P. Ratnasamy,
Actas do 90 Simp6sio Iberoamericano de Catdlise, Volume 2, Lisbon, 1984,
pp. 1418-1425.
15 P. Ratnasamy, R.B. Borade, S . Sivasanker and V.P. Shiralkar, Acta Phys.
Chem., 31 (1985) 137-146.
16 R.B. Borade, A.B. Halgeri and T.S.R. Prasado Rao, in Y. Murakami, A. Lijima
and J.W. Ward (Editors), New Developments in Zeolite Science and Technolo-
gy, Proc. 7th Int . Zeolite Conference, Tokyo, 1986, Elsevier, Kodansha,
Amsterdam, etc., 1986, Studies in Surface Science and Catalysis 28, pp.
851-858.
17 W.J. Ball, J. Dwyer, A.A. Garforth and W.J. Smith, ibid., pp. 137-144.
18 T. Inui, A. Miyamoto, H. Matsuda, H. Nagata, Y. Makino, K. Fukuda and
F. Okazumi, ibid., pp. 859-866.
19 S . Sivasanker, K.J. Waghmare, M. Reddy and P. Ratnasamy, Proc. 9th Int.
Congress on Catalysis, Calgary, 1988, vol. I, 16-C2, p. 120.
20 V.J. Frilette, W.O. Haag and R.M. Lago, J. Catal., 67 (1981) 218-222.
21 M.F.M. Post, J. van Amstel and H.W. Kouwenhoven, in D. Olson and A. Bisio
(Editors), Proc. 6th Int. Zeolite Conference, Reno, Nevada, USA, July
1983, Butterworths, Guildford, Surrey, UK, 1984, pp. 517-527.
22 D.H. Olson, W.O. Haag and R.M. Lago, J. Catal., 61 (1980) 390-396.
23 W.O. Haag, R.M. Lago and P.B. Weisz, Nature, 309 (1984) 589-591.
24 D.E.W. Vaughan, M.T. Melchior and A.J. Jacobson, in G.D. Stucky and
F.G. Dwyer (Editors), Intrazeolite Chemistry, ACS Symposium Series No. 218,
1983. .. 231-242.
. DD.
25. N.C.M. Alma-Zeestraten et al., to be published.
26. H. Beens et al., to be published.
27. H.G. Karge, J. Ladebeck, 2. Sarbak and K. Hatada, Zeolites, 2 (1982)
94-102.
28. J . Dwyer, in P.J. Grobet, W.J. Mortier, E.F. Vansant, G . Schulz-Ekloff,
B. Delmon and J.T. Yates (Editors), Innovation in Zeolite Materials
Science: Proc. Int. Symposium, Nieuwpoort, Belgium, September 1987, Studies
in Surface Science and Catalysis 37, Elsevier, Amsterdam etc., 1988, pp.
333-354.
29. H.G. Karge and J. Ladebeck, Acta Phys. Chem., 24 (1978) 11.
30. R.C. Weast (Editor), Handbook of Chemistry and Physics, 68th Edition, CRC
Press, Boca Raton (Florida), 1987.
This Page Intentionally Left Blank
H.G. Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science PublishersB.V.. Amsterdam - Printed in The Netherlands

CALORIMETRIC INVESTIGATION OF THE ACIDITY OF DEALUMINATED Y-TYPE ZEOLITES USING

VARIOUS BASIC PROBES

A. AUROUX, Z . C . SHI, N. ECHOUFI, Y. BEN TAARIT

Institut de Recherches sur la Catalyse, C.N.R.S., Conventionne a l'universite
Claude Bernard, LYON I, 2 , Avenue A. EINSTEIN, 69626 - Villeurbanne Cedex -
FRANCE

ABSTRACT
Y-type zeolites of various Si/A1 ratios have been obtained by dealumination
of NaY zeolites using silicon tetrachloride as the dealuminating agent at
various reaction temperatures. All samples were highly crystalline.
Microcalorimetric measurements of ammonia, pyrrole, dimethylether and
acetonitrile adsorption unveiled various strength distributions among the acid
population of these samples. Ammonia proved to be a reliable probe when Bronsted
acid sites were investigated. It helped to unveil two site populations whose
proportions varied in Si/A1 ratio. These two populations differ by the local
environment of the associated A10 tetrahedra. Ammonia, however, failed to
reveal the inhomogeneity in one parttcular acid population. Dimethylether, a too
weak base, did not appear to be any better than ammonia, whereas pyrrole
appeared as a rather acidic probe which helped visualize the basicity difference
between the parent material and the dealuminated samples. Acetonitrile proved to
be a reliable probe to monitor quantitatively and qualitatively Lewis acidity.

INTRODUCTION
The huge quantities of zeolites involved in the F.C.C. process account for
the continuous or even growing interest manifested for the acidity
investigation of these catalysts. Among the methods which proved to be most
suitable and accurate to monitor acidic solids, microcalorimetric methods were
recognized as a most powerful tool. Previous studies, however, showed the
dependence of the results on the choice of the basic probe and on the
experimental conditions of the calorimetric measurements, especially the
adsorption temperature and the importance of the base doses with respect to the
total number of acid sites of the sample under investigation and their strength
distribution. This prompted one of us to use various basic probes to monitor the
acid strength distribution within ferrierite samples (1). In the course of that
investigation other parameters appeared to be crucial with respect to the
correct evaluation of the experimental results. In particular, the size of the
probe with respect to the channel or cavity openings and the possible existence
of cumbersome extraframework species may greatly influence the relevance of the
results to the actual acidity properties. Therefore we selected samples of
Y-type zeolites with identical cavity openings which permit the equal diffusion
of the selected basic probes.
378

EXPERIMENT AND MATERIALS

NaY samples from Union Carbide (LZY 52) were dried overnight at 400°C under
flowing oxygen and finally under dry nitrogen. They were subsequently cooled
down to the desired temperature to be subjected to the action of SiC14 following
the procedure described by Beyer and Belenykaja ( 2 ) . Samples of dealuminated NaY
zeolites were thus obtained over a broad range of Si/A1 ratios by varying the
dealumination temperature between 250 and 450°C while the Sic1 partial pressure
4
in the nitrogen flow was kept constant by maintaining the SiC14 condenser in a
cold trap at 0°C. The flow rate was also kept constant at 1 1.h-'. The average
sample weight was within 5 g. The dealumination reaction was carried out for one
hour, at which time dry N2 was substituted for the SiC14-N2 flow mixture for an
additional hour and the temperature raised to 450°C for yet another hour so as
to remove any volatile reaction products from the zeolite. The samples were then
progressively cooled down to room temperature and repeatedly washed with
deionized water.
Ammonium exchange was performed using an aqueous acetate solution. Chemical
analysis for aluminium and the residual sodium showed that the exchange level
was within 90 X for all samples. The samples were then kept in a dessicator
containing a saturated solution of CaCl
2'

Analysis. Besides chemical analysis, all samples were analyzed for crystallinity
using X.R.D techniques. The parent NaY (LZY 52) was used as reference. All
samples retained over 98 X crystallinity. The unit cell parameter was determined
and used to final the residual framework aluminium content and consequently the
Si/Al ratio, assuming the linear relation between the unit cell parameter and
the number of aluminium atoms per unit cell ( 3 ) .
The different Si/A1 ratios were also monitored using infrared
spectrophotometry. Anhydrous KBr was thouroughly mixed with the zeolite powder
at a content of less than 1 X to allow for better resolution as sharper
absorptions were recorded at low zeolite loadings. The frequency shift of the
appropriate lattice vibrations was then used to determine the Si/Al ratios and
simultaneously to monitor the crystallinity of the zeolite by surveying the
intensity of the vibration related to the double 6-ring representative of the
hexagonal prisms.

--
MAS NMR. Magic Angle Spinning NMR spectra for "Si and "A1 were obtained on a
commercial Brucker MSL 300 NMR spectrometer equipped with a MAS probe. The
powder samples were placed in cylindrical rotors of the "double bearing" type
 379

and typically spun at an average rate of 3400 Hz.

Framework Si/A1 ratios were determined on the basis of the relation

4 a

using the 29Si NMR spectra ( 4 ) .

27Al NMR was essentially used to monitor the framework or non framework
nature of the residual aluminium.
Adsorption of pyridine was studied using infrared spectroscopy. Zeolite
powder samples were pressed into thin self-supporting disks of 18 nnn in diameter
and 8-10 g weight and placed in pyrex or quartz sample holders. These wafers
were subjected to heating in flowing O2 up to 350°C or alternatively 760°C and
subsequently evacuated at the same temperature for 2hr to a residual pressure of
Torr.
After cooling they were contacted with purified and thoroughly dessicated
pyridine vapour for 2hr. after which excess pyridine was removed by room
temperature evacuation. It was subsequently desorbed at 50°C intervals.
Following each desorption IR spectra were recorded on a Perkin-Elmer
grating spectrophotometer Resolution in the ring-vibration-mode absorption
domain was better than 3 cm
-1
.
Microcalorimetry. The zeolite samples were activated by heating in 02 and then
in vacuo 100 mg quantities in a specially designed cell in separate activation
apparatus and allowed to cool down to room temperature. The cell was then
introduced into the microcalorimeter of the Tian Calvet type (from Setaram).
At equilibrium small doses of purified vapour (dried over 4 A molecular
sieve and degased by freeze-pump thaw cycles) were allowed into the sample. The
evolved heat was recorded continuously together with the equilibrium pressure.

RESULTS AND DISCUSSION

Sample Characterization. Dealuminated NaY samples were obtained upon varying the
temperature of the reaction of SiC14 over the NaY parent material between 200
and 375°C.
All samples showed high crystallinity to X-rays and 27Al NMR confirmed that
all the residual aluminium was in tetrahedral coordination. Thus the
dealumination reaction as reported initially by Beyer and Belenkaja (2)
apparently proceeds at rather moderate temperatures using SiC14 and anhydrous
NaY zeolite. The overall reaction depicted by the following scheme:
380

0 0
\ / \ / - -Ir \ / \ /
( Si A1 ) Nat t SiC14+NaCl t A1C13 t Si Si
/ \ / \ / \ / \

seems to undermine the production of NaAlC1-

4 since nonframework aluminium was
detected either before or after washing the samples.
The Si/Al ratios and the residual A1 atoms per unit cell were reported for
these various samples in table 1.

TABLE 1.
Structural analysis of zeolites

dealumination Framework A1 per unit cell Si/A1 ratio

O C XRD IR NMR N M R X R IR
200 32 30 37 4.25 4.94 5.3
300 24 21 27 6.36 7.06 8.1
350 20 17 20 9.49 8.32 10.6
375 5 7 36.6
450 2 3 5 37.1

Examination of this table indicates that despite obvious divergence of the

three methods used to determine the lattice Si/A1 ratio, the trend exhibited by
each pattern of results is self-consistent. All X-ray-derived ratios were
consistently lower than those derived via infrared measurements. 29Si NMR-
derived ratios were fairly close to the former ratios ; however, at low residual
aluminium content these are less reliable than those derived via X-rays or
infrared measurement in view of the poor accuracy in the determination of the
vanishing Si(1 Al) NMR signal.

Nature of the acid sites. As indicated by 27Al NMR no extra framework A1 was
present following dealumination or activation at 350 to 650°C.
t
On the other hand, the IR spectrum of NH4-exchanged dealuminated samples
exhibited 9 OH bands at 3650 and 3550 cm-l with slight shoulders at 3600 cm-l
whose intensity was barely affected upon varying the activation temperature over
the 350-650°C range. In addition, pyridine adsorption as monitored by infrared
spectroscopy showed the characteristic pattern of the ring vibrations associated
with the presence of pyridinium ions. In particular, the band at 1540 cm- 1
relative to the 19b mode, that at 1630 (8a mode) characteristic of pyridinium
ions kept an invariant intensity as the activation temperature of the zeolite
sample increased from 350 to 650°C. Only the band at 1450 cm-l and a shoulder at
1620 cm-l could be seen, and these were more pronounced at the highest
activation temperatures, probably indicating that Lewis acid sites start to be
created beyond activation temperatures of 600°C. The predominant acid sites
 381

were, however, unambiguously 'of the Bronsted type over this activation
temperature range.

Microcalorimetry measurements. Adsorption of ammonia was conducted as described

in the previous section while the calorimeter temperature was set at 150°C which
precluded, at the low pressures. the physical adsorption of this base. Only the
strongest acid sites could reasonably interact with this probe. Samples
dealuminated over the broad range indicated above were activated at 350°C and
allowed to interact with small doses of MI3. The evolved differential heats, as
a function of the corresponding adsorbed quantities are reported in figure 1.

z
0
I-
n
a
0
In
0
*
U
0
I-
4
W
I

AmouuT N H A
~ DSORBED (cm3.g-1)

Fig. 1 : Differential heats of MI adsorption vs coverage at 150°C for samples

dealuminated at 200°C (a), 300°C (g), 350°C(c), 375°C (d), 45OOC (el, activated
at 350°C.

The most striking feature lies in the close similarities of these diagrams. All
samples exhibit, to various degrees, two distinct populations whose relative
importance of which varies with the extent of dealumination.

The least dealuminated samples exhibited the largest important population of the
weakest acid sites corresponding to the lowest differential heats. The
dealumination caused the corresponding plateau to shrink progressively and the
corresponding heat to slightly increase or remain approximately constant.
The most energetic site population was almost unaffected as the residual
aluminium content decreased from 56 to within 20 - 16. As the dealumination was
pursued the average strength of the latter sites increased, indicating the
sensitivity of the residual sites to the local environment as far as the
mobility of the protons is concerned. This is in excellent agreement with
earlier reports suggesting that the acid strength of ZSM-5 and mordenite-type
382

zeolites increased with increasing Si/Al ratios (5,6,7).However, several authors

have provided evidence for the heterogeneous nature of the acid sites in various
zeolites (81, thus it would not seem sensible to consider the observed constant
heats as actually indicating a population of equally strong sites. Because the
population dealt with was of the Bronsted nature, we felt the use of a less
basic probe was necessary to confirm or disprove the apparent homogeneity of
these populations. Pyrrole whith pka = 0.4 compared to 9.24 for ammonia should
be far more appropriate to detect site heterogeneity. Figure 2 shows the
variation of the differential heats of room temperature adsorption of pyrrole.

PVRROLE

Fig. 2 : Differential heats of pyrrole adsorption vs coverage at 23°C for

samples activated at 350°C : ITY (a), dealuminated at 350°C (b) - 375°C (c).

The histograms show patterns very similar to those already observed in the case
of ammonia. However, the trends are totally reversed with respect to the parent
HY zeolite not only exhibited a population of equally strong sites, but these
sites appeared to be stronger than those of the dealuminated samples, in
constrast to previous observations and the generally accepted view (5.7).
Furthermore, the initial differential heats of adsorption of this supposedly
weaker base are higher than 140 kJ.mol-' which was measured for ammonia at the
same temperature ( 9 ) . which is rather odd. Thus the question arises as to
whether pyrrole was acting as a basic probe! One cannot indeed reconcile the
higher heat observed for pyrrole and the heat trend with dealumination.
Therefore it became vital to consider the hypothesis of pyrrole acting as an
acidic probe. In fact, this latter compound, in spite of the nitrogen lone pair,
was reported in a recent review ( 1 0 ) to behave as an acidic probe. It has a l s o
been claimed that this molecule, barely water-soluble, is the least liable,
among the secondary "aminas", to accept a proton because of the important loss
of stabilisation energy upon formation of the ammonium cation. The lone pair,
 383

indeed, contributes, when free, to ensure an aromatic type resonance, which can
no longer be ensured upon addition of a proton. On the contrary, the carbanion
is usually more stable than the neutral molecule for these very reasons (11). It
is then concievable that if pyrrole is behaving as an acid probe the
differential heats could be higher than those measured for ammonia. It is also
quite reasonable that the basic character of the zeolite decreased with
dealumination as the acidic character increased. Thus the results obtained in
the case of pyrrole, while incoherent when considering this probe as a base, are
entirely self-consistent and in total agreement with the known pattern of
zeolite acidity when this molecule is considered as an acid probe.
Dimethylether with a low pka is not suspected to behave as an acid.
Therefore it was investigated as an alternate basic probe in the hope that it
would help give a more accurate picture of the strength distribution among the
acid sites of a given zeolite. Figure 3 shows the differential heats of room
temperature adsorption of this molecule on Y zeolites of different Si/A1 ratios.
Again, the heats observed for these samples do not show the increase in strength
demonstrated via ammonia adsorption. These results probably can be accounted for
in terms of the non-specificity of this latter probe towards Bronsted-type
sites. Dimethylether was indeed reported to adsorb rather strongly and
specifically on Lewis acid sites and to give rise only to H- bonding with acidic
hydroxyl groups ( 1 2 ) .

I.1 CH, 0 CH,

Fig. 3 : Differential heats of CH OCH3 adsorption vs coverage at 23°C for

-
samples activated at 350°C : HY (a), 3dealuminated at 350 (b) 375 (c).

Therefore ammonia still appears to be the most reliable probe to monitor

the acid strength distribution of solid acids provided the appropriate
experimental conditions are chosen in view of the acid surface under study.
384

Especially, extreme care should be taken in choosing the adsorption temperature.

Whatever the merits and the drawbacks of the use of ammonia,it helped
unveil the fact that dealumination occurs selectively since the population of
the lowest acid strength is affected first while the other population is hardly
affected by dealumination using silicon tetrachloride vapour. The weakest acid
population might be related to the OgH type silanol groups which were shown to
react only poorly with pyridine at room temperature and were restored first upon
pumping. This population of silanol groups is associated with aluminium centres
that are apparently more reactive towards SiC14 or less stable in tetrahedral
coordination then those associated with the 0 H groups. However, as the
1
faujasite-type structure does not provide for more than one crystallographic
site, the difference in strength of the populations could be rationalized in
terms of local environment : aluminium-centred tetrahedra may be only linked to
silicon-centred tetrahedra ; however, the next nearest neigbours could be either
aluminium-or silicon-centred. Thus the ratio of the aluminium-centred to the
Silicon-centred nearest neighbours is likely to induce sensitive differences in
the mobility of the attached protons and give rise to two apparently distinct
populations. Assuming that the protons having the highest number of
aluminium-centred nearest neighbours are the least mobile, progressive
substitution of aluminium by silicon decreases more sensitively these very
populations of sites while slightly affecting the population characterised by
the least number of aluminium-centred nearest neighbours. This is what is
actually observed using ammonia adsorption. However, for reasons that were
already emphasized, this method is not sensitive enough to unveil the structural
heterogeneity stemming from the effect of the more or less remote "nearest
neighbours".
o kJ.rnol-'

Ol
0 6 10 16 20
.
v cma.s-'
Fig. 4 : Differential heats of NH adsorption vs coverage at 150°C for sample
dealuminated at 350°C and activate2 at 350°C (a) and 760°C (b).
 385

The Lewis acid titration is even more difficult to achieve: previous

studies ( 1 3 , 1 4 ) have indicated that these are more energetic than the strongest
Bronsted acid sites. Therefore, the relevant heats of neutralisation cannot
but be underestimated when titrated by a base which is not exclusively
interacting with such types of sites. In the case of ammonia, as shown in figure
4 , heat treatment at high temperature of a sample containing about 16 to 20
residual aluminium-centred tetrahedra resulted in a significant increase of the
initial differential heat of adsorption, confirming that, under these activation
conditions, some Lewis acid sites have been formed.

CH, cw

oi
0 20 40 60
V cm'.g-t

Fig. 5 : Differential heats of' CH3CN adsorption vs. coverage at 23°C for sample
dealuminated at 350°C activated at 350°C (a) and 760°C (b).

In a quest for a more specific basic probe we investigated the adsorption

of acetonitrile, reported to be a good probe for Lewis acid sites, following
well documented infrared studies (15, 16). Figure 5 shows, for a given sample,
the effect of increasing activation temperature on the initial heat of
adsorption of acetonitrile. Clearly, higher heats were evolved when Lewis acid
centres were created following appropriate activation. The presence of Lewis
sites in the sample activated at 760°C was confirmed on the basis of pyridine
adsorption as monitored using infrared spectroscopy and additional 27A1 NMR. The
increase of 15 kJ/mole is certainly underestimated, again, because of the
predominance of Bronsted sites under these conditions. It is noteworthy to
compare the adsorption of ammonia and acetonitrile over the same sample. Figure
6 illustrates the variation of the differential heats of adsorption of these two
compounds over the latter sample. Clearly, ammonia seems to indicate the
occurrence of two distinct and almost homogeneous populations. The most
energetic one could be ascribed to the Lewis acid centres, no matter what their
structure ; the least energetic ones could be identified with the residual
386

proton population, in agreement with the results observed with the same sample
activated at milder temperatures. Acetonitrile indeed showed less variation of
the differential heats, indicating a more heterogeneous nature of the created
Lewis centres than would be apparent from the adsorption of a stronger base over
even stronger acid sites. Of course the initial heats in this case are lower
than those recorded with ammonia. which is consistent with the acidity
difference. Thus acetonitrile proved to be a more appropriate base than ammonia
to discriminate the Lewis centres from Bronsted sites v i a the respective
neutralisation heats. These proved to be different enough, to ensure a more
accurate representation of the strength distribution among Lewis sites.

0 LJ.mol-1
t

Fig. 6 : Differential heats of NH adsorption vs. coverage at 150°C (a) and of

CH CN adsorption vs. coverage at 33.C (b) for sample dealuminated at 350°C and
ac%ivated at 760°C.

CONCLUSION
Ammonia remains the probe of choice in the titration of Bronsted type
sites. However, it has to be used under the most appropriate conditions, which
may vary depending on the solid under study. It is less convenient when both
strong Bronsted sites and medium Lewis sites are present within the same sample,
since then it may be very difficult to distinguish these sites on the sole basis
of the heat values. A less strong base remains to be found to give an accurate
picture of the acid strength distribution within a given sample.
Acetonitrile would appear to be a reasonable probe to investigate the
distribution of rather strong Lewis sites even in the presence of strong
Bronsted sites.
Pyrrole could hardly be considered as a basic probe. On the contrary it
 387

would prove to be convenient acid probe which does not drastically alter the
structure of delicate materials such as zeolites.
Dealumination via the silicon tetrachloride reaction with thoroughly
dehydrated NaY zeolites proved to proceed as a clean reaction with no
nonframework aluminium left within the porous structure or at the surface. It
produced variously dealuminated crystalline materials whose acidity strength
increased as the residual aluminium decreased up to a value of about 5 aluminium
atoms per unit cell. Beyond such a limit the acid strength started to decrease
again. Two distinct proton populations could be discriminated using ammonia
adsorption. The strongest acid population resisted dealumination up to a limit
of 16 residual aluminium atoms per unit cell. The difference in strengths
between the two populations is interpreted in terms of the nature of the next
nearest neighbours. The sites which have a maximum "aluminium" as nearest
neighbours are the least strong sites. They are the first to be eliminated upon
dealuminating substitution.

REFERENCES
1. A. AUROUX in Innovation in Zeolite Materials Science, P.J. Grobet et a1
Eds, Elsevier, Amsterdam (1987) 385.
2. H.K. BEYER and I. BELENYKAJA in Catalysis by Zeolites, B. Imelik et al.
Eds, Elsevier, Amsterdam 5 (1980) 203.
3. J.R. SOHN, S.J. DECANIO. J.H. LUNSFORD and D.J.0' DONNELL, Zeolites 6
(1986) 225.
4. G. ENGELHARDT, U . LOHSE, E. LIPPMAA, M. TARMAK and M. MAGI, Z. anorg. allg.
chem. 482 (1981) 49.
5. N. GIORDANO, P. VITARELLI, S. CAVALLARO, R. OTTANA and R. LEMBO, Proceed.
of the 6th Intern. Zeolite Conf., D. OLSON and A. BISIO Eds., Butterworths,
Guildford (1984) 331.
6. F.R. CHEN, G. COUDURIER and C. NACCACHE in new Developments in Zeolite
Science and Technology, Y. Murakami et al. Eds., Kodansha, Tokyo (1986)
773.
7. A. AUROUX, P.C. GRAVELLE, J.C. VEDRINE and M. REKAS, Proceed. of 5th
Intern. Conf. on Zeolites, L.V. REES. Ed. Heyden, London (1980) 433.
8. D. BARTHOMEUF, Acta Physica et Chemica 24 (1978) 71.
9. A. AUROUX, Y.S. JIN. J.C. VEDRINE and L. BENOIST, Appl. Catal. 36 (1988)
323.
10. D. BARTHOMEUF, G. COUDURIER and J.C. VEDRINE, Materials Chemistry and
Physics 18 (1988) 553.
11. J. MARCH, Advanced Organic Chemistry, Kogakusha Eds., Mc Graw Hill, (1977).
225.
12. J.C. LAVALLEY and J. CAILLOD, J. Chimie Physique 77 (1980) 373.
13. J.C. VEDRINE, A. AUROUX. G. COUDURIER, Catalytic Materials, Relationship
between Structure and Reactivity, A.C.S. Symposium Series 248 (1984) 254.
14. A. MELCHOR, E. GARBOWSKI, M.V. MATHIEU and M. PRIMET. J.C.S. Faraday Trans.
I, 82 (1986) 3667.
15. J.C. LAVALLEY and C. GAIN, C.R. Acad. Sc. Paris 288 (1979) 177.
16. H. KNOEZINGER and H. KRIETENBRIK, J. Chem. SOC. Faraday Trans I. 71 (1975)
2421.
This Page Intentionally Left Blank
H.G. Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
Amsterdam - Printed in The Netherlands
0 1989 Elsevier Science PublishersB.V..

THE ACIDITY OF A MODIFIED FAUJASITE STRUCTURE, ZEOLITE CSZ-1

2 2
S . CARTLIDGEl, R.L. COTTERMAN and M.L. HOWES

'Grace GmbH, In der Hollerhecke 1. Postfach 1445, 6520 Worms (W.-Germany)

'W.R. Grace & Co., Washington Research Center, 7379 Route 32, Columbia,
MD 21044 (USA)

ABSTRACT
This work establishes unifying concepts between structure and acidity for Y
and CSZ-1 zeolites. Characterisation data are presented which support the
proposal that CSZ-1 has a modified faujasite structure. Catalytic cracking of
pure hydrocarbons show that CSZ-1 and Y have comparable numbers of acid sites
when zeolite aluminium contents are similar but that the acid sites in CSZ-1
are weaker. Differences in acidity can be attributed to structure effects.
After hydrothermal treatment and aluminium extraction, acid site strengths
are similar for both zeolites.

INTRODUCTION
Zeolite acidity plays a key role in determining the performance of fluid
catalytic cracking (FCC) catalysts (1). The number and strength of zeolite acid
sites determine the extent of hydrogen transfer reactions which, in turn,
control gasoline quality and quantity. For example, ultrastable Y (US-Y)
zeolites in FCC catalysts enhance gasoline octane in comparison to rare-earth Y
zeolites which are used to maximise gasoline barrels.
Acid strength of US-Y increases with decreasing sodium levels (2). Bronsted
acid sites in US-Y attain a constant maximum acid strength when Si/Al >6 which
corresponds to isolated framework aluminium atoms (3). Lewis acidity, associ-
ated with non-framework aluminium in US-Y zeolites (4). has important effects
on catalyst activity and product selectivity during gas oil catalytic cracking
(5).
The conversion of model hydrocarbons under cracking conditions can be used
to characterise zeolite structure and acidity. Hexadecane cracking has been
widely used to simulate the conversion of petroleum oils over zeolite catalysts
(6). Recently activity and selectivity for n-paraffin cracking has been used to
investigate the mechanism of catalytic cracking over zeolite Y (7).
390

Acidity is also influenced by zeolite structure ( 8 ) . Modification of the

faujasite framework may modify acidic properties and hence alter catalytic
properties. Zeolites CSZ-1 (9). ZSM-3 (lo), and ZSM-20 (11) are claimed to have
framework topologies related to faujasite. The effect of the structure of
near-faujasite materials on acidity can be determined by comparing catalytic
properties. The aim of this work is to relate the structural differences
between zeolite Y and CSZ-1 to observed acid catalysis.

EXPERIMENTAL
Zeolite CSZ-1 was prepared by following the methods given in Examples 1 and
2 of ref ( 9 ) . Sodium silicate, aluminium chloride and sodium aluminate were the
sources of silica and alumina. A homogenous seed gel having molar composition
11.94 Si02 : A1203 : 12.7 Na20 : 247 H 0 was prepared and aged overnight. A
2
second hydrogel having molar composition
10 Si02 : A1203 : 0.5 CsCl : 4 NaZO : 1.4 NaCl : 150 H20 and containing
6 mol X A1 0 from the seed gel was heated at 95°C for 16 hours. The CSZ-1
2 3
product was filtered, washed and dried.
Commercial Na-Y and as-synthesised CSZ-1 were ammonium ion exchanged,
steamed at 550°C and exchanged again to give US-Y and US-CSZ-1. A further steam
treatment of the US-zeolites at 720°C was followed by an acid treatment in
aqueous hydrochloric acid to give USE-Y and USE-CSZ-1.
Catalytic experiments were conducted in atmospheric pressure, fixed bed
reactors at 500°C. Heptanelheptene cracking was carried out over the US-
zeolites. The WHSV was changed by varying the flowrate of a feed saturated
nitrogen stream. The products were collected at 30 second intervals on-stream
and analyzed by GC for instantaneous conversions.
Hexadecaneltetradecene cracking experiments used kaolin-bound samples
steamed at 760°C. The WHSV was varied by changing the catalyst loading. Cumu-
lative liquid and gas products were collected over three minutes and were
analyzed by capillary GC for total conversion and product selectivity.

RESULTS AND DISCUSSION

Structural considerations
Zeolite CSZ-1 is prepared from a synthesis gel which would produce
faujasite in the absence of caesium ions. Caesium is quantitatively incorpo-
rated into CSZ-1 as an exchangeable cation (Table 1). Modified faujasite
synthesis gels have been studied previously (9-13). For example platelet
faujasite is prepared from potassium containing sodium aluminosilicate gels. In
the presence of lithium, faujasite syntheses are directed towards ZSM-3 (10).
 391

Phe hexagonal platelet morphology of CSZ-1 is also shared by ZSM-3 and platelet
faujasite. The CSZ-1 crystallites prepared in this work are 0.5 to 3 pm.

PABLE 1
Physical and Chemical Characterisation Data for CSZ-1 and Y Zeolites

Framework *
~~ ~~~~ ~~ ~

BET N2
Molar Composition Surface Area Molar Ratio
Sample Si02 A1203 Na20 Cs20 m2/g Si02/A1203

csz-1 4.9 1 0.78 0.22 750 4.6

us-csz- 1 4.7 1 0.05 0.06 760 7.4
USE-CSZ-1 18 1 ND 0.04 750 34
Y 5.3 1 0.97 - a20 5.6
us-Y 5.6 1 0.05 - 830 8.6
USE-Y 213 1 0.05 - 860 46

ND = not detected * Si-29 MASNMR

Zeolites CSZ-1 and Y have comparable Si/A1 ratios (Table 1). The high
surface area measured for as-synthesised CSZ-1 (Table 1) indicates a well
developed microporous structure. However, the X-ray powder diffraction pattern
of CSZ-1 has relatively few sharp and intense diffraction peaks in contrast to
faujasite (Fig. 1). The poor quality of the CSZ-1 powder pattern may arise from
structural disorder at the unit-cell level. Electron microscopy studies of

Fig. 1
X-ray Powder
Diffraction Patterns
for As-Synthesised
Na-Y (top) and
Na.Cs-CSZ-1

B s B B
! ! ? ?
c 4
?
n
?
0
? ?
D 2 N N n n
392

CSZ-1 (14, 15) and ZSM-3 (16) point towards framework structures which are
based on the sodalite cage as the building unit. CSZ-1 may have a faulted
faujasite structure created by varying the stacking sequences of single
6-membered rings. A series of such structures has been observed (17) and
enumerated (18). Furthermore, the formation of hypercages in Y zeolites by
recurrent twinning (19) has been proposed.
The identical Si-29 MAS-NMR spectra of as-synthesised Y and CSZ-1 (Fig. 2
atd) show that the two structures are similar on a T-atom scale. It is
interesting, however, to compare the Si-29 MAS-NMR spectra of the zeolites
after the dealumination. As the extent of dealmination increases, the peak
corresponding to Si(0Si) 4 groups increases in intensity for Y zeolite. The
ultrastable zeolite structures (Fig. 2 b,e) have very different T-atom
distributions. The chemical shifts of peaks in Si-29 MAS-NMR spectra of highly
dealuminated zeolites (Fig. 2 c.f) show that primarily Si(OA1). (0SiI3 and
Si(OSi)4 sites are present.
The rearrangement of framework silicon and aluminium in CSZ-1 with increas-
ing steaming severity is different to that for zeolite Y (Fig. 2 a,b,c cf Fig.
2 d,e,f). In particular the peak corresponding to Si(OSi)4 groups in USE-CSZ-1
(Fig. 2 f) has a shoulder peak at ca. -110 ppm which might represent a second
crystallographically inequivalent T atom site. This assignment would explain
the structural disorder indicated by X-ray powder diffraction data.

A,dA,
b
Fig. 2
Silicon-29 MASNMR Spectra for
As-Synthesised, Steamed and
Acid Extracted CSZ-1 and Y
a) Na-Y, b) US-Y, c) USE-Y,
d) Na,Cs-CSZ-1. e) US-CSZ-1,
f) USE-CSZ-1

cAfA
-70 -80 -90 -100 -110 -120 -70 -80 -90 -100 -110 -120

Chemical Shift (ppm)

 393

Catalytic Cracking Activity

The acidities of CSZ-1 and Y zeolites were probed using two sets of madel
compound reactions at cracking conditions. In the first set, heptanelheptene
feeds were passed over the US-zeolites; in the second set, hexadecaneltetra-
decene feeds were converted over the steamed kaolin-bound US and USE-zeolites.

The apparent first order rate constants reported in Table 2 were observed
to be invariant to ? 2 units for average feed space velocities from 9-25 h-1 .
Rate constants have been normalised with respect to total moles of aluminium in
zeolite and are related to acid site turnover numbers.

TABLE 2
Initial Rate Constants for HeptanelHeptene Cracking over US-CSZ-1 and US-Y

Feed n-heptane n-heptaneln-heptene

Zeo1ite us-Y us-csz-1 us-Y us-csz-1

Initial Rate 32.2 6.7 43.6 29.5
Constant*
* Rate constant expressed as ( m o l hydrocarbon converted)/
(mol A1 atoms-atm-h).

The low initial first order rate constant for n-heptane conversion over
US-CSZ-1 compared to US-Y (Table 2 ) shows that US-CSZ-1 is less active although
the total aluminium contents of the zeolites are similar (Table 1). When 5wtX
n-heptene is co-fed with n-heptane, the initial rate constant of US-Y increases
(Table 2) as expected due to the higher rate of cracking of olefins over acidic
catalysts (1) . However, the four fold increase in initial rate constant for
US-CSZ-1 (Table 2 ) upon heptene addition indicates that additional acid sites
are accessible which convert heptene but not heptane.
The values of the initial rate constants are determined by the number and
strength of catalytically active acid sites. The heptanelheptene conversion
data suggest that US-CSZ-1 has a similar number, but weaker, acid sites com-
pared to US-Y. This conclusion is supported by the Si-29 MAS-NMR data for US-Y
and US-CSZ-1 (Figures 2 b and 2 e). The framework of US-CSZ-1 contains more
aluminium than that of US-Y. Consequently the acid sites associated with
framework aluminium atoms in US-CSZ-1 will be weaker.
394

Hexadecaneftetradecene testing of the steamed, kaolin-bound US-zeolites

presents further evidence in support of the proposed difference in acidity for
US-CSZ-1 and US-Y. The catalytic activity is presented as a function of space
time in Figure 3 where the slopes of the lines represent apparent first order
rate constants. The increase in average rate constant for the steamed US-Y
catalyst when tetradecene is co-fed (Table 3) is similar in magnitude to that
observed for the heptanelheptene cracking. The corresponding increase in
activity of steamed US-CSZ-1 is not as dramatic as for the heptanelheptene
case. This is due to an observed loss of micropore surface area after steaming
US-CSZ-1 at 760’C.

TABLE 3
Average First Order Rate Constants for HexadecaneITetradecene Cracking over
Steamed Kaolin-Bound US and USE-Zeolites

Average First Order Rate Constant*

Feed n-C H /n-C14H28
n-C16H34 16 34
CATALYST**
us - csz-1 52 07
us-Y 171 212
USE-CSZ- 1 119 169
USE-Y 170 236
* Rate constant expressed as (mol hydrocarbon converted)/
(mol A1 atoms-atm-h).
** Zeolites kaolin bound and steamed at 760°C

D
I / W H S V ( x 10’)). hr

Fig. 3: Activity of Steamed, Bound US-CSZ-1 and US-Y for Hexadecanel

Tetradecene Cracking
A US-CSZ-1, [7 US-Y 100 2 Hexadecane
A US-CSZ-1, US-Y 95.3% Hexadecane, 4.7% Tetradecene
 395

0.8-

-- 0 . 6
0.4 /4+
0.2

0.0 ' " I " "

16
' " '
24
" "
32
" '

I / W H S V ( X l o 3 ) , hr

Fig. 4: Activity of Steamed, Bound USE-CSZ-1 and USE-Y for Hexadecanel

Tetradecene Cracking
A USE-CSZ-1 0 USE-Y 100 X Hexadecane
A USE-CSZ-1 USE-Y 95.3% Hexadecane, 4.7% Tetradecene

The two steamed, kaolin-bound acid extracted zeolites, USE-Y and USE-CSZ-1,
show comparable activity for hexadecane conversion (Figure 41, however, the
acid strength of USE-CSZ-1 is lower than USE-Y when normalized with respect to
aluminium content (Table 3). When tetradecene is co-fed with hexadecane, the
increases in catalytic activity are similar for the steamed USE-zeolites (Table
3). This observation strongly suggests that, after extensive dealumination,
isolated acid sites in the USE-zeolites have a similar acid strength. The Si-29
MAS-NMR spectra for the USE-zeolites (Figure 2 c and 2 f) show a high degree of
dealumination which must be even more extensive after steaming at 760°C.

Catalytic Cracking Selectivity

A summary of the product selectivities from hexadecane and hexadecaneltetra-
decene cracking over steamed, kaolin-bound US-Y and US-CSZ-1 is presented in
Table 4. The selectivities to Paraffins, Isoparaffins, Olefins, Eaphthenes and
Aromatic hydrocarbons are calculated after identification of ca. 200 components
in the C5-C12 fraction. It is important to note that the comparisons between
CSZ-1 and Y are made at approximately constant conversion.
396

The gross similarity of the framework topologies of CSZ-1 and Y is con-

firmed by the almost identical C5-C12 selectivities and nearly identical PIONA
distributions (Table 4). The steamed US-CSZ-1 catalyst appears to produce less
aromatics and more olefins than US-Y indicating that steamed US-CSZ-1 has
poorer hydrogen transfer. This observation is consistent with weaker acid
sites.

TABLE 4
Product Selectivities for Hexadecane and HaxadecanelTetradecene Cracking over
Steamed, Kaolin Bound US-CSZ-1 and US-Y

Feed n-C H /n-C14H28

n-C16H34 16 34
CATALYST* us-Y us-csz-1 us-Y us-csz-1
WHSV , h- 290 83 193 83
Conversion, wtX 21 20 38 34
Selectivity C5-CI2,X 64.1 63.7 60.5 60.7

Selectivities
(in c5-C12). %
Paraffins 13.2 14.1 11.1 11.7
Isoparaffins 32.8 31.6 33.2 31.4
Olefins 46.0 47.9 46.9 49.4
Napthenes 4.6 3.8 4.3 4.6
Aromatics 3.4 2.6 4.6 3.0

* Zeolites kaolin bound and steamed at 760°C

CONCLUSIONS
Zeolite CSZ-1 represents a modification of the faujasite structure in which
there appears to be disorder at the unit-cell level. When CSZ-1 and Y zeolites
are prepared with similar Si/A1 ratios, large differences can be seen in
catalytic cracking activities. The acid sites in CSZ-1 are weaker than those in
Y.
When CSZ-1 and Y zeolites are dealuminated and acid extracted to high Si/A1
ratios, acid strengths of the two zeolites are similar. This indicates that
structural effects on acid site strength are less pronounced when acid sites
become diluted.
 397

ACKNOWLEDGEMENTS
The authors thank W. R. Grace and Co. for permission to publish this work.
We also thank Dr. M. P. Shatlock for providing the NMR spectra and D. M.
Roberts, D. G. Nelson and A. Siege1 for assistance with experimental work.

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(W.R. Grace & Co.)
13 G.C. Edwards, D.E.W. Vaughan, E.W. Albers, U.S. Patent 4,175,059,
1979 (W.R. Grace)
14 G.R. Millward, J.M. Thomas, S. Ramdas. M.T. Barlow, Proc. 6th Int.
Zeolite Conf., D. Olson and A. Bisio (Editors). Butterworth (1984) 793
15 M.M.J. Treacy, J.M. Newsam, R.A. Beyerlein, M.E. Leonowicz, and D.E.W.
Vaughan, J. Chem. SOC., Chem. Commun. (1986) 1211
16 G.T. Kokotailo and J. Ciric, Adv. Chem. Ser., 101,(1971) 109
17 J.A. Gard and J.M. Tait, Adv. Chem. Ser., 101,(1971) 230
18 J.V. Smith and J.M. Bennet, h e r . Mineral, 6 6 , (1981) 777
19 M. Audier, J.M. Thomas, J. Klinowski, D.A. Jefferson and L.A. Bursill,
J . Phys. Chem. &, (1982) 5 8 1
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Control of catalytic properties of ZSM- 5 made by fast and template- free

synthesis.
A . TISSLERI, P. POLANEKZ. U. GIRRBACH3, U. M U L L E R l a n d K . K . LINGER'
1 l n s t i t u t f u r Ano rg an is ch e Chemie und A n al yt i sche Chem i e,
J o h a n n e s G u t e n b e r g - U n i v e r s i t a t , D- 6500 M ai n z. FRG;
2 p r e s e n t a d d r e s s : BASF AG. D- 6700 L u d w i g s h a f e n , FRG
3 p r e s e n t a d d r e s s : H o e c h s t AG, D- 6230 F r a n k f u r t , FRG.

ABSTRACT
Th e f a s t t e m p l a t e - f r e e s y n t h e s i s of ZSM-5 w a s a c c o m p l i s h e d in b o t h st at i c.
a nd s t i r r e d a u t o c l a v e s e m p l o y i n g s o d i u m w a t e r g l a s s . s i l i c a h y d r o g e l an t i p) -
r o g e n i c s i l i c a s a s s i l i c a s o u r c e s . H ig h l y p u r e c r y s t a l l i n e ZSM- 5 w a s o b t a i n e d
in t h e s o d i u m w a t e r g l a s s r e a c t i o n s y s t e m in t h e s t i r r e d a u t o c l a v e s w i t h o u t
s e e d s w i t h i n 3 h o u r s . A d d i t i o n o f 2 % ( w / w ) of s e e d s r e d u c e d t h e r e a c t i o n t i m e
t o 2 h o u r s . T h e c a t a l y t i c a c t i v i t y a n d s h a p e s e l e c t i v i t y o f t h e H - ZS M- S .t est c- d
by t h e d i s p r o p o r t i o n a t i o n o f e t h y l b e n z e n e , w a s f o u n d t o b e l a r g e l y co n t r o l l Pci
by t h e s y n t h e s i s p a r a m e t e r s a n d by t h e p o s t t r e a t m e n t s . T h e h o m o g r n e o u s a i u -
inintiin d i s t r i b u t i o n a c r o s s t h e c r y s t a l s a c h i e v e d by t h i s s y n t h e t i s r o u t e r e s u l t e d
i n a g r e a t e r shape selectivity compared t o t h o s e with an uneven aluminum
d i s t r i b u t i o n b e i n g p r e p a r e d by a d d i n g t e m p l a t e s . V a r i o u s k i n d s o f p o s t t r e a t -
m e n t s , e.g. "alkaline calcination",led t o an addi t i onal e n h a n c e m e n t of t h e
s h a p e s e l e c t i v i t y y i e l d i n g u p t o 99% o f p - i s o m e r in t h e e t h y l b e n z e n e d i s p r o -
port ion a t i on reac t io n .

INTRODUCTION
A l t h o u g h t h e t e m p l a t e f r e e s y n t h e s i s o f Z S M - 5 w a s t h e s u b j e c t o f s e v e r a l in-
v e s t i g a t i o n s ( r e f s . 1,2,3), a n u m b e r o f i m p o r t a n t a s p e c t s s t i l l n e e d t o h e c l a r i f i e d .
- T h e i m p a c t o f t h e s i l i c a s o u r c e o n t h e k i n e t i c s o f t h e ZSM- 5 f o r m a t i o n a n d
on t h e resulting crystallisation fields was n o t essentially established:
- no detailed s t u d i e s were p erfo rmed on t h e c r y s t a l l i s a t i o n ki net i cs. except
t h a t they were reported t o be s l o w
- t h e r e l a t i o n s h i p b etw een c r y s t a l morphology a n d chemical hom ogenei t y of t e m -
p l a t e - f r e e s y n t h e s i z e d ZSM- 5 a n d its c a t a l y t i c p r o p e r t i e s w a s n o t e x a m i n e d .
T h e p a p e r a d d r e s s e s t h e t e m p l a t e - f r e e s y n t h e s i s o f ZS M- 5 in t h e r a n g e o f
Si/AI o f 10- 2 0 0 e m p l o y i n g s o d i u m w a t e r g l a s s . s i l i c a h y d r o g e l a n d p y r o g e n i c
s i l i c a s a s s i l i c a s o u r c e s . I t f u r t h e r i n v e s t i g a t e s t h e k i n e t i c s o f Z S M - 5 frrrnia-
ti on ti n d e r c o n c e 11t r a t io 11 a n d t e m p e r a t u r e - g r a d i e n t - f r e e c o n d i t i o 11 s t o p r o v i d r
t h e b a s i s f o r a f a s t s y n t h e s i s p r o c e d u r e . S p e c i a l e m p h a s i s is p l a c e d o n t h e c o r r e -
l a t i o n b e t w e e n t h e c a t a l y t i c p r o p e r t i e s a n d t h e d eci si v e p a r a m e t e r s o f t h e
synthesis aiming a t ZSM- 5 products with optimum catalytic activity and
s e l e c t i v i t y . In p a r t i c u l a r , t h e Z S M - 5 c r y s t a l s w e r e s u b j e c t e d t o v a r i o u s p o s t -
treatments a s a means t o enhance t h e shape-selective p r o p e r t i e s in t h e
d i s p r o p o r t i o n a t i o n of e t h y l b e n z e n e ( r e f . 4 I .
400

EXPERIMENTAL
The materials used f o r t h e s y n t h e s i s were commercial sodiumwaterglass
( 2 7 . 7 5 wtX SiO,; 0.11 w t % A 1 2 0 3 ; 7.99 w t % Na,O). a l u m i n u m s u l p h a t e ( M e r c k ,
GR g r a d e ) , s u l p h u r i c acid ( M e r c k , 9 5 - 97 wtX p.A.1 a n d d i s t i l l e d w a t e r . S t i r r e d
s t a i n l e s s s t e e l a u t o c l a v e s of 1.4 1 and 2.4 1 v o l u m e s e r v e d a s r e a c t i o n v e s s e l s
allowing on-line s a m p l i n g d u r i n g t h e r e a c t i o n r u n s . In a d d i t i o n , s t a t i c
T e f l o n - l i n e d a u t o c l a v e s of 140 ml w e r e e m p l o y e d f o r t h e e x p e r i m e n t s with py-
r o g e n i c s i l i c a s and s i l i c a h y d r o g e l .
The crystallinity o f t h e p r o d u c t s was determined using q u a n t i t a t i v e X-ray
p o w d e r t e c h n i q u e s (Philips APD 1 5 ) . Chemical a n a l y s i s of t h e p r o d u c t s was c a r -
ried o u t w i t h s t a n d a r d m e t h o d s . The a l u m i n u m d i s t r i b u t i o n a c r o s s t h e c r y s t a l s
was a s s e s s e d by w a v e l e n g t h - d i s p e r s i v e e l e c t r o n microprobing ( Camaca.
Camebax).
T h e c a t a l y t i c t e s t s were c o n d u c t e d in a f l o w - t y p e a p p a r a t u s w i t h a s a t u -
r a t o r f o r e t h y l b e n z e n e and a f i x e d - bed r e a c t o r f r o m g l a s s o n - l i n e - c o n n e c t e d
t o t e m p e r a t u r e - p r o g r a m m e d c a p i l l a r y GC.The r e a c t i o n t e m p e r a t u r e w a s 523 K.

RESULTS A W DISCUSSION

I n t h e w h o l l y i n o r g a n i c r e a c t i o n s y s t e m of ZSM - 5 t h e a l k a l i n i t y
(OH-/SiO,) a n d t h e a l u m i n u m c o n t e n t ( S i / A I ) w e r e t h e key p e r a m e t e r s i n
determining t h e crystallisation. Pure c r y s t a l l i n e ZSM- 5 p r o d u c t s were obtained
only in a n a r r o w r a n g e of well d e f i n e d c o n d i t i o n s .

Si/A L

200

100
m

50

1 I I I I I I I I

0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 OHXi(

Fig.1 Phase d i s t r i b u t i o n in t h e r e a c t i o n s y s t e m with pyrogenic silicas
 401

T h e i n f l u e n c e of t h e s i l i c a s o u r c e on t h e c r y s t a l l i s a t i o n w a s i n v e s t i g a t e d
using s t a t i c aut o clav es . The cry s tal li s ati o n r a t e was f o u n d t o b e i ncr eased in
t h e s e q u e n c e p y r o g e n i c s i l i c a s t o s i l i c a h y d r o g e l t o s o d i u m - w a t e r g l a s s . In t h e
same sequence t h e domain a t which pure ZSM-5 was formed in t h e crystalli-
s a t i o n f i e l d d e c r e a s e d s u b s t a n t i a l l y . As i l l u s t r a t e d in Fig.1 f o r p y r o g e n i c
s i l i c a s t h e c r y s t a l l i s a t i o n f i e l d w a s c o m p a r a t i v e l y b r o a d ( S i / A I = 12-200 a n d
OH- / S i 0 2 = 0 . 1 5 - 0.6). I t became much s m a l l e r f o r silica hydrogel (Si/AI=
12- 6 0 a n d O H - / S i 0 2 = 0 . 2 - 0.31, a n d i t w a s i m p o s s i b l e t o o b t a i n Z S M - 5
under t h e s e c o n d i t i o n s w i th o u t any i mp u rit i es ( a m o r p h o u s m at er i al . i m p u r e -
S i 0 2 o r c r i s t o b a l i t e ) w h e n s o d i u m w a t e r g l a s s w a s u s e d . H o w e v e r , w i t h t h e use
of s t i r r e d a u t o c l a v e s w i t h very h i g h h e a t i n g r a t e , t h e s o d i u m w a t e r g l a s s s y s t e m
p r o d u c e d p u r e Z S M - 5 in t h e r a n g e o f S i /A I = 12-50 a n d O H - / S i 0 2 = 0.13- 0.17.
Hence all f u r t h e r investigations were carried out with t h i s reaction s y s t e m .

K i n e t i c s of c r y s t a l l i s a t i o n
Crystallisation curves of t h e sodiumwaterglass reaction system obtained
w i t h a n d w i t h o u t t h e u s e o f s e e d s a r e i l l u s t r a t e d in F i g .2 . T h e m o l a r c o m p o -
s i t i o n of t h e o p t i m i z e d r e a c t i o n m i x t u r e a m o u n t e d t o S i / A I = 2 0 . 5 , O H - / S i 0 2 =
0.153, H 2 0 / S i 0 2 = 39. T h e r e a c t i o n t e m p e r a t u r e w a s 4 9 8 K .

100

8
a 80
X

). 60
.-
4-

.-c
d

Z
c
40
v)
%
L
U

20

0
0 50 100 150 2 00 25(
synthesis- time [ min 1

Fig. 2 C r y s t a l l i s a t i o n c u r v e s w i t h a n d w i t h o u t a d d i t i o n o f s e e d s a t 4 9 8 K

T h e c r y s t a l l i s a t i o n c u r v e s o b t a i n e d w i t h o u t s e e d i n g e x h i b i t e d a si g n i o i d al
s h a p e wh i ch is c h a r a c t e r i s t i c f o r p r o c e s s e s i n v o l v i n g t w o d i s t i n c t s t a g e s : an
402

i n d u c t i o n p e r i o d , w h e r e n u c l e i a r e f o r m e d . f o l l o w e d by a c r y s t a l g r o w t h p e r i -
o d . w h e r e n u c l e i g r o w i n t o c r y s t a l s . When s e e d s w e r e a d d e d , t h e c r y s t a l l i s a t i -
o n c u r v e s s h o w e d n o i n d u c t i o n p e r i o d . The c r y s t a l l i s a t i o n r a t e is d e f i n e d a s
t h e r a t e of c r y s t a l l i s a t i o n a t t h e s t e e p e s t p a r t o f t h e c r y s t a l l i s a t i o n c u r v e
e x p r e s s e d a s p e r c e n t p e r m i n u t e . Fig.3 s h o w s t h e i n f l u e n c e o f t h e m o s t i m p o r t a n t
r e a c t i o n p a r a m e t e r s , Si/AI a n d O H - / S i 0 2 , 011 t h e i n d u c t i o n period a n d o n t h e
crystallisation rate.

1 OH/SiO2 = 0.15 I
1201

.-
-.-
c
Y 901
aJ aJ
.-E .-E aJ
+
+

I
60 +
I 60- b r[)
L
+.
<.-
U

30

Il l r l
I l
10 20 30 40 50 0.1 0.12 0.14 0.16 0.18 0.20
Si/AL OH ' / S i 02

Fig.3 I n f l u e n c e of Si/AI ( a ) a n d O H - / S i 0 2 ( b ) o n t h e i n d u c t i o n p e r i o d a n d t h e
c r y s t a l l i s a t i o n r a t e ( T = 498 K)

The s e n s i t i v i t y of t h e r e a c t i o n s y s t e m t o s m a l l v a r i a t i o n s of' t h e a l k a l i -
nity is i n d i c a t e d by t h e d i s t i n c t maximum of t h e c r y s t a l l i s a t i o n r a t e n e a r a
value OH-/SiO, = 0.155. Only a t t h i s r a t i o was i t p o s s i b l e t o o b t a i n 100%
p u r e ZSM- 5 a t a b r o a d r a n g e of t h e Si/AI r a t i o within a b o u t 3 h o u r s (-298 k).
The s y n t h e s i s time was s h o r t e n e d t o a b o u t t w o h o u r s (Fig.2) by adding a t
l e a s t 2 % ( w / w ) of s e e d s .
T h e i n f l u e n c e which t h e a l u m i n u m c o n t e n t of t h e r e a c t i o n m i x t u r e had o n t h e
c r y s t a l l i s a t i o n r a t e w a s in c o n t r a d i c t i o n t o r e s u l t s g e n e r a l l y o b t a i n e d in
ZSM- 5 s y n t h e s i s in t h e p r e s e n c e o f t e m p l a t e s ( r e f . 5 ). The c r y s t a l l i s a t i o n
r a t e w a s a c c e l e r a t e d w i t h i n c r e a s i n g a l u m i n u m c o n t e n t t o a maximum of
Si/AI%13. E m p l o y m e n t o f a r e a c t i o n m i x t u r e of Si/AI=9 y i e l d e d o n l y a m o r p h o u s
m a t e r i a l . For r e a c t i o n m i x t u r e s r i c h e r in s i l i c a t h e c r y s t a l l i s a t i o n r a t e d e c r e a s e d
r a p i d l y . Exceeding t h e value o f S i / A l 4 50 o n l y ZSM-5 p r o d u c t s w i t h less t h a n
50%c r y s t a l l i n i t y were o b t a i n e d . I t a p p e a r s t h a t w i t h i n c r e a s i n g s i l i c a c o n t e n t t h e
MFI lattice,becoming more and more h y d r o p h o b i c , is t h e r m o d y n a m i c a l l y
 403

u n s t a b l e in t h e a b s e n c e of any organic m o l e c u l e s ( r e f . G 1 which s t a b i l i r e

t h e l a t t i c e by r e a l t e m p l a t i n g o r pore f i l l i n g ( r e f . 7 ) . A f t e r a d i s t i n c t r e -
a c t i o n p e r i o d , which was mainly d e p e n d e n t o n t h e a l u m i n a c o n t e n t a n d t h e
t e m p e r a t u r e of t h e r e a c t i o n m i x t u r e , c r y s t o b a l i t e o r CI -quartz was formed.
Hence r e a c t i o n c o n d i t i o n s had t o be c h o s e n s u c h t h a t t h e f o r m a t i o n of
ZSM-5 was c o m p l e t e d a t t h i s s t a g e .
The k i n e t i c s o f c r y s t a l l i s a t i o n was s i g n i f i c a n t l y a f f e c t e d by t h e r e a c t i o n
t e m p e r a t u r e . T h e e n e r g i e s of a c t i v a t i o n f o r t h e n u c l e a t i o n En a n d t h e c r y s t a l
g r o w t h E, f o r t h e s y n t h e s i s s y s t e m w i t h a Si/AI- r a t i o o f 40 w e r e e v a l u a t e d
f r o m t h e A r r h e n i u s p l o t s ( F i g . 4 ) t o E,=59 k J / m o l a n d E,=46 k J / m o l . The
r e a c t i o n t e m p e r a t u r e f u r t h e r m o r e influenced t h e c r y s t a l s i z e . H i g h e r r e a c t i o n
t e m p e r a t u r e s r e s u l t e d in bigger c r y s t a l s .

O.!
E, = 4 6 KJ/mol

0
- I \

-
r’
I x L

- -0.5
c

-1

Fig.4 Arrhenius p l o t s f o r n u c l e a t i o n ( a ) and f o r c r y s t a l l i s a t i o n ( b ) a t Si/A1=40

Catalytic properties
The d l s p r o p o r t i o n a t i o n of e t h y l b e n z e n e . i n t r o d u c e d by Karge e t a l . ( r e f . . $ ) .
is a s u i t a b l e t e s t r e a c t i o n f o r p r o b i n g t h e a c t i v e and s h a p e - s e l e c t i v e p r o p e r -
t i e s of z e o l i t e s . Unmodified H-ZSM- 5 c a t a l y s t s s y n t h e s i z e d w i t h t e m p l a t e s
yielded a p r o d u c t c o m p o s i t i o n c l o s e t o 6 0 1 4 0 ( w / w ) o f m e t a - d i e t h y l b e n z e n e
(MDEB) t o p a r a - d i e t h y l b e n z e n e (PDEB)[ref.B). N o o r t h o - i s o m e r w a s f o r m e d
u n d e r t h e s e c o n d i t i o n s . This r a t i o of MDEBIPDEB was f o u n d t o be only s l i g h t l y
i n f l u e n c e d by t h e s y n t h e s i s p a r a m e t e r s ( r e f . 9 1, e x c e p t f o r l a r g e c r y s t a l s . In
c o n t r a s t , t e m p l a t e - f r e e s y n t h e s i z e d ZSM- 5 e x h i b i t e d l a r g e d i f f e r e n c e s in its
shape-selective properties, depending on t h e synthesis p a r a m e t e r s t h a t allow
one t o tailor c a t a l y s t s with predetermined properties.
404

T h e i n c r e a s e of t h e Si/AI r a t i o o r t h e s y n t h e s i s t e m p e r a t u r e r e s u l t e d in
a n e n h a n c e m e n t o f PDEB f o r m a t i o n in t h e e t h y l b e n z e n e r e a c t i o n ( F i g . 5 ) .
S a m p l e s w i t h a Si/AI r a t i o o f 13 d i s p l a y e d very h i g h a c t i v i t i y b u t o n l y m o d e -
r a t e s h a p e s e l e c t i v i t y (35% P D E B ) , w h i l e c r y s t a l s w i t h a Si/AI r a t i o u f 4.0 g a v e
l o w e r a c t i v i t y b u t high s e l e c t i v i t y (70% PDEB). T h e s h a p e s e l e c t i v i t y s e e m s t o b e
i n f l u e n c e d by t h e S i / A I - r a t i o . T h i s is in a g r e e m e n t w i t h t h e f i n d i n g s o f
Karge e t al ( 8 ) a n d Kaeding e t al ( r e f . 1 0 1 u s i n g H-ZSM- S s y n t h e s i z e d w i t h
templates.

I Si/Al= 40 I

- 60
>
c
0
U

-40
A
m
w
.-t n
.-> a
4-
U
I0 -20s
1 I I
2 3 4 6 5 7 470 480 4.90 500
AL-atoms/unit- cel I syn.- temp. [ K I
Fig.5 I n f l u e n c e o f t h e a l u m i n a c o n t e n t ( a ) a n d t h e t e m p e r a t u r e ( b ) of t h e r e -
a c t i o n m i x t u r e o n t h e a c t i v i t y a n d s e l e c t i v i t y of t h e c a t a l y s t s (activity. %
c o n v e r s i o n a t W / F = 300 g . h / m o l : s e l e c t i v i t y - % PDEB a t a c o n v e r s i o n of 2 % ) .

T h e c a t a l y t i c a c t i v i t y varied l i n e a r l y w i t h t h e n u m b e r o f a l u m i n u m a t o m s
located in t h e zeolite framework over a broad range of t h e Si/Al r a t i o between
20 a n d 5 0 , a s e x p e c t e d a n d d e s c r i b e d e l s e w h e r e (ref.11 ) . T h e m o s t
a l u m i n a - r i c h s a m p l e s (Si/Al=13) e x h i b i t e d a n a c t i v i t y a b o u t t w i c e as h i g h a s
e x p e c t e d by e x t r a p o l a t i n g t h e v a l u e s o f t h e m o r e s i l i c a - r i c h samples. I t
s e e m s t h a t t h i s m i g h t b e c a u s e d by t h e g e n e r a t i o n of n e w a c t i v e sites
w i t h e n h a n c e d a c t i v i t y which w e r e a l r e a d y d e s c r i b e d by L a g o e t al ( ref.12 1.
B e c a u s e p a i r e d a l u m i n u m f r a m e w o r k a t o m s a r e r e q u i r e d For t h e f o r m a t i o n o f
t h e s e s i t e s , i t b e c o m e s r e a s o n a b l e t h a t o n l y t h e s a m p l e s w i t h a l o w Si/AI - r a t i o
show this effect.
 405

The h i g h e r p a r a - s e l e c t i v i t y of t h e t e m p l a t e - f r e e s y n t h e s i z e d ZSM- 5
p r o d u c t s is a s s u m e d t o be c a u s e d by t h e more h o m o g e n e o u s a l u m i n u m
d i s t r i b u t i o n a c r o s s t h e c r y s t a l s ( F i g . 6 ) . which r e s u l t s in t h e d e c r e a s e of t h e
catalytically active s i t e s a t t h e external s u r f a c e of t h e c r y s t a l s compared t o
s a m p l e s syr,chesized w i t h t e m p l a t e . I n c r e a s i n g t h e r e a c t l o n t e m p e r a t u r e f r o m
468 K t o 498 K r e s u l t s in b i g g e r c r y s t a l s ( 4 6 8 K e l - 3 p ; 4 9 8 K ZY 5-10 p ) which

a
a l s o e x p l a i n s t h e e n h a n c e m e n t of t h e p a r a - s e l e c t i v i t y of t h e s e s a m p l e s .

ALLMINIUH ,
0,/J b, , 8, ~ ?.I , , 16, ,e
0 2 1 6 8 l o p 0 b 8 ?.I 16 2Op

Fig.6 Aluminum d i s t r i b u t i o n of ZSM- S c r y s t a l s s y n t h e s i z e d t e m p l a t e - f r e e ( a )

and w i t h TPA ( b ) .

E n h a n c e m e n t of s h a p e - s e l e c t i v e p r o p e r t i e s
The r e m a r k a b l e s h a p e - s e l e c t i v e p r o p e r t i e s of ZSM- 5 a r e c a u s e d by i t s
unique p o r e s t r u c t u r e . T h e r e f o r e , t h e acid s i t e s a s s o c i a t e d with t h e f r a m e -
work a l u m i n u m o n t h e e x t e r n a l s u r f a c e of t h e c r y s t a l l i t e s d o n o t c o n t r i b u t e
t o t h e s h a p e s e l e c t i v i t y . P r o c e d u r e s which a r e u s e d t o e n h a n c e s h a p e s e l e c t i -
v i t y s e e k t o maximize t h e r e l a t i o n of i n t e r n a l t o e x t e r n a l a c t i v e s i t e s o r t o in-
c r e a s e t h e d i f f e r e n c e in d i f f u s i o n r a t e s b e t w e e n t h e s m a l l ( e . g . p a r a - i s o m e r )
and t h e bulky ( e . g . o r t h o - o r m e t a - i s o m e r ) m o l e c u l e s . I m p r o v e m e n t o f t h e
s h a p e - s e l e c t i v e p r o p e r t i e s t h e n c a n be achieved by :
- g r o w i n g l a r g e r a n d / o r more s i l i c a - r i c h c r y s t a l s (ref.13.14),
- s e l e c t i v e removal of aluminum f r o m t h e e x t e r n a l s u r f a c e (ref.15 1,
- c o a t i n g t h e c r y s t a l s with a s i l i c e i o u s s h e l l ,
- modifying t h e c a t a l y s t w i t h m e t a l s a l t s c o n t a i n i n g p a r t i c u l a r l y P a n d / o r M g
( r e f . 1 6 1.
T h i s s t u d y r e p o r t s t h e e f f e c t s of t w o s i m p l e p o s t t r e a t m e n t p r o c e d u r e s
showing a n extraordinary enhancement of shape-selective properties especially
of template-free synthesized ZSM- 5 s a m p l e s . F i r s t t h e e f f e c t o f a
( t e m p l a t e - f r e e ) s i l l c a c o a t i n g o n a c t i v e (SI/AI=20) ZSM- 5 s a m p l e s w a s
i n v e s t i g a t e d . The c o a t i n g was e f f e c t e d by u s i n g a l a r g e n u m b e r ( 50%) o f c r y s t a l s
a s " s e e d s " and s t a r t i n g a s e c o n d s y n t h e s i s in t h e s i l i c a r i c h e n v i r o n m e n t ,
406

This approach produced adequate b u t n o t excellent r e s u l t s . S e c o n d , c a t a l y s t

s a m p l e s w e r e t r e a t e d w i t h a s o d i u m h y d r o x i d e s o l u t i o n f o l l o w e d by c a l c i n a t i o n .
T h i s s i m p l e p r o c e d u r e h a d a r e m a r k a b l e i m p a c t o n t h e c a t a l y t i c p r o p e r t i e s . It
is w o r t h n o t i n g t h a t c a l c i n a t i o n of t h e s a m p l e s a f t e r t h e y w e r e w a s h e d t o
n e u t r a l i t y , did n o t i mp ro v e t h e s h a p e - s e l e c t i v e p r o p e r t i e s . Whi l e t h e c o a t i n g
i n c r e a s e d t h e a m o u n t o f PDEB in t h e t e s t r e a c t i o n m e a s u r e d a t 2 % c o n v e r s i o n
f r o m a b o u t 36% t o a b o u t 7 0 %, t h e “ a l k a l i n e c a l c i n e d ” c a t a l y s t s g a v e p r o d u c t s
w i t h a y i el d o f g r e a t e r t h a n 99% PDEB. T a b l e 1 s h o w s t h e e f f e c t of c a l c i n a t i o n
temperature on t h e catalytic properties of t h e treated samples.

temp.
( K )
Si/AI = 13
activity selec-
tivity
Si/AI = 2 0
activity selec-
tivity
_ _..-
._
Si/AI = 4.0
activity selec-
- ._.
..
..-
. .

tivity
. - .-. .. .
-1
- - . . .. ~. __
298 8.1 35 3.9 37 3 70
623 n.m. n.m. 4..5 4 4. n . ti1 . n .m .
773 19 53 3.8 92 2.8
923 n.m. n.m. 2.8 99 n.m. n.m.

Although t h e “alkaline calcination” had an enormous influence 011 the shape-

s e l e c t i v e p r o p e r t i e s of th e c a t a l y s t s . t h e a c t i v i t y of m o s t s a m p l e s r e m a i n e d
a l m o s t unchanged. However, t h e m o s t alumi na- r i ch s a m p l e (Si/AI=13) s h o w e d
o n l y a m o d e r a t e e n h a n c e m e n t of t h e s h a p e s e l e c t i v i t y b u t a n e n n r m o u s i n c r e a s e
in a c t i v i t y , w h i c h i s a s s u m e d t o be a s s o c i a t e d w i t h t h e f o r m a t i o n o f ad d i t i r i n al
c e n t e r s w i t h e n h a n c e d a c t i v i t y . A c a l c i n a t i o n t e m p e r a t u r e of a t l e a s t 7 7 3 h:
was required t o achieve t h e optimal catalytic properties. Exceeding t h e calci-
n a t i o n t e m p e r a t u r e o f 923 K l e d t o a d e c r e a s e d a c t i v i t y if t h e t r e a t e d s a m p l e s .
A c t i v i t y a n d s e l e c t i v i t y o f t h e u n t r e a t e d a n d t r e a t e d s a m p l e s a r e s h o w n in
Fig. 7. A l l c a t a l y s t s deactivated slowly,which is c o m m o n f o r Z S M - 5 c a t a l y s t .
The high s h a p e selectivity of t h e “alkaline calcined” s a m p l e s remained a l m o s t
u n c h a n g e d e v e n w h e n w o r k i n g a t h i g h e r c o n v e r s i o n s (F i g . 8 ) .
 407

1 W/F=300 g.h/mol
I C

80 -

1 2 3 4 5
time on stream [ h l
m 60
W
0

- 1 2 3 4 5
time on stream [ h I
b

Fig. 7 C a t a l y t i c p r o p e r t i e s of u n t r e a t e d ( a 1 , c o a t e d (b) a n d " a l k a l i n e c a l c i n e d " ( r : )

samples a s a function of time on s t r e a m

0 60
n

2 4 6 8 1 0
conv. [%I

Fig. 8 A m o u n t of P D E B in t h e e t h y l b e n z e n e d i s p r o p o r t i o n a t i o n r e a c t i o n u s i n g
u n t r e a t e d (a) c o a t e d ( b ) and "alkaline calcined" (c) s a m p l e s a s a ftincticin
of t h e c o n v e r s i o n
408

The "alkaline calcined" s a m p l e s possessed a reduced aluminum c o n t e n t

c o m p a r e d t o t h e u n t r e a t e d c a t a l y s t . I t is p r o b a b l e t h a t a l u m i n u m w a s r e m o v e d
f r o m t h e o u t e r s u r f a c e o f t h e c r y s t a l s . T h e c r y s t a l s w e r e t o o s m a l l t o p er -
m i t d e t e c t i o n o f t h i s r e m o v a l by m i c r o p r o b e t e c h n i q u e s . " A l k a l i n e c a l c i n a t i o n "
o f ZS M - S c r y s t a l s s y n t h e s i z e d w i t h t e m p l a t e s , s h o w i n g a d e t e c t a b l e z o n i n g .
produced only a s l i g h t e n h a n c e m e n t of t h e s h a p e - s e l e c t i v e p r o p e r t i e s h u t a
r e m a r k a b l e d e c r e a s e i n a c t i v i t y . T h i s is also a h i n t t h a t t h e a l u m i n u m h a s
b e e n s e l e c t i v e l y r e m o v e d f r o m t h e c r y s t a l s u r f a c e . A n o t h e r e x p l a n a t i o n is b a s e d
upon t h e a s s u m p t i o n t h a t a p a r t of t h e alu mi num s t a y s a s " e x t r a - f r a m e w o r k
aluminum" inside t h e channels, influencing t h e diffusion of t h e p r o d u c t s .
E x t e n s i v e e x a r n i n a t i o n s . e . g . by m e a n s o f s o l i d - s t a t e NMR a n d I R s p e c t r o s c o p y .
a r e n e e d e d f o r a more d e t a i l e d u n d e r s t a n d i n g of t h e o b s e r v e d p h e n i ~ i n e n a .

ACKNOWLEDGEMENTS

F i n a n c i a l s u p p o r t by BMFT ( 0 3 C 236) a n d D e u t s c h e F o r s c h u n g s g e n i e i n s r : h a f t
is g r a t e f u l l y a c k n o w l e d g e d .

REFERENCES
1 P.A. J a c o b s a n d J . A . M a r t e n s , S t u d . S u r f . S c i . C a t a l . , a (1987) 134
2 C . B e l l u s s i e t a l . , S t u d . S u r f . S c i . C a t a l . . 37 (1988) 37
3 A . T i s s l e r , U . M i i l l e r a n d K.K. U n g e r , N a c h r i c h t e n ails C h e m i e . T e c h n i k u n d
L a b o r a t o r i u m ,V o I . 3 6 , N o . 6 , 62 4 - 6 3 0 (19 8 8
4. H . C . Kar g e. Z . S a r b a k , K. H a t a d a . J . W e i t k a m p . P.A. J a c o b s . J . C a t a l .
82 11983) 236
5 m. C h a m a n i a n d L . S a n d . Z e o l i t e s . 3 (1983) 1SS.
6 G . O o m s , R.A. van S a n t e n , R.A. J a c k s o n a n d C.R.A. C a t l o w . S t u d . S u t - f .
S ci . C a t a l . 37 (1988) 317
7 H . A . Ar av a a n d B a r r ie M . L o w e . Z e o l i t e s . 6 (1906) 111
8 H . G . Kar d e. Y. W a d a . 1. W e i t k a m o . S . E r n s t . U. G i r r b a c h a n d H . L B r \ e r
S t u d . Suyf.. S c i . c a t a i . (1984.) '101
7 U. G i r r b a c h . T h e s i s , J o h a n n e s G u t e n b e r g - U n i v e r s i t y . Mai n z FRC ( 1007)
1 0 W . W . K a e d i n a . 1 . C a t a l . . 9 s (1985) 512
11 D.H. O l s o n , W . O . H a a g , R-M. Lago. J . C a t a l . , l (19801390
12 R . M. Lag o , W . O . H a a g , R . J . M i k o w s k y , D . H. O l s o n , S . D . H e l l r i n g ,
K.D. S c h m i t t a n d C . T . K e r r , S t u d . S u r f . S c i . C a t a l . , 28 (19861 677
13 M u l l e r , U., D a n n e r . A , , H o l d e r i c h . W . , U n g e r . K.K.: DE P 37284.51.7(1987)
1 4 , T i s s l e r , A . , M u l l e r . U.,D a n n e r , A . , U n g e r , K .K ., Z . K r i s t . , l 8 2 (1988) 2 5 8 - 2 6 0
15 S . Nai n b a, A . l n a k a a n d T . Y a s h i m a , Z e o l i t e s , 6 (1986) 107
16 C h u . C . C . ( t o M o h i l O i l ) . E.P. 38,116 (1981)
H.G.Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent BuiMers
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THEORETICAL STUDIES OF BRmSTED ACIDITY I N ZEOLITES

R. VETRIVELl, C. R. A. CATLOWI, E. A. COLBOURN2 a n d PI. LESLIE3

IDepartment of Chemistry, University of Keele, Keele, Staffordshire,

ST5 5BG, U.K.
2Wilton Materials Research Centre, I.C.I. Plc., Wilton, Middlesborough,
Cleveland, TS6 8JE., U.K.
3SERC Daresbury Laboratory, Daresbury, Warrington W.44 4AD, U.K.

ABSTRACT
A quantum chemical c l u s t e r (QCC) is t r e a t e d explicitly b y a n a b initio
technique, a n d is embedded in a point c h a r g e c l u s t e r (PCC). The l a t t e r i s
chosen to r e p r e s e n t t h e long-range electrostatic terms in t h e zeolite lattice.
Calculations h a v e been c a r r i e d o u t on a s e r i e s of zeolite c l u s t e r s namely,
Zeolite-AILTA), ZShI-Il(?lEL), ZSM-5(NFI), Offretite(OFF), hlordenite(FlOR),
Faujasite( FAU) a n d Zeolite-L(LTL). The predicted acidic p r o p e r t i e s of t h e s e
zeolites, t h e effect of t h e substitution of silicon by aluminium or boron a n d
t h e values of t h e vibrational f r e q u e n c y are r e p o r t e d a n d compared with
esperimental data.

INTRODUCTION
Zeolites a r e c a t a l y s t s f o r numerous hydrocarbon conversion reactions, a n d
it is h e l l known that t h e i r catalytic behaviour is d e p e n d e n t o n t h e i r acidic
p r o p e r t i e s (ref.1). Many techniques have been used to s t u d y t h e i r acidic
characteristics; these include t h e adsorption of basic molecules (ref.2),
temperature-programmed desorption (ref.J), spectroscopic techniques [i.r.
(ref.$), n.m.r.(ref.5)] and t h e investigation of t h e catalytic activity f o r certain
t e s t reactions (ref.6). However, each of t h e methods i s limited ( s e e e.g. ref.5).
In t h e p r e s e n t p a p e r , we t h e r e f o r e explore t h e possibility of developing a
unified approach based o n theoretical techniques for t h e evaluation of t h e
comparative acidities of different zeolites.

blETHODOLOGP
The basis of t h e method i s t h e embedding of a quantum chemical
cluster(QCC) in a n a r r a y of point c h a r g e s as illustrated i n Fig.1. The point
c h a r g e cluster(PCC) containing nearly 80 atoms i s used to r e p r e s e n t t h e more
410

\ I
1-n-p

F i g . 1. The p o i n t charge cluster(PCC) models used f o r various z e o l i t e s .

(a)-LTA; (b)-MEL; (c)-MFI; (d)-OFF; (e)-MOR; (f)-FAU; (9)-LTL and
(h)- a t y p i c a l quantum chemical cluster(QCC)-[HT207].
 411

d i s t a n t atoms in t h e zeolite lattice. The number of atoms a n d t h e geometry of

t h e c l u s t e r a r e chosen in s u c h a way t h a t t h e Madelung e n e r g y a n d g r a d i e n t
of f o r c e s of a n infinite lattice are simulated by t h e PCC, The quantum
chemical c l u s t e r containing nearly 10 atoms, which is embedded at t h e c e n t r e
of t h e PCC, i s treated by a n a b initio technique. The positions of t h e atoms
in t h e QCC a n d PCC a r e those reported from crystallographic s t u d i e s as shown
in Table 1. Charges of 2 t and 1- a r e assigned f o r silicon and oxygen atoms
in t h e PCC, in view of t h e partially ionic n a t u r e of zeolites. A detailed
explanation of t h e procedure f o r generation of t h e PCC f o r ZSM-5 zeolite i s
given in o u r earlier paper (ref.14). The same p r o c e d u r e i s used f o r all t h e
zeolites mentioned in t h e p r e s e n t work. Fig.1 s h o w s t h e PCC model u s e d for
different zeolites. The computer program used here to perform a b iriitio
calculations i s t h e G.4IIESS (General Atomic a n d Molecular Electronic S t r u c t u r e
System) package as esteiided b y Guest a n d Kendriclc (ref.15). The caiculations
r e p o r t e d t h r o u g h o u t t h i s p a p e r were c a r r i e d o u t using t h e SV-3-21G basis
s e t s (ref.16).

The following details of t h e calculations should be noted:

i) The substitution of Si b y e i t h e r A1 or B i s effected only in t h e QCC.
The PCC in all t h e zeolites c o r r e s p o n d s to a completely siliceous framework.
ii) The QCC i s chosen so t h a t t h e b r i d g i n g osygen i s i n t h e l a r g e s t r i n g
opening of the zeolite pore. Escept f o r Zeolite A, t h e r e i s no conclusive
evidence available to fis the preferential sites for aluminium/boron
substitution. Moreover, t h e s i t e s chosen f o r the s u b s t i t u t i o n of Si b y e i t h e r
A1 or B d o not significantly influence t h e results.
iii) The geometry of t h e T2O7 c l u s t e r i s not varied since optimisation of
t h e T2O7 c l u s t e r in different zeolites leads to t h e same final configuration in
all cases. Hence t h e geometry of T2O7 c l u s t e r i s as r e p o r t e d b y X-ray
diffraction studies. However, t h e geometry of t h e h y d r o g e n atom i n t h e HT2O.;
c l u s t e r i s optimised.

RESULTS AND DISCUSSION

The crystallographic information a n d t h e s i t e s chosen f o r t h e p r e s e n t
s t u d y a r e summarised i n Table 1. Results of t h e calculations carried o u t o n
t h e [Si207l6- c l u s t e r f o r different zeolites are given i n Table 2. The effect of
s u b s t i t u t i o n of silicon b y aluminium or boron on t h e electronic p r o p e r t i e s i s
studied b y replacing one of t h e Siat by A13+ or B3+. The r e s u l t s of t h e
calculations c a r r i e d o u t on [SiA10717- a n d [SiB07I7- c l u s t e r s are g i v e n i n
Tables 3 and 4 respectively. The Bronsted acidic p r o p e r t i e s of t h e s e zeolitic
412

TABLE 1
The c r y s t a l l o g r a p h i c i n f o r m a t i o n f o r t h e selected z e o l i t e frameworks and the
d e t a i l s o f t h e c l u s t e r models.

Zeolite Code Space Ref. Number o f c r y s t a l l o - B r i d g i n g oxygen Number o f

* group graphically chosen i n t h e atoms i n the
different sites present study PCC c l u s t e r
T n
I U

Zeolite-A LTA Fm3c 7 2 3 T1 - 02 - T2 73(Fig.la)

ZSM-11 MEL 141112 8 7 15 T4 - 012 - T5 78(Fig.lb)
ZSM-5 MFI Pnma 9 12 26 T2 - 013 - T8 82(Fiq.lc)
Offretite OFF P6m2 10 2 6 T2- 06 - T2 84iFiG.ldj
Mordenite MOR Pbcn 11 6 13 T1- 07 - T1 78(Fig.le)
Faujasite FAU Fd3m 12 1 4 T - 01 - T 80(Fig.lf)
Zeolite-L LTL P6/mmm 13 2 6 T1 - 01 - T1 85(Fig.lg)

*The nemonic code adopted f o l l o w i n g IUPAC recommendations (R.M. Barrer,

Pure & Appl. Chem. , g,1091(1979)).

TABLE 2
The calculated properties of [Si2O7l6- cluster embedded in point charge
clusters of different zeolites

Electronic total P a r t i a l charges calculated

Zeolite energy energy by Mdliken population
(a.u.1 (a.u.) analysis
-
Si O* Si

LTA -1763.8911 -1119.2947 t1.76 -1.11 t1.73

A m -1790.2582 -1121.5762 t1.89 -1.16 +1.93
MFI -1789.2342 -1125.6955 t1.92 -1.22 t1.96
OFF -1775.3437 -1121.1837 t1.85 -1.16 t1.85
MOR -1791.4322 -1121.4406 t1.92 -1.18 +1.83
FAU -1772.6411 -1122.2070 t1.77 -1.11 t1.77
LTL -1775.7055 -1120.4051 t1.77 -1.13 +1.77

*bridging oxygen

frameworks a r e studied by replacing the 02- ion sharing the corners of the
two tetrahedra by a n OH- ion. Thus the results of the calculations including
the calculated proton affinity carried out on [HSi207I5-, [HSia10716- and
[HSiB07I6- clusters a r e given in Tables 5, 6 and 7 respectively.
 413

TABLE 3
The c a l c u l a t e d p r o p e r t i e s of [Si.U07]7- c l u s t e r embedded i n p o i n t
charge c l u s t e r s of d i f f e r e n t z e o l i t e s .

Electronic Total P a r t i a l charges c a l c u l a t e d

Zeolite energ>- enargj- by Plulliken population
(a.u.) (a.u. 1 analysis
~~~ ~

Si O* A1**
-
LT.4 -1700.8916 -1071.9m t1.z -1.15 t1.o2('r2)
PEL -1726.0537 -1C74.1698 t1.90 -1.18 +1.21(T4)
)IF1 -1725.2639 -1078.3163 t1.96 -1.23 +1.21(T=)
OFF -1711.5069 -1073.7651 t1.82 -1.16 +1.12(12)
PlOR -1727.2988 -1074.0401 t1.92 -1.19 t1.07(T1)
FX -1708,9524 -1074.8601 t1.77 -1.12 t1.03(1')
L'I'L -1711.8380 -1073.0107 t1.76 -1.15 tI.Ol(T1)
~~~

*bridging oxygen
**site a t vhich S i is replaced by A 1 is given i n bi*acltets

TS3LE 4
The c a l c u l a t e d p r o p e r t i e s of [SiB07l7- c l u s t e r embedded i n p o i n t
charge c l u s t e r s of d i f f e r e n t z e o l i t e s .

Electronic Total Partial charges c a l c u l a t e d

Zeolite energy energy by Mullilren population
(a.u. ) (a.u.) analysis

- ~ _ _ _ _
Si O* B* *
LT.1 -1358.9229 -855.6375 t1.67 -1.02 to.91 ( T2 )
,TI, -1375.4298 -857.9309 t1.81 -1.04 +1.09(T1) '
?lFI -1376.2867 -862.0686 t1.88 -1.07 t1.07(T2)
OFF -1363.9171 -855.5207 t1.75 -1.02 t1.02(T2)
MOR -1377.1815 -857.7857 t1.83 -1.05 tI.Ol(T1)
FAU -1361.9257 -858.5699 t1.69 -1.00 t0.96(T)
LrL -1363.9584 -836.7358 t1.69 -1.02 to.97(Ti)
*bridging oxygen
**site a t which S i is replaced by B is given i n b r a c k e t s

Effect of A1 and B Substitution

I t is not possible to fix t h e positions of h y d r o g e n s from crystallographic
studies. Hoxever, t h e r e a r e speculations, made o n t h e basis of I R s t u d i e s
(ref.4), that t h e protons a r e attached t o oxygen ions in t h e vicinity of A13+,
which indeed would be espected because t h e p r o t o n s are p r e s e n t as c h a r g e
compensators for t h e Al substitutionals a n d will be a t t r a c t e d b y t h e negative
c h a r g e of t h e species. Hence t h e proton was attached to t h e bridging oxygen
and i t s distance from t h e oxygen atom and i t s a n g l e s with t h e 'T' atoms were
optimised to yield a minimum e n e r g y configuration. I t is i n t e r e s t i n g t o note
414

TABLE 5
The calculated properties of [HSi2O7I5- cluster embedded in point charge
clusters of different zeolites.
Zeolite Electronic Total Partial charges calculated by Optimi sed Proton
energy energy Mu1 1 i ken population analysis 0-H affinity
(a.u.) (a.u.) distance (a.u.)
si o* Si H (A)
LTA -1786.4069 -1120.1171 t1.77 -1.03 t1.74 t0.44 1.0328 -0.8224
MEL -1811.2913 -1122.4240 t1.89 -1.08 t1.94 t0.51 0.9756 -0.8478
MFI -1811.8302 -1126.4814 t1.89 -1.13 t1.95 t0.46 1.0040 -0.7859
OFF -1797.4488 -1122.0514 t1.86 -1.07 t1.86 t0.48 1.0032 -0.8677
MOR -1812.5797 -1122.2891 t1.93 -1.08 t1.82 t0.50 0.9749 -0.8485
FAU -1793.1469 -1123.0563 t1.79 -1.04 t1.79 t0.50 0.9712 -0.8493
LTL -1796.0577 -1121.2527 t1.79 -1.05 t1.79 t0.49 0.9676 -0.8476
~ ~~

* bridging oxygen

TABLE 6
The calculated properties of [HSiA107]6' cluster embedded in point charge
clusters of different zeolites.
Zeolite Electronic Total Partial charges calculated by Optimised Proton
** energy energy Mu1 1 i ken popul at ion anal ysi s 0-H affinity
(a.u.) (a.u.) distance (a.u.)
._
si O* A1 H (A)
LTA(T2) -1723.4843 -1073.0435 t1.79 -1.04 t1.08 t0.43 1.0222 -1.0467
MEL(T4) -1747.2020 -1075.2485 t1.97 -1.10 t1.23 t0.47 0.9697 - 1.0787
MFI (T2) -1747.9627 -1079.3291 t2.01 -1.12 t1.20 t0.45 1.0035 -1.0128
OFF(T2) -1733.7101 -1074.8657 t1.91 -1.08 t1.17 t0.46 0.9988 -1.1006
MOR(T1) -1748.5562 -1075.1182 t2.00 -1.10 t1.09 t0.47 0.9697 -1.0781
FAU(T ) -1729.5246 -1075.9278 t1.86 -1.05 t1.06 t0.47 0.9639 -1.0674
LTL(T, ) -1732.2827 -1074.1082 t1.85 -1.05 t1.05 t0.46 0.9616 -1.0675
- - .- _- __ - __ - ___
* bridging oxygen
**site at which Si is replaced by A1 is given in brackets

TABLE 7
The calculated properties of [HSiBO7I6' cluster embedded in point charge
clusters of different zeolites. ___ -
--

Zeolite Electronic Total Part i a1 charges cal cul ated by Optimised Proton
** energy energy Mulliken population analysis 0-H affinity
(a.u.) (a.u.) -- * distance (a.u.)
-__ _.. .-
Si - 0 B H (A)
LTA(T2) -1379.2589 -856.7228 t1.76 -0.96 t0.88 t0.43 1.0155 -1.0853
MEL(T4) -1394.5589 -859.0367 t1.90 -0.96 t1.08 t0.43 0.9694 -1.1058
MFI(T2) -1396.7069 -863.1140 t1.94 -0.99 t1.00 t0.42 0.9946 - 1.0454
OFF(T2) -1383.9055 -858.6593 t1.86 -0.97 t1.00 t0.43 0.9979 -1.1386
MOR(T1) -1396.3953 -858.8932 t1.93 -0.97 t0.98 t0.42 0.9702 -1.1075
FAU(T ) -1380.5648 -859.6638 t1.80 -0.94 t0.95 t0.44 0.9646 - 1.0939
LTL(T1) -1382.4181 -857.8305 t1.79 -0.92 t0.96 t0.42 0.9606 - 1.0947

* bridging oxygen
**site at which Si is replaced by B is given in brackets
 415

t h a t t h e minimum e n e r g y position f o r h y d r o g e n in all t h e zeolites i s t h e one in

which t h e hydrogen atom points towards t h e l a r g e s t possible pore i n t h e
zeolite.
I t i s well known (ref.1) t h a t t h e s e p r o t o n s a r e t h e source of Bronsted
acidity. For example, t h e correlation between t h e ammonia adsorption capacity
and t h e absorbance of t h e band in t h e infra-red region range 3400-3800 cm-1
corresponding to hydrosyl g r o u p vibration h a s been r e p o r t e d (ref.18). The
chemical shift (C,) of t h e proton magnetic resonance (ref.5) i s also known to
increase when t h e acid s t r e n g t h of t h e zeolite increases. The partial c h a r g e s
o n hydrogen calculated f o r t h e different c l u s t e r s a r e also shown in Tables
5-7. The partial c h a r g e on hj-drogen i s found t o be d e p e n d e n t o n t h e
optimised 0-H distance, t h e dimension of t h e pore in t h e zeolite a n d T-0-T
angle. There is a repulsive interaction between the 'T' atom and the
hydrogen. When Si4+ i s replaced by A13+ or B3+, this repulsive force
d e c r e a s e s and t h e r e i s increase i n t h e proton affinity (which i s calculated as
the difference between t h e values of t h e total e n e r g y of t h e HT2O7 a n d T2O7
c l u s t e r s ) , and a decrease in t h e partial c h a r g e on t h e proton. The values of
proton affinity for different c l u s t e r s a r e shown i n Tables 5-7. However it
should be noted t h a t HSi207 i s only a hypothetical c a s e as t h e r e i s n o need
f o r the presence of a proton in t h e all siliceous framework. I t should also
be noted t h a t or B3+ s u b s t i t u t i o n s c a u s e t h e introduction of t h e protons
a s c h a r g e compensators. On comparing boron s u b s t i t u t i o n with aluminium
substitution, we find t h a t t h e proton affinity increases with a c o r r e s p o n d i n g
decrease in Bronsted acidity which c o r r e l a t e s v e r y well with experimental
r e p o r t s based on temperature-programmed desorption s t u d y (ref.21) of
ammonia and t h e s t u d y of activity of acid-catalysed reactions (ref.17) f o r
ZSM-5 zeolite. F i g 2 shows t h a t t h e proton affinity is i n t h e o r d e r B-zeolites
> Al-zeolites. However, t h e differences i n t h e calculated values of proton
affinity f o r different zeolites with same IT' atom (say for 'Al' substituted
c l u s t e r s shown i n Table 6 ) a r e much smaller.

Acidity Correlations
The partial c h a r g e s calculated on t h e b r i d g i n g oxygen atoms are a n
indication of t h e i r capacity to bind additional protons. We compared t h e
charge on the bridging oxygen f o r d i f f e r e n t zeolite c l u s t e r s with their
reported acidity d a t a where available. The acidities of t h e proton forms of
different zeolites (except LTA) have been investigated by carrying out
catalytic t e s t reactions (ref.6) a n d by t h e TPD s t u d y of ammonia (refs. 18-21).
These r e s u l t s are summarised in Table 8. The calculated partial c h a r g e s o n
t h e bridging oxygen f o r different zeolites are plotted a g a i n s t t h e i r a c t i v i t y f o r
416

TABLE 8
R e s u l t s of a c i d i t y esperirnents c a r r i e d o u t on t h e H-exchanged
forms of d i f f e r e n t z e o l i t e s .

Zeolites Activity for Temperature programmed

i sopropanol d e s o r p t i o n of ammonia
decomposition
(ref. 6) Peak Maxinm Ref.
(mi05 sec-i) temperature
(K)

FAU 5 586 18
LTL 15 618 18
OFF 21 673 19
MOR 28 68 1 20
PIEL 32 673 21
MFI 39 723 21

isopropanol d e h y d r a t i o n (Fig.3) and t h e Tma, in t h e TPD spectrum of ammonia

(Fig.4). A linear correlation i s found to exist. This s u g g e s t s t h a t it i s
possible to make u s e f u l predictions of t h e relative acidities of zeolites u s i n g a
simple, theoretically derived parameter.

The Madelung e n e r g y calculated f o r t h e b r i d g i n g oxygen in 2S?I-5 h a s a

l a r g e value ( 10 eV h i g h e r t h a n f o r t h e o t h e r s t r u c t u r e s examined) i n
c o r r e s p o n d e n c e with its s t r o n g acidity. For all the other zeolites, the
Madelung e n e r g y o n t h e b r i d g i n g oxygens ha\;e almost t h e same value. The
partial c h a r g e o n t h e bridging oxygen is f o u n d to b e d e p e n d e n t o n i t s
distance from t h e a d j a c e n t 'TI atom. When t h e T-0 bond length d e c r e a s e s ,
t h e r e is more t r a n s f e r of electron d e n s i t y from t h e 'T' atom to t h e oxygen.
Since t h e oxygen i s a t t a c h e d t o two 'T' atoms t h e T-0 distance i s taken a s t h e
a v e r a g e distance of oxygen from both t h e 'T' atoms. Hence T-0 [(Tl-O) t
(0-T2)]/2, where T I and T2 a r e t h e two t e t r a h e d r a l cations bonded t o the
oxygen atom. The linear relationship e s i s t i n g between t h e T-0 distance a n d
t h e formal c h a r g e o n t h e oxygen atom is e v i d e n t from Fig.5. The two
important r e s u l t s t h a t emerge from t h e a b o v e o b s e r v a t i o n s of t h e calculations
are:
i ) t h e geometry of t h e local s t r u c t u r e , more specifically t h e geometry of
each t e t r a h e d r a l g r o u p in t h e zeolites, influences t h e i r acid s t r e n g t h .
ii) when t h e heteroatoms s u c h as A13+ or B3+ replace t h e Silt ions, t h e
local s t r u c t u r e will r e a r r a n g e , which i n t u r n will a l t e r t h e acidic properties.
These e f f e c t s cannot, however, be investigated i n t h e p r e s e n t s t u d y as we
were not a b l e t o s t u d y t h e variation of t h e geometry of o u r QCC o n
substitution of heteroatoms. Future studies with larger clusters will
i n v e s t i g a t e t h i s effect.
 417

-1.081

Y -1.18
a
3
0
-120

-'5
7.0 t 10 20 30 40 50
a - I u u J 6 4n TURNOVER FREOUENCY x 10' (s-9
2 5 g g g z
ZEOLITES

Fig. 2. The proton affinity values o f Fig. 3. The correlation between the
zeolites calculated for different calculated partial charge on the
cl uster model s . bridging oxygen and the experimental
acidity measured as the activity for
the isopropanol decomposition for
different zeolites.

A-.

-1.04
m
-1.08
0
9 -1.12
a m
z
0
-1.16
0 -1.16 -
w -120
P = -120-
4 -124 I
I 0
u -I -124. Q*
-I -126
S
c 1.56 1.60 1.64 1.68
560 600 640 680 720 760 U
4
n
TEMPERATURE (K) if T - 0 DISTANCE 6)
Fig. 4. The correlation between the Fig.5. The variation of the ca culated
calculated partial charge on the partial charge on the bridging oxygen
bridging oxygen and the experimental with T-O(where T-0 = [(TI-O)t( 2-0)1/2
acidity measured as the T in the distance.
TPD spectrum of ammonia f!Px
different zeolites.

Legend to Figs. 2-5:

0 - 0 - 0- S i2O7 c lu s t er,o-0-0- S i A lo7 c luster,
A-A-A- SiB07 cluster,

a o i - FAU, W A - LTL, @@A-OFF,

.OA-MOR, H@&-MEL, EOA-MFI.
418

Vibrational F r e q u e n c y of t h e Hydrosyl Group

Having optimised t h e 0-H d i s t a n c e i t i s possible t o calculate t h e force
constant for the 0-H bond and hence its vibrational frequency. The
s t r e t c h i n g vibration of t h e 0-H g r o u p i n zeolites g i v e s r i s e to a b s o r p t i o n in
t h e infra-red region at approsimately 3400 t o 3800cm-1 d e p e n d i n g o n w h e t h e r
t h e 0-H bond i s in a silanol g r o u p or i n t h e b r i d g i n g s i t e a n d on t h e
dimension of t h e pore in which t h e hydroxyl g r o u p i s situated. All zeolites
have more t h a n a single t y p e of hydroxyl g r o u p , a n d t h e o b s e r v e d spectrum
i s a n a v e r a g e over t h e various s i t e s with a BWHII (Band Width a t Half Masima)
of 200cm-1. Though t h e deconvolution of t h e s p e c t r a h a s been attempted, t h e
p r e s e n c e of a t least 16 possible cationic sites, e v e n in Faujasite zeolite (ref.22)
which contains only one crystallographic 'T' site, p o s e s g r e a t difficulties.
However, t h e vibrational f r e q u e n c y of t h e hydroxyl g r o u p in the largest
possible pore of these zeolites h a s been r e p o r t e d (ref.4). These values are
compared with t h e calculated values of t h e vibrational f r e q e n c y f o r different
c l u s t e r s shown in Table 9. The calculated v a l u e s are always higher compared
to experiment. Despite t h e f a c t t h a t t h e vibrational f r e q u e n c y of t h e 0-H
g r o u p a t a single s i t e i s calculated a n d t h e e f f e c t of Si/AI ratio i s neglected
in t h e p r e s e n t calculation, t h e calculated values a r e within t h e r a n g e expected
from t h e esperimental s t u d i e s , when we note that t h e esperimental p e a k s
normally have a width of 200 cm-l. F u r t h e r s t u d i e s , which esamine all
possible sites, are now needed.

TABLE 9
The experimental and t h e c a l c u l a t e d v i b r a t i o n a l frequency of t h e
hydros3-1 group i n t h e l a r g e s t pore of d i f f e r e n t z e o l i t e s .

ZEOLITES V i b r a t i o n a l frequency of 0-H bond ( c m - l )

Experimental Calculated Calculated Calculated

reports ( r e f . 4 ) Value for Value f o r Value for
for t h e hydrogen mi207 HSi.UO7 HSiBO7
zeolites cluster cluster cluster

LTA - 3028 3584 3509

MEL 3605 3853 3017 3884
MFI 3601 3594 3732 3652
OFF 3618 3669 3602 3639
MOR 3610 3778 3926 3926
FAU 3659 3782 3843 3814
LTL 3630 3778 4032 4026
 419

SUMMARY
The work h a s shown the value of embedded quantum mechanical c l u s t e r
calculations in s t u d y i n g t h e acidity of zeolites. Our r e s u l t s emphasise t h e
importance of the small differences in t h e bond l e n g t h s a n d bond a n g l e s which
exist in different zeolites as well as i n different s i t e s of single zeolite. The
calculated values of t h e proton affinity are s t r o n g l y affected by heteroatom
substitution. bloreover, the electronic charge on the bridging oxygen,
calculated by t h e llullilten population analysis f o r different zeolites has a
linear correlation with the acidity of different zeolites determined by
esperiniental techniques. Greater difficulty is encountered i n t h e calculation
of t h e vibrational frequency of t h e h y d r o s y l group. The techniques can be
refined with more sophisticated calculations u s i n g l a r g e r c l u s t e r s .

Acknowledgements
We a r e g r a t e f u l to I.C.I. Plc. f o r s u p p o r t i n g t h i s work via t h e Joint
Research Scheme. We also t h a n k Dr. R. A. Jackson f o r helpful discussions.

REFERENCES
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C. Naccache (Ed.), Zeolites: Science a n d Technology, l l a r t i n u s Nijhoff
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This Page Intentionally Left Blank
H.G. Karge, J . Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V.. Amsterdam - Printed in The Netherlands

NMR AND IR STUDIES OF ZEOLITES OF THE ERIONITE TYPE

F . ROESSNERI, K.-H. STEINBERG1, D. FREUDE2, M. HUNGER2 and

H. PFEIFER~
lSektion Chemie der Karl-Marx-Universitaet Leipzig, Talstr.35,
Leipzig, 7010 (G.D.R.)
2Sektion Physik der Karl-Marx-Universitaet Leipzig, Linnestr.5,
Leipzig, 7010 (G.D.R.)

ABSTRACT
Infrared spectroscopy (IR) and proton, aluminium and silicon
magic-angle-spinning nuclear magnetic resonance spectroscopy ( L H ,
27A1 and 29Si MAS NMR) yield information about the location and
concentration of Broensted acid sites, the distribution of alumi-
nium in the framework and the concentration of non-framework spe-
cies in erionite. Most of the bridging O H groups are formed on the
O(1) oxygens located in the double-six-ring between two cancrinite
cages. Other OH groups are in the large cavity at O(5) or O(6)
oxygens as well as in the cancrinite cages. The differences of the
Si/Al-ratios determined by different methods were explained i n
term of thermal decomposition of a parasite phase.

INTRODUCTION
Among the zeolite catalysts used o n a larger scale in industry,
erionite is unique with respect to the smallest available pore
diameter (elliptical pore opening: 0.30 x 0 . 5 2 nm). A bifunctional
Pt/H-erionite is applied for formselective reforming where n-alka-
nes are selectively hydrocracked in the feed. A study on the na-
ture and location of hydroxyl groups influenced by the lattice
structure m a y contribute to a better understanding of this pro-
cess.
Figure 1 shows a model of the erionite structure. The cancri-
nite cages are linked to hexagonal prisms and single six-membered
rings. In contrast to faujasite there are six crystallographically
different oxygens in the erionite structure:

O(1) -
connecting the six-rings of the hexagonal prism,
O(2) -
shared among the four-ring of the hexagonal prism and the
six-ring of the cancrinite cage,
O(3) - shared among thc four-ring of the hexagonal prism and the
four-ring of the cancrinite cage,
O(4) - shared among the four- and six-rings of the cancrinite
cage I
422

Fig, 1 Model of the erionite structure

O(5) - oxygen of the single six-ring connecting two cancrinite

cages, and
O ( 6 ) - shared among the single six-ring and the four-ring of the
cancrinite cage.
Information about the Si/A1 ratio and the aluminium distribu-
tion o n nonequivalent tetrahedral T-sites is available from 29.31
M A S N M R spectra. Based o n such results Lillerud (ref. 1) made the
assumption of a prefered occupation of the T2-sites ( s e e F i g . 1)
by aluminium. For the best f i t between the measured and calculated
spectra he found 0 . 1 7 Al/T1 in comparision t o 0.35... 0.45 Al/T2.
Taking into account that for erionite T1/T2=2 it c a n be expeated
that nearly the same number of bridging OH groups must b e formed
i n the environment of aluminium at T 1 and T2 positions.

EXPERIMENTAL
The ammonium-exchanged erionite w a s prepared by repeated i o n
exchange of synthetic NaK-erionite w i t h NH4N03 solution at 363 K.
The parent zeolite (Si/A1-3, by the chemical analysis) w a s ob-
tained from VEB Chemiekombinat Bitterfeld, G.D.R. NMR measurements
were performed o n a Bruker MSL-300 spectrometer at resonance i r e -

TABLE 1
Si/Al ratios determined from 27Al and 29Si M A S N M R spectra and
concentration of cations determined by chemical analysis

Sample Si/Al cations

determined by per unit cell
2 7 1~ 29si
MAS N M R NHq+ K+ Na+

NaK-erionite 3.0 2.0 0.0 4.9 4.1

0.77NHq-erionite 3.6 2.3 6.9 1.0 0.2
0.91NH4-erionite 3.6 2.4 8.2 0.8 0.04
0.93NHq-erionite 4.5 2.4 8.4 0.6 0.02
 423

quencies of 300, 78 and 5 9 . 6 MHz for l H , 27Al and 29Si NMR, res-
pectively. The experimental error of intensities w a s 1 0 X . F o r
HNMR measurements shallow-bed activation conditions were used in
a glass tube o f 5 . 5 mm diameter containing a 1 0 mm layer of zeo-
lite. The temperature was increased w i t h a rate o f 10 K/h. After
maintaining the sam les for 24 h at the final temperature of 670 K
they were sealed. 2fA1 and 29Si MAS NMR measurements were gene-
rally carried out o n rehydrated samples.
The infrared spectra were recorded on a UR-20 spectrometer (VEB
Carl-Zeiss-Jena) . The samples (thickness: 5-12 mg/cm2) were a l s o
activated in-situ at 670 K and 10-1 P a for 3 0 min. T o increase the
transmission all samples were deuterated by repeated treatment
with D20 at 373 K .

RESULTS AND DISCUSSION

The synthesis of erionite is normally accompanied by the f o r -
mation of other aluminosilicates (ref. 2). X-ray studies o n the
parent NaK-erionite have shown a contribution of zeolite P (ref.
3). Since the H-form of zeolite P is thermally unstable, a compar-
ision of the 27Al NMR spectra of the fresh and 720 K calcined
samples must indicate intensity changes of the line at 60 ppm as-
signed to tetrahedrally coordinated framework aluminium. T h i s as-
sumption is supported by the results shown in Table 2 (see columns
5 and 6). The Si/Al ratio of NaK-erionite before and after calci-
nation remains constant and corresponds to the value obtained by
wet chemical analysis. However, the calcined ammonium-exchanged
erionites lost approximately 30 % of their framework aluminium.
Unlike NMR spectra, the framework vibration bands observed by in-
frared spectroscopy were not shifted, i.e. the Si/A1 ratio o f
erionite was not changed. Both results c a n only b e explained in
terms of thermal decomposition of the zeolite P. T h e calculated
amounts of zeolite P agree with the calculations based o n NH3-
t . p . d . and H/D-isotopic exchange (ref. 3).

TABLE 2
Concentrations of different species /in lOl9 per gramme/ in the
erionite calculated from I H and 27Al M A S NMR

SiOH re s idua 1 framework A 1

or SiOHAl NH4+ before/after
AlOH calcination

Chem. shift /ppm/ 1.9-2.6 3.9 6.7 601

Zeolite

NaK-erionite 14 0 0 246 246

0.37 H-erionite 18 54 0 234 205
0.77 H-erionite 25 95 0 214 154
0 . 9 1 H-erionite 23 100 17 214 154
0 . 9 3 H-erionite 28 105 56 178
0 . 9 3 H-erionite2 52 95 5 123

IChemical shift of z ' ( A l M A S NMR.

2Calcined at 720 K .
424

In zeolite structures, where each s i l i c o n has four nearest-

neighbour silicon or aluminium a t o m s , the 29Si NMR chemical shift
falls into five ranges w h i c h c a n be correlated with the n u m b e r of
aluminium neighbours surrounding a g i v e n silicon (ref. 4):
Si(4A1): -80 to -
89 ppm
Si(3A1): -88 to -
97 ppm
Si(2A1): -94 to -103 ppm
Si(lA1): -98 to -107 ppm
Si(OA1): -103 to -114 ppm
The ion-exchanged erionites activated at 720 K for 2 h s h o w a
complex 29Si M A S spectra (Fig. 2) for different reasons:
(i) superposition of signals from the erionite phase and phases
of crystalline impurities mainly zeolite P ,
( i i ) different lines f o r different number n (n=O ...
4) of alumi-
nium atoms i n the first s i l i c o n ’ s coordination sphere
Si(nAl), and
( i i i ) different lines for Ti and T 2 , i . e . for Si(nAlT1) and
S i ( n A 1 ~ 2 ) (ref. 5).
Unfortunately, for erionite the effect of the site inequiva-
lence (5.3 ppm) is almost exactly the same as the effect of alu-
minium in the first coordination sphere (5.5 ppm) (ref. 5). U s i n g
a line f i t , Lillerud (ref. 1) demonstrated a favourite occupation
of T2 positions f o r aluminium atoms i n erionite. Nevertheless, the
splitting procedure dividing the signal into two (or three) parts
is very problematic. Our experiments prove the result of Lillerud
(ref. 1) that aluminium atoms oocupy preferably T2 positions in
NaK-erionite. I n case of H-erionite n o reliable information c a n be
derived w h e n we take into account a 10% error in measurement. T h e
difference between the spectra of NaK- and H- erionite c a n be ex-
plained by thermal decomposition of zeolite P w h i c h contributes a
broad unresolved 29Si MAS NMR signal.

. . .

NmK-mrionlt*

arlonlte

- I I I F i g . 2. 29Si MAS NMR spectra

-80 -100 -120 S,,,I/ppm of NaK- and 0.91 11-erionite.
 425

Information o n the nature and location of hydroxyl groups is

available from infrared spectroscopy. In the spectra of a deutera-
ted 0.91 H-erionite activated at 670 K, bands r e m a i n at 2 6 4 0 ,
2670, 2 7 1 0 and 2760 cm-l (Fig. 3a). The band at 2760 cm-l, a l s o
observed for ion-exchanged Y zeolites and
silica. is assigned to S e m i n a l hydroxyl
groups located o n the external surfaoe or
o n lattice defects. W h e n the activated
erionite is exposed to ammonia at 130 P a
and room temperature (Fig. 3b), the in-
tensity of the band at 2670 om-I decreas-
es, the shoulder at 2640 cm-l vanishes
completely, while the bands at 2 7 1 0 and
2760 cm-1 remain as i n the unloaded Sam-
ple. To confirm the location of the hy-
droxyl groups, a H-erionite caloined in
air was ion-exchanged w i t h 0 . 1 M CsC1-so-
lution at room temperature. Comparing the
spectra of H- and CsH-erionite deuterated
(Fig. 3 a and 3 c ) the shoulder at 2640

Fig. 3. OD stretching vibration spectra

of a 0 . 9 3 H-erionite activated at 670 K
(a) and exposed to 1 3 0 P a NH3 (b). and of
a CsH-erionite activated at 670 K (c).
VIUn.’

cm-l is completely eliminated and the intensity of the band at

2670 cm-I i s drastically reduced.
It is known that the Cs+ ion is too large (d-0.338 nm) to enter
the hexagonal prism and cancrinite cages through the six-ring nin-
dows (d=0.26 nm). Taking into account these results w e c a n con-
clude that the bands at 2640 and 2670 cm-l represent acidic bridg-
ing OH groups located in the large cavity (gmelenite cage). T h e
similarity i n structure between erionite and Y zeolite allows the
assignment of the most intensive band at 2670 am-l to O(1)H
groups. Hence the band at 2640 cm-1 represents perturbed acidic O H
groups vibrating in 6-membered rings /compare ref. 6 /, i.e. they
were formed, perhaps, o n O(5) and/or O ( 6 ) oxygens i n the large
cavity. Furthermore, the 2 7 1 0 cm-l band should be assigned to
hydroxyl groups i n the cancrinite cage (0(2)H, O(3)H and/or O(4)H
groups) inaccessible f o r large cations or hydrocarbons (ref. 7).
The I H MAS NMR spectra of ammonium-exchanged erionites (Fig. 4 )
contain information about both the nature and the concentration or
hydroxyl species (Table 1). In agreement with earlier studies o n
zeolites H-Y (ref. 8 , 9 ) , mordenite and ZSM-6 ( r e f . lo), the fol-
lowing assignment is made: the line at 1.9 ppm is caused by non-
acidic SiOH groups at the external surface or at lattice defects:
the line at 2.6 ppm represents hydroxyl groups associated w i t h
non-framework aluminium; the line at 3 . 9 ppm is ascribed to acidic
bridging OH groups and the line at 6.7 ppm is due t o residual
426

amounts of ammonium ions.

The amount of S i O H and A l O H groups (Table 2, column 2) is a
measure of the lattice defects formed by deoomposition of the zeo-
lite P and by dealumination. The intensity of the line at 3.9 ppm
c

i )i i i i iaH/ppm
Fig. 4. 1 H MAS N M R spectra of H-erionite activated at 670 K w i t h
a n exohange degree of 0 (a), 37 (b), 7'7 (c), 9 1 (d) and 93 % (0).
Spectrum ( f )represents a 0.93 H-erionite activated at 720 K
( * spinning side-bands).

depends o n the degree of ion exchange (Table 2). However, the in-
tensity of the line was not changed i n the range of ion exchange
between 77 and 93 % , i.e. the OH species formed at higher values
of ion exchange have a lower concentration. Indeed, the intensity
of the band at 2670 cm-l in the IR spectra assigned to aoidic
O(1)H groups was not drastically increased for ammonium exchange
higher than 77 X . I n this range the intensity of the band at 2 7 1 0
cm-1 due to O H groups located i n the cancrinite cage increases
(ref. 3). The amount of bridging O H groups of the calcined erio-
nite determined by l H M A S NMR is more than 20 % lower than the
amount of lattice aluminium determined by 27Al M A S NMR. Besides
the residual ammonium, the existence of non-framework aluminium
could cause this difference. Furthermore. the acidity of H-erio-
nite is comparable with zeolite Y , taking into consideration the
chemical shift of the unperturbed bridging O H groups at 3.9 and
4.2 ppm ( r e f . lo), respeotively. However. the relatively large
amount of residual ammonium ion in H-erionite activated i n vacuum
at 670 K indicates the presence o f strong acidic sites a s shown by
t.p.d. of ammonia (ref. 3).

CONCLUSION

(i) During the synthesis of erionite an parasite phase (zeolite

P) was formed. Its thermal decomposition causes changes i n
the 29Si MAS NMR spectra.
(ii) Different Si/A1 ratios determined by 29Si, 27Al M A S N M R and
chemical analysis c a n be explained in terms of thermal de-
 427

composition of the zeolite P and erionite.

(iii) Three different bridged hydroxyl groups are detected upon
deammonization of NH4-erionite.
(iv) Acidic OH groups located in the large cavity are preferen-
tially formed at ion exchange degrees up to 77 % .
(v) Potassium ions located in the cancrinite cages are only sub-
stituted by multiple ammonium-exchange and intermediate cal-
cination. Furthermore, stronger acidic sites are formed as
indicated by the presence of ammonium ions in the erionite
activated 670 K.
(vi) The existence of OH groups associated with non-framework
aluminium was shown.

REFERENCES

1 K.P. Lillerud. ZEOLITES, 7 (1987) 14.

2 D . W . Breck, Zeolite Molecular Sieves, Wiley, New York, 1974.
3 A. Kogelbauer. J . Lercher, K.-H. Steinberg, F. Roessner.
A. Soellner and R.V. Dmitriev, ZEOLITES, (in press).
4 C.A. Fyfe, J . M . Thomas and G . C . Gobbi, Anger. Chem..
95 (1983) 257.
5 C.A. Fyfe, G . C . G0bbi.G.J. Kennedy, J.D. Graham, R.S. Ozubko,
W.J. Murphy, A. Bothner-By, J . Dadok and A.S. Chesnik,
ZEOLITES, 5 (1985) 179.
6 P . A. Jacobs and W.J. Mortier, ZEOLITES, 2(1982) 226.
7 F. Roessner. K.-H. Steinberg and S . Rechenburg, ZEOLITES,
7 (1987) 488.
8 H. Pfeifer, D. Freude and M. Hunger, ZEOLITES, 5 (1985) 274.
9 U. Lohse. E. Loeffler. M. Hunger, J . Stoecker and V.Patze-
lova, ZEOLITES, 7 (1987) 11.
10 D. Freude, M. Hunger and H. Pfeifer, Z. phys. Chem. (NF),
152 (1987) 171.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

S P E C I F I C PLATINUM PARTICLES PROPERTIES I N B A S I C ZEOLITES

A. de MALLMANN and D. BARTHOMEUF

L a b o r a t o i r e de R e a c t i v i t e de S u r f a c e e t S t r u c t u r e , UA 1106, CNRS, U n i v e r s i t e
P A R I S V I , 4 Place Jussieu, 75252 P A R I S Cedex 05, France.

ABSTRACT
The i n f r a r e d wavenumber o f l i n e a r CO adsorbed on P t - f a u j a s i t e s decreases i n
t h e o r d e r P t H Y > PtHNaY > PtNaY > PtNaX as t h e z e o l i t e a c i d i t y decreases and
t h e b a s i c i t y i n c r e a s e s . New bands a t 1960-2000 cm-1 assigned t o l i n e a r CO a r e
formed which a l s o p a r a l l e l t h e z e o l i t e b a s i c i t y . The r e s u l t s suggest a s t r o n g
P t / z e o l i t e i n t e r a c t i o n i n v o l v i n g t h e n e g a t i v e l y charged framework oxygen.

INTRODUCTION
A l a r g e amount o f work d e s c r i b e s t h e a d s o r p t i o n o f CO on P t - s u p p o r t e d c a t a -
l y s t s . A major p o i n t i s t o understand whether o r n o t t h e CO bond i s changed
upon a d s o r p t i o n on P t ( 1 - 3 ) . I f so,CO c o u l d be used as a probe t o check anymod-
i f i c a t i o n i n t h e e l e c t r o n i c s t a t e o f P t due t o metal s u p p o r t i n t e r a c t i o n
( 2 - 3 ) . According t o t h e b a s i c o r a c i d i c c h a r a c t e r o f t h e support,one may e x p e c t
a d i f f e r e n t i n t e r a c t i o n , w h i c h may be r e f l e c t e d i n t h e CO wavenumber. Upon ad-
s o r p t i o n o f CO i n P t - L z e o l i t e s s a t u r a t e d w i t h a l k a l i n e c a t i o n s new CO bands
were observed i n a range below 2000 cm-' i.e. a t wavenumbers l o w e r t h a n usual f o r li-
n e a r l y adsorbed CO and h i g h e r t h a n f o r b r i d g e d CO(4). They were assigned t o P t - C O
species formed on b a s i c z e o l i t e s . The p r e s e n t paper r e p o r t s a d e t a i l e d s t u d y o f
CO adsot-ptiuti or1 P t - s u p p o r t e d f a u j a s i t e s which c o v e r a range o f a c i d i t y and ba-
s i c i t y . I t w i l l show t h e dependence o f t h e m e t a l / s u p p o r t and P t / C O i n t e r a c t i n n z
on t h e s u p p o r t p r o p e r t i e s , i n t h e same z e o l i t e s t r u c t u r e .

EXPERIMENT
Ma t e r i a1 s
Samples o f HY, NaY and NaX p r o v i d e d by Union Carbide were used . Partial
exchange o f NaY by ammonium a c e t a t e y i e l d e d , a f t e r h e a t i n g , d HNaY sample. P l a t i -
num was i n t r o d u c e d as i n ( 5 ) by c a t i o n exchange u s i n g a 0.01M s o l u t i o n o f
Pt(NH3)4C12, H20 a t 363 K. A f t e r f i l t r a t i o n and washing,the samples were d r i e d
a t 353 K o v e r n i g h t . The u n i t c e l l formulae o f t h e m a t e r i a l s were Pt3.1Na5.8(NH4)44
Y, Pt3Na20( NH4)30Y, P t 3 . 2Na43( NH4)6. 6Y and Pt3.4Na70( NH4)9X. T h i s corresponds
t o a p p r o x i m a t e l y 4.5 w t % P t . The t r e a t m e n t b e f o r e use c o n s i s t e d o f an o x i d a t i o n
t o decompose t h e complex under an oxygen f l o w (30 l / h ) w h i l e t h e temperaturewas
r a i s e d up t o 573 K a t 15 Wh. A f t e r e v a c u a t i o n a t 573 K f o r 3 h and r e d u c t i o n
430

w i t h H2 a t 623 K f o r 15 h , t h e samples wereevacuated a t 573 K f o r 3h Upon .

2+
r e d u c t i o n each P t i o n should have generated two protons which increased t h e number
o f protons on each samples by around 6 per u n i t c e l l . A f t e r t h e r e d u c t i o n t h e
m a t e r i a l s were r e f e r r e d t o as P t H Y , PtHNaY, PtNaY, PtNaX. The p l a t i n u m p a r t i -
c l e s i z e was evaluated by e l e c t r o n microscopy. For a l l t h e samples t h e s i z e s
were r a t h e r uniform, around 1.2 t 0.2 nm i n diameter b e f o r e o r a f t e r CO adsorp-
tion.

CO a d s o r p t i o n s t u d i e s
CO a d s o r p t i o n was c a r r i e d o u t on s e l f - s u p p o r t e d wafers (about 15 t o 20 mg)
t r e a t e d i n s i t u as described above.CO was adsorbed a t room temperature a t va-
r i o u s pressures which determine t h e number, nC0,of CO molecules adsorbed p e r
u n i t c e l l . The r a t i o s nCO/nPt can be c a l c u l a t e d from t h e number nPt o f P t atoms
per u n i t c e l l .
I n o r d e r t o achieve a good d i s p e r s i o n o f CO on a l l t h e metal p a r t i c l e s t h e wa-
f e r w a s h e a t e d i n t h e presence o f CO f o r 15 h i n t h e c l o s e d c e l l (2,3). The
spectrawere recorded a t t h a t p o i n t o r a f t e r an evacuation f o r 0.5 h a t 448 K.
I s o l a t e d CO molecules a r e expected t o occur i n those experimental c o n d i t i o n s
(2,3).
The i n f r a r e d measurements were performed w i t h a spectrophotometer P e r k i n E l -
mer 580 B equipped w i t h a Data S t a t i o n . The s p e c t r a l r e s o l u t i o n was b e t t e r than
1 cm-l i n t h e s p e c t r a l range considered.

RESULTS
-
Ac id i t y bas ic it y
The a c i d i c h y d r o x y l s were c h a r a c t e r i z e d by i n f r a r e d spectroscopy on t h e
samples p r e t r e a t e d as above. I t was confirmed by t h e disappearance o f t h e band 61(Ni3)
a t about 1350-1380 cm-’ t h a t t h e complex Pt(NH3)4C12 had decomposed. The absor-
bances o f t h e h y d r o x y l s wereranked i n t h e o r d e r PtNaX % PtNaY < PtHNaY << PtHY
which i s i n l i n e w i t h t h e chemical formulae. The PtNaY and PtNaX e x h i b i t e d o n l y
a weak OH band a t 3650 cm-l, i n agreement w i t h t h e low a c i d i t y resulting from
pt2+ r e d u c t i o n .
+
The b a s i c i t y o f oxygen should i n c r e a s e as protons a r e exchanged by Na i o n s
and as t h e z e o l i t e A1 c o n t e n t r i s e s (6,7). The oxygen charge has been c a l c u l a -
t e d u s i n g t h e Sanderson e l e c t r o n e g a t i v i t y e q u a l i z a t i o n p r i n c i p l e ( 8 ) which ex-
presses t h e mean b a s i c i t y expected i n z e o l i t e s (7). The a b s o l u t e values i n c r e a s e
from HY t o t h e most b a s i c z e o l i t e NaX ( t a b l e 1 ) . P y r r o l e a d s o r p t i o n s t u d i e s
i n NaY and NaX c o n f i r m t h e h i g h e r NaX b a s i c i t y ( 6 ) .

CO a d s o r p t i o n
CO wasadsorbed a f t e r r e d u c t i o n and evacuation o f t h e wafers as d e s c r i b e d
above. Fig. 1 r e p o r t s t y p i c a l experiments f o r PtHNaY and PtNaY. A f t e r adsorp-
 431

2200 2000 1800

-2200 2000 1900 cm- 1

F i g . 1. CO a d s o r p t i o n on PtNaY ( A ) and PtHNaY (B) ; a : b e f o r e CO a d s o r p t i o n ;

b : i n t r o d u c t i o n o f CO a t R.T. (nCO/nPt = 0.29) ; c : H e a t i n g f o r 15 h i n the
c l o s e d c e l l a t 573 K and e v a c u a t i o n f o r 0.5 h a t 448 K.

TABLE 1
Wavenumber o f adsorbed CO, a r o m a t i z a t i o n a c t i v i t y and b a s i c i t y o f t h e z e o l i t e s .
Zeol it e vCO(cm-l) benzene‘ a) S( b, O(b)
HF LF (%I charge

PtHY 2063 no band (c) 4.095 - 0.234

PtHNaY 2060 1993 (C) 3.79 - 0.300
(weak)
PtNaY 2049 1993 23.7 3.54 - 0.352
PtKL 2060(d) 1960-1980(d) 47.2 3.50 - 0.356
PtNaX 2033 1968 54.8 3.25 - 0.413

( a ) Benzene ( % ) formed a t 773 K f r o m n-hexane ( 1 7 )

( b ) I n t e r m e d i a t e e l e c t r o n e g a t i v i t y and oxygen charge c a l c u l a t e d f r o m i t ( f r o m
reference 7)
Z e o l i t e s c o n t a i n i n g p r o t o n s a r e n o t benzene-selective ( 1 7 )
( d l N o n - i s o l a t e d adsorbed CO molecules ( f r o m r e f e r e n c e 4 )

t i o n o f CO a t room temperature on PtNaY (nCO/nPt = 0.29);spectrum b i n figure

1A shows a band a t 2076 cm-l assigned t o l i n e a r CO and bands n e a r 1863 and 1802
-1
cm c o r r e s p o n d i n g t o b r i d g e d CO (1-3). H e a t i n g t h e w a f e r f o r 15 h i n the
c l o s e d c e l l a t 573 K i n o r d e r t o r e d i s p e r s e CO on a l l t h e p a r t i c l e s as i n (2,3)
and e v a c u a t i o n a t 448 K f o r 0.5 h produced spectrum c. A new band i s formed a t
1993 cm-l i n a d d i t i o n t o t h e band o f l i n e a r CO which s h i f t e d t o 2049 cm-’. The
b r i d g e d CO bands a r e decreased i n i n t e n s i t y and t h e i r wavenumbers s h i f t e d t o
lower values w i t h a broad maximum a t around 1776 cm-’. A similar set o f treat-
ments f o r PtNaY s h i f t s t h e s t a r t i n g CO band f r o m 2082 t o 2060 cm-l and genera-
t e s a new band a t 1993 cm-l ( f i g u r e l a ) .
432

2063 2049

1 I
2200 2000 1900 1800 I
2200 2000 1900 crn

F i g . 2. CO a d s o r p t i o n a t R.T. on a : PtHY(nCO/nPt = 0.19) ; b :PtHNaY(nCO/nPt =

0.29) ; c : PtNaY(nCO/nPt = 0.29) ; d : PtNaX(nCO/nPt = 0.32).Spectra r e c o r d e d
a f t e r h e a t i n g f o r 15 h a t 573 K i n t h e c l o s e d c e l l and e v a c u a t i o n f o r 0.5 h
a t 448 K. Note t h e d i f f e r e n t s c a l e f o r a, b and c, d.

F i g u r e 2 r e p o r t s t h e changes i n t h e r e l a t i v e absorbance o f t h e bands i n t h e

range 1900-2100 cm-l as a f u n c t i o n o f Na and A1 c o n t e n t i n t h e z e o l i t e s . The
sodium i n c r e a s e s f r o m c u r v e s a t o c i n Y z e o l i t e s and c u r v e d d e p i c t s PtNaX.
The w a f e r s a r e h e a t - t r e a t e d a t 573 K i n t h e presence o f CO i n t h e c l o s e d c e l l
and evacuated a t 448 K f o r 0.5 h The s t a b i l i t y o f t h e bands upon e v a c u a t i o n
a t i n c r e a s i n g temperatures f o r 0.5 h i s shown i n t i g u r e 3 f o r PtNaY (3A) and
PtNaX ( 3 8 ) a f t e r s a t u r a t i o n o f t h e w a f e r s w i t h CO. F i g u r e 4 r e p o r t s t h e
changes i n t h e s p e c t r a o f adsorbed i s o l a t e d CO m o l e c u l e s on PtNaY upon adsorp-
t i o n o f e l e c t r o n donor (NH3 o r H20) and e l e c t r o n a c c e p t o r m o l e c u l e s (02). The
b e h a v i o r o f PtNaX i s compared i n f i g u r e 4B t o t h a t o f PtNaY i n t h e presence o f
CO + NH3.

Discussion
The r a t h e r good homogeneity o f t h e p a r t i c l e d i a m e t e r s and t h e i r s i z e (1.2 nm),
c l o s e t o t h a t o f t h e supercage o f f a u j a s i t e , s u g g e s t s t h a t they are located i n
t h o s e c a v i t i e s and f i l l c o m p l e t e l y t h e cage volume.
The CO bands d e p i c t e d i n t h e i n f r a r e d s p e c t r a can be c l a s s i f i e d i n t o two
main c l a s s e s a c c o r d i n g t o t h e i r b e h a v i o r . First, t h e u s u a l CO bands observed
i n p l a t i n u m m e t a l s u p p o r t e d on o x i d e s a r e seen a f t e r a d s o r p t i o n ( f i g u r e s 1-3) i n
t h e range 2080-2040 cm-l f o r l i n e a r CO and around 1900-1800 cm-l f o r b r i d g e d CO.
The bands o f l i n e a r and b r i d g e d CO a r e observed i n t h e f o u r samples s t u d i e d a t a kd-
venumber s p e c i f i c f o r each m a t e r i a l . Secondly, b e s i d e s t h o s e bands new bands a r e
formed between 2000-1960 cm-l, i.e. close t o l i n e a r COY i n t h e three materials
w i t h t h e h i g h e r Na content. I t was c o n f i r m e d t h a t t h o s e new bands a r e due t o CO
 433

* I

2083

w
U
z

e
, . . - f
* I

-1
2200 2000 1900 1800 2000 1900 cm

Fig. 3. CO a d s o r p t i o n a t R.T. and t h e n e v a c u a t i o n a t i n c r e a s i n g temperature.

(A) : PtNaY ; a : 5.5 t o r r CO ; b : e v a c u a t i o n f o r 0.16 h a t R.T. ; C t o g :
e v a c u a t i o n f o r 0.5 h a t 423 K ( c ) , 473 K ( d ) , 523 K ( e ) , 573 K ( f ) , 623 K ( 9 ) .
(B) : PtNaX ; a : 4.2 t o r r CO ; b : 0.5 h r a t R.T., c t o e : as f o r PtNaY.

F i g . 4. Change i n CO s p e c t r a a f t e r a d s o r p t i o n of NH3(A,B), O,(C) and H20(D) on

PtNaY (A,C,D) and PtNaX(B).
(A) : NH a d s o r p t i o n on PtNaY ; a : nCO/nPt = 0.29, h e a t i n g a t 573 K f o r 15 h
i n t h e c j o s e d c e l l and e v a c u a t i o n f o r 0.5 h a t 448 K. b : i n t r o d u c t i o n o f 8
t o r r NH3 ; (B) : NH3 a d s o r p t i o n on PtNaX ; a : s a t u r a t i o n w i t h CO a t R.T., hea-
t i n g f o r 2 h a t 448 K and e v a c u a t i o n f o r 0.5 h a t 448 K ; b : i n t r o d u c t i o n
o f 8 t o r r NH3.
(C) : 02 a d s o r p t i o n on PtNaY ; a : as a-A ; b : i n t r o d u c t i o n o f 100 t o r r 02 ;
c : h e a t i n g f o r 15 h a t 573 K.
(D) : H20 a d s o r p t i o n on PtNaY ; a : as a-A ; b : i n t r o d u c t i o n o f 10 H20 mole-
c u l e s p e r u n i t c e l l ; c : h e a t i n g a t 423 K f o r 15 h.
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by adsorbing I 3 C O i n s t e a d o f "CO. A l l t h e bands were s h i f t e d by about 50 cm-'.

The weak and broad bands o f b r i d g e d CO w i l l n o t be s t u d i e d f u r t h e r . The two
s e t s o f bands a t 2080-2040 and 2000-1960 cm-' w i l l be considered s e p a r a t e l y and
r e f e r r e d t o r e s p e c t i v e l y as h i g h frequency (HF) and low frequency (LF) bands.

High frequency band

The wavenumber o f adsorbed CO i n t h e i n f r a r e d range a t 2040-2080 cm-' depends
on several parameters. The d i p o l e - d i p o l e c o u p l i n g between CO molecules (1) and
t h e e l e c t r o n t r a n s f e r o f d e l e c t r o n s from t h e metal t o t h e 2n* o r b i t a l s o f CO
(2,3, 10,11) a r e t h e two main e x p l a n a t i o n s i n v o l v e d . The s h i f t o f vco t o lower
wavenumbers as t h e coverage decreases i s due t o b o t h e f f e c t s ( 1 y 2 y 1 0 ) . The
s h i f t r e s u l t i n g from metal-support i n t e r a c t i o n s i s r e l a t e d o n l y t o t h e second
one ( 2 ) .
I n Pt/A1203 a vco v i b r a t i o n f r e e of CO-CO c o u p l i n g can be reached c l o s e t o
2052 cm'l e i t h e r by i s o t o p i c d i l u t i o n o f I 3 C O i n "CO a t f u l l CO coverage (1)
o r by h e a t i n g t h e m a t e r i a l i n t h e presence o f low CO pressure i n a c l o s e d c e l l
which r e s u l t s i n i s o l a t e d CO molecules ( 2 ) . I n a P t f a u j a s i t e t h e wavenumber
o f l i n e a r CO i s observed a t 2053 cm-l when t h e i s o t o p i c method i s used. I t
corresponds t o vc0 f r e e o f d i p o l e c o u p l i n g and which v e r y l i k e l y i s n o t d i s -
turbed by metal support i n t e r a c t i o n a t h i g h CO coverage ( 3 ) . I t i s v e r y c l o s e
t o t h e value obtained f o r Pt/A1203 ( 2 ) .
The experimental c o n d i t i o n s described i n f i g u r e s 1-3 include heating o f
t h e wafers a t 573 K i n a closed system i n t h e presence o f a small amount o f CO. T h i s
should r e s u l t i n i s o l a t e d CO molecules. The vco should n o t be d i s t u r b e d e i t h e r
by CO-CO c o u p l i n g o r coverage e f f e c t s (2). The vco d i f f e r e n c e s between t h e f o u r
samples c o u l d be regarded as being m a i n l y due t o metal-support i n t e r a c t i o n . From t h e
r e s u l t s o f f i g u r e 2 one may rank t h e z e o l i t e s according t o t h e i r v c o which de-
creases i n t h e o r d e r P t H Y > PtHNaY > PtNaY > PtNaX. T h i s sequence f o l l o w s t h e
decrease i n a c i d i t y expressed by the hydroxyl groups absorbances o r a1 t e r n a t i -
v e l y t h e increase i n b a s i c i t y e v a l u a t e d from t h e charge on oxygen s i n c e t h e two
p r o p e r t i e s v a r y i n o p p o s i t e d i r e c t i o n s (6,7). One may c o n s i d e r t h a t t h e e x t e n t
o f e l e c t r o n back-donation from P t t o CO increases as t h e a c i d i c c h a r a c t e r
of the zeolite decreases and as simultaneously its basi-
c i t y r i s e s ( t a b l e l ) . This s h i f t s t h e HF band t o lower vCO.The "zero" o r i g i n o f
t h e wavenumber o f CO adsorbed on a P t p a r t i c l e w i t h no CO-CO c o u p l i n g and no
Pt-support i n t e r a c t i o n i s n o t known. I n a f i r s t approximation i t c o u l d be con-
sidered t h a t t h e value o f 2052 cm-l,obtained f o r i s o l a t e d CO adsorbed on Pt/A1203
where t h e metal-support i n t e r a c t i o n s i s weak, would be c l o s e t o t h i s "zero"
o r i g i n . I t f o l l o w s t h a t t h e f o u r samplesmay be s p l i t i n t o two groups. For P t H Y
and PtHNaY t h e vco value i s h i g h e r than t h i s reference. T h i s would i n d i c a t e a
decrease i n back donation from P t t o CO due t o t h e P t - z e o l i t e i n t e r a c t i o n . T h i s
 435

would be i n l i n e w i t h t h e a c i d i c c h a r a c t e r o f t h o s e two m a t e r i a l s , t h e m e t a l
p a r t i c l e s i n t e r a c t i n g w i t h t h e e l e c t r o n - a c c e p t i n g a c i d i c s i t e s . I n PtNaY and
PtNaX t h e CO wavenumber i s l o w e r t h a n t h e r e f e r e n c e a t 2052 cm-'. T h i s may be
e x p l a i n e d as an i n c r e a s e i n back-donation f r o m P t t o CO as a r e s u l t o f t h e P t
i n t e r a c t i o n w i t h e l e c t r o n donor framework atoms, which can be t h e n e g a t i v e l y
charged l a t t i c e oxygen. Those b a s i c s i t e s would p l a y t h e same r o l e as e l e c t r o n
donor molecules s h i f t i n g t o lower values t h e wavenumber o f CO adsorbed on P t p a r -
t i c l e s . T h i s was observed w i t h benzene o r ammonia on Pt/A1203 (1,2) o r Pt-zeo-
l i t e ( 3 , l l ) o r w i t h molecules such as e t h y l e n e on Pt/A$03(1,2). The s h i f t s de-
pend on t h e e l e c t r o n donor molecule. They may be as l a r g e as 30 t o 67 cm-'. A
s i m i l a r b e h a v i o r i s a l s o observed on t h e p r e s e n t samples ( f i g u r e 4). F o r i n s -
tance,the i n t r o d u c t i o n o f a n 8 t o r r p r e s s u r e o f NH3 on PtNaY o r PtNaX w a f e r s a l -
ready c o n t a i n i n g d i s p e r s e d CO s h i f t s t h e HF band by about 50 cm" t o l o w e r wave-
1
numbers. The s h i f t i s s l i g h t l y l e s s ( % 14 cm- ) upon w a t e r a d s o r p t i o n on a
PtNaY w a f e r w i t h preadsorbed i s o l a t e d CO.These r e s u l t s suggest t h a t i n a d d i t i o n
t o t h e e l e c t r o n t r a n s f e r due t o p a r t i c l e i n t e r a c t i o n w i t h t h e b a s i c s i t e s of t h e
framework,ammonia and w a t e r a d s o r p t i o n i n c r e a s e s t h e e l e c t r o n back-donation f r o m
P t t o CO. The e l e c t r o n a c c e p t o r oxygen m o l e c u l e shows t h e o p p o s i t e e f f e c t on
PtNaY. N e v e r t h e l e s s , i n t h a t case t h e f o r m a t i o n o f CO i s l a n d s s h i f t i n g vco t o
h i g h values cannot be excluded (1,2). I n t e r e s t i n g l y , t h e absorbances o f t h e CO
bands decrease upon O2 a d s o r p t i o n down t o complete disappearance. Simultaneous-
l y bands o f adsorbed C02 and c a r b o n y l species a r e o b s e r v e d , i n d i c a t i n g t h e
t r a n s f o r m a t i o n o f CO.

The l o w frequency band

The ease o f f o r m a t i o n o f t h i s band depends on t h e sample. F i g u r e 2 shows
t h a t t h e L F band i s n o t formed i n P t H Y even a f t e r h e a t i n g a t 573 K i n t h e pre-
sence o f CO. F o r t h e o t h e r t h r e e samples i t s i n t e n s i t y and wavenumber depend
on t h e e x p e r i m e n t a l c o n d i t i o n s and f o r s i m i l a r c o n d i t i o n s on t h e z e o l i t e . A f t e r
s a t u r a t i o n w i t h CO a t room temperature, t h e band appears i n PtNaY and PtNaX ( f i -
gure 3) as a s h o u l d e r a t 2029 and 2015 cm-l r e s p e c t i v e l y . It i s s h i f t e d s i m u l t a -
neously w i t h t h e h i g h frequency band t o l o w wavenumbers as t h e d e s o r p t i o n tem-
perature increases,i.e. as t h e coverage decreases and as CO i s r e d i s t r i b u t e d on
t h e p a r t i c l e s . When s t a r t i n g f r o m l o w l o a d i n g (nCO/nPt = 0.29 on f i g u r e 1) t h e
band i s almost n o t d e t e c t a b l e a t room temperature. I t i s necessary t o h e a t t h e
sample t o see f i r s t a s h o u l d e r t h e n a d i s t i n c t band. S i m i l a r s t a t e s a r e o b t a i n -
ed f r o m b o t h methods - high o r low loading -if the zeolites i n i t i a l l y saturated
w i t h CO a r e evacuated a t 423 K ( f i g . 3 ) o r i f a small CO amount i s heated w i t h
t h e sample i n a c l o s e d c e l l a t 573 K f o r 15 h ( f i g . 2). This indicates simi-
l a r CO c o n t e n t and l o c a t i o n on t h e P t p a r t i c l e s .
The thermal s t a b i l i t y o f t h e LF band i s h i g h e r t h a n t h a t o f t h e HF one,as
436

seen i n f i g u r e 3. The l a r g e r decrease o f t h e HF band a t temperatures h i g h e r

than about 423 K r e s u l t s i n a l a r g e o v e r l a p p i n g o f t h e two bands which may
b r i n g t h e i r wavenumbers a r t i f i c i a l l y c l o s e r . For s i m i l a r experimental condi-
t i o n s , f i g u r e 2 shows t h a t f o r a decrease i n t h e z e o l i t e a c i d i t y (and a s i m u l -
taneous increase i n i t s b a s i c i t y ) t h e LF band i n t e n s i t y and t h e r a t i o LF/HF
i n c r e a s e w h i l e t h e wavenumber o f t h e LF band decreases.
The adsorption, on wafers w i t h h i g h l y dispersed CO, o f e l e c t r o n donor mole-
cules, such as ammonia and water s h i f t s t h e LF band t o lower wavenumber simul-
taneously w i t h t h e usual l i n e a r CO HF band ( f i g u r e 4 ) . I n t h e case o f oxygen
a d s o r p t i o n b o t h bands a r e s i m i l a r l y s h i f t e d t o h i g h e r frequencies, and t h e i r
i n t e n s i t y decreases a t t h e same time. The p a r a l l e l behavior o f t h e two CO bands
w i t h r e g a r d t o a d s o r p t i o n o f those molecules and w i t h evacuation ( f i g . 3) sug-
gest great s i m i l a r i t i e s i n t h e i r o r i g i n .
The f o l l o w i n g hypothesis may e x p l a i n t h e presence and t h e p r o p e r t i e s o f t h e
LF bands. Adsorption o f CO on b a s i c oxides may l e a d f i r s t t o t h e f o r m a t i o n o f
2
k e t e n e - l i k e s t r u c t u r e s O=C=C02- (12,13). They may be s t a b l e up t o room tempera-
t u r e and g i v e r i s e t o a band near 2033 cm-l i n t h e i n f r a r e d range considered
here. Z e o l i t e NaX, w i t h o u t platinum, does n o t y i e l d any CO band i n t h e range above
1600 cm-'. I f t h e LF band a r i s e s from such species i t should be assumed t h a t p l a t i -
num would c a t a l y s e t h e i r formation. I n a d d i t i o n i t i s n o t c l e a r why these species
would r e q u i r e h e a t i n g t o be formed w h i l e they a r e n o t s t a b l e above 300 K on b a s i c
oxides. A more 1 i k e l y hypothesis i s t o c o n s i d e r s i m i l a r i t i e s between t h e p r e s e n t
LF band and t h e l i n e a r CO bands observed a t 1970-1990 cm-l i n p l a t i n u m C h i n i
complexes i n THF s o l u t i o n (14) o r f o r such compounds supported on y-A1203 (15).
For aluminas c o n t a i n i n g 1 . 8 t o 2w t % P t i n t h e form o f supported C h i n i comple-
xes t h e CO i n f r a r e d bands a r e s t a b l e up t o 473-623 K upon evacuation. Those ne-
2-
g a t i v e l y charged c l u s t e r s have t h e general formula [Pt3(CO)3( LJ2C0)3]n w i t h
n = l t o 5. They a r e found i n s o l u t i o n i n b a s i c media upon r e d u c t i o n o f Pt2+ ca-
t i o n s by CO. Complexes o f t h i s type a r e supposed t o be generated i n unreduced
PtNaY t r e a t e d w i t h CO under s p e c i f i c c o n d i t i o n s (16).
I n t h e p r e s e n t case i t i s proposed t h a t l o c a l l y some s u r f a c e P t o atoms o f a
p a r t i c l e m i g h t be i n t e r a c t i n g so s t r o n g l y w i t h a d j a c e n t and n e g a t i v e l y charged
framework-oxygen atoms, f o r i n s t a n c e i n t h e 12-R window, t h a t a s u r f a c e recon-
s t r u c t i o n might occur. Those atoms would be l e s s s t r o n g l y bonded t o t h e o t h e r P t
atoms o f t h e p a r t i c u l e and could, i n t h e presence o f CO, form some species w i t h
CO l i n e a r l y bonded as i n t h e C h i n i complexes. The s t r o n g PtO-0'- interaction
would f a v o r t h e e l e c t r o n t r a n s f e r t o t h e p l a t i n u m atom, i n c r e a s i n g i n t u r n t h e
back-donation t o t h e CO molecule. T h i s would l e a d t o a decrease i n vco g r e a t e r
than when CO i s adsorbed on an i n d e f i n i t e P t atom o f a p a r t i c l e . F i g u r e 5 shows
a p o s s i b l e scheme f o r t h e d i f f e r e n c e i n P t / z e o l i t e i n t e r a c t i o n g e n e r a t i n g a h i g h
o r low CO frequency band. A f t e r f u l l evacuation o f CO a t 573 K t h e readsorp-
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Pt HF p t y l T E LF
BAND PARTICLE BAND

fl

F i g . 5. Schemes f o r P t / C O a d s o r p t i o n g i v i n g two forms o f l i n e a r CO.

t i o n o f CO returns t h e i n i t i a l s p e c t r a showing t h e r e v e r s i b i l i t y o f t h e phe-

nomenon. I t has t o be p o i n t e d o u t t h a t t h e i n t e r a c t i o n p o s t u l a t e d h e r e i s q u i t e
d i f f e r e n t f r o m t h e one where P t i s o x i d i z e d by c o a d s o r p t i o n o f gaseous oxygen
and CO which generates an i n f r a r e d band a t 2120 cm-l.

Correlations w i t h c a t a l y t i c properties
A s h i f t t o a l o w e r wavenumber o f CO adsorbed on p l a t i n u m a1 k a l i n e L z e o l i t e s was
observed s i m u l t a n e o u s l y w i t h t h e f o r m a t i o n o f new CO bands (LF bands) between
1930-1980 cm-l w i t h a dependence on z e o l i t e b a s i c i t y q u i t e s i m i l a r t o t h e r e -
s u l t s presented h e r e (4). Those samples e x h i b i t e d a h i g h n-hexane a r o m a t i z a t i o n a c t i -
v i t y which i n c r e a s e d a s t h e L z e o l i t e s became more b a s i c f r o m t h e L i t o t h e Cs
form ( 4 ) o r as p r o t o n s were exchanged f o r K+ ( 1 7 ) . The same r e a c t i o n i s
a l s o c a t a l y z e d by PtNaY and PtNaX, t h e y i e l d o f benzene produced b e i n g i n t h e
o r d e r PtNaX > PtKL > PtNaY ( 1 7 ) ( t a b l e 1 ) . Comparison o f the catalytic
properties w i t h the platinum behavior w i t h regard t o CO i n d i c a t e s a p a r a l l e l
dependence on z e o l i t e b a s i c i t y . S i n c e t h e r e a c t i o n i s m o n o f u n c t i o n a l on t h e p l a -
t i n u m s i t e s ( 1 7 ) , d i f f e r e n c e s i n c a t a l y t i c p r o p e r t i e s may v e r y l i k e l y a r i s e
from m o d i f i c a t i o n o f t h e p l a t i n u m i n t h e z e o l i t e cages. The g r e a t i n f l u e n c e o f
z e o l i t e b a s i c i t y on P t p r o p e r t i e s evidenced h e r e by t h e ease o f e l e c t r o n t r a n s -
f e r f r o m P t t o t h e adsorbed CO m o l e c u l e suggests t h a t t h e most a c t i v e P t s i t e s
f o r n-hexane a r o m a t i z a t i o n c o u l d be t h e P t atoms a c t i v a t e d by i n t e r a c t i o n w i t h
t h e n e g a t i v e l y charged framework oxygen atoms. The s p e c i f i c e x i s t e n c e o f aroma-
t i z a t i o n a c t i v i t y i n z e o l i t e s which show t h e LF bands a l s o suggests a s t r o n g
involvement i n t h i s c a t a l y t i c r e a c t i o n of more h i g h l y d i s t u r b e d P t atoms.

CONCLUSION
The p l a t i n u m p a r t i c l e s i n systems l i k e Pt/Si02, Pt/A1203 a r e v e r y l i k e l y
d i f f e r e n t f r o m t h o s e i n z e o l i t e s . I n t h e f i r s t case t h e m e t a l p a r t i c l e s l i e on
438

r a t h e r f l a t s u rf a c e s , w h i l e i n z e o l i t e s t h e y a r e embedded i n c a v i t i e s where t h e y
exp erie nc e t h e i n f l u e n c e o f a l l t h e framework atoms o f supercages. As a conse-
quence t h ey f o r m s m a l l p a r t i c l e s w h i c h a r e more s e n s i t i v e t o any e l e c t r o n t r a n s -
f e r between t h e metal and t h e support. The s t r o n g i n f l u e n c e o f t h e acid-base
p r o p e r t i e s o f t h e z e o l i t e evidenced h e r e on t h e e l e c t r o n i c s t a t e o f p l a t i n u m
suggests t h a t such m e t a l atoms would have v e r y s p e c i f i c r e a c t i v i t y i n t h e c a t a -
l y s i s o f many r e a c t i o n s .

References
F. Stoop, F.J.C.M. Toolenaar, V. Ponec, J. Catal., 73 (1982) 50.
M. P rime t , J. Catal., 88 (1984) 273.
M. Primet, L.C. de Menorval, J. F r a i s s a r d , T. I t o , J. Chem. SOC. Far. Trans
I, 81 (1985)2867.
C. Besoukhanova, J. Guidot, D. Barthomeuf, M. Breysse, J.R. Bernard, J. Chem.
SOC. ,Farad. Trans. I, 77 (1981) 1595.
H. A r a i , T. Seiyama, M. Harakawa, H. Tominaga, C a t a l y s t D e a c t i v a t i o n (B.
Delmon e t a l . , ed.), E l s e v i e r , Amsterdam, 1980, 167.
D. Barthomeuf, J. Phys. Chem., 88 (1984) 42.
D. Barthomeuf, A. de Mallmann, " I n n o v a t i o n i n Z e o l i t e M a t e r i a l s Science" (P.
Grobet e t al. , ed.) ,Stud. Surf. S c i . C a t a l. , E l s e v i e r , Amsterdam, 37 (1988)
365.
W. M o r t i e r , J. Catal., 55 (1978) 138.
L.C. de Menorval, J. F r a i s s a r d , T. I t o , M. Primet , J. Chem. SOC. Far. Trans,
I, 81 (1985) 2855.
10 G.J. B l y h o l d e r , J. Phys. Chem., 79 (1975) 756.
11 P. G a l l e z o t , J. Datka, J. Massardier, M. Primet , B. I m e l i k , Proceed. I n t e r n .
Cong. Catal., The Chemical S o c i e t y , London, 2 (1977) 696.
12 M.A. Babaeva, A.A. Tsyganenko, React. K i n e t . C a t a l . L e t t . , 34 (1987) 9.
13 E. G u g l i e l m i n o t t i , S. C o l u c c i a , E. Garrone, L. C e r r u t i , A. Zecchina, J.C.S.
Farad. Trans. I, 75 (1979) 96.
14 J.C. Calabrese, L.F. Dahl, P. C h i n i , G. Longoni, S. Martinengo, J.A.C.S.,
96(8) (1974) 2614.
15 M. Ichikawa, Chemistry L e t t e r s , 1976, 335.
16 A. de Mallmann, D. Barthomeuf, t o be p u b l ished.
17 J.R. Bernard, Proceed. F i f t h I n t . Conf. Z e o l i t e s (ed. L.V.C. Rees), Heyden,
London, 1980, 686.
II. SORPTION
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

FUNDAMENTAL RESEARCH AND MODELING FOR A TECHNICAL PROCESS OF SELECTIVE

ADSORPTION OF NORMAL PARAFFINS P PAREX"-PROCESS OF DDR) BY ZEOLITE A

W. SCHIRMER, K. FIEDLER, H. STACH AND M. SUCKOW

Z e n t r a l i n s t i t u t f u r physikalische Chemie der Akademie der Wissenschaften der
ODR, Rudower Chaussee 5, 1199 B e r l i n , DDR

ABSTRACT
A survey i s given o f the experience obtained over 25 years o f modeling o f
the technical e x t r a c t i o n o f normal p a r a f f i n s by means o f z e o l i t e 5A (the so-
c a l l e d "Parex"-process o f ODR). It i s shown t h a t the technical tasks were a con-
s t a n t challenge f o r the fundamental research, while, on the other hand, any pro-
gress i n the research work influenced the technlcal procedure.

INTRODUCTON
We intend t o g i v e a survey o f 25 years o f experience i n the modeling o f t h e
e x t r a c t i o n o f normal p a r a f f i n s from a gaseous phase by means o f z e o l i t e 5A.
These developments were c a r r i e d out I n close cooperation with t h e chemical en-
t e r p r i s e s o f Leuna and Schwedt. Here we s h a l l not t r y t o f o l l o w the h i s t o r i c a l
path o f development, but we want t o show how fundamental research and technolo-
g i c a l p r a c t i c e influenced each other. The technical aim, t h e adsorption-process,
was a constant source and challenge f o r the formulation o f new tasks of funda-
mental research, while any progress i n research allowed us t o complete t h e tech-
n i c a l process.
I t i s w e l l known t h a t the production p r o f i l e o f Leuna includes r e a c t i o n s on
the basis o f long-chained normal paraffins. A t the beginning o f the s i x t i e s ,
they were produced i n a Fischer-Tropsch plant, usually i n a high q u a l i t y . But
the time o f the p r o f i t a b i l i t y o f the Fischer-Tropsch process was over. We were
forced t o look f o r cheaper sources o f n-paraffins, and t h a t was why we d i r e c t e d
our a t t e n t i o n t o various types o f crude o i l o f the Soviet Union, which, a t t h a t
time, contained between 15 and 20 % o f normal paraffins.
Having had some experience i n the fundamental research o f adsorption, we
made up our minds t o work i n close cooperation w i t h Leuna, l a t e r on a l s o w i t h
Schwedt and w i t h several production plants f o r chemical equipment i n our coun-
t r y . The choice o f hydrocarbons (single components and mixtures), e s p e c i a l l y
long-chained normal paraffins, as adsorptives f o r fundamental research, repre-
sented a c e r t a i n r i s k , f o r we could not know how f a r we should be able t o gene-
r a l i z e the results. By measuring the adsorption behaviour o f d i f f e r e n t types o f
hydrocarbons (paraffins, o l e f i n s , and aromatics) on corresponding z e o l i t e s , we
440

became acquainted with the thermodynamic and k i n e t i c p r o p e r t i e s o f these sy-

stems. Trying t o meet the requirements o f Leuna where the development o f t h e
technical process o f s e l e c t i v e adsorption meanwhile was i n f u l l progress, we
were able t o develop t h e f i r s t model o f the so-called "Parex" (paraffin-extrac-
t i o n ) process. We were able t o gain time, and our r i s k s turned out t o be an ad-
vantage. By our model, we helped t o a t t a i n a scaling-up f a c t o r o f 1:8000 d u r i n g
the development o f the Parex process, a r e l a t i o n , which allowed us t o omit one
stage i n t h e t r a d i t i o n a l process of technological development ( r e f . 1).
The flow-sheet o f the Parex process i s represented by f i g u r e 1 (refs. 2-3).
The gaseous raw material, mixed with a carrier-gas, enters t h e p l a n t a t E,
passes the adsorbers A(l-3) a t a pressure o f 0.8 - 1.1 MPa and a temperature o f
360 -380°C. Usually, one adsorber A i s working i n t h e adsorption stage, w h i l e
two adsorbers are needed f o r the process o f desorption, using ammonia as a de-
s o r p t i o n medium. The desorbed product, containing a mixture o f n - p a r a f f i n s and
desorption agents, i s condensed i n column K4, where i t i s separated. The so-
c a l l e d denormal i s a t e passes K1, while the ammonia and the carrier-gas are washed
and, f i n a l l y , returned i n t o t h e process. The process i s r a t h e r f l e x i b l e ; i t can
be r e a l i z e d a t d i f f e r e n t temperatures i n order t o o b t a i n various f r a c t i o n s o f n-
p a r a f f i n s . The o v e r a l l y i e l d o f n-paraffins amounts t o 95-96% and t h e i r p u r i t y
i s 98.5 - 99.1 %.Special measures are necessary i n order t o separate the con-
t e n t s o f approximately 0.5 % o f aromatics. There are now d i f f e r e n t v a r i a n t s o f
the process, allowing, f o r instance, the use o f feed-stocks containing o n l y 7 %
o f n-paraffins.

Fig. 1 P r i n c i p a l f l o w sheet o f the Parex process (ODR), (E-raw material,

w-water, A-residual heat, 0-denormal isate, P-n-paraff in)
 441

The cooperation between the i n d u s t r i a l enterprises and the i n s t i t u t e was

continuous over the past two decades. It was enhanced by a h i g h l y e f f e c t i v e co-
operation w i t h the department o f physics o f t h e Karl-Marx-Universtiy o f L e i p z i g
(Prof. P f e i f e r ) and w i t h the producer o f t h e zeolites, t h e Chemical Combined
Enterprise o f B i t t e r f e l d (Dr. Furtig). The s i n g l e steps o f adsorption, which are
t a k i n g place i n columns packed w i t h biporous adsorbents ( z e o l i t e s i n form of
p e l l e t s ) , are
a) mass transport i n the void space o f the column, i n the macropores of
p e l l e t s between t h e c r y s t a l s (molecular and Knudsen d i f f u s i o n ) and i n t h e micro-
pores ( d i f f u s i o n o f the adsorbed phase w i t h i n t h e crystals);
b) mass t r a n s f e r through the external surface o f the p e l l e t s , through t h e
surface o f crystals, characterized by a barrier;
c) adsorption i n the microporous channel network o f the z e o l i t e f o l l o w i n g a
s o r p t i o n isotherm (equi 1ibrium) ; and
d) the heat phenomena: conduction through p e l l e t s , owing t o temperature r i s e
by adsorption, t r a n s f e r through the external surface o f p e l l e t s , and t r a n s p o r t
i n t h e void space o f the column.
Under technical conditions, the most important phenomena are adsorption,
mass transport i n macro- and micropores. and conduction o f heat. We t r i e d ,
therefore, t o o b t a i n r e l i a b l e data especially i n these f i e l d s . Furthermore, the
influence o f temperature and pressure, the replacement data of adsorbed hydro-
carbons by water and ammonia, and the c a t a l y t i c behaviour o f a c i d centres t o -
wards hydrocarbon conversion are phenomena t o be considered.
The Drocedure o f modelinq
Using fixed-bed adsorbers containing p e l l e t i z e d zeolites, our task was t o
develop an optimal model f o r t h i s non-stationary process, where m a t e r i a l and
heat transports between a s o l i d and a f l u i d phase and adsorption e q u i l i b r i a p l a y
the decisive roles. We were f u l l y aware o f the necessity f o r various s i m p l i f i c a -
tions.
a) We t r i e d t o represent the mixture o f n-paraffins ( i n the range o f CIO-
CIS) by one s i n g l e component: we chose a f i c t i v e hydrocarbon o f a composition o f
approximately 13.5 C-atoms. Thus, we reduced t h e number o f components f o r t h e
mass balance t o 2, i = 1 representing the mean n-paraffins component and i = 2
the concentration o f amnonia. A l l the other materials were not adsorbed t o a
marked extent; therefore, they can remain disregarded.
b) For f u r t h e r s i m p l i f i c a t i o n s we proposed t h a t f o r large-scale conditions
the f l o w p a t t e r n i s s u f f i c i e n t l y described by a x i a l l y dispersed plug flow.
The material and heat transport i n the void space o f the column i s described
by the following equations (assuming the plug f l o w model):
442

(A glossary of the smybols used see at the end of the paper; quantities cha-
racterized by top line represent integral mean values in the volume).
The mass balance in the macropores of the biporous pellets, for which the
adsorption can be neglected, is given by Fick's law:

vc
aCi
-8- + vq 3 = V, div ( Dc,i grad c i ) (3)

and the mass transfer by convection i s fixed by the equation:

The mass transport in the micropores in the adsorpbed phase is represented

by the thermodynamic di ffusion-equat ion:

In this case, the driving force of diffusion is the gradient of the chemical
potential. The effective coefficient of micropore diffusion Dp contains the re-
sistance of the surface barrier as well as the resistance of diffusion within
the adsorbed phase.
The equilibrium of adsorption is given. by a modified Langmuir isotherm:

derived on the basis of statistical thermodynamics and our cellular theory.

f (0) denotes the function of replacement depending on the competing adsorption
of other components. We assume that the spreading of heat within each zeolite
pellet only depends on time. Gradients of temperature only exist between diffe-
rent crystals. Heat conduction within the pellet is then represented by

while the heat transfer on the surface between pellet and surrounding gas phase
is given by:
 443

The system of the coupled and the partial differential equations (1) - (8)
is completed by the choice of appropriate initial and boundary conditions. The
parameters for the calculation of the model were determined by data from funda-
mental research in the institute. The calculation of the model was made for one
adsorber, whose performance in ad- and desorption was studied, until it reached
a periodic-stationary stage. Finally, we calculated the breakthrough curve of
the system.
Fundamental research in the laboratory
One of the most important tasks we had to undertake in the first period of
our research was the exact determination of adsorption equilibria of the corres-
ponding hydrocarbons, sometimes under the influence of water and ammonia. We
found that the isotherms of n-decane on a zeolite o f the type 5A are characte-
rized by a general step. As the maximum capacity of one zeolite cavity amounts
to two molecules of n-decane, we can distinguish between the adsorption of the
first and the second molecules of n-decane. This phenomenon is best realized in
the temperature range between 480-520K.
By measuring the adsorption isotherms of a system at different temperatures,
of course, we had access to very important data: the heat of adsorption of
hydrocarbons and their enthalphy and entropy values.
Depending on the errors in measuring isotherms, these quantities are some-
times not very precise. We, therefore, paid more attention to the direct calori-
metric determination of heats of adsorption and of specific heats of the adsorp-
tion systems. We came to the conclusion that calorimetry is an indispensable
method in adsorption research.
I should like to mention here our efforts to determine parameters, which
depend on the zeolitic adsorbent -- for instance, the influence of the binding
material necessary to form pellets. We not only observed the blocking of trans-
port-pores by the binder, but also the exchange of ions and a certain influence
on the existence of OH groups. The 20 % addition of binding material to the zeo-
lite proved to be a rather active agent, changing the properties of the whole
system. It turned out that the stability of the zeolitic material against water
is a first-class quality, especially for long-time technical use. The acid cen-
tres of the zeolites are very often the source of catalytic decomposition of
hydrocarbons, especially for temperatures higher than 570 K. Although the Parex
process is in rather a happy situation by the fact that the use o f ammonia
"softens" and neutralizes the acid character of the adsorbent, we studied the
problems of decompositon of hydrocarbons extensively, with the result that the
life-time o f the zeolites (measured by a certain yield of adsorbed n-paraffins)
was finally increased by a factor of 5. There are adsorbers, now, which have
been operating on-stream, without interruption, for more than two years.
Returning to the interdependence between technical practice and theory, we
must mention now our efforts to elaborate theoretical approaches, by which we
444

became able t o c a l c u l a t e the most important data necessary f o r t h e model. The

experimental determination o f these values i s time-consuming. A general theore-
t i c a l t o o l would represent a great e f f e c t o f r a t i o n a l i z a t i o n , and hence i t
should g i v e us also a more general understanding o f the phenomenon o f z e o l i t i c
adsorption. That i s why we developed our c e l l u l a r theory o f adsorption, which
considers some c h a r a c t e r i s t i c features o f these systems ( r e f . 4).
Using the general expressions o f s t a t i s t i c a l thermodynamics, we took i n t o
consideration t h a t each c a v i t y i n t h e z e o l i t i c micropore-system i s separated
from other c a v i t i e s by an a c t i v a t i o n b a r r i e r , thus p e r m i t t i n g us t o regard the
c a v i t y as a very small independent thermodynamic system. The number o f p o s s i b l y
adsorbed hydrocarbons being very small, we have the f u r t h e r advantage t h a t the
number o f energy l e v e l s must also be very l i m i t e d . I n other words, a z e o l i t e
c a v i t y , f i l l e d w i t h adsorbed hydrocarbon molecules, represents an i d e a l system
f o r thermodynamic calculations. S t a r t i n g w i t h the most simple assumptions we de-
veloped a Monte Carlo procedure, i n order t o c a l c u l a t e values. The c e l l u l a r
theory o f adsorption i s characterized by the f o l l o w i n g approach:
The grand p a r t i t i o n f u n c t i o n Z i s devided i n t o a product o f powers o f the
corresponding funcitons o f small thermodynamic systems (Nk c e l l s o f type k, k = l ,
..., k). Each c e l l may have o n l y a few states i (1 = 1, ....,
I k ) , characterized
by the number n k i o f occupation and the canonical p a r t i t i o n functions Qki. The
most important p o s s i b i l i t y f o r evaluation i s the d e r i v a t i o n o f an equation o f
isotherm f o r t h e degree o f coverage a:

"ki
nki Q k i
i=l (9)
Nk

(@k representing the mean number o f occupation i n the c e l l s o f type k, A r=

(p/po) / (T/To); Po, To - normal pressure, temperature).
By means o f t h i s system of equations, which we f u l l y described elsewhere
( r e f . 5), we are able t o c a l c u l a t e p r o b a b i l i t i e s o f occupation and, f i n a l l y , a l l
thermodynamic functions o f t h e system o f adsorption, t h a t i s t o say: enthalpy,
entropy, s p e c i f i c heat, and p o r e - f i l l i n g factors. We f i n a l l y devised t h r e e
d i f f e r e n t and independpt ways t o o b t a i n the thermodynamic values needed f o r our
models: experimental methods, calorimetry, and the c e l l u l a r theory o f adsorp-
tion.
I n t h i s way, we calculated the values needed f o r a homologous s e r i e s o f
hydrocarbons as w e l l as f o r d i f f e r e n t types of zeolites. We a l s o obtained data
descrlbing the f u n c t i o n o f displacement o f hydrocarbons by water and amnonia.
 445

In combining these results with other calculations based on well known

Lennard-Jones potential functions, we tried to obtain a deeper insight into the
distribution of potentials within the cavities of different types of zeolites.
Thus we were able to know where the adsorbed molecules were situated within the
cavity and which details of structure may be prevailing. This knowledge about
the structure is especially interesting for long-chained hydrocarbons (ref. 5).
Another approach, more recently developed, concerns the well known fact that
the adsorption as well as the desorption cause some changes of the lattice para-
meters either by compression or dilatation. The changes of length are within the
factor of to of the total crystal dimensions. On the basis of a gene-
ralized mechanical compression and dilatation theory, we derived approaches
which permitted us to calculate the values of interest. The efficiency of these
calculations was demonstrated by the fact that it was possible to find the
correct sign - that is, to know whether compression or dilatation are prevai-
ling. Thus we could contribute to the practical performance of the pelletized
zeolites by giving suggestions as to their formation as well as to their treat-
ment within the bulk of the adsorber.
We were lucky enough to devise a series of modern physical methods of struc-
ture determination and analysis. We emphasize here that the application of mo-
dern methods of infrared and NMR-spectroscopy i s absolutely necessary in adsorp-
tion research, and that concerns not only the fundamental research, but also the
development of a technical process. I am going. to give only two examples, cha-
racteri st ic of our experience:
The use of the photo-electron spectroscopy a1 lows determinations of the
distribution of elements of the zeolite lattice between the bulk and the surface
o f the crystals. We were interested in knowing whether the elements Si, Al, Na,
Mg are homogeneously distributed over the crystal or not. The results, found by
ESCA measurements at various depths under the surface of the crystals compared
with the bulk concentration determined by chemical analysis, were as follows:
a) The element silicon shows the same concentration in the surface as well
as in the bulk phase.
b) The element A1 is enriched in the surface especially for all dealuminated
zeolites.
c) The concentrations of sodium are lower in the surface than in the volume
for all zeolites of type A, X, and Y, while magnesium is enriched in the surface
by a factor of more than two (ref. 6).
We observed that the pretreatment of the zeolites had a great influence on
the homogeneity of the adsorbent. The fact that the distribution of elements is
heterogeneous throughout the crystals must be regarded as normal.
The dynamics of adsorption are of great Influence on the technical process.
Assuming that 10.000 kg of n-paraffins are daily adsorbed by 1 m3 of adsorbent,
we must take for granted that 1017 - 10l8 molecules per second can be adsorbed
446

i n 1 g o f z e o l i t e . Each a v a i l a b l e pore must transport, then, several dozens o f

molecules per second i n t o the c a v i t i e s o f the microporous system. These data r e -
present i n a very rough way t h e importance o f the d i f f u s i o n phenomena. We have
t o d i s t i n g u i s h between d i f f u s i o n and s e l f - d i f f u s i o n . I n the case o f sorbed mole-
cules, s e l f - d i f f u s i o n represents the random molecular motion o f the sorbed spe-
c i e s i n t h e z e o l i t i c channel network a t s o r p t i o n equilibrium. This process i s
described by the E i n s t e i n equation

where D, (?*), and t denote the s e l f - d i f f u s i o n c o e f f i c i e n t , the mean squared

displacement, and the observation time, respect1,vely.
The d i f f u s i o n c o e f f i c i e n t 00 i s given, on the other hand, by F i c k ' s law
4

j, = - DD grad c (11)

with as the d i f f u s i o n f l u x density and grad c as the concentration gradient

o f the sorbed molecules i n the c r y s t a l . The r e l a t i o n between 0, and Do i s appro-
ximated by the Darken r e l a t i o n

DD = Ds
d Inc

denoting the adsorbate pressure a t e q u i l i b r i u m w i t h the sorbate concentration c.

Up t o 1975, we had measured the d i f f u s i o n data e x c l u s i v e l y by sorption-up-
take techniques. A t t h a t time, we began t o use the NMR pulsed-field-gradjent
technique i n close c o l l a b o r a t i o n w i t h H. P f e i f e r , Leipzig, and we were g r e a t l y
astonished t o f i n d t h a t the Ds-values were up t o 3-5 orders o f magnitude l a r g e r
than t h e corresponding data o f Do! A long discussion concerning the correctness
o f these NMR values followed. F i n a l l y , the q u a n t i t i e s determined by t h e NMR
technique were regarded as correct, and we found ways t o change the conditions
o f the sorption-uptake technique, so t h a t nowadays a l l values o f s e l f - d i f f u s i o n
and d i f f u s i o n are i n good agreement ( r e f . 7).
We now have a f i n a l , very essential task: t h a t i s t o i n t e g r a t e a l l these de-
t a i l e d f a c t s and experiences i n t o a technical adsorption process, working w i t h
high e f f i c i e n c y . These problems are o f a technological nature and t h a t i s why we
founded a speclal department, "Chemical engineering o f adsorption", under t h e
d i r e c t i o n o f t h e l a t e Prof. 0. Gelbin. The model enabled us t o i n v e s t i g a t e t h e
dynamic behaviour o f the adsorber. Figure 2 represents the loading p r o f i l e s over
the height o f t h e column as a f u n c t i o n o f t h e adsorption-desorption cycle. For
d i f f e r e n t phases ( d i f f e r e n t r e l a t i v e time r) o f the adsorption process ( f u l l
curves) we observe the formation o f a loading f r o n t . A t T = 0.33 the adsorption
i s finished; we see t h a t the concentration o f the adsorbate (n-paraffins) i s
 447

high (approximately 0.9 - 0.95 of qlm) near the entrance of the adsorber, descen-
ding to values o f nearly 0.05 near the exit.

Fig. 2 Loading profils over column height and adsorption-desorption cycle

(x = normalized time)
With the beginning of the desorption (dashed lines), the concentration pro-
files thoroughly change. At the entrance of the adsorber, the concentration is
negligible, while the exit concentration is still considerable. Obviously, the
desorption process is slower than adsorption. That is why we chose a relation o f
two adsorbers working in the desorption regime to one adsorber on adsorption. We
must confirm that this is not the last improvement; It seems to us that there
could be other relations with a somewhat higher efficiency. The dashed curve at
T = 1 represents the end o f the whole cycle; the exit concentration is now lower

than 0.1. a degree of coverage which can be attained under advantageous economic
conditions allowing us to repeat the whole cycle once more.
Of high value is the measurement of breakthrough curves and their theoreti-
cal modeling. Dependent on time of adsorption, the method consists of the deter-
448

mination, easily accomplished, of the exit concentration of normal paraffins.

The breakthrough curve for a fresh (not used) sieve I s compared with the break-
through curves o f aged and used zeolites. We see that the adsorption capacity
decreases with increasing time of ageing. In order to be able to calculate these
breakthrough curves, we developed a method of calculation, based on the use of
the method o f moments, described by us elsewhere. We see that the measured and
the calculated curves can be compared, although we must confess that, up to now,
we could not solve all problems which hinder an exact comparison between mea-
sured and calculated data.
One of the decisive economic factors of the Parex process i s the use of
a m n i a . It must be regained completely; losses are not acceptable. The amount
of desorption gas must be sufficient, of course, to replace the adsorbed hydro-
carbons completely. But going beyond an optimum amount leads to a reduction in
the yield of desorbed hydrocarbons. By changing the used principle of forward-
flow desorption to reverse-flow desorption, the degree of desorption is greater
and therefore the yield increases. It seems to be possible to reduce the amount
of desorption agent by approximately 50 % without lowering the yield. This would
lead to a lower energy input for the whole process. Unfortunately, it has not
yet been possible to introduce the principle of reverse flow into the existing
plants. It is probable that, under these conditions, the whole adsorption-
desorption cycle must be changed. We calculated models of the Parex process with
various circuits of the adsorbing-desorbing regime, and we are convinced that
"the final word is not yet spoken" in this direction (ref. 8).
We now want to summarize our results and to give a survey of the efficiency
of our Parex model. We hope that our intention, to show the interdependence be-
tween technical progress and fundamental research, has been elucidated. We were
forced here to omit certain developments, especially methods of the NMR tech-
nique, and theoretical questions.
What is our model now good for?
- It allows the simulation of large-scale adsorption-desorption processes
on the basis o f model parameters determined in laboratory-scale experi-
ments.
- It is not necessary to make an a-posteriori fit o f free model parameters
to large-scale measurements.
- The model has shown its universal applicability to various types of pro-
cesses of selective adsorption from the gaseous phase.
- The model allows calculations for the variation of:
. The adsorber geometry,
. the number of the adsorbers and their switching (circuit of products),
. the cycle times,
. the amount of feed and purge gas.
. the composition of these gases,
 449

. the type and the state of ageing of the zeolite,

. the energy consumption of the process.
The fact that our chemical enterprises could sell this process dozens of
times to other countries and that negotiations for further plants are in pro-
gress is the best evidence for its efficiency. The annual production capacity of
normal paraffins based on the Parex process, by our present estimate, amounts to
more than 1.5 millions of tons.

GLOSSARY
1 ) Latln letters:
amount adsorbed, g/g or mmol/g
vertical vectors In general transport equatlon
matrix in general transport equation
equi 1 ibrium constant in Langmuir equation
vector in general transport equation
operator in general Ized form in transport quation
gas concentration In mac o por s, mol m- 9
diffusion coefficient, m5 s-'
diffusion coeff i ci ent of axi a1 di spersi on
diffusion coefficient under the influence of concentration
gradients
coefficient of self-diffusion
source of material in general transport equation
gas concentration In void space of column, mol N3
flux of material, mol s-1 m-3
.
mass-transfer coefficient from gas ous phase, m s-l
adsorbate concentration, mol cm- 9
-
heat of adsorption, J mol-l
radial coordinate of pellet, m
radius of pellet, m
.
universal gas constant, J mol-1 ~ - 1 .
fictive gas concentration in macropores, mol m-3
time o f observation, s or min
interstitial gas velocity, m s-1 .
relative volume of pellet (V ) , of macropores (V,), Micropores(Vq)
axial coordinate of the bed gf column, m
2) Greek letters:
(1 = overall heat transfer coefficient, W m-* - K-l
0

Y
yg. yp
0
=
=
=
factor of proportionality in general transport equation
-
volumetric heat capacity of flowing gas, of pe let, J mol-l
potential of adsorption in cavities, KJ mol- 1 -
hax,hp =
=
thermal conductivity of flow ng gas, of pellet, W m - l
.
chemical potential, J mol- 1 .K1 .
P
T = normalized time in adsorption-cycle
0 = loading of cavities
T = normalized function in adsorption-isotherm
3) Subscripts, indices
ax = property belonging to axial dispersion
C = property of the macropore-system
9 = property of the void space in column
i = component in the gaseous phase
P = states in the gaseous phase
q = property of the micropore-system
P = diffusion in mlcropores
Lo = property in the state o f saturation
450

REFERENCES
K. Fiedler, A., Roethe, K.-P. Roethe and 0. Gelbin, Z. phys. Chem., L e i p z i g
259 11978) 979.
K. Wehner; J. Welker and 6. Seidel, Chem. Techn. 2 1 (1969) 548.
G. Seidel, J. Welker, W. Ermischer and K. Wehner, Chem. Techn. 31 ( 1979)
405.
W. Schirmer, K. F i e d l e r and H. Stach, Thermodynamics o f Adsorption on
Zeolites, Molecular Sieves 11, ACS Symp. Ser. 40, Washington, 1977, p. 305.
K. Fiedler, U. Lohse, J. Sauer, H. Stach, H. Thamn and W. Schirmer, Proc.
5 t h Int. Conf. on Zeolites, Naples 1980, Heyden (London) p. 490.
K.-H. Richter, Workshop "Adsorption o f Hydrocarbons i n Zeolites",
Proceedings B e r l i n (DDR) 1979 p. 231.
H. P f e i f e r , J. Karger, A. Germanus, W. Schirmer, M. Bulow and J. Caro, Ads.
Sci. Technol. 2 (1985) 229.
M. Suckow, Thesis 1986, Humboldt-Universitat, B e r l i n (DDR).
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

SORBEX TECHNOLOGY FOR INDUSTRIAL SCALE SEPARATION

J . A. JOHNSON AND A. R. OROSKAR

UOP I nc . , 25 E . A l g o n q u i n Rd., Des P l a i n e s , I l l i n o i s , 60017, U.S.A.

INTRODUCTION
N e a r l y ev ery chemical m a n u f a c t u r i n g o p e r a t i o n r e q u i r e s t h e use o f separa-
t i o n processes i n o r d e r t o r e c o v e r and p u r i f y t h e d e s i r e d product . I n most
c a s e s , t h e e f f i c i e n c y o f t h e s e p a r a t i o n process has a s i g n i f i c a n t impact on
b o t h t h e q u a l i t y and t h e c o s t o f t h e p r o d u c t (1). Because o f i t s s i m p l i c i t y
and bro ad a p p l i c a t i o n , d i s t i l l a t i o n has become t h e st andard a g a i n s t which
O t her s e p a r a t i o n processes
a1 t e r n a t i v e s e p a r a t i o n t e c h n o l o g i e s a r e compared.
ba s e d on f e ed component physicochemical p r o p e r t i e s , such as c r y s t a l 1 i z a t i o n
and s o l v e n t e x t r a c t i o n , a r e also used i n t h e chemical i n d u s t r y . However,
t h e r e a r e many cases t h a t i n v o l v e t h e b u l k s e p a r a t i o n o f c h e m i c a l l y s i m i l a r
components o r t h e removal o f components t h a t a r e p r e s e n t a t l o w concen-
trations. I n t he s e s i t u a t i o n s t h e t r a d i t i o n a l s e p a r a t i o n t echniques based on
p h y s i c o c h e m i c a l p r o p e r t i e s h a v e l i m i t e d usef ulness and may even be un-
workable. For t h i s l a t t e r c l a s s o f s e p a r a t i o n problems, adsorption o f f e r s a
s u i t a b l e approach.

A d s o r p t i v e s e p a r a t i o n processes o f f e r g r e a t e r degrees o f freedom i n p e r -

f o r m i n g d i f f i c u l t s e p a r a t i o n problems, because t hey can e x p l o i t d i f f e r e n c e s
i n t h e molecular structure, s t e r i c h i n d r ance and e l e c t r o c h e m i c a l surface
i n t e r a c t i o n among f e e d components v i s - a - v i s t h e adsorbent. These small d i f -
f e r e n c e s on t h e m o l e c u l a r s c a l e can be a m p l i f i e d t o p r o v i d e o v e r a l l adsorbent
s e l e c t i v i t i e s and c a p a c i t i e s t h a t a r e o f i n t e r e s t f o r p r o d u c t i o n s c a l e eco-
nomics. A lt h ough t h e investment c o s t o f an a d s o r p t i o n process i s g e n e r a l l y
h i g h e r t h an t h a t o f a d i s t i l l a t i o n u n i t w i t h an e q u i v a l e n t number o f t h e o -
r e t i c a l stages, much h i g h e r s e p a r a t i o n f a c t o r s a r e commonly a t t a i n e d . Thus,
a t l o w r e l a t i v e v o l a t i l i t y , an a d s o r p t i o n process becomes t h e more economic
o p t i o n ( 2 ) . For p u r i f i c a t i o n processes i n v o l v i n g l i g h t gases where t h e a l -
t e r n a t i v e i s c ry o g e n i c d i s t i l l a t i o n , a d s o r p t i o n i s p r e f e r r e d even when t h e
r e l a t i v e v o l a t i l i t y i s high (3).

UOP has s u c c e s s f u l l y a p p l i e d a d s o r p t i v e s e p a r a t i o n on an i n d u s t r i a l
s c a l e v i a t h e Sorbex* process f o r t h e p u r i f i c a t i o n and r e c o v e r y o f b u l k
chemicals (4). The f i r s t commercial a p p l i c a t i o n o c c u r r e d i n 1964 w i t h t h e
452

advent o f the UOP Molex* process f o r recovery o f h i g h - p u r i t y n - p a r a f f i n s .

Since t h a t time, Sorbex technology has been a p p l i e d t o a broad range o f
problems i n c l u d i n g i n d i v i d u a l isomer separations and class separations. New
applications a r e c o n t i n u a l l y being i d e n t i f i e d and developed. While a l l
Sorbex a p p l i c a t i o n s share t h e same basic well-proven and e f f i c i e n t process
design, the adsorbent p r o p e r t i e s and t h e performance requirements are d i f -
f e r e n t f o r each type o f separation. O f t h e various m a t e r i a l s a v a i l a b l e f o r
use as adsorbents, z e o l i t e s o f f e r a p a r t i c u l a r l y wide range o f parameters
t h a t can be manipulated t o make them e f f e c t i v e as adsorbents f o r i n d u s t r i a l
scale separations.

I n t h i s paper we g i v e an overview o f e x i s t i n g Sorbex processes, describe

t h e d e s i r a b l e c h a r a c t e r i s t i c s o f adsorbents, discuss some o f t h e unique capa-
b i l i t i e s o f z e o l i t e s as adsorbents and suggest p o t e n t i a l a p p l i c a t i o n s f o r t h e
future.

ZEOLITES AS PRACTICAL ADSORBENTS

The search f o r a s u i t a b l e adsorbent i s g e n e r a l l y the f i r s t step i n the
development o f a Sorbex process. There are f o u r primary requirements f o r a
p r a c t i c a l adsorbent: s e l e c t i v i t y , capacity, mass t r a n s f e r r a t e and l o n g term
stability. The requirement f o r adequate adsorptive c a p a c i t y r e s t r i c t s t h e
c h o i c e o f adsorbents t o microporous s o l i d s w i t h pore diameters ranging from a
few angstroms t o a few hundred angstroms. M a t e r i a l s such as s i l i c a g e l ,
a c t i v a t e d alumina, a c t i v a t e d carbons, polymeric r e s i n s and molecular sieve
z e o l i t e s are, therefore, s u i t a b l e p r a c t i c a l adsorbents.

T r a d i t i o n a l adsorbents such as s i l i c a , a c t i v a t e d alumina and a c t i v a t e d

carbon e x h i b i t l a r g e surface area and micropore volume. The surface chemical
p r o p e r t i e s o f these adsorbents make them p o t e n t i a l l y u s e f u l f o r separations
by m o l e c u l a r class. However the micropore s i z e d i s t r i b u t i o n i s f a i r l y broad
f o r t h e s e m a t e r i a l s , as shown i n Figure 1. This c h a r a c t e r i s t i c makes such ma-
t e r i a l s u n s u i t a b l e f o r use i n separations where s t e r i c hindrances could po-
t e n t i a l l y be e x p l o i t e d .

Polymeric r e s i n s are widely used i n t h e food and pharmaceutical indus-

t r i e s as cation/anion exchangers, f o r t h e removal of t r a c e components and f o r
some b u l k separations such as fructose/glucose. They are p r i m a r i l y a t t r a c t i v e
f o r aqueous phase separations and o f f e r a f a i r l y wide p o t e n t i a l range o f
s u r f a c e chemistries t o f i t a number o f separation needs. For example, they
a r e e f f e c t i v e i n p a r t i t i o n i n g by s i z e and molecular weight, and may a l s o be
e f f e c t i v e i n i o n exclusion.
 453

ACTIVATED CARBON

30
ZEOLITE l b

2 5 10 20 50
PORE DIAMETER, ANGSTROM
, ~, ,
u o ~

Fig. 1. Pore size distribution (Ref. 6).

TABLE 1

Molecular sieve pore structures.

COMMON RING FREE
-
NAME OPENING APERATURE
PORE
STRUCTURE
FAUJASlTE 7.4 A 30
MORDENITE 2.9 x 5.7A
6.7 x 7.0 A 1D
L 7.1 A 1D
ZSM-5 5.4 x 5.6 A
5.1 x 5.6 A
ERIONITE 3.6 x 5.2 A 2D
A 4.2 A 3D
“1 D” “20” “30”

In contrast to these adsorbents, zeolites offer increased possibilities

for exploiting molecular level differences among adsorbates. Zeolites are
crystalline aluminosilicates containing an assemblage of SiO4 and A104
tetrahedra joined together by oxygen atoms to form a microporous sol id, which
has a precise pore structure (5). Nearly 40 distinct framework structures
have been identified to date. Table 1 summarizes some of those that have been
widely used in the chemical industry. The versatility o f zeolites lies in
454

t h e f a c t t h a t w i d e l y d i f f e r e n t a d s o r p t i v e p r o p e r t i e s may be r e a l i z e d by ap-
p r o p r i a t e c o n t r o l o f t h e framework s t r u c t u r e , S i / A 1 r a t i o and t h e c a t i o n
form. F o r example, z e o l i t e A, shown i n F i g u r e 2, has a t h r e e dimensional
i s o t r o p i c channel s t r u c t u r e c o n s t r i c t e d b y an eight-membered oxygen r i n g .
I t s e f f e c t i v e p o r e s i z e can be c o n t r o l l e d a t about 3A, 4A and 4.5A by ex-
changing w i t h potassium, sodium and c a l c i u m , r e s p e c t i v e l y . The pot assium
f o r m , w i t h 3A pores, i s used f o r removing wat er f rom o l e f i n i c hydrocarbons.
The sodium f o rm can be used t o e f f i c i e n t l y remove w a t e r f rom n o n - r e a c t i v e
hydrocarbons, such as a l k a n e s . S u b s t i t u t i o n o f c a l c i u m can p r o v i d e a p o r e
s i z e t h a t w i l l admit normal p a r a f f i n s , and e xclude o t h e r hydrocarbons.

W)P imia

F i g . 2 . Three z e o l i t e s w i t h t h e same s t r u c t u r a l polyhedron (cubo-octahedron).

L a r g e p o r e z e o l i t e s , X, Y and m o r d e n i t es have pores d e f i n e d b y t w e l v e -

membered oxygen r i n g s w i t h a f r e e d i a m e t e r o f 7.4A. The framework s t r u c t u r e
o f X and Y f a u j a s i t e s , sketched i n F i g u r e 2 c o n s i s t s o f a t o t a l o f 192 SiO2
and A102 u n i t s . The s i l i c a - t o - a l u m i n a r a t i o f o r X i s g e n e r a l l y between 1
and 1.5, whereas f o r Y i t i s between 1.5 and 3 . W i t h s u i t a b l e procedures, Y
can be "dealuminated" t o Si/A1 r a t i o s exceeding 100. A d s o r p t i o n p r o p e r t i e s
o f f a u j a s i t e s a r e s t r o n g l y dependent on n o t o n l y t h e c a t i o n f orm b u t a l s o t h e
Si/A1 ratio. The f l e x i b i l i t y p r o v i d e d f a n j a s i t e s i n t h e a d s o r p t i o n o f c8
a r o m a t i c s i s shown i n Ta b l e 2. The s e l e c t i v i t y order, f r o m most s t r o n g l y
a d s o r b e d t o t h e most r e a d i l y r e j e c t e d , can be changed s i g n i f i c a n t l y by t h e
choice o f z e o l i t e p r o p e r t i e s .
 455

TABLE 2
S e l e c t i v i t y o f z e o l i t e s i n C8-aromatic system.

1 = MOST SELECTIVELY ADSORBED

4 = LEAST SELECTIVELY ADSORBED

ADSORBENT ADSORBENT ADSORBENT ADSORBENT

#l #2 #3 #4

p XYLENE
~ 1 2 3 4
ETHYLBENZENE 2 1 4 3
m - XYLENE 3 3 1 2
o-XYLENE 4 4 2 1
WP itai.?

The s e p a r a t i o n o f f r u c t o s e from g l u c o s e serves t o i l l u s t r a t e t h e i n t e r -

a c t i o n between t h e framework s t r u c t u r e and t h e c a t i o n i n F i g u r e 3. Ca i s
known t o f o rm complexes w i t h sugar molecules such as f r u c t o s e . Thus, Ca-Y
shows a h i g h s e l e c t i v i t y f o r f r u c t o s e o v e r glucose. However, Ca-X does n o t
e x h i b i t any s e l e c t i v i t y f o r t h e hexoses. On t h e o t h e r hand, K-X shows s e l e c -
t i v i t y f o r gluc o s e o v e r f r u c t o s e . I t i s t h e p o l a r n a t u r e o f f a u j a s i t e s and
t h e i r unique s h a p e - s e l e c t i v e p r o p e r t i e s more so t h a n t h e m o l e c u l a r s i e v i n g
p r o p e r t i e s t h a t makes them most u s e f u l as p r a c t i c a l adsorbents.

TIME

I C P

F i g . 3. F ruc t o s e- g l u c o s e s e p a r a t i o n on f a u j a s i t e adsorbents.
456

Mordenites represent another class of large pore zeolites, but in con-

trast to faujasites the mordenite pore opening is one-dimensional . Although
mordenites can exhibit some interesting adsorption properties, the single-
dimensional pore structure makes these adsorbents more sensi tive to "pore-
plugging" by trace feed components, which may be too strongly adsorbed. As a
result, no significant commercial uses have been found for mordenite ad-
sorbents. On the other hand, many catalytic uses of mordenite are well known
to the chemical industry.

Most zeolites are synthesized as 1-10 micron crystals, in an ionic form

which is usually most convenient for the synthesis step. This particle size
is unsuitable for direct use in liquid or gas phase continuous adsorption
processes, and may also 1 imit the commercial scale post-treatment techniques
(ion exchange, hydrothermal treatment) that need to be employed to impart the
desired adsorption properties. As a result, the microporous zeolite powder
is typically combined with a suitable binder and formed into macroporous par-
ticles, which meet the hydrodynamic constraints of the process unit. While
it is desirable to maximize the volumetric capacity, it is also important to
have low macropore resistance to mass transfer and acceptable particle
strength. Proper choice o f the binder and the binding method are essential
to the formulation of an acceptable adsorbent. Clays have generally been
used as binders for zeolitic adsorbents in hydrocarbon service. The ad-
sorbents may be either granular or spherical in shape and should be narrow in
size distribution, which is an important factor in the control of axial,
convective dispersion.

ADSORPTIVE SEPARATIONS PROCESSING STRATEGIES

Industrial scale adsorption processes can be classified according to
whether they are batch or continuous (2). In a batch process the adsorbent
bed i s saturated and regenerated in a cyclic operation, while in a continuous
process a countercurrent staged contact between the adsorbent and the feed
and desorbent is established by either a true or a simulated recirculation of
the adsorbent.

Batch processes generally operate in three regeneration modes: thermal

swing, pressure swing and displacement desorption (6). The choice of mode is
determined primarily by the feed composition and the adsorbent character-
istics. Thermal-swing operation requires long cycle times and thus is suited
for the removal of trace contaminants. Pressure-swing operation, on the other
hand, allows very low cycle times and i s , thus, effective for bulk
 451

s e p a r a t i o n s i n vapor phase. The c h o i c e o f a desorbent i s c r u c i a l i n a d i s -

placement mode, w h i c h can be used f o r t r a c e as w e l l as b u l k separat ions.
Examples o f bat ch a d s o r p t i o n processes i n i n d u s t r i a l p r a c t i c e a r e p r o v i d e d i n
T a ble 3 .

TABLE 3
Some examples o f b a t c h a d s o r p t i o n processes (Ref. 3 ) .

TRACE COMPONENT SEPARATION ADSORBENT __

TYPE

H 2 0 I NATURAL GAS, CRACKED GAS SILICA, ALUMINA THERMAL REGENERATION

AIR, ETC. ZEOLITES
C 0 2 I NATURAL GAS, ETHYLENE, ETC. ZEOLITES THERMAL REGENERATION
ORGANICS I VENT STREAM ACTIVATED CARBON STEAM REGENERATION
NO,, SO2 I VENT STREAMS ZEOLITES THERMAL REGENERATION

BULK SE PARATlZS

NORMAL PARAFFIN I I S 0 PARAFFIN ZEOLITES THERMAL SWING

DISPLACEMENT DESORPTION
ZEOLITES PRESSURE SWING
CARBON MOLECULAR SIEVE PRESSURE SWING
(KINETIC SEPARATION)
SOLVENTS I VENT GASES ACTIVATED CARBON VACUUM DESORPTION
ux tMld

The e f f i c i e n c y o f an a d s o r p t i o n process i s s i g n i f i c a n t l y h i g h e r i n a con-

t i n u o u s mode o f o p e r a t i o n t h a n i n a c y c l i c b a t c h mode ( 7 ) . I n a b a t c h chroma-
tographic operation, t h e l i q u i d c o m p o s i t i on a t a g i v e n l e v e l i n t h e bed
u n d e r g o e s a c y c l i c change w i t h time, and l a r g e p o r t i o n s o f t h e bed do n o t
p e r f o r m any u s e f u l f u n c t i o n a t a g i v e n t i m e . On t h e o t h e r hand, i n con-
t i n u o u s o p e r a t i o n t h e c o m p o s i t i o n a t a g i v e n l e v e l i s i n v a r i a n t w i t h t i m e and
e v e r y p a r t o f t h e bed performs a u s e f u l f u n c t i o n a t a l l t imes. The HETP i n a
b a t c h o p e r a t i o n i s r o u g h l y t h r e e t i m e s t h a t i n a cont inuous mode. For d i f -
f i c u l t s epara t i o n s , b a t c h o p e r a t i o n may r e q u i r e t w e n t y - f i v e t i m e s more ad-
s orb ent i n v e n t o r y and t w i c e t h e desorbent c i r c u l a t i o n r a t e t han a c o n t i n u o u s
operation. I n a d d i t i o n , i n a b a t c h mode, t h e f o u r f u n c t i o n s o f a d s o r p t i o n ,
p u r i f i c a t i o n , d e s o r p t i o n and displacement o f t h e desorbent f rom t h e adsorbent
a r e i n f l e x i b l y l i n k e d , whereas a c o n t i n u ous mode a l l o w s more degrees o f
f r e e d o m w i t h r e s p e c t t o t h e s e f u n c t i o n s and, thus, a b e t t e r o v e r a l l opera-
tion.

C o n t i n u o u s c o u n t e r c u r r e n t c o n t a c t , however, i n c r e a s e s t h e c o m p l e x i t y o f
d e s i g n and t h e d i f f i c u l t y o f c o n t r o l . One o f t h e f i r s t at t empt s a t con-
t i n u o u s c o u n t e r c u r r e n t a d s o r p t i o n p r o c e s s i n g was t h e H y p e r s o r p t i o n process
458

f o r t h e gas phase recovery o f ethylene ( 6 ) . T h i s process i n v o l v e d actual

movement o f t h e adsorbent along w i t h a temperature swing desorption. The
s e p a r a t i o n e f f i c i e n c y was high, but t h e steady a t t r i t i o n o f t h e adsorbent and
t h e more complex design u l t i m a t e l y 1 i m i t e d wider commercial a p p l i c a t i o n o f
t h i s process.

The UOP Sorbex process ( 4 ) , f i r s t commercialized i n 1964, sought t o g a i n

t h e t h e o r e t i c a l advantages o f t r u e countercurrent processing w i t h o u t physi-
c a l l y moving t h e adsorbent. This was done through t h e use o f a design con-
cept t h a t simulated t h e countercurrent movement o f t h e 1 i q u i d process streams
p a s t t h e s o l i d adsorbent. By maintaining t h e adsorbent bed s t a t i o n a r y , par-
t i c l e a t t r i t i o n was prevented. Also, very importantly, t h e Sorbex design
preserved p l u g f l o w o f l i q u i d past the adsorbent, avoiding the non-uniform
f l o w p a t t e r n s and d i s p e r s i o n t h a t would n a t u r a l l y r e s u l t from p h y s i c a l l y
moving the adsorbent past t h e l i q u i d . Therefore, t h e i n t r i n s i c separation
e f f i c i e n c y o f t h e adsorbent p a r t i c l e could be r e a l i z e d on a macroscopic
p r o c e s s scale. The basic Sorbex design has been perfected over t h e years and
extended t o many a p p l i c a t i o n s . I t i s used worldwide f o r b u l k separation and
recovery o f h i g h p u r i t y products.

THE SORBEX PROCESS

A schematic f l o w diagram o f the adsorption s e c t i o n of the Sorbex process
i s shown i n Figure 4 . The adsorbent i s d i v i d e d i n t o several beds o f equal
s i z e . A t t h e t o p and the bottom o f each bed i s a l i q u i d d i s t r i b u t o r t h a t i n
t u r n i s connected t o a bed l i n e . Each bed l i n e can t r a n s f e r l i q u i d i n t o o r
o u t o f t h e adsorbent chamber, but a t any given t i m e o n l y a c e r t a i n number o f
t h e bed l i n e s are activated. These bed l i n e s terminate a t t h e r o t a r y valve,
t h e i n d u s t r i a l analog o f a m u l t i - p o r t stopcock. The r o t a r y v a l v e i s a l s o
connected t o the external process streams: feed, desorbent, e x t r a c t and
r a f f i n a t e . The i n f l u e n t feed and desorbent are d i r e c t e d by the r o t a r y valve
t o bed l i n e s t h a t are several adsorbent beds apart. S i m i l a r l y , t h e e f f l u e n t
e x t r a c t and r a f f i n a t e streams are withdrawn from bed l i n e s t h a t are several
adsorbent beds apart. The r o t a r y valve step time i s constant and s p e c i f i c
f o r a given separation.
 459

F i g . 4 . Sorbex process, s i m u l a t e d moving bed f o r a d s o r p t i v e s e p a r a t i o n .

I n t h e ex a m p l e o f F i g u r e 4 , o n l y f o u r o u t o f t h e t w e l v e bed l i n e s a r e
a c t i v e a t any g i v e n t i m e , and t h e i n t e r v a l between each o f t h e a c t i v e l i n e s
r e m a i n s f i x e d , d e f i n i n g d i s t i n c t f u n c t i o n a l zones f o r t h e Sorbex process.
A d s o r p t i o n t a k e s p l a c e i n t h e beds between t h e f eed and t h e r a f f i n a t e
s t r e a m s . R e c t i f i c a t i o n t a k e s p l a c e i n t h e beds between t h e e x t r a c t and t h e
f e e d streams. D e s o r p t i o n t a k e s p l a c e i n t h e beds between t h e desorbent and
t h e e x t r a c t streams. A f o u r t h zone, l o c a t e d i n t h e beds between t h e r a f f i n a t e
and des orb ent streams, d i s p l a c e s desorbent f rom t h e adsorbent pores e n t e r i n g
t h e a d s o r p t i o n zone, w h i l e p r e v e n t i n g t h e cont aminat ion o f t h e d e s o r p t i o n
zone w i t h r a f f i n a t e components.

L i q u i d i s pumped from t h e t o p t o t h e b ot t om o f t h e chamber, i n t h e same

d i r e c t i o n as t h e r o t a r y v a l v e advances. The f l o w r a t e changes whenever t h e
r o t a r y v a l v e causes t h e pump t o c r o s s a new zone boundary. Steady st epwise
advancement o f t h e r o t a r y v a l v e combines w i t h t h e p a r t i c u l a r n e t l i q u i d f l o w
i n e a c h zone t o s i m u l a t e t h e c o n t i n u o u s c o u n t e r c u r r e n t movement o f t h e l i q u i d
and s o l i d phases, e s t a b l i s h i n g t h o s e c o n d i t i o n s t h a t a r e most s u i t a b l e f o r
t h e f u n c t i o n o f t h a t p a r t i c u l a r zone. I n e f f e c t , t h e r o t a r y v a l v e i s c i r c u -
l a t i n g t h e s e l e c t i v e and n o n - s e l e c t i v e adsorbent volume a t a c o n s t a n t r a t e ,
and t h e n e t l i q u i d f l o w r a t e i n any g i v e n zone i s r e f l u x e d a g a i n s t t h a t ad-
so rb ent volume c i r c u l a t i o n r a t e . The c o n c e n t r a t i o n p r o f i l e shown i n F i g u r e 4
460

moves w i t h t h e advancement o f the r o t a r y valve, w i t h t h e s o l i d and l i q u i d

phases being i n e q u i l i b r i u m w i t h each other. A t y p i c a l steady s t a t e l i q u i d
c o m p o s i t i o n p r o f i l e f o r t h e UOP C 4 O l e x * p r o c e s s (8) i s shown on a
desorbent-free basis i n Figure 5. The r a t e s o f e x t r a c t and r a f f i n a t e are
c o n s t a n t , as are t h e compositions o f these streams going t o t h e desorbent
recovery section.

40-

F i g . 5. Steady s t a t e l i q u i d concentration p r o f i l e s f o r a C4 Olex p i l o t

p l ant.

As shown i n Figure 4, the e x t r a c t and r a f f i n a t e streams c o n t a i n de-

sorbent, w h i c h must be removed i n order t o achieve t h e d e s i r e d p u r i t y .
Desorbent must be c a r e f u l l y selected along w i t h t h e adsorbent i n order t o
achieve a completely r e v e r s i b l e process. Too strong a desorbent i n t e r f e r e s
w i t h t h e adsorption f u n c t i o n , w h i l e a weak desorbent may l i m i t p u r i f i c a t i o n
o r recovery. The desorbent must be compatible w i t h t h e feed components and
be e a s i l y recovered by evaporation o r simple f r a c t i o n a t i o n f o r t o t a l recycle.

The Sorbex process operates i n t h e l i q u i d phase a t a constant tempe-

r a t u r e , which i s selected t o maximize mass t r a n s f e r w h i l e maintaining selec-
t i v i t y and c o m p a t i b i l i t y w i t h t h e feed components. A t t h e o p e r a t i n g tempera-
t u r e o f choice, t h e r e i s an e q u i l i b r i u m r e l a t i o n s h i p between t h e composition
i n t h e l i q u i d phase and t h a t i n t h e adsorbent phase. This relationship i s
analogous t o t h a t o f v a p o r / l i q u i d e q u i l i b r i u m i n f r a c t i o n a l d i s t i l l a t i o n .
T y p i c a l adsorption isotherms are sketched i n Figure 6. The simplest i s a
 461

l i n e a r is ot h erm . I n t h i s case, t h e p r o p e r n e t zone f l o w r a t e s a r e dependent

s o l e l y upon t h e Henry’s Law c o n s t a n t s and n o t t h e f eed c o n c e n t r a t i o n .

1I
WUlD PHASE
CONCPNTR 0N UOP leal4

Fig . 6. T y p i c a l a d s o r p t i o n i s o t h e r m s encountered i n Sorbex s e p a r a t i o n .

N o n - l i n e a r a d s o r p t i o n i s o t h e r m s r e s u l t i n n e t zone f l o w r a t e s which a r e
a f u n c t i o n o f b o t h t h e Henry’s Law c o n s t a n t s and t h e s l o p e o f t h e isot herms
a t t h e f eed c o n c e n t r a t i o n s . Secondary e f f e c t s , such as t h e dependence of
s e l e c t i v i t y f o r one component on t h e c o n c e n t r a t i o n o f anot her component, have
been n o t e d and pose a d d i t i o n a l problems i n i d e n t i f y i n g t h e most f a v o r a b l e n e t
zone f l o w r a t e s . O v e r a l l , however, t h e Sorbex system has been proven e f -
f e c t i v e f o r a b r o a d r a n g e o f s e p a r a t i o n problems i n t h e pet rochemical,
c hemic a l and food/biochemical i n d u s t r i e s . We have r a r e l y been d i s a p p o i n t e d
i n t r a n s 1 a t i n g f r o m 1 a b o r a t o r y p r o o f - o f - p r i n c i p l e t e s t i n g t o cont inuous
operation. Lik e w i s e , we have been s u c c e s sf ul i n s c a l i n g up f rom o u r p i l o t
p l a n t s d i r e c t l y t o commercial p r o d u c t i o n , w i t h adsorbent chamber diamet ers as
l a r g e as 6 . 5 meters.

S orb ex t e c h n o l o g y i s used f o r a wide range o f i n d u s t r i a l s c a l e separa-

t i o n s , w i t h p r o d u c t i o n c a p a c i t i e s r a n g i n g f rom about 30,000 t o 400,000 t o n s
p e r y e a r (9). The v e r s a t i l i t y o f l i q u i d phase s e p a r a t i o n i s shown i n T able
4 , w h i c h l i s t s t h e v a r i o u s Sorbex processes i n use t hroughout t h e world.
More t h a n seventy u n i t s have been l i c e n s e d , account ing f o r n e a r l y 8 m i l l i o n
t o n s p e r y e a r o f product capacity. I n a d d i t i o n , UOP has developed and
commerci a1 i z e d s e v e r a l o t h e r Sorbex processes f o r p r o d u c t i o n o f s p e c i a l t y
chemicals a t o u r Shreveport, L o u i s i a n a , l o c a t i o n .
462

TABLE 4
Sorbex for commodity chemicals.

PROCESS SEPARATION

PAREX p-XYLENEICg AROMAmS 44

MOLEX n-PARAFFINS/ BRANCHED AND

CYCLIC HYDROCARBONS 21

OLEX OLEFINSIPARAFFINS 6
CYMEX p or m-CYMENEICYMENE ISOMERS 1

CRESEX p or mCRESOLICRESOL ISOMERS 1

SAREX FRUCTOSEI DEXTROSE PLUS

POLYSACCHARfDES -5
78

WIAL PRODUCT CAPACITY > 8 MILUON TONS IW

UOP 1u5.1
uw 1Wl-12

COMPARISON OF ZEOLITE AND RESIN ADSORBENTS

The UOP Sarex* process has been used for the separation of high purity
fructose from a mixture of fructose, glucose and polysaccharides. This was
the first aqueous phase application of the Sorbex process, with the first com-
mercial unit on-stream in 1978. The Sarex process has employed both zeolitic
and polymeric resin adsorbents for the production of high fructose corn syrup
(HFCS). The operating characteristics of these two adsorbents are sub-
stantially different.

A1 though both adsorbents exhibit similar selectivity for fructose over

glucose and polysaccharides, we find that the zeolitic adsorbent can be
operated at a reduced rotary valve cycle time. This gives a throughput ad
vantage for a unit of fixed size or, conversely, a lower adsorbent require-
ment to achieve fixed capacity. Further constraints are placed on the resin
system due to its shrink/swell response to osmotic changes and its compressi-
bility. On the other hand, the resin adsorbent tends to provide higher
extract solids concentrations, meaning lower desorbent usage and reduced
evaporation requirements.

Ho, et al. (10) have compared these two types o f adsorbents in terms o f
fundamental characteristics such as capacity, selectivity and adsorption
kinetics. Here we can expand on their results and discuss other properties
of the two types of adsorbents that are equally important to commercial oper-
ability. Elution chromatographic results of Ho, et al., are summarized in
Table 5. Particle based adsorption equilibria are similar for both ad-
 463

sorbents, w i t h fructose/glucose s e l e c t i v i t e s on t h e order o f 1 . 5 - 2 . 4 .

S i m i l a r r e s u l t s have been seen i n UOP t e s t s . There i s , however, a large
d i f f e r e n c e i n mass t r a n s f e r c o e f f i c i e n t s between the r e s i n and t h e z e o l i t i c
adsorbent i n the data reported by Ho, e t a l . , w i t h values t h a t are 4-5 times
slower f o r the r e s i n adsorbent. Analogous t e s t s run by UOP on commercial
a d s o r b e n t show t h e same trends, w i t h values t h a t are 2 - 3 times slower f o r t h e
r e s i n system tested. These substantial d i f f e r e n c e s i n mass t r a n s f e r r a t e s
r e f l e c t i n t h e c y c l e time d i f f e r e n c e s experienced i n continuous operation o f
these two adsorbents.

TABLE 5
Adsorption c h a r a c t e r i s t i c s o f z e o l i t e s and r e s i n s (Ref. 10).

EQUlUBRlUM MASS-TAINSFER
SOURCE MATERIAL CONSTANT COEFFICIENT
KFRUCTOSE KQLUCOSE (1 I KK)F, SK (1 I KKk;, S6C

HO,ET AL. Ca-Y (300p) 0.68 0.44 13 12

DUOUTE (300,~) 0.46 0.31 67 141
ZEROUTE (300p ) 0.49 0.21 61 139
UOP leu, 9

As reported by Ho, e t al., the z e o l i t e and the r e s i n adsorbents show d i f -

f e r e n t adsorption isotherm c h a r a c t e r i s t i c s , p a r t i c u l a r l y a t higher concen-
tration. The r e s i n adsorbents have an isotherm t h a t i s s l i g h t l y concave
upwards, whereas t h e z e o l i t e isotherm i s l i n e a r , o r even s l i g h t l y concave
downwards. Resins, therefore, would have an advantage i n a Sarex operation
t h a t involves a h i g h feed sol i d s concentration.

Apart from such fundamental parameters as s e l e c t i v i t y , capacity and mass

t r a n s f e r rate, t h e r e are other l e s s t a n g i b l e f a c t o r s t h a t p l a y an important
p a r t i n the commercial v i a b i l i t y o f a Sarex adsorbent, namely pressure drop
c h a r a c t e r i s t i c s and adsorbent 1 i f e .

Pressure O r O D C h a r a c t e r i s t i c s -- I o n exchange r e s i n s are compressible

and e x h i b i t a c h a r a c t e r i s t i c s t r e s s / s t r a i n r e l a t i o n s h i p as shown i n Figure
7. I n a d d i t i o n they undergo shrink/swell as a r e s u l t o f osmotic pressure
v a r i a t i o n r e s u l t i n g from concentration changes. Z e o l i t e adsorbents are r i g i d
464

an d d o n o t e x h i b i t much s t r a i n w i t h p r e s s ure. When r e s i n s a r e used as ad-

sorbents, t h e i m p l i c a t i o n s o f shrink/swell and c o m p r e s s i b i l i t y must be con-
s i d e r e d i n o r d e r t o ensure s a f e o p e r a t i o n below t h e d e s i g n p r e s s u r e drop.
The p re s s ure d ro p c a n o f t e n become a m a j o r f a c t o r i n t h e d e t e r m i n a t i o n o f
maximum t hro ughpu t .

F i g . 7 . C o m p r e s s i b i l i t y c h a r a c t e r i s t i c s o f adsorbents.

Adsorbent L i f e -- Long t e r m s t a b i l i t y under rugged c o n d i t i o n s i s a v e r y

i m p o r t a n t c h a r a c t e r i s t i c o f an adsorbent. Z e o l i t e s by t h e i r v e r y n a t u r e a r e
n o t v e r y s t a b l e i n an aqueous environment. We have f ound t h a t t h e y have t o
be s p e c i a l l y f o r m u l a t e d t o enhance t h e i r s t a b i l i t y i n o r d e r t o o b t a i n s e v e r a l
y e a r s o f service. P o l y m e r i c r e s i n s do n o t s u f f e r f rom d i s s o l u t i o n problems.
However, t h e y a r e prone t o chemical a t t a c k (11).

FUTURE DIRECTIONS FOR SORBEX

We h a v e a l r e a d y shown t h e p r o m i n e n t p o s i t i o n o f t h e Sorbex process i n
s e v e r a l a p p l i c a t i o n s f o r t h e p r o d u c t i o n o f h i g h p u r i t y chemicals on a com-
m o d i t y scale. Many o f t h e s e processes were a t t r a c t i v e when t h e y were f i r s t
i n t r o d u c e d t o t h e i n d u s t r y , and c o n t i n u e t o i n c r e a s e i n v a l u e as UOP works t o
d e v e l o p improved adsorbents, d e s o r b e n t s and process designs. I n t h e UOP
P a r e x * pro c es s alone, t h e r e have s o f a r been t h r e e g e n e r a t i o n s o f adsorbent
 465

and f o u r g e n e r a t i o n s o f desorbent. A t t h e same time, t h e r e i s reason t o

e x p e c t t h a t t h e Sorbex process can be a p p l i e d t o a much more d i v e r s e range o f
p r o b l e m s t h an t h o s e presented i n Table 4 . T h i s i s even more l i k e l y w i t h t h e
d i s c o v e r y and a v a i l a b i l i t y o f new m a t e r i a l s --
p a r t i c u l a r l y molecular sieves
and z e o l i t e s -- f o r use as adsorbents. Over t h e y e a r s UOP has i n v e s t i g a t e d
many new a d s o r p t i v e s e p a r a t i o n s as a r e s u l t o f general market s t u d i e s as w e l l
as s p e c i f i c c l i e n t i n t e r e s t .

The v a l u e o f many chemical p r o d u c t s , from p e s t i c i d e s t o pharmaceut icals

t o h i g h performance polymers, i s based on unique p r o p e r t i e s o f a p a r t i c u l a r
i s o m e r f rom which t h e p r o d u c t i s u l t i m a t e l y d e r i v e d . I n t h e case o f t r i s u b -
s t i t u t e d aro ma t i c s t h e r e may be as many as t e n p o s s i b l e geomet ric isomers
( F i g u r e 8), whose r a t i o i n t h e m i x t u r e i s det ermined by e q u i l i b r i u m . Often
t h e p u r i t y re qu i r e m e n t s f o r t h e d e s i r e d p r o d u c t i n c l u d e an upper l i m i t on t h e
c o n t e n t o f one o r more o f t h e o t h e r i s o m e r s . T h i s i s a complicat ed
s e p a r a t i o n problem, b u t o f t h e k i n d where numerous p r o p e r t i e s o f z e o l i t i c ad-
s orb ent s o f f e r t h e g r e a t e s t chances f o r success.

& bBC
C
A

& B

& ac
A

B @Jc B B

B 4 C

F i g . 8. Geometric isomers o f t r i - s u b s t i t u t e d aromat ics.

FUTURE ADSORBENT NEEDS

A s u r p r i s i n g l y l a r g e number o f i m p o r t a n t i n d u s t r i a l s c a l e s e p a r a t i o n s
c a n b e accomplished by t h e r e l a t i v e l y small number o f z e o l i t e s t h a t a r e com-
466

m e r c i a l l y available. The discovery, c h a r a c t e r i z a t i o n and commercial a v a i l a -

b i l i t y o f new z e o l i t e s and molecular sieves may very l i k e l y m u l t i p l y t h e
number o f p o t e n t i a l s o l u t i o n s t o separation problems. I n t h e f u t u r e , we hope
t o see a wider v a r i e t y o f pore diameters, pore geometries, hydrophobicity i n
new z e o l i t e s and molecular sieves, as w e l l as more p r e c i s e c o n t r o l o f com-
p o s i t i o n and c r y s t a l l i n i t y i n e x i s t i n g z e o l i t e s . These accomplishments w i l l
help t o broaden t h e a p p l i c a t i o n s f o r adsorptive separations, and may very
l i k e l y l e a d t o improvements i n separations t h a t are c u r r e n t l y i n commercial
practice.

CONCLUSIONS
The Sorbex process i s one o f t h e most widely used adsorptive separation
technologies i n t h e chemical i n d u s t r i e s today. Z e o l i t e s have played a c r u c i a l
r o l e i n i t s successful a p p l i c a t i o n , p a r t i c u l a r l y i n t h e petrochemical indus-
try. I n aqueous service, care must be taken i n t h e f o r m u l a t i o n o f z e o l i t i c ad-
s o r b e n t s . The b e n e f i t s o f improved mass t r a n s f e r and p a r t i c l e r i g i d i t y must
be balanced against the shape o f t h e adsorption isotherm and feed s o l i d s
concentration.

The v e r s a t i l i t y o f z e o l i t e s i n the c o n t r o l o f adsorption s e l e c t i v i t y by

changing t h e framework, Si/A1 r a t i o and the c a t i o n makes them one o f the most
p r a c t i c a l classes o f adsorbents. The widespread use o f Sorbex processes f o r
l i q u i d phase adsorptive separation provides a strong basis f o r developing and
s c a l i n g up new l i q u i d phase separations i n areas such as biochemicals, f a t s
and o i l s and i n d u s t r i a l chemicals. The a v a i l a b i l i t y o f new z e o l i t e s , o r i m -
provements i n e x i s t i n g z e o l i t e s , may s i g n i f i c a n t l y expand t h e number o f
Sorbex applications.

* UOP, Sorbex, Molex, Olex, Sarex and Parex are trademarks and/or
service marks o f UOP I n c .
 461

REFERENCES

1. S e p a r a t i o n and P u r i f i c a t i o n : C r i t i c a l Needs and O p p o r t u n i t i e s .

N a t i o n a l Research C o u n c i l Report, N a t i o n a l Academy Press, 1987.

2. D. M. R u t h e v e n , " P r i n c i p l e s o f A d s o r p t i o n and A d s o r p t i o n , "

Processes. John W i l e y and Sons, New York, 1984.

3. 6. E. K e l l e r 11, " I n d u s t r i a l Gas Separat ion" (T. E. Whyte, e t al.,

Eds.), ACS Symposium S e r i e s No. 223, Washington, DC, (1983).

4. D. B. B r o u g h t o n , " A d s o r p t i v e Separat ions- L i q u i d s " , K i rk-Othmer,

Encyclopedia o f Chemical Technology, Vol. I, 3 r d ed., John W i l e y &
Sons, New York, NY, 1978.

5. R. M. B a r r e r , " Z e o l i t e s and C l a y M i n e r a l s as S o r b e n t s and

M o l e c u l a r Sieves," Academic Press, London, England, 1978.

6. R. T . Yang, "Gas S e p a r a t i o n by A d s o r p t i o n Processes", B u t t e r w o r t h

S e r i e s i n Chemical E n g i n e e r i n g , 1986.

7. D. B. B r o u g h t o n , e t a l . , "The P a r e x P r o c e s s f o r Recovering
m - X y l e n e , " Chem. Ens. Proq., 66 (9), 70 (1970).

8. J. A. Johnson. S. R. Raghuram and P. R. Pujado, "Olex: A Process

f o r Producing H i g h P u r i t y O l e f i n s , " Presented a t t h e AIChE Summer
N a t i o n a l Meeting, M i n n e a p o l i s , MN, August 1987.

9. Handbook o f P e t r o l e u m R e f i n i n g Processes, R. A. Meyers, ed.,

McGraw H i l l , New York, NY, 1986.

10. C . Ho, e t a l . , "A Comparative Study o f Z e o l i t e and Resin Adsorbent

f o r t h e S e p a r a t i o n o f Fructose-G1 ucose Mixt ures, " I n d . Enq. Chem.
Res., 26, 1407 (1987).
11. S.A. F i s h e r and G. O t t e n , "Sloughage o f O rganic M a t e r i a l f rom
F i e l d D e c r o s s l i n k e d S u l f o n i c A c i d C a t i o n Exchange Resins," Proc.
o f t h e 4 2 n d I n t e r n a t i o n a l W a t e r Conf . , Eng. SOC. o f W .
Pennsylvania, P i t t s b u r g h (1981).
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

GAS O I L DEAROMATIZATION BY ADSORPTION

A . L A K T I C , J.MUHL, I.BECK and M.BEER

INA-Research and Development, Proleterskih brigada 78, 41000 Zagreb
(Yugoslavia)

ABSTRACT
Gas o i l 228/286OC (37.3 w t X o f aromatics) was d i s s o l v e d i n low-aromatic
gasoline 76/117OC and dearomatized by adsorption on z e o l i t e 13X. The c y c l i c
fixed-bed adsorption was performed under m i l d c o n d i t i o n s , and aromatics were
desorbed c o u n t e r c u r r e n t l y by displacement w i t h ammonia a t a higher temperature.
The r e f i n e d gas o i l product was c o l o u r l e s s and odourless and meets US FDA
requirements f o r technical-grade white o i l s i n a l l wavelength regions o f UV
absorption except 300 - 320 nm. The d i f f e r e n c e s o f t h e o u t l e t p t r e a m
composition i n r e l a t i o n t o the o r i g i n a l gas o i l were determined by H NMR
spectrometry. The r e s u l t s confirmed the s p e c i f i c aromatic a d s o r p t i o n a f f i n i t y
on z e o l i t e 13X. The y i e l d s i n r e l a t i o n t o t h e gas o i l consumption were: low
aromatic product 29.95 w t % , t o t a l desorbed product 33.52 w t % and p a r t i a l l y
dearomatized gas o i l 36.53 w t X .

INTRODUCTION
Contact w i t h lubricant-based o i l s over an extended time i s associated w i t h a
r i s k o f inducing d e r m a t i t i s and s k i n cancer. Petroleum d i s t i l l a t e s i n t h e
l u b r i c a t i n g o i l b o i l i n g range may c o n t a i n a wide v a r i e t y o f p o l y c y c l i c aromatic
hydrocarbons, some o f which a r e known t o be potent carcinogens ( 1 ) . To overcome
such hazards these petroleum d i s t i l l a t e s have t o be a d d i t i o n a l l y r e f i n e d . A
number o f r e f i n i n g steps, such as e x t r a c t i o n w i t h s o l v e n t s , hydrogenation a t
varying s e v e r i t i e s , treatment w i t h s u l f u r i c a c i d and f i l t r a t i o n through b a u x i t e
or c l a y s a r e - c u r r e n t l y i n use. Although t h e c a t a l y t i c hydrogenation i s probably
most i n t e r e s t i n g ( 2 , 3 ) , adsorption w i l l p o s s i b l y meet t h e requirements, if
market demands a r e s m a l l .
There a r e some r e p o r t s ( 4 , 5 ) t h a t i t i s p o s s i b l e t o remove small q u a n t i t i e s
o f aromatics from gas o i l f r a c t i o n s by a d s o r p t i o n on z e o l i t e 13X. Adsorbed
aromatics can be desorbed by d i s p l a c i n g them w i t h p o l a r compounds such as NH3
CO, NO, C02 ( 5 ) .
The i n v e s t i g a t i o n s presented i n t h i s paper were begun, bearing i n mind t h e
Yugoslav market demands f o r 3000 - 5000 t / y o f low-aromatic gas o i l f o r s p e c i a l
applications .
470

EXPERIMENT
Gas o i l 228/286OC, obtained by d i s t i l l a t i o n o f a Yugoslav crude m i x t u r e , was
dissolved i n low-aromatic g a s o l i n e 76/11 7 O C , and dearomatized by a d s o r p t i o n on
zeolite 13X. Characteristics of gas oil 228/286OC, low-aromatic gasoline
7 6 / 1 1 7 T and the s o l u t i o n are given i n Table 1.

TABLE 1
C h a r a c t e r i s t i c s o f gas 0 i l 2 2 8 / 2 8 6 ~ CI l l , low-aromatic gasoline 76/117OC / 2 / and
the gas o i l s o l u t i o n / 3 / .

Characteristic 1 2 3 Method

Gas o i l content, w t % 100 - 33.33

V i s c o s i t y a t 4OoC, mnL/s
-
S p e c i f i c g r a v i t y a t l5OC 0.8697
2.80
0.6929
-
0.7460
1.18
I S 0 3675
ASTM D 445
Distillation, OC 228/286 76/11 7 761281 JUS E. H8.028
Aromatics, w t % 37.3* 0.44** 12.43***
vol% - 0.50 - ASTM D 1319
H aromatic, % 4.2 - -
Corrosion, Cu 3h, 5OoC C 1 A - ASTM D 130-74

* determined by NMR spectrometry (6)

** determined by UV spectrometry (UOP 495 - 75)
*** c a l c u l a t e d (37.3 x 0.3333) w t %

Experiments were performed i n the bench s c a l e adsorption equipment, designed

and constructed i n our own workshop ( F i g . 1 ) . The c y c l i c fixed-bed adsorption
was c a r r i e d out from the l i q u i d phase under m i l d c o n d i t i o n s , and aromatic
hydrocarbons were desorbed c o u n t e r c u r r e n t l y by displacement w i t h annnonia a t a
higher temperature.
The adsorption step was finished when the bed was saturated with
aromatics.The column hold-up was emptied by n i t r o g e n ; amnonia was added f o r
displacing previously adsorbed aromatics, and because of the better bed
r e a c t i v a t i o n the r e c i r c u l a t i o n system was a c t i v a t e d a t the same moment as the
bed heating up t o 30OoC was s t a r t e d . Nitrogen was used as a r e c i r c u l a t i n g gas
( a c t u a l l y a nitrogen/amnonia m i x t u r e was r e c i r c u l a t e d ) . The system pressure was
close t o one atmosphere. During the r e c i r c u l a t i o n two p o r t i o n s o f e f f l u e n t were
collected, the f i r s t up t o l4OoC ( a t the bottom o f the bed) and t h e second
above t h i s temperature. Amnonia desorbing d u r i n g t h e bed heating was absorbed
i n an a c i d t r a p a t t h e o u t l e t .
The o u t l e t streams were analysed a f t e r amnonia and gasoline s e p a r a t i o n by
 471

STREAMS
@ feed
@ product
FEED 0 nitrogen
RESERVOIR @ amonia
recirculating
@ m i x t u r e N2/NH3
@ column hold-up

@ ;;u;
0 desorbate
mixture

ROTAMETER

PREHEATER

COLUMN/
ZEOLITE 13X BED RECIRCUL A TING
A COMPRESSOR

VAL VES
1 - feed i n l e t
2 - product outlet
- N i n l e t (emptying
LIQUID
t 6 e column)
- NH3 i n l e t S€PARA TOR

3 - column hold-up o u t l e t
4 - recirculation i n l e t
5 - recirculation outlet
@
---- 1
6 - desorbate o u t l e t m

DESORBA TE ABSORP .
ACID
Fig. 1. Schematic o f experimental apparatus
 P
-E5
3

TABLE 2
Characteristics of low-aromatic gas oil / l / , oartially dearomatized gas oil 121, desorbate <140°C (bottom) /3/, desorbate
>140°C (bottom) /4/ and the regenerated solvent /5/

Characteristic 1 2 3 4 5 Method
Specific gravity at 1 5 O C 0.8078 0.8342 0.8562 0.8916 0.6942 I S 0 3675
Distillation, OC 109/287 109/291 101/275 125/289 76/129 JUS. B.HB.028
Aromatics, vol% - - - - 1.63 ASTM D 1319
H aromatic, % 0.2 2.4 5.4 9.3 -
UV Absorption, max/cm (FDA)
280-289 nm (4.0) 3.5
290-299 (3.3) 3.3
300-329 nm (2.3) 3.2
330-350 nm (0.8) 0.5
Corrosion Cu 3h, 5OoC - - - - 3A ASTM D 130-74
Yields, kg/100 kg 13X 12.53 15.28 6.17 7.85
% wt (from the gas oil consumption) 29.95 36.53 14.75 18.77
 473

d i s t i l l a t i o n . Their composition was changed i n comparison w i t h t h e o r i g i n a l gas

o i l . The differences were determined by NMR spectrometry through a hydrogen
f u n c t i o n a l group d i s t r i b u t i o n . I t i s p o s s i b l e t o determine t h e hydrogen content
for the following functional groups: - 9.0 ppm, Ha,),
aromatic r i n g s (6.5
6-alkyl groups t o aromatic r i n g (2.0 - 3.8 ppm, He I , h,p ... CH, CH2 t o
aromatic r i n g and p a r a f f i n i c CH, CH2 ( 1 .O - 2.0 ppm, Ha ), and h , p . .. CH3 t o
aromatic r i n g and p a r a f f i n i c CHJ ( 0 . 5 - 1.0 ppm, H b 1. The aromatic resonance
area c o n s i s t s o f monoaromatic-ring proton s i g n a l s (Hir from 6.5 - 7.05 ppm) and
condensed-aromatic-ring proton s i g n a l s ( H i ; from 7.05 - 9.0 ppm). Thus i t i s
possible to estimate the relationship between the condensed and the
monoaromatic systems. NMR spectra were obtained by a Varian EM-390 NMR
spectrometer without s o l v e n t . The i n t e r n a l standard was TMS.
The aromatic content o f l o w - x o m a t i c product was determined by UV a b s o r p t i o n
o f u n d i l u t e d samples, i n t h e wavelength regions d e f i n e d by US FDA requirements
f o r technical-grade w h i t e o i l s ( 2 ) , w i t h a UV-VIS Pye Unicam spectrometer.

RESULTS AND DISCUSSION

The o u t l e t stream c h a r a c t e r i s t i c s a f t e r t h e a m o n i a and g a s o l i n e s e p a r a t i o n
by d i s t i l l a t i o n a r e given i n Table 2. I t should be mentioned t h a t s u b s t a n t i a l
s o l v e n t losses i n t h e d e s o r p t i o n s t e p were noted.
Lowering o f t h e i n i t i a l b o i l i n g p o i n t s o f a l l gas o i l streams, as w e l l as
e l e v a t i o n o f the f i n a l p o i n t o f d i s t i l l a t i o n o f t h e regenerated s o l v e n t , a r e
caused by the separation procedure.
The s p e c i f i c g r a v i t y changes and the aromatic hydrogen content a r e r e l a t e d
t o a composition change o f a p a r t i c u l a r stream. A t t e n t i o n should be p a i d t o t h e
q u a l i t y changes o f t h e regenerated s o l v e n t , because i t s r e u t i l i z a t i o n could
become impossible because o f increased aromatic content and o f products o f
c o r r o s i v e nature.
The low-aromatic gas o i l i s c o l o u r l e s s and odourless and meets US FDA
reqirements f o r technical-grade w h i t e o i l s i n a l l wavelength regions o f UV
absorption except 300 - 320 nrn.
Since the adsorption of the aromatics is essentially physical, the
structural c h a r a c t e r i s t i c changes o f the o u t l e t streams a r e caused almost
exclusively by the hydrocarbon distribution depending on its adsorption
a f f i n i t y t o z e o l i t e 13X. Z e o l i t e 13X could a l s o a c t c a t a l y t i c a l l y a t increased
temperatures causing a c a t a l y t i c c r a c k i n g o f hydrocarbons, but t h i s a c t i v i t y i s
l i m i t e d by using ammonia as displacement agent.
The differences in structural characteristics of outlet streams are
i l l u s t r a t e d by the data presented i n Table 3.
As a r e s u l t o f t h e removal o f aromatics, t h e hydrogen content o f aromatic
 *
-a
P

TABLE 3
Distribution of the hydrogen on functional groups of the gas o i l 228/286OC and the outlet streams of the dearomatization
1
process by H NMR saectrometry

Gas oil 228/286OC 4.2 9.3 49.1 37.4 49 51 0.96

Low-aromatic gas oil 0.2 3.6 52.1 44.2
Partially dearomatized gas o i l 2.4 8.0 50.0 39.6 61 39 1.56
Desorbate (140OC (bottom) 5.4 11.0 46.3 37.3 50 50 1
Desorbate >14OoC (bottom) 9.3 15.8 42.7 32.2 43 57 0.75
 415

r i n g s f H a r ) and A - a l k y l groups (HA I of t h e low-aromatic gas o i l i s diminished

compared t o the values o f t h e o r i g i n a l gas o i l . The hydrogen content o f h,~..
-alkyl groups (Hfi , H p a r e increased. A s i g n i f i c a n t increase of the
p r o p o r t i o n Ha /Har (from 2.2 t o 1 8 ) p o i n t s t o a p r e f e r e n t i a l a d s o r p t i o n o f t h e
less substituted aromatics, which is in agreement with their specific
adsorption a f f i n i t y t o z e o l i t e 13X.
S t r u c t u r a l c h a r a c t e r i s t i c s o f t h e p a r t i a l l y dearomatized gas o i l a r e changed
w i t h respect t o t h e o r i g i n a l gas o i l , too. The data show, simultaneously,
n e a r l y 2 - f o l d increase o f t h e p r o p o r t i o n H&/H;; ( f r o m 0.96 t o 1.561, which
implies a change of the aromatic hydrocarbon nature (to prevailing
monoaromatics), and o n l y a l i t t l e increase o f t h e p r o p o r t i o n H a / H a r ( f r o m 2.2
t o 3 . 3 ) . I n s p i t e o f t h a t , i t i s allowed t o use t h e p a r t i a l l y dearomatized
process stream as feed i n t h e next adsorption step.
The increased Har and Hd c o n t e n t , decreased H f i content, f i x e d H p , and
almost unchanged p r o p o r t i o n H a r /Ha'; o f t h e desorbate below 14OOC ( b o t t o m ) ,
i n d i c a t e t h a t , besides t h e monoaromatics, some condensed aromatics a r e desorbed
as w e l l . I t i s p o s s i b l e t h a t t h e a l k y l chains o f t h e s u b s t i t u t e d aromatics a r e
s h o r t e r than those o f t h e o r i g i n a l gas o i l .
The most significant changes are found in the desorbate above 140OC
( b o t t o m ) . Remarkable increases o f t h e aromatic hydrogen (Har) and d - a l k y l
hydrogen (Hd ) content and decreases o f t h e &,p...-a l k y l hydrogen (He, H f i )
content, indicate the desorption of the condensed aromatic hydrocarbons
s u b s t i t u t e d by s h o r t e r a l k y l chains. These data c o n f i r m t h e n e c e s s i t y for
i n c r e a s i n g the temperature w i t h the a p p l i c a t i o n o f amnonia as t h e displacement
agent, and i f e f f e c t i v e regeneration o f t h e z e o l i t e bed i s desired.

CONCLUSION
Results of the investigation proved the possibility of gas oil
dearomatization by adsorption from gas o i l s o l u t i o n on z e o l i t e 13X. The r e f i n e d
gas o i l product was c o l o u r l e s s and odourless, meeting US FDA requirements f o r
technical-grade w h i t e o i l s i n a l l wavelength regions o f UV a b s o r p t i o n except
300 - 320 nm.
The y i e l d s i n r e l a t i o n t o t h e gas o i l consumption were: low-aromatic product
29.95 wt%, t o t a l desorbed product 33.52 wt%, and p a r t i a l l y dearomatized gas o i l
36.53 wt%, which might be used as feed i n t h e next adsorption step.
The composition o f o u t l e t streams i n r e l a t i o n t o the o r i g i n a l gas o i l was
changed. The d i f f e r e n c e s determined by ' H NMR spectrometry confirmed the
s p e c i f i c adsorption a f f i n i t y o f aromatics on z e o l i t e 13X.
The increase o f the aromatic content o f t h e s o l v e n t , i t s c o r r o s i v e nature
and the substantial solvent losses in the desorption step suggest that
476

investigations of t h e process under more severe a d s o r p t i o n c o n d i t i o n s and

without gas o i l d i s s o l u t i o n a r e s t i l l necessary.

REFERENCES
1 T.M. Warne, C.A. Halder, Lubr. Eng. 42, 2 (1886) 97-103.
2 W. H i m e l , T . Anstock, R. Spahl, K. Kussner, Erdol und Kohle-Erdgas-
-Petrochentie v e r e i n i g t m i t Brennstoff Chemie, 39, 9 ( 1 9 8 6 ) 408-414.
3 F.M. Nooy, S.R. Lee, J.R. YOeS, " A p p l i c a t i o n o f K e t j e n f i n e 840ft, Ketjen Cat.
.
Symp '86.
4 M.N. F r i d , 1. V . Borisova, E . V . Zubareva, Neftepererabotka i n e f t e h i m i j a . 9
(1977) 31-33.
5 J.L. Robertson, W.R. Epperly, U S . Pat. 3,476,822 1969.
6 J. Muhl, V . S r i f a , 6 . Mimica, M. Tomadkovid, Anal. Chem., 54 (1982) 1871-
-1874.
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

MODELING DIFFUSION PATHWAYS IN MFI MATERIALS BY TIME-RESOLVED

POWDER DIFFRACTION TECHNIQUES

B. F. MENTZEN
Laboratoire de Physico-Chimie Min6rale IA, U.A du CNRS No. 116, Blt. 731, UniversitC
Claude-Bernard,LYON I, 43 Ed du 11 Novembre 1918. F-69622 Villeurbanne, France.

ABsTRAm
Interpretation of time-resolved X-ray powder diffraction data (TRXRD) by profile analysis,
shows that the spontaneous desorption of a high-coverage MFUp-xylene system (8 sorbate
molecules/uc) yielding the low-coverage one (up to 4 sorbate molecules/uc) proceeds via a
two-phased system. Similar results are observed for the MFUbenzene system. Rietveld-type
refinements of diffraction profiles show that the distributions of the sorbed molecules in both
saturated systems are different. Preliminary results on the MFUpyridine and MFUtoluene systems
are also presented.

INTRODUCTION
MFVsorbate systems have been extensively investigated this past decade by using several
complementary techniques. Single-crystal(refs. 1,2) or powder diffraction (refs.3.4) and solid-state
deuterium NMR (ref.5) or BSi masNMR (ref.6-9) have proven to give valuable information on the
nature of some sorbent/sorbate interactionsin these systems.
In the case of low-coverage MFVp-xylene (ref.10) and benzene (ref.11) systems (labelled
XYLI and BENZI forms respectively), Rietveld-type refinements of X-ray powder diffraction
profiles (ref.12) and computer-assisted graphical simulations show that in both systems the organic
guest is localized near the channel intersections (4c sites at y=1/4,3/4 of the Pnma space group).
Site-occupancy factor refinements yield 2.67(7) p-xylene/uc and 3.55(8) benzenehc (ref. 13).
Interpretation of Fourier-differencemaps shows that the p-xylene molecules (labelled xyll') have
their long axis parallel to the straight channel (fig.lb) and present partial disorder (hindered
rotation), whereas the benzene molecules (labelled benzl') lie on the m mirror plane of the Pnma
space group (fig.ld) and present rotational disorder (an almost sphericalrotator).
In the case of saturated highcoverage phases containing a eight organic guest molecules per
unit-cell (refs.5,14,15) it has been shown that for the MFUp-xylene phase at room temperature
(labelled XYLII phase), two distinct xyll and xy12 sorbate molecules are localized near the channel
intersections and in the sinusoidal channel junctions (fig.la) with 4.08(6) and 3.92(8) mole/uc
respectively (refs.16.17). Neutron powder diffraction on a saturated MFI/benzene system at 77K
(labelled BENZIIb phase) shows that there are three distinct locations for the benzene species
(refs.4,18) : the benzla and benzlb species form a cluster at the channel intersections, and benz2
sites near the inversion centers (fig.le) in the snaight channels (4b sites at y=O,1/2) with 2.43(3),
2.36(3) and 3.26(4) mole/uc for the three benzene types respectively. Figure 1 represents the
410

schematic hydrocarbon distribution in the XYLYXYLII and BENZUBENZII phases respectively.

BENZIIb corresponds to ref.4 and BENZIIa to our results (vide infra).

’ 1’ (d)BENZ I

Fig. 1. Schematic hydrocarbon distribution

in the Wp-xylene and benzene systems.

I ( e ) BENZ i I b

It has recently been shown that time-resolved X-ray powder diffraction (TRXRD) might give
some complementary information on the structural modifications of sorbendsorbate systems
undergoing spontaneous desorption (refs.19.20). Results concerning the desorption of saturated
highcoverage MFI/p-xylene, toluene, benzene and pyridine systems are presented.

EXPERIMENT
The usual experimental conditions are described in refs.19 and 20. The investigated MFI
material is a boron-substitueted ZSM-5 (3.2 B/uc). The W s o r b a t e systems have been prepared by
pouring directly the anhydrous just-calcined and nearly-cooled material into airtight bottles
containing an excess of the liquid aromatic hydrocarbon. Complete sorbendsorbate interaction is
ensured after three days. For TRXRDexperiments, step-scannedprofiles have been obtained in the
 479

22.5-25 and 44.5-47'213 regions, by using a standard Philips PW1720 diffractometer, which has
been automated via an Apple II micro-computer. In order to slow down the benzene desorption at
room temperature, the sample has been covered with a 5 pm thick polyester film. The crystallinity of
the investigated materials has been checked by using a method described elsewhere (ref.21), and the
distribution of the guest molecules in the MFI/sorbate systems determined by recording and refining
(ref. 12) some XRD step-scanned profiles (6-48'28 range) corresponding to various MFI/sorbate
compositions.

22.5
'2 8 25
c
.
..I

$
-
c)

0 4 22.5 25
'2 8
Jh@)

Fig. 2. Time-resolved XRD profiles for the MFI/p-xylene system. (a) 3D plot, (b) five selected
profiles and (c) kinetic interpretation.

RESULTS

Figure 2a represents a 3D-TRXRD plot (22.5-25'28 region) corresponding to the spontaneous

XYLII + XYLI desorption reaction. In figure 2b five selected profiles are directly compared.
Profile analysis andor peak-height analysis (full details in ref. 20) of the XRD trace corresponding
to t = 31 hours, clearly shows that the investigated system is a mixture of two distinct oxthorhombic
Pnma phases : in order to simulate the complete spectrum we need ten individual components (the
relative intensities and angles in '28 are given in fig.3b). If we just use the five components
corresponding to a single 501/051/151/303/133 quintuplet, the simulation cannot be achieved
(fig.3~).The peak-shape parameters used for these graphical simulations have been determined by
analyzing the isolated 013 peak at 20.325 028 (fig.3a).
480

I000 23185
(b) t-31 h 360 2329
270 2339
460 2348
.-x
c)
105 2382

--
In 350 2391
5 150 2400
c
\ // 140 2410
63 2445
160 24523

20.05 .2e 20.525 22 6 24 as

'2 0

1000 23 190
570 23470
375 23915
Fig. 3. Peak-shape analysis. (a) Profile 170 24055
x 175 2451
analysis of the 013 reflection (Hk : full .-
c)

width at half maximum in 028, As : a

c)

asymmetry parameter, n :peak shape w

parameter of the Pearson VII function

T 1 , , , , , ,
(ref.12). r : ul/a2ratio) . (b) graphical 22 6
'2 8
24 a5

simulation of the profile observed at

t = 31 h (fig.2b) by using ten components
and (c) by using five components.

Similar analysis of all the TRXRD profiles enables one to determine the relative amounts of the
XYLII and XYLI phases. Accordingly, the desorption reaction might be formulated as :
MFv8p-xyl + np-xyl? + (l-n/4)MFV8p-xyl + n/4MFV4p-xyl [l]
(XYLII form) (p-xylene gas) (XYLII form) (XYLI form)

If the amounts of the XYLII phase (the x=l-n/4 values) in the desorbing system are plotted
versus the square-root of time, the straight line represented in figure 2c is obtained. The average
dimensions of the investigated B.ZSM-5 sample being 90x15~15pm, the overall diffusion
coefficient Dd=0.4x10-10cm*s-1corresponding to the spontaneaous desorption of an MFV p-xylene
system may now be calculated from the line represented in figure 2c, and compared to values
reported in the literature (ref.22). The desorption proceeds monotonically. and accordingly, it might
be assumed that there are no specific sorbenthbate or sorbate/sorbate interactions during reaction
[11. Thamm et al. have observed that there are unusual coverage dependences of the calorimetrically
determined molar heats of adsorption of benzene (ref.14) and toluene (ref.23) on silicalite. In order
to determine if such unusual behaviour can be evidenced by TRXRD experiments, B.ZSM-5
samples have been saturated with benzene, toluene and pyridine and further investigated.
 481

Figures 4a, b and c show some selected time-resolved XRD profiles corresponding to the
MFUbenzene (protected), toluene and pyridine systems respectively. The profile at t 4 8 h (figda)
corresponds to a monoclinic m n z e n e low-coverage phase which contains slightly less than
four benzenehc; accordingly. the monoclinic/orthorhombic phase transition occurs when the benzl'
species occupy completely the channel intersections (vide supra fig.1d). All the other individual
profiles correspond to orthorhombicsingle or two-phased systems.

I 2
5

.x
c)

!
c1
c
I

22 5 '29 25
MFVbenzenu

Fig. 4. Selected XRD profiles. (a) MFI/benzene,(b) toluene and (c) pyridine systems.

Interpretation of the individual MFI/sorbate TRXRD profiles by using the above mentioned
method shows that for all the investigated systems the spontaneousdesorption seems to proceed via
a two-phased system. As previously developed in the case of an Wp-xylene system (refs. 19,20),
investigation of another characteristic angular domain (the 44.5-46.5 '20 region where the
10,0,0/804 and 0,10,0 medium intensity peaks appear) yields essentially the same results. The
time-dependence of the desorption for the MFI/benzene and toluene systems are reported in figures
5a and b and directly compared to the results given i n ref.14 and ref.23 respectively. For the
pyridine system only the unit-cell content versus tln dependence is given (fig&). Compared to the
p-xylene one (fig.2c), all the other systems exhibit unusual behaviour. In order to interpret these
observations, the localizations of the guest organic molecules in both the high- and low-coverage
MFVsorbate systems had to be determined. Hence, the corresponding step-scanned XRD profiles
collected in the 6-48'2e range have been exploited by using the direct-characterization method
(refs.10,24).Full details concerning the Rietveld refinements will be published elsewhere.
482

i13-
s
7
P
0

3 6
bemene/uc

Fig. 5. Kinetic interpretation of the TRXRD

experiments. Comparison of kinetic and
calorimetric results (ref.14) for the (a)
4 MFI/benzene and (b) toluene systems
t
respectively. (c) the MFUpyridine system.
0 4 8
Jtime (h)

For the discussion, some preliminary results are reported in Table 1. Under our experimental
conditions, the distribution of the sorbed molecules in the saturated MFI/benzene system
corresponds to fig.lc. Critical interpretation of an intermediate data-collection corresponding to a
BENZII/BENZI mixture (overall coverage about 7.2 benzenehc), shows that benzene-
clusterizarion at the channel-intersections (fig.le) might only be observed for partially desorbed
high-coverage phases. A partial plot of the observed/calculated/differencespectra corresponding to
the refined (Rp/Rb = lS.Ol7.8%; for the definitions of Rp and Rb see ref. 12) BENZII
high-coverage phase is given in fig.6a. For the MFUtoluene system, the hydrocarbon distribution is
comparable to that observed for p-xylene (fig.la and lb), and the Rietveld plots for the
high-coverage TOLII form (Rp/Rb = 16.6/8.1%) are reported in fig.6b. If the low-coverage TOLI
complex is further desorbed, the orthorhombic/ monoclinic phase transition can be observed. The
Rietveld refinement (Rp/Rb = 14.6/8.8%) of the profile corresponding to the high-coverage PYRII
complex (fig.6~)can be achieved by distributing the pyridine molecules statistically over all the
possible sites, i.e., the 4c sites at y=1/4,3/4, the sinusoidal channel junctions, and the 4b sites at
y=0,1/2.

DISCUSSION
As far as B.ZSM-5 materials are concerned, it is clearly shown that time-resolved XRD might
be used as a complementary technique for the investigation of sorbent/sorbateand/or sorbate/sorbate
interactions in some MFVsorbate systems.
 483

.-x
c)

:
L

24
'20
MpUtOlun* ryrl.m

Fig. 6. Rietveld refinements. Observed

(full-line), calculated (+) and difference
partial plots for the high-coverage (a)
m n z e n e , (b) toluene and (c) pyridine
systems.

a 24
"20
MFUpyidim ryrbrn

Table 1. Unit-cell parameters for high @) and low (I) coverage B.ZSM-S/sorbate
systems (3.2 B/uc)

XYL II* 20.014(3) 19.721(3) 13.378(2) 5280(2) +31(4)

XYL I 19.908(3) 19.812(3) 1 3.307(2) 5249(2)
TOL II 19.970(1) 19.727(4) 13.369(1) 5267(2) +13(6)
TOL I 19.938( 1) 19.787(7) 13.319(2) 5254(3)
BENZ I1 19.934(3) 19.875(3) 13.325(2) 5279(2) -28(4)
BENZ I 20.021(3) 19.805(3) 13.383(2) 5307(3)
PYR I1 19.984(3) 19.888(3) 13.358(2) 5309(2) -34(4)
PYR I 20.062(3) 19.859(3) 13.410(2) 5343(2)
* XYL, TOL, BENZ, PYR for p-xylene, toluene benzene and pyridine
sorbates, respectively

Interpretation of TRXRD profiles observed for the above-mentioned saturated W s o r b a t e

systems shows that the high + low-coverage reaction [l] (spontaneous desorption) may be
generalized. The results given in Table 1 show that the sorbate-induced structural changes are
different for the X W O L and BENZPYR complexes, i.e., in the first case, the high- --t low-
coverage wansfonnation corresponds to a unit-cell volume decrease (31 and 13 A 3 respectively),
484

whereas in the second case, the reverse situation is observed (28 and 34 A3 volume expansions,
respectively). Accordingly, when interpreting calorimetric (refs.14.23) or 29SimasNMR (refs.6,9)
results concerning such MFUsorbate systems containing more than four guest molecules/uc, the
structural modificationsof two-phased systems have to be considered.
Furthermore, in order to get a better knowledge of the desorption mechanisms and elaborate
realistic diffusion pathways, the distribution of the individual guest molecules for all the overall
loadings between 4 and 8 molecules/uc have to be established. But as already stated in ref.18,
Rietveld refinement concerning single-phased MFI materials is not a trivial problem, and refining
two-phased MFI systems is far more complex. Nevertheless, by considering a 7.2 benzene/uc-
containing system as a singlephase (vide supra), Rietveld refinements show that the XRD profile is
better approximated if the benzene molecules adopt the distribution (benzene-clusterization at the
channel-intersections)given by Taylor (ref. 18).
Accordingly, as far as MFUbenzene and toluene systems are concerned, our results are
consistent with those reported in the literature (refs.5,14,18,23). These preliminary TRXRD
investigationson some MFI/sorbate. systems have now to be further developed in order to determine
if the nuo-phase problem might be generalized for other systems and/or topologies.

REFERENCES
1 K.J. Chao, J.C. Lin, Y.Wang and G.H. Lee. Zeolites, 6 (1986) 35-68.
2 H. van Koningsveld, H. van Bekkum and J.C. Jansen, Acta Cryst., B43 (1987) 127-132.
3 C. Baerlocher, in D.H. Olson and A. Bisio (Editors), Proceedings of the Sixth International
Zeolite Conference, Reno, USA, July 10-15, 1983, Butterworth, UK, pp. 823-833.
4 J.C. Taylor, Zeolites, 7 (1987) 311-318.
5 R. Eckman and A.J. Vega, J. Phys. Chem., 90 (1986) 4679-4683.
6 C.A. Fyfe, G.J. Kennedy, C.T. De Schutter and G.T. Kokotailo, J.Chem.Soc., Chem.
Commun., (1984) 541-542.
7 G.T. Kokotailo, C.A. Fyfe, G.J. Kennedy, G.C. Gobbi,H. Strobl, C.T. Pasztor,
G.E. Barlow, S. Bradley, W.J. Murphy and R.S.Ozubko, Pure & Appl. Chem., 58
(1986) 1367-1374.
8 J. Klinowski, T.A. Carpenter and L.F. Gladden, Zeolites , 7 (1987) 73-78.
9 C.A. Fyfe, J.H. OBrien and H. Strobl, Nature, 326 (1987) 281-283.
10 B.F. Mentzen et F. Vignt-Maeder, Mater. Res. Bull., 22 (1987) 309-321.
1 1 B.F. Mentzen, Mater Res. Bull., 22 (1987) 337-343.
12 D.B. Wiles and R.A. Young, J. Appl. Cryst., 14 (1981) 149-151.
13 B.F. Mentzen, Mater. Res Bull., 22 (1987) 489-496.
14 H. Thamm,Zeolites, 7 (1987) 341-346.
15 C.G. Pope, J. Phys. Chem., 90 (1986) 835-837.
16 B.F. Mentzen, F. Bosselet et J. Bouix, C.R. Stances Acad.Sci.,Ser.B,305 (1987) 581-584.
17 B.F. Mentzen and F. Bosselet, Mater. Res. Bull., 23 (1988) 227-235.
18 J.C.Taylor, J.Chem.Soc., Chem. Commun., (1987) 1186-1187.
19 B.F. Mentzen, F. Bosselet et J. Bouix, C.R. SCances Acad. Sci., Ser. B, 306 (1988) 27-32.
20 B.F. Mentzen, J. Appl. Cryst.. 21 (1988), 266-271.
21 R. Khouzami, G. Coudurier, B.F. Mentzen and J.C. Vedrine. in P. Grobet, W. Mortier,
G. Schulz-Ekloff and E. Vansant (Editors), Studies in Surface Science and Catalysis, Vol.
37 (1988), Elsevier, Amsterdam, NL, pp. 355-363.
22 Y.T. Ma, T.D. Tang, L.B. Sand and L.Y. Hou in Y. Murakami, A. Iijima and J.W. Ward
(Editors),Proceedings of the Seventh International Zeolite Conference, Tokyo, Japan,
August 17-22, 1986, Elsevier, NL. pp. 531-538.
23 H. Stach, H. Thamm, J. Jiinchen, K. Fiedler and W. Schirmer, in D.H. Olson and A. Bisio
(Editors), Proceedings of the Sixth InternationalZeolite Conference, Reno, USA, July
10-15, 1983, Butterworth, UK, pp. 225-231.
24 B.F. Mentzen, C.R.Stances Acad. Sci., Ser. B, 303 (1986) 1299-1303.
H.G.Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
Amsterdam - Printed in The Netherlands
0 1989 Elsevier Science Publishers B.V.,

MEASUREMENT OF INTRACRYSTALLINE DIFFUSIVITIES OF HZSM-5 ZEOLITE AT HIGHER

TEMPERATURES AND PREDICTIONS OF SHAPE SELECTIVITY

K. HASHIMOTO, T. MASUDA and M. KAWASE

Department of Chemical Engineering, Kyoto University, Kyoto 606 (Japan)

ABSTRACT
A model is developed which describes the activity and the shape selectivity
of methylation of toluene to produce xylenes over HZSM-5 zeolite catalysts by
taking account of both intracrystalline diffusion and acid strength
distributions inside and outside the crystallite. The shape selectivity is
strongly affected by the relative rates of intracrystalline diffusions of
hydrocarbon molecules. Uptake curves of amounts of benzene, toluene and
xyleneisomers adsorbed on high-silica HZSM-5 zeolites, which have no catalytic
activities, were measured in the range of temperature from 373-673 K.
Effective intracrystalline diffusivities were calculated from the uptake curves
over the temperature range. The ratio among the diffusivities of para-, meta-
and ortho-xylene was about 1 O : l : l in the above temperature range. Each acid
strength distribution of acid sites inside and outside the crystallite was
measured by combining the two methods developed by us. Rate constants of
methylation and isomerizations of xylenes inside and outside the crystallite
were estimated by performing these reactions over two kinds of the catalysts:
one has acid sites only inside the crystallite, the other only outside the
crystallite. Using these values, the proposed model was found to predict well
the apparent shape selectivity. A chart based on the proposed model was also
presented which provides a guide in preparing more highly selective HZSM-5
catalysts f o r the methylation of toluene.

INTRODUCTION
HZSM-5 zeolite catalysts show high shape selectivity, since they have very
fine micro-pores located inside the zeolite crystallites, the diameter of which
is almost equal to sizes of mono-aromatic molecules. HZSM-5 catalysts are
typical solid-acid catalysts, and their acid sites are distributed not only
inside but also outside the crystallite. Therefore, the shape selectivity of
HZSM-5 catalysts are affected strongly by the size of the crystallite, the
magnitude of the intracrystalline diffusivities of hydrocarbons and the acidic
properties inside and outside the crystallite (ref. 1). Reactions are usually
carried out at temperatures higher than 5 7 3 K. Although data of
intracrystalline diffusivities at lower temperatures have been published,, few
diffusivities at such higher temperatures have been reported (ref. 2). No data
is available for the accurate acidic properties inside and outside the
crystallites of zeolites. Wei (ref. 1 ) presented a mathematical model for
describing the shape Selectivity of HZSM-5 zeolites, in which the reaction on
the outer surface of the crystallite'was ignored, and the validity of his model
486

Fig. 1 Model for methylation

of toluene over HZSM-5 zeolite.

was not examined experimentally.

An improved mathematical model is presented for describing the shape
selectivity of HZSM-5 zeolite by taking account of intracrystalline diffusion
and acid strength distributions inside and outside the crystallite. The
methylation of toluene to produce xylene-isomers w a s performed. The
intracryatalline diffusivities at higher temperatures and the acid strength
distributions both inside and outside the cryatallite was directly measured,
and then these data were used to examine the validity of the proposed model.

U-TICAL MODH. FOR SWPE SELECTIVI'K

The methylation of toluene to produce xylene-isomers and the isomerization
of xylenes occur over HZSM-5 zeolite catalyst. In order t o develop a
mathematical model, follcwing assumptions and simplifications were made: 1 ) The
concentration of toluene is large enough to simplify the kinetics and assume
the rate of the methylation to be of first-order with respect to methanol. 2)
The diffusion of methanol inside the crystallite is so rapid in comparison with
the rate of the methylation that its concentration can be regarded as almost
constant, C A , inside the crystallite. The validity of this assumption was
confirmed by the fact that the modified Thiele modulus for the methylation of
toluene inside the crystallite was less than 0.1. 3) The rates of methylations
per unit surface area inside and outside the crystallite are approximately the
same to each other. The surface area outside the crystallite was less than 1 X
of that inside the crystallite. Hence, the methylation occurring outside the
crystallite was ignored. 4 ) The resistance to diffusions of xylene-isomers is
large inside the crystallite, resulting i n the decrease in the rate of the
isomerization of xylenes inside the crystallite. The selectivity of the
isomerization of xylenea inside the cryetallite is different from that outside
the crystallite. Therefore, the isomerizations of xylenes inside and outside
the crystallite were considered.
With these considerations, the methylation of toluene with methanol proceeds
 487

Methylation of toluene Isomerizations of xylenes

%ENpm
X p o t R A : methanol kOm
B: toluene
A+B -P,+R P: xylenes
R: water
b PP +R
P
P
Subscript S is added to all symbols
of rate constants for reactions
out side cryst allite )

Fig. 2 Stoichiometriea of mL*hylation of toluene and

isomerizations of xylene-isomers.

by the following steps (see Fig. 1): 1 ) Diffusion of toluene and methanol into
the zeolite crystallite. 2) Methylation of .toluene over acid sites inside the
crystallite. 3 ) I s o m e r i z a t i o n o f x y l e n e s over acid sites i n s i d e the
crystallite. 4 ) Diffusion of xylenes produced inside the crystallite toward the
outside of the crystallite. 5) Further isomerisation of xylenes over acid sites
on the outer surface of the crystallite.
The stoichiometry of the reactions occurring in the above steps 2), 3) and
5) are shown in Fig. 2. On the basis of the physico-chemical steps shown in
Fig. 1 , mass balance equations for xylene-isomers were obtained over a
d i f f e r e n t i a l catalytic reactor, and w e r e solved analytically. The
concentrations of xylenes, (Co,Cm,Cp)out in the exit gas are given by

where
. . 1

D
k=(ko ,km ,kP IT, D=( Dm \, N=(
H
Hm '), K=(
kom+kop
-k
-kmo
k +k -k
'0 D
P
' \O np/ \ -k
om

OP
mo mp
-k
mp
k
PO
pm
+k
pm
J
Here, K in Eqs. ( 1 ) and (2) represents a matrix of rate constants of the
isomerization of xylenes inside the crystallite, whereas Ks is that outside the
crystallite. However, Wei (ref. 1 ) ignored this matrix. Subscripts 0, m and
p, respectively, represent ortho-, meta- and para-xylene and "out" and l1inl1
refer to the outlet and the inlet gas streams, whereas subscript S means the
outside of the crystallite. tI repres,ents a matrix of.Henry constants for
adsorption on the outer surface of the crystallite. p is a density of the
crystallite, w and vo are the mass of the zeolite crystallite and the flow rate
of gas, respectively, and h i 2 (i=1,2,3) are eigenvalues and P represents a
matrix of eigenvector. When these values are known, the concentrations of the
xylene-isomers in the outlet gas can be calculated by use of Q. (1). Then the
para-shape selectivity is easily obtained by Cp/(Co+Cm+Cp). The selectivity
488

Table 1
Physico-chemical properties of IIZSM-5 zeolites used in this work.
depth of outer surface shape of
catalysts Si/Al crystallite of crystallite crystallite
2L [WI a,,,[ m2/kg 1

HZSM-5(1) 25 1.9 1650 cubic

HZSM-5(2) 65 1.3 2415 cubic
HZSM-5(3) 20 2.1 1494 cubic
SilicaI.ite(1) 3.4 923 cubic
~iiicalite(2) m 2.7 1163 cubic

calculated thus represents an initial differential selectivity under the

condition that the conversion of methanol approaches zero. This value is
regarded as a representative index of the para-shape selectivity.

PREPARATION OF CATALYSTS
Several kinds of HZSM-5 zeolites and silicalites (high-silica HZSM-5) listed
in Table 1 were prepared hydrothermally from reactive aluminosilicate gels
containing tetrapropylammonium bromide as template in the range of temperature
from 4 3 3 to 4 7 3 K . The prepared zeolites were found to have the
characteristics of the HZSM-5 zeolites by analysis of X-ray diffraction. The
crystal sizes of the zeolites were measured by scanning electron microscopy and
are also listed in Table 1. In order to discriminate each contribution of two
kinds of acid sites located inside and outside the crystallite to the
reactivity and the selectivity of the HZSM-5 zeolite, two modified zeolites,
was HZSM-5 zeolite,
%atalyst-Itt and Ilcatalyst-S", were prepared. ttCatalyst-Itt
acid sites distributed only inside the crystallite, and was prepared by a
modification of the method proposed by Beyer et al.(ref.3). Vatalyst-S" was
zeolite having acid sites only outside the crystallites, and was obtained by
thermal treatment with AlC13 (ref.4).

MEASUREMENT OF INTRACRYSTALGINE DIFFUSIVITIES

Silicalite, which has no catalytic activity for the cracking and the
isomerization of adsorbates, was used in the diffusion experiment. The
intracrystalline diffusivities for xylene-isomers were measured over the
temperature range from 473 to 673 K by use of the apparatus shown in Fig. 3. A
small amount of sample (25-50 mg) was held in vacuum at 873 K. Pure vapor of
adsorbate was introduced, and then the transient change in the total pressure
was recorded by use of a piezometric sensor with transducer (Baratron type
221A, MKS), the response of which is first enough to measure accurately the
transient change in pressure. To eliminate the influence of several factors
(such as mass conductivity between the sorbent and the pressure sensor) on the
transient change in pressure, the blank test was performed without zeolite. By
comparing the data of the blank test with that with zeolite, an uptake curve of
the amount of adsorption was obtained, as shown in Fig. 4. The diffusivity, D,
was calculated by comparing the uptake-curve with the following theoretical
equation (ref.5):
 489

r------------ 1

Fig. 3 Apparatus for measurement

of effective intracrystalline
diffusivity.
(1)sample (2)adsorbate (3)helium
vacuum ( 5 ) heater (6)recorder

1
1

I-:::: 0.0 10

0.008
f0.5 OD0 6
I

aoo 4
aoo z
_ _
- a 0
0 0.2 0.4 0.6 0.0 I 1.2
0 1000 2000
t [I1 equllibrkrm pressure C kPal

Fig. 4 Transient changes in amounts Fig. 5 Linear relationship

of adsorbed xyleneisomers. between adsorption amount
para-xylene : equilibrium pressure and equilibrium pressure.
=110 Pa,
M, =1.04~10-~ mol/kg,
partition fac or 68.9
meta-xylene : 262, 1.25x10-$ 76.9
ortho-xylene: 520, 3.83~10'~: 81.3

where the qns are the non-zero positively roots Of

and a=V/(a,wHL), Mt and M, are the amount of adsorption at time t and that
after infinite time, respectively, and L represents the half depth of the
crystallite. In this experiment, the amount o f sample was taken to be small
enough that the temperature rise caused by adaorption could be ignored, and
decrease in pressure was kept to within 10 X during adsorption, since equations
(3) and (4) were derived under the above conditipns. From the uptake curves of
490

I ' " " " " ' l " " 1

Fig. 6 Arrhenius p l o t s of e f f e c t i v e
intracrystalline diffusivities.

t h e amounts of adsorbed xylene-isomers, t h e i r d i f f u s i v i t i e s w e r e c a l c u l a t e d .

The t e m p e r a t u r e r i s e s were c a l c u l a t e d as 0.2 t o 0.8 I[ from t h e amounts and were
small enough t o f u l f i l l t h e i s o t h e r m a l conditions. The r e l a t i o n s h i p between
a d s o r p t i o n amount a n d e q u i l i b r i u m p r e s s u r e was f o u n d t o b e l i n e a r u n d e r t h e
c o n d i t i o n s of p r e s s u r e l e s s t h a n 1.47 kPa and t e m p e r a t u r e h i g h e r t h a n 473 K , as
t y p i c a l l y shown i n F i g . 5. Hence, t h e d i f f u s i v i t i e s w e r e i n d e p e n d e n t on t h e
a d s o r p t i o n amount a n d were e q u a l t o l l s e l f - d i f f u s i v i t i e s " d e f i n e d i n Darken's
equation (ref. 7).
F i g u r e 6 d e m o n s t r a t e s t h e A r r h e n i u s p l o t s of t h e d i f f u s i v i t i e s . The open
k e y s , O , A , u , v , O , r e p r e s e n t t h e d a t a o b t a i n e d i n t h i s work by u s e of two
s i l i c a l i t e s w i t h d i f f e r e n t c r y s t a l s i z e s l i s t e d i n Table 1. The each kind of
t h e k e y s l i e s on a s t r a i g h t l i n e , i n d i c a t i n g t h a t t h e i n t r a c r y s t a l l i n e
d i f f u s i v i t i e s were a c c u r a t e l y measured. Zikanova e t al. (ref. 2) measured t h e
i n t r a c r y s t a l l i n e d i f f u s i o n of benzene under t h e c o n d i t i o n s of a s e m i - i n f i n i t e
medium. The m e a s u r e d u p t a k e c u r v e c o u l d be e x p r e s s e d by Eq. ( 5 ) jn p l a c e of
Eq. ( 3 ) ( r e f s . 5 and 9)
W

_ --
Mt
1- r:
0
exp[-D(n+
1 2 2 t
5 ) m (.2)1 (5)
MQa n=O ( 2 n + 1 ) 'II L

They used, however, a f o l l o w i n g s i m o l i f i e d form of Eq. (5):

_ - 2A D
M t- (+Hi)
1/2@2
MW P
where A p and Vp a r e t h e s u r f a c e and t h e volume o f t h e c r y s t a l l i t e ,
r e s p e c t i v e l y . Equation (6) can be a p p l i e d only t o t h e uptake-curve for M t / M m <
0.3 ( r e f . 9 ) , i n which t h e t e m p e r a t u r e r i s e i s l i k e t o o c c u r and t o a f f e c t t h e
d i f f u s i v i t y . The i n t r a c r y s t a l l i n e d i f f u s i v i t y of benzene a t 33 K c a l c u l a t e d
f r o m t h e i r d a t a a t i n i t i a l p e r i o d ( F i g u r e 1 i n r e f . 2) by u s e of Eq. ( 6 ) was
 491

O.IS
1 1

- Calalyrl: HZSM-5
, 0 I I 3 . u 1 I - I . .
-
'

- crlcrnol surlacc Inlracryslalllnc

n
~
- (calculalcd from TPD sprclrum)
5
--3 0.10
crlcrnal surlocc
(Indicalor adsoplin
Fig. 7 Acid strength distribution
nE curves inside and outside
0.05 - t n r l h o j h - crystallite of HZSM-5 zeolite.

0 ''"''lT
--- --l-+--r-.
-/-.I I x I , ,

1.9~10-14m 2 / s , and that recalculated from their all data by use of E q . (5) was
8.6~10-l6m2/s (shown by closed circle key, , in Fig. 6. This discrepancy is
considered to be resulted from several reasons, such as the error caused by the
simplification used for derivation of Eq. (6) from Eq. (5) and the temperature
rise occurring at initial period of adsorption, at which Eq. (6) can be
applied. Hence, in this work, the intracrystalline diffusivities were
calculated from all data measured for long time by use of the exact equation
(Eq. ( 3 ) ) . The closed circle key 0 , as well as the closed triangle k e y A
measured for para-xylene (ref. 8), is considered to lie on the same line as our
experimental data. The diffusivity of para-xylene is the largest among three
xylene-isomers. This is considered to be resulted from the fact that the
effective molecular size of the para-xylene is the smallest. A difference
observed among diffusivities of xylene-isomers is smaller than those which have
been supposed.

ACIDIC PROPERTIES
Acid sites inside and outside the crystallite were discriminated from each
other and their acid strength distribution curves were accurately measured by
the indicator adsorption method (ref. 10) and the analysis of temperature-
programmed desorption spectrum of ammonia desorbing from the catalyst (refs. 12
and 13), as shown in Fig. 7, where HO is Hammett acidity function (ref. 11) and
g,(HO) is a density distribution function of acid strength Ho such that gmdHo
represents the number of acid sites of acid strength between Ho and HO+dHO per
unit mass of catalyst. Although a small amount of acid sites are distributed
on the outer surface of the crystallite, these sites 'decrease considerably the
para-shape selectivity, because the isomerization of xylenes over these acid
sites proceeds under conditions of no steric restriction. Hence, the existence
of acid sites on the outer surface of the crystallite cannot be ignored, as
discussed in the following sections.

ESTIMATION OF RATE PARAMHXFG

Isomerization of xylenes and methylation of toluene occur not only inside
but also outside the crystallite, as shown in Figs. 1 and 2. It is obviously
difficult to estimate the rate parameters of these reaction all at once.
Therefore, two kinds of catalysts were used in the reactions carried out in a
calculaled 1 rnela<30.0)l para-Xylene(68.5 % )
' Fig. 8 Comparison of c a l c u l a t e d
experimental ( 28.0) (65.2) shape s e l e c t i v i t y w ith

d i f f e r e n t i a l r e a c t o r a t 673 K t o e s t i m a t e t h e r e a c t i o n parameters: one i n which

a c i d s i t e s a r e d i s t r i b u t e d o n l y o n t h e o u t e r s u r f a c e of t h e c r y s t a l l i t e
(catalyst-S), t h e o t h e r having a c i d s i t e s only i n s i d e t h e c r y s t a l l i t e
(catalyst-I).
I s o m e r i z a t i o n o f one of t h e x y l e n e i s o m e r s , f o r e xa m ple p a r a - x y l e n e , was
c a r r i e d o u t by u s e of c a t a l y s t - I i n a d i f f e r e n t i a l r e a c t o r . The r e s u l t s
o b t a i n e d i n t h e e x p e r i m e n t wer e a n a l y z e d i n t e r m s of a r e d u c e d f o r m (Eq. (7))
o f Eq. (1).

Only t u o p a r a l l e l i r r e v e r s i b l e r e a c t i o n s o cc urre d t o produce o t h e r two xylene

i s o m e r s , o r t h o - an d met a- x y l en e, b e c a u s e t h e r e v e r s i b l e r e a c t i o n s and
i s o m e r i z a t i o n b e t w e e n o r t h o - an d met a- xyle ne c o u l d be i g n o r e d u n d e r t h e
conditions of a d i f f e r e n t i a l reaction. Hence, f r o m t h e v a l u e s of
c o n c e n t r a t i o n s of xylene-isomers i n e x i t g as of t h e r e a c t o r , two r a t e c o n s t a n t s
w e r e e s t i m a t e d for i s o m e r i z a t i o n of p a r a - x y l e n e t o o r t h o - and m e ta -xyle ne .
This k i n d of experiment and a n a l y s i s was r epe a te d for t h e remaining o t h e r two
x y l e n e i s o m e r s , y i e l d i n g t h e matrix (IS) c o n s i s t i n g of t h e r a t e c o n s t a n t s of
isomerization inside the crystallite.
I n a s i m i l a r way t o t h e c a s e of i s o m e r i z d t i o n i n s i d e t h e c r y s t a l l i t e , t h e
rate c o n s t a n t s (6s) of i s o m e r i z a t i o n o u t s i d e t h e c r y s t a l l i t e were e va lua te d by
u s e of Eq. (8) f r o m t h e r e s u l t s o f i s o m e r i z a t i o n s of x y l e n e i s o m e r s o v e r
c a t a l y s t - S.

By u s e o f t h e r a t e p a r a m e t e r s of i s o m e r i z a t i o n s i n s i d e and o u t s i d e t h e
c r y s t a l l i t e , t h e m a t r i c e s o f t h e r a t e p a r a m e t e r s a p p e a r i n g i n Eq. ( 1 ) were
e s t i m a t e d except t h a t of methylation (k). Methylation of toluene was performed
over c a t a l y s t - I . The rate p ar amet er s of m e thyla tion were e va lua te d from t h e
e x p e r i m e n t a l d a t a by u s e of a r e d u c e d f o r m (Eq. ( 9 ) ) 'of Eq. (1).

Thus, a l l of t h e r a t e p a r a m e t e r s a p p e a r e d i n E q s . ( 1 ) a nd ( 2 ) w e re
e s t i m a t e d . By use of t h e s e v al u es an d i n t r a c r y s t a l l i n e d i f f u s i v i t i e s , s h a p e
s e l e c t i v i t y of a c a t a l y s t having a c i d s i t e s i n s i d e and o u t s i d e t h e c r y s t a l l i t e
can be predicted.
A t y p i c a l comparison between c a l c u l a t e d and e xpe rim e nta l mole f r a c t i o n s of
t h e i s o m e r s f o r HZSM-5(3) i n Table 1 i s demonstrated i n Fig. 8, i n d i c a t i n g good
agreement between them.
 493

h
I -
v
meta-xylene
?al
! -
E
0
.-I
v)
-
aJ -
C Fig. 9 Effect of ratio of acid amount
5 0.5 -
9,
outside crystallite to that inside
-
0 - para-xylene -
crystallite on fractions of xylene-
isomers.

- 0
o4
1 1i2 1
acid amount outside crystallite
4-1
Ic, acid amount inside cryslallite

GUIDE TO THE PREPARATION OF CATALPST

An increase i n the relative amount, $, of acid sites outside the
crystallite decreases the para-shape selectivity. Figure 9 demonstrates the
effect of the $ value on the fractions of xylene-isomers calculated by use of
the proposed model. The para-shape selectivity was found to increase with the
decrease in the 0
value, namely the decrease in acid amount outside the
crystallite, because the selectivity becomes to be contro'lled by the
intracrystalline diffusion. Under these conditions, the shape selectivity is
affected by the crystal size.
Figure 10 shows the effect of the crystal size and the $ value on the
initial para-shape selectivity calculated by the proposed model. Curves in
this figure represent contour lines of the initial para-shape Selectivity.
Under conditions of a differential reactor, the maximum and minimum values of
the para-shape selectivity are 80 and 40 X , respectively. The area hatched in
the figure represents region with maximum selectivity, i.e. 80 X . Two keys,
and 'I,represent experimental data points measured for two HZSM-5 zeolites.
The figures in parentheses represent the observed selectivities. These values
are well predicted by the proposed model. The selectivity of the catalyst (v)
approaches almost the optimum value of the selectivity, viz. 80 X . The
selectivity of the other catalyst ( 0 ) may be improved by decrease in the
value, i.e., decrease in the acid amount outside the crystallite. Thus, the
chart shown in Fig. 10 gives a guide to the preparation of highly selective
HZSM-5 catalysts.

CONCLUSIONS
1) Diffusivities of xyleneisomers inside the crystallitee of pentasil zeolites
can be directly measured at higher temperatures 473-673 K. The ratio among the
diffusivities of para-, meta- and ortho-xylene was about 1O:l:l.
494

,para-shape Selectivity
1

Fig. 10 Dependence of para-shape

lC2 selectivity on crystal size and
ratio of acid amount outside
crystallite to that inside
the crystallite.

1 v

10-8 10-
0 crystal size L(m)
3

2) Acid strength distributions were measured inside and outside the

cryatallites of HZSM-5 zeolites. The contribution of acid sites outside the
crystallite to the para-shape selectivity can not be ignored.
3 ) An improved mathematical model was developed for describing the initial
differential selectivity of HZSM-5 zeolite by taking account of the
intracrystalline diffusion and acid strength distributions inside and outside
the crystallite. The proposed model was found to predict well the shape
selectivities of HZSM-5 zeolites.
4) A chart was presented for illustrating contour curves of para-shape
selectivity expressed in terms of crystal size and relative acid amount outside
the crystallite, which gives a guide for preparing high-selective catalysts.

REFERENCES
1 J.Wei, J.Catal., 76( 1982)433-439.
2 A.Zikanova, M.Buelow and H.Schlodder, Zeolites, 7(1987)115-118.
3 H.K.Beyer, I.M.Belenykaja, F.Hange, M.Tielon, P.J.Crobet and P.A.Jacobs,
J.Chem.Soc.Faraday Trans.1, 81 (1985)2889-2901.
4 C.C.Chan C.T.W.Chu, J.N.Miale, R.F.Bridger and R.B.Calvert, J.Am.Chem.
SOC., 1067\984)8143-8146.
5 J.Crank, The Mathematics of Diffusion, Clarendon Press, Oxford,Znd ed.,
1975.
6 R.M.Barrer and D.J.Clarke, J.Chem.Soc.Faraday Trans. 1 , 70(1974)535-548.
7 M.Buelow, P.Lorenz, W.Mietk, P.Struve and N.N.Samulevic, J.Chem.Soc.Faraday
Trans. I, 79 ( 1983) 1099-1 108.
8 Y.H.Ma, T.D.Tang, L.B.Sand and L.Y.Hou, Stud.Surf.Sci.Catal., 28( 1986)531-
538.
9 D.M.Ruthven, Principle of Adsorption & Adsorption Processes, John Wiley &
Sons, Tronto, 1984.
10 K.Hashimoto, T.Masuda, H.Motoyama, H.Yakushi j i and M.Ono, 1nd.Eng.Chem.
Prod.Res.Dev., 25( 1986)243-250.
11 K.Tanabe, Solid Acids and Bases, Academic Press, New York, 1970.
12 K.Hashimoto, T.Masuda and T.Mori, Stud.Surf.Sci.Catal., 28(1986)503-510.
13 K.Hashimoto, T.Masuda and Y.Takagi, Shokubai (Tokyo), 29( 1987)406-409.
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

MEASUREMENT OF HYDROCARBON DIFFUSION COEFFICIENT I N A NON-ISOBARIC

CHROMATOGRAPHIC COLUMN OF ZEOLITE CRYSTAL POWDER

E. AUST, W. HILGERT and G.EMIG

Institut fur Technische Chemie I, Universitat Erlangen-Nurnberg,
Egerlandstr. 3, D-8520 Erlangen (West Germany)

ABSTRACT
Chromatographic columns filled with powder of Linde Na-13X
crystals were used to measure diffusions coefficients of benzene and
various alkyl benzenes in the temperature range of 553 t o 673 K . The
influence o f the carrier gas pressure ( N z ) was tested by increasing
the latter t o as much as 140 bar. Finally, the concentration depen-
dence of the diffusion coefficient of benzene was determined at 573
and 598 K. The activation energies of diffusion and the sorption
enthalpies at infinite dilution showed a noticable correlation.

INTRODUCTION
The measurement of the diffusion rate of sorbates or reactants in
zeolites is crucial for the design and interpretation of the
performance of adsorption equipment and reactors which incorporate
molecular sieves. The experimental techniques to measure mass fluxes
of sorbed components in these materials are confronted with the
following problems:
I small diffusion coefficients
I highly exothermic sorption process
I very small particle size
Besides the classical sorption uptake method, chromatographic
experiments have evolved as a major source for reliable diffusion data
in zeolites. In addition, the NMR-technique has extensively 'been
utilized to determine self diffusion coefficients.
Unfortunately, one frequently encounters large discrepancies
between experimental diffusion coefficients in the literature. Often
this flaw is being attributed to unsatisfactory design of experiments
or improper measurement conditions.
496

METHODS
In this work we have tested the chromatographic method and measured
diffusion rates of aromatic hydrocarbons in 13 X zeolite. The
temperature range was 553 to 673 K , and the carrier gas pressure ( N z )
was elevated up to 140 bar. We also measured the concentration depen-
dence of the diffusion coefficient D for benzene by partially satura-
ting the carrier gas with this component and injection of the tracer
at the column inlet in the usual way. The chromatographic column was
filled with zeolite powder with dilution of the zeolite packing by
inert material to reduce the retention times. This method ensures a
more uniform gas flow as the Zero Length Column (ref.l3).Carrier gas
velocity was always high enough to ensure isothermal behaviour of the
sorption - diffusion process and exclude limiting external transport
resistance at the particle-gas interface.
In addition the influence of axial dispersion was eliminated by
high gas velocities and the pressure drop along the column axis
accounted for in the transport model o f the column. A very similar
model for chromatographic experiments with zeolite powder was given by
Chiang et al. (ref.1).
The Transport Model for the Nonisobaric Chromatoqraphic Column
Since we used unpelletized zeolite powder we could describe
the concentration distribution in the gas and particle phases by
the following equations:
gas phase:
( d?X
-) D a2X
= A*( + - - (-)ax t 3(1-~,; NRC
at cg L at E ~ L at Rc a 5
with

particle phase:
ac*
=o/Rf(apz
a2c* 2 a
x ( 6 )
-
at + P aP

c* ( P I t=O) =0 ( 7 )
(%*) . = 0 (Symmetry)
ap p=o
 497

The transport model i s based on the following assumptions:

* linear sorption equilibrium at solid-gas interface
* ideal gas behaviour in interparticle voids; v-l/p, Da,-l/p (ref.14)
* column pressure drop described by Blake-Kozeny equation
* Danckwerts-boundary conditions at column inlet and outlet
* isothermal column, no influence o f carrier gas on diffusion rate
* ideal concentration input function (Dirac)
In blank trials was shown that the influence of dead volume ist not
significant. The key parameters in eq. (1) and (2) are the adsorption
equilibrium constant K and the diffusion coefficient D .
Parameters were determined by fitting of numerically computed
elution curves to experimental data. The moment method was employed
to obtain parameter estimates. Details of the numerical procedure and
the nomenclature have been reported before (ref. 2).
Experimental Procedure
-
The flow chart of the experimental setup is shown schematically
in Fig. 1. The carrier gas flow rate was controlled by a flow con-
troller and maintained at constant pressure by an appropriate back-
pressure regulator (HITEC).
Before entering the steel column with the zeolite powder a high-
pressure sampling valve (VALCO) injected the content of the sample
loop into the carrier gas stream.
The column outlet gas stream was split and the smaller part of it
injected into the flame of a standard flame ionization detector
(DANI). The voltage signal was sampled at regular intervals by the
interface of a personal computer and stored on disk for off-line
processing.
The zeolite crystal powder (Na-13X o f Union Carbide: mean diameter:
2-3 pm)) was mixed with a certain amount of quartz sand (mean
diameter: 90 pm) and ratios of up to 100 parts of sand per 1 part of
zeolite. The column with inner diameter of 4 to 4.5 mm and lenght
between 20 and 40 mm was then filled with the zeolite - sand mixture,
-
sealed with stainless steel HPLC fittings and at last heated at 673
K overnight with continuous flow of nitrogen to remove moisture and
impurities from the adsorbent surface. The values for porosity cg were
about 0.7. The tracer was saturated in nitrogen at moderate pressures
(up to 3 bar) and passed through the sample loop of an injection
valve. The typical amount of injected tracer was approximately 3 ng.
For determining the concentration dependence of the diffusion rate of
benzene, the carrier gas stream was partially saturated with benzene
prior to tracer injection.
498

1 -

[D\--&-B
.rnpllller recorder
-
- _.healed IltleS

Fig. 1. Schematic flow diagram of experimental setup for chromato-

graphic measurements at high pressures.

EXPERIMENTAL RESULTS
Temperature Dependence of Limiting Diffusion Coefficient and Sorption
-
Equilibrium Constant
The assumption of constant diffusion coefficient D and linear
sorption equilibrium constant K requires very small amounts of injec-
ted tracer. Experimentally, this was accomplished by varying the
sample volume and checking the variation of peak retention time and
peak shape. This procedure is well known for chromatographic experi-
ments and seems essential before further evaluating the collected data
(ref.l,3). The mean retention time of the peaks could be influenced by
adjusting the proper column bed dilution ratio (less zeolite lowered
retention time) and setting the flow rate of the carrier gas. I n most
cases experimental peaks appeared between retention times of 30 and
120 seconds, where experiments showed that in this interval1 nonideal-
ities of the input peaks (finite input peak width) and dead volume
effects were insignificant in the evaluation of parameters from expe-
rimental peaks.
Measurement of sorption and diffusion of various aromatic hydro-
carbons were thus conducted at infinite tracer dilution within a
temperature range o f 553 to 673 K . Fig. 2 and 3 contain plots of
the experimentally determined diffusion coefficients D for benzene,
toluene, ethylbenzene as well as di-methyl and di-ethylbenzenes. The
 499

regression o f the lnD, respectively 1nK vs. 1 / T plots yielded the

activation energies of diffusion, Eact, and heat of adsorption, Hads,
respectively. Table 1 lists the values of these quantities for each
experimental system.

“ t
. IC-09
.
0
, 1 , , 1 1 , , ,,,,,,,I,, a , , , , I 11,,,,,1,, 4 1 I ,

1.45 1.5 1.55 1.6 1.65 1.7 1.75 1.8

I / T iia-3 P I

Fig. 2. Experimentally determined diffusion coefficients D for

benzene, toluene, ethylbenzene and 1-3-di-methylbenzene.

.IE-OB

k-4H
.5t-09

1 - 3- Di et hyl be n z e n e 1 -4-Diethylbenzene
.2E-09

0016 ,0017 .001a .on16 ,0017 ,0018

Fig. 3. Experimentally determined diffusion coefficients D for

1 - 2 - , 1-3-, 1-4-di-ethylbenzene.
500

TABLE 1
Experimental limiting values of heat of adsorption and activation
energy for diffusion in Na-13X zeolite
~

- 59.9 Benzene
- 69.3 Toluene
- 78.3 Ethylbenzene
Heat of Adsorption - 66.5 1-2-Diethylbenzene
AHads [kJ/mole] - 83.0 1-3-Diethylbenzene
- 95.8 1-4-Diethylbenzene
- 80.5 1-2-Dimethylbenzene
- 80.5 1-4-Dimethylbenzene
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
54.6 Benzene
69.4 Toluene
Activation Energy 72.0 Ethylbenzene
of Diffusion 43.4 1-2-Diethylbenzene
Eact [ k J / m o l 0 1 54.2 1-3-Diothylbonaono
95.1 1-4-Diethylbenzene
80.9 1-2-Dimethylbenzene
I 80.5 1-4-Dimethylbenzene

The magnitude of the diffusion activation energies is quite

striking. From the figures in Tab. 1 it seems that there is an unques-
tionable correlation between Eact and Hads for diffusion of aromatics
in Na-13X zeolite. This dependence of Eact with sorption strength
rather than molecular size and steric hindrance (compare values for
di-ethylbenzenes in Tab. 1) indicates that the passage of molecules
through the cage windows is not the limiting step for the diffusion
of these molecules. This is in agreement with potential calculations
of Ragaini and coworkers (ref.4) who showed that the corresponding
activation of ethylbenzene molecules for passing through the window
barrier of 13X cages would merely amount to approximately 1 2 kJ/mole.
The high values of Eact and Hads in this work are in qualitative
agreement with literature data given for sorption/diffusion of
aromatic hydrocarbons 'in various zeolites (see Table 2 ) .
The combination of high sorption enthalpies and highly temperature
dependent diffusion rates pose considerable problems for reliable
measurements of the simultaneous sorption and diffusion process.
Excellent sorption heat removal is, therefore, essential and renders
the chromatographic method superior t o sorption uptake measurements.
In addition, the use of unpelletized zeolite powder further facili-
tated the realization of isothermal conditions within the column.
 501

TABLE 2
Literature values of heat of adsorption and activation energy for
diffusion of aromatic hydrocarbons

Tracer Zeolite Temperature Exp. *, -AHads Eoct Author

[I 1 Method [ ~ / m o ~ e l motel
Benzene CeNa-Y 463-623 GC 56,a - Choudhary et al./ref.5/
Benzene Na-Y 613-713 GC 55 46 Fomi et al./ref.B/
- * _
Toluene Na-Y 613-713 GC 63 22
Ethylbenzene Na-X 403-477 s 74 27 Goddard et al. hef.61
p-Xylene Na-X 403-477 S 72 26 -,I-

m-Xylene Na-X 403-477 S 74 26 -I,-

o-Xylene Na-X 403-477 S a0 27 -I,-

Xylene Na-Y 613-713 GC 76-81 43-144 -"-

Xylene Na-Y 406-477 S 77-91 - Goddard et al. hef.101
Ethylbenzene Na-Y 406-477 S 90 - - I, -
Benzene 13 X 285-440 NMR - 19 Urger et al./ref.Il/
Benzene 13 X 400-450 s - 37 _ I -

o-Xylene 13 X 423-463 GC - 63 Ragaini et al. Iref.41

m-Xylene 13 X 423-463 GC - 103 _ I _

p-Xylene 13 X 423-463 GC - 45 _ I _

Ethylbenzene 13 423-463 GC - ioa _ * _

Benzene, Toluene
Na-X 293-473 NMR - 20-25 Germanus et al./ref.lZ/
Xylene
Neopentan Na-X 187-370 S - 14 B i i l o ~ et al. /ref.7/
Benzene Na-X 350-400 S - 25 BUow et al. /ref.9/

*) GC : Gaschromatographic method
S : Sorptionmethod
NMR: Selfdiffusion measurements (NMR-method)

One of the common problems with zeolite diffusion measurements is

the quite frequent discrepancy between values of D determined by
different experimental methods and zeolites of different origin and
particle size. As for the diffusion results in this work, direct
comparison is possible with data for benzene in Linde-13X of Ruthven
and Doetsch (ref.15) and also Karger and Ruthven (ref.11) (benzene in
large 13X crystals). In both cases diffusion data were collected by
the sorption uptake method. Extrapolation of the diffusion coeff i-
cients to the temperatures chosen in reference 15 showed fair agree-
ment (less than one order of magnitude) while the values o f D in
(ref.11) with the large 13X crystals were o f f by more than one order
of magnitude. It is not clear if this difference is to be attributed
to a different origin o f the zeolite crystals o r problems with the
502

diffusion measurements themselves, especially since data given in

(ref.11) for two different crystal size fractions showed large
deviations i n D.
-
Pressure Dependence of D and K
I n some of the above experiments the pressure drop across the
zeolite powder bed was considerable and exceded 10 bar. Since the
presence of the carrier gas was neglected in the mass balance
equations of the trace component, an experimental test of the validity
o f this assumption seemed indispensible. We, therefore, extended our
experiments into a pressure range that has hardly ever been reached by
previous measurements of diffusion in porous solids. In the same
fashion, as reported in the preceding section, diffusion coefficients
D and adsorption equilibrium constants K were determined for benzene
i n 13X in the temperature range of 573 to 663 K and carrier gas pres-
sures of u p to 140 bar (Nz). No significant alteration of the parame-
ters 0 and K was observed. An estimation of the adsorbed amount of
nitrogen under these conditions, using a generalized isotherm equation
(ref.16) gave pore filling factors for Nz of u p to 10% (ref.17). Since
the carrier gas molecules are expected to have a much higher mobility
than the more strongly adsorbed benzene molecules, the nonapparent
pressure dependence of D does not seem unexpected.
- -
Concentration Dependence of D
The limitation of the above experiments to highly diluted systems
( i n terms of tracer) is extremely dissatisfying to the engineer who i s
concerned with the design of chemical reactors or adsorption
equipment. It is, therefore, only logical to extend diffusion measure-
ments into the concentration ranges of practical interest. We adopted
a method that has been employed to determine adsorption isotherms by
chromatographic experiments, and used it t o evaluate the diffusion
coefficient at various concentrations of the trace component in the
zeolite (compare with procedure in (ref.18)). The carrier gas was
partially saturated with the trace component,’ here benzene, and an
additional tracer peak injected on top of this base concentration.
The diffusion ceofficient D can be considered c m s t a n t if the ratio of
peak height to base concentration height i s sufficiently small. The
determination of parameters D and K followed in the same fashion as
with pure carrier gas. Fig. 4 contains the concentration dependent
diffusion coefficient o f benzene at 573 K up to concentrations of
1.5 molecules of benzene per cage. It can be shown that for s u f f i -
ciently small peak heights the K parameter is no longer the ratio of
c*/cg but describes the slope of the isotherm at the base concentra-
 503

tion c*b. After collecting these slope values at various concentra-

tions the isotherm itself can be constructed by numerical integration.
I I I I I 1
r

t
I I

I
loe i
I
I

0 .L .I .I .4 .I .I .I .a .9 1.0 1.1 1.2 1.1 1.4 1.1

Konzentration [mol./csge]

Fig. 4 . The dependence of the diffusion coefficient of benzene on

the concentration at 573 K.

The experimental isotherms on the other hand can be used to compute

the correction factors in Darken's equation:
d In p
D = Do
d In c*

where dlnp/dlnc* is obtained from the experimental isotherm. The

corrected diffusion coefficients are plotted in Fig. 4 along with the
values of 0. The peculiar drop of D and D in the initial concentra-
tion range was previously reported for the same experimental system by
Ruthven and Doetsch (ref.15) at lower temperatures. After an initial
region, the diffusivities exhibit the usual increase with concentra-
tion. The thermodynamic correction for the increase of the activity of
the sorbate by the Darken equation can, obviously, give no explanation
of this unusual concentration dependence. One can therefore argue that
sorbate-sorbate interactions are responsible for the observed results.
Di'scussion of Results
One of the goals of this work was to demonstrate the feasability of
chromatographic diffusion measurements in zeolites over a wide range
of experimental conditions. Thus, the temperature was varied between
553 to 673 K and the pressure of the carrier gas was increased up to
140 bar. Within this range of conditions and for the different sorba-
tes employed in this work the diffusion coefficients varied over
almost three orders of magnitude. In order to avoid unfavorable ex-
perimental conditions under which diffusion parameters cannot be de-
termined reliably, column packing dilution with inert material and
504

adjustment of carrier gas flow rate were chosen. The presented method
is elegant in that it avoids simultaneous determination of axial dis-
persion and macro pore diffusion contribution (if bidisperse sorbent
was used). The chromatographic method was also shown to be capable of
measuring the cotlcentration dependence of the zeolite diffusion and
adsorption characteristic. The latter method can be extended to binary
diffusion measurements if the tracer is chosen as a substance dif-
ferent from the one that is used to saturate the carrier gas. If com-
ponent selective detectors were available, these measurements could be
extended into wider ranges of concentrations for the binary diffusion
system.

REFERENCES
1 Chiang, A.S.; Dixon, A.G.; Ma, Y.M.; Chem.Eng.Sci. 39 (1984)
1451-1459.
Aust, E.; Dahlke, K.; Emig, G.; Chem.Eng.J. 35 (1987) 179-
190.
F u , C.-C.; Ramesh, M.S.P.; Haynes, H.W.Jr.; AIChE J. 2
(1986)1848-1857.
Ragaini, V . ; Mazzola, E.; Bart, J.C.J.; Z. physik. Chem.
Neue Folge -
115 (1979) 43-50.
5 Choudhary, V.R.; Srinivasan, K.R.; Chem.Eng.Sci.a (1987)
382-385.
6 Goddard M.; Ruthven D.M.; Zeolites, a(1986) 275-289
7 Billow M.; Lorenz P . ; Mietk W.; Struve P . ; J.Chem.Soc Faraday
Trans 1,1983,79,1099-1108
8 Forni, L.; Viscardi, C.F.; Oliva, C.; J. Catal. 97 (1986)
469-479.
9 Biilow M.; Lorenz P . ; Mietk W.; Struve P.; J.Chem.Soc Faraday
Trans 1,1983,&2457-2466
10 Goddard, M.; Ruthven, D.M.; Proc. of 6th Int. Conf. on
Zeolites, Reno(Nevada) (Jul i 1983) , Butterworths ,
Guildford England, 1984, S. 268-275.
11 Karger, J.; Ruthven, D . M . ; J.Chem.Soc., Faraday Trans. I 11
(1981) 1485-1496.
12 Germanus, A , ; Karger, J.; Pfeifer, H . ; Samulevic, N.N.;
Zdanov, S.P.; ZEOLITES 5 (1985) 91-95.
13 Ruthven 0. M.; Eic M.; Zeolites,l988,t3,40-45
14 Carleton F.B.; Kershenbaum L.S.; Wakeham W.A.; Chem.Eng.Sci.
1978,2,1239-1246
15 Ruthven, D.M.; Doetsch, I . H . ; AIChE J. 2 (1976) 882-886.
16 Wakasugi, Y . ; Ozawa, S.; Ogino, Y . ; J.Colloid Interface Sci.
=( 1981) 399-409.
17 Aust, E.; PhD dissertation, University of Erlangen-Nurnberg,
1988
1 8 Kumar, R.; Duncan, R.C.; Ruthven, D.M.; Canad. J.Chem.Eng.
-
60 (1982) 493-499.
H.G.Karge, J. Weitkamp (Editors1, Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Mr)l-ECULAR MOBILITY OF BENZENE AND P-XYLENE I N MFI' TYPE ZEOLITES

M. BIJLOW, J . CARO, B. W5HL-MJHN and B. ZIBROWILlS

C e n t r a l I n s t , i t u t , e of P h y s i c a l Chemistry, Academy of S c i e n c e s of
t h e G.D.R., DDR-1199 B e r l i n , Rudower Chaussee 5 ,
(German Democratic R e p u b l i c )

ABSTRACT
I n f o r m a t i o n c o n c e r n i n g t h e dynamics of benzene and p - x y l e n e i n
MFI t y p e z e o l i t e s h a s been o b t a i n e d from s o r p t i o n u p t a k e measure -
rnents and from a l i n e s h a p e a n a l y s i s o f t h e '8 and 1 3 C NMH.
s p e c t r a . F o r b o t h m o l a o u l e s , t h e i n t , r a c ~ y s t alli n e d i f f u s i v i t i e s
d e t e r m i n e d by s o r p t i o n u p t a k e and treated by t h e Darken e q u a t i o n
d e c r e a s e w i t h i n c r e a s i n g sorbate c o n c e n t r a t i o n . p-Xylcne shows a t
h i g h c o n c e n t r a t i o n A much more restricted m o b i l i t y t h a n benzene.
From t h e NMR spectra i t f o l l o w s t h a t t h e s o r b e d benzene molecule^^
perform f a s t r e o r i e n t a t i o n s a b o u t t h e i r hexad axes. Superimposcd
OII t h i s C6- r e o r i e n t . a t : i o n , t h e benzene m o l e c u l e s jump between
' I intion s i t e s . The mean rc:siclenc:e t , i m e bet.ween two suc:c:eeding
j i p p s depends s i g n i f i c a n t l y on tsmperal;ure and s o r b a t e c u n a e n t r a
1.iot-i. W i t h j u s t i f i e d ~ s s u m p t i o n sf o r t,he jump lengt.hs, c I i f f u s i v i - -
t i e s f o r benzene can be estimated. These da1;a are i n good agree .
l i m i t , w i t h t h o s e d e t e r m i n e d by s~.irpI,ioriu p t a k e mmsurc:rricnt.s,

INTRODUCTION
MFI t y p e z e c 1 1 i t . e ~show a h i g h cat.alytict acA,ivit,y. Since t h e
o a t a l y t i c reac1;im p r o c e e d s w i t h i n t h e z e o l i t ic v o i d volume,
a c c u r a t e knowledge of t h e i n t r a c r y : i l . a l l i n e d i f f u s i u n of nrcrl~:cular
species i n v o l v e d i n t h o r e a c t i o n is needed t o f u l l y u n d o r s t a m l
the mechanisms (of t h e p r o c e s s , and a l s o tm model t h e c!l.JmpleX
b e h a v i o u r of t h e c a t a l y t i c system. The s o r p t i o n k i r i n t i c s and
iriolecular dynamics of benzene arid p - - x y l e n e have btteri inve:A.,igatxd
t o o b t a i n r e l i a b l e i n f o r m a t i o n 011 t h e i r i n t r a c r y s t a l l i n c m o t i o n s .
506

crystal s u r f a c e which t a k e s a c t i v e l y part; i n t h e m a s s t r a n s p o r t

and t h e volume of t h e c r y s t a l s , r e s p e c t i v e l y . The o b t a i n e d d i f f u -
s i v i t i e s , D, were c o r r e c t e d for t h e s o r p t i o n i s o t h e r m c u r v a t u r e
by means of t h e Darken e q u a t i o n , D = Do(61n p/61n c ) ~ I. s o t h e r m a l
e v a l u a t i o n of t h e d a t a is j u s t i f i e d because t h e i n f l u e n c e of t h e
s o r p t i o n h e a t g e n e r a t e d d u r i n g t h e u p t a k e p r o c e s s w a s minimized
by an a p p r o p r i a t e c h o i c e of e x t e r n a l t h e r m a l c o n d i t i o n s (Tv To, >
T, and To b e i n g t h e t e m p e r a t u r e of t h e s o r p t i o n v e s s e l (zeolite
crystals) and t h e d o s i n g volume ( g a s e o u s p h a s e p r i o r t o s o r p t i o n
u p t a k e ) , r e s p e c t i v e l y ; c f . ( r e f . 1 ) ) . The u p t a k e measurements
were c a r r i e d o u t w i t h i n t e m p e r a t u r e and p r e s s u r e r e g i o n s r a n g i n g

---
f c u n 274 t o 423 K and lo-' t o 10 t o r r , respectively. The MFI
samples used are l i s t e d i n Table 1 .

Table 1
ht,umatics/MFI s y s t e m s i n v e s t i g a t e d by s o r p t i o n u p t a k e .
.. - __ -.......-.I.--._-________ . ...

sorbate sorbent Si / A 1 .c.ry?t.&l-gi---2

z e/p m-.
- .--2
cr y st a 1
habit,
b - 4(V/A) /cm
_..... .. --____. .
p-xy 1m e
o-xylene (Na,H) -ZSM-5 135 3 f r . ~ f 5 _ 10
.~ polyhedral
benzene * (a) 3 . 6 2 lo-.7---- twinninge

benzene ( NFI, H) --zsM--~' *50 55 x 12__

.- x 10 polyhedral
(b) 2 . 9 7 - 1 0 "T - monocrystn 1s
benzene i 1ical itc.-l"+> 1000 190 X 56 Z 2 . 5 polyhedral
(1:) 4 64 *
I monocryst a 153
benzene* s i 1i o a l i t c - 1' > 1000 _3>2._5_~-15 s p h e r u l i t i c :
(d) 8.79 - t w inn i n g s
.* -- . .. ~.
.. ~ __ __
+ Data p u b l i s h e d i n ( r e f . 4 )
+,. MFI samples used for t h e NMR measurements, c f . (refs. 5 , 6 , 7 ) .
Fur t h e q u a l i t y of t h e z e c ~ l i t e sused cf. F i g . 1 as example.

Nt.1 H mmsLI ramants.

'I'he '11 NMR expt?rimt?ntr; were pcrforrnecl on 1 . h hotnts- ~ ~ a d NMR e
spectrometer lJDRIS (Karl Marx I J n i v o r s i t y of L e i p a i g ) atid on ;3
nIZUKER MSL, 400 :spacl.rometc?r a t a frequency of 1 3 . 8 MIIe nrid
6 1 . 4 MHz, r e s p e c t i v e l y . The s o l i d - l i k e spectra were o b t a i n e d by
t h o quniirupole echo p u l s e sequence ( n / 2 , y - 'r -- 3~/2,x; ( r e f . 9 ) ) .
'J'he spectra at low f i e l d are presanl.et1 as h a l f - spectra r e s u l t i n g
from F o u r i e r tratisforrnnt inn of the accumulated non-.qiiadraturl:
echo decays (ref. 7 ) . In w d e r t-o enlargc: the s p o u t r n l excit.at,iun
width, compoeite p u l s e s ( r e f . 10) were i~:;ed i n t h e case 13f
~~--wlene. The best, r e s u l t s w e r e obt.airiccl tly n compcJsite p u 1 ~ ; ~ :
quenc:e
::I ( 1 3 5 3-80 90 133 45 g%i 180 90 1 3 5 ) proposed LY
Sirninuvitch a t a l . (ref. 1 1 ) .
P e r d e u t e r a t e d benzene and p- x y l e n e - d 4 were used a s s u r h a t e s .
 507

A l l measurements of sorbed species w e r e performed w i t h s e a l e d

samples. The experimental e r r o r of t h e s o r b a t e c o n c e n t r a t i o n does
n o t exceed 10 %.
The proton-decoupled 13C NMR s p e c t r a of sorbed benzene w i t h
t h e n a t u r a l 13C abundance were a l s o recorded w i t h t h e UDRIS
s p e c t r o m e t e r a t a frequency of 22.6 MHz (ref. 5 ) . Most of them
were t a k e n u s i n g s i g n a l enhancement by c r o s s p o l a r i z a t i o n ,
The '%i MAS NMR spectra were measured on t h e MSL 400 at a
frequency of 7 9 . 5 MHz u s i n g a s i n g l e p u l s e e x c i t a t i o n and a
s p i n n i n g r a t e of about 3 k h .

F i g . 1. "Si MAS NMll

spectrum for t h e MFI- ( c )
sample s y n t h e s i z e d arid
kindly supplied by
D . T . Hayhurst ( r e f . 8 ) .

HKSIILTS
Benzeno -
Wig. 2 shows t h e concentmition p a t t e r n s of t h e d i f f u s i v i t y D,,
of benzene f o r MFI samples (1)) and (c), r e s p e c t i v e l y . The d i f f u
s i v i t i e s i n both samples d e c r e a s e w i t h i n c r e a s i n g c o n c e n t r a t i o n
although for s i l i c a l i t e - 1 (MFI-(c)) t h e y are s l i g h t l y e n l a r g e d
compared with ZSM-5 ( M F I - ( b ) ) . The data correspond b o t h q u a l i t a -
t i v e l y and q u a n t i t a t i v e l y t o t h e r e s u l t s published f o r t h e
samples MFI (a) and MFI-(d) i n ( r e f . 4 ) . Thus, changing b o t h t h e
crystal s i z e (and t h e o r i g i n of t h e samples u s e d ) d i d n o t show
s i g n i f i c a n t , i n f l u e n o e on t h e d i f f u s i v i t i e s . From Arrhenius' p1ol.s
f o r t h e parameter range:: c o n s i d e r e d , i t f o l l o w s t h a t t h e d i f f u
% i o n of benzene i n s i l i c u l i t e - 1 is c h a r a c t e r i z e d n o t o n l y by a
h i g h e r m o b i l i t y , b u t a l s o by a lower energy of a c t i v a t i o n
(Ea= 27 kJ-mo1"' (ZSM-5); 2 0 kJ-mol ( s i l i c a l i t e - 1 ) ) . The m t i -
vrAion energy d a t a f o r benzene ore i n s a t i s f a c t o r y agraemcint with
t h o s e from model 1ing t h e i n t r a c r y s t a l l i n o t r a n s p o r t by cornputor
s i m u l a t i u n meLhOd% ( r e f s . 12, 1 3 ) .
J o i n t c o n s i d e r a t i o n of s o r p t i o n u p t a k e and NMR d a t a p r o v i d e s a
deeper insight i n t o t h e mir:r.ophysic:al mechanism of inLrar:ryst,nl
l i n e molecular m o b i l i t y . Due t o t h e c l o s e s i z e s of benzene molt:!
508

0 +423 K
B x 393K
A X 363 K
*
r 343 K

- C3 323 K

I
303 K
274 K

01
I
0.2
I
0.3
I
0.4
I
05
I
06
I
a7
F ig . 2 . Concentration de-
pendence

(b)
of d i f f u s i v i t y
d a t a , Do, f o r benaene/MFI-
( f u l l s y m b o l s ) and
n/ mmot g‘ MFI-(c) ( c r o s s e s ) .

c u l e s and t h e MFI c h a n n e l d i m e n s i o n s ( r e f . 1 4 ) , sorbed benzene i s

e x p e c t e d t o p r o v i d e r a t h e r s o l i d t h a n l i q u i d l i k e NMR s p e c t r a .
The l i n e shape:; of tihe ‘H and 1 3 C NMR s p e c t r a are d e t e r m i n e d by
e l e c t r i c q u a d r u p o l e i n t e r a c t i o n and by the chemical s h i f t a n i s o - -
tropy, respectively. Both t y p e s of i n t e r a c t i o n depend on the
r e l a t i v e o r i e n t a t i o n of t h e sorbed m o l e c u l e s w i t h r e s p e c t , t o t h e
d i r e c t i o n of t h e magnetic f i e l d a p p l i e d . T h e r e f o r e , s e v e r a l k i n d s
of m o l e c u l a r motions give rise t o c h a r a c t e r i s t i c l i n e shape
patterns.
For t h e banzene/MFI--(b) system, t h e dependenoet.; of t h e ‘H NMlZ
l i n e s h a p e on b o t h t e m p e r a t u r e and l o a d i n g art: g i v e n i n F i g . 3.
From a comparison o f t h e s p e c t r u m € o r h i g h s o r b a t e c o n c e n t r a t i o n
( 7 . 6 molecules per u . c‘. ) and 1 C J W t e m p e r a t u r e ( 3 2 5 K) w i t h t h e
theoretical line shapes for different mo%ional statc;
( r e f s . 7 , 1 5 1 , i t h a s ~ C be J c o n c l u d e d t h a t t h e s o r b e d benzene
mo1ecu1es perfurrn f a s t r e o r i e n t a t i o n s a b o u t t h e i r C6-axes; even
a t 125 K t h e c o r r e l a t i o n L i m e of t h e C6 r e o r i e n t a t i o n is mur:h
s h o r t e r t h a n 1 v s . With i n c r e a s i n g t e m p e r a t u r e , t h e 1ine s h a p e
which i s c h a r a c t e r i s t i c of a n e x c l u s i v e C6 r e o r i e n t a t i o n d i s -
appears. A t t e m p e r a t u r e s above 1 7 0 . . . 180 K, a r e c t a n g u l a r c u r v o
js found. Apart from t h i s , above 270 K n o q u a d r u p o l e e c h o i s
o b s e r v e d f o r t h e used pulse i n t e r v a l of 60 v s . As i t f o l l o w s from
l+’i.g. 3, a r e d u c t i o n of t h e s o r b a t e c o n c e n t r a t i o n c a u s e s a similar
e f f e c t as a rise i n t e m p e r a t u r e .
 509

LL
concenhation/
35

molecules per u. c.:

70

1.6
0 35
[(w
70

4.0
k
0
- w o ) / 2 d /kHz

Fig. 3 . 2H NMR spectra of perdeuterated benzene sorbed on

(MFI-(b)) for various concentrations and temperatures.
spacing (4096 scans).
35

ZSM-5

13C NMR line shapes of benzene molecules sorbed in the MFI-(d)

The
spectra were obtained using 3 . 5 CIS n / 2 pulses and a 60 CIS pulse
70

5.6 7.6

sample are shown in Fig. 4 . For high sorbate concentrations and

low temperatures, powder spectra are obtained, which are charac-
teristic of an axially symmetric shielding tensor. This linc

260 K

200 K

150 K
concentration/ & 6iso 4
molecules per u.c.: 3.2 6.0 8.0

Fig. 4 . 13C NMR spectra of benzene sorbed on silicalite-1 (MFI-

( d ) ) for various temperatures and concentrations. The spectra at
200 K were taken using signal enhancement by cross polarization.
510

shape is known to be generated by a fast mottion of the benzene

molecules about their hexad axes of symmetry (ref. 16). With
increasing temperature and decreasing loading, t h e 1 ine shape
changer. into a Lorentzian one, i.e. an additional molecular mo
tion becomes fast enough to average out the chemical shift aniso-
tropy. In the transition range, there are spectra which seem to
rwult from a superposition of both line shRpe types.

€J_:ULC-E?
'he concentxation patterns of the diffusivity D,, of p-xylem
for the MFI-(a) sample are given in Fig. 5. In general, the
curves are similar to those for the benzene/MFI system.

0 423 K
393 K
A 363 K
- I m
1

Fig. 5. Concentratinn
dependence of diffusi-
vity data, Do, for the
p-xylen/MFI-(a) system.

But the Do data of p-xylene for the MFI sample considered tend
to exceed those for the bensene/MFI system at sorbate concentra-
tions lower than 4 molecules per u.c., cf. Fig. 6 . In contrast,
the decrease in Do with increasing concentration (exceeding
4 molecules per u.c.) becomes stronger for p-xylene than for
benzene. At room temperature and below, the sorbed p-xylene
molecules are highly immobile. This behaviour is also reflected
by a concentration dependence of the activation energy of intra-
crystalline diffusion (25...55 kJ-rnol-' with increasing Ea values
at increasing concentration) approximated from Arrhenius' plots.
Therefore, the p-xylene/MFI system appears to be more complex
than t h e benzene/MFI one.
 511

I
F i g . 6 . Comparison
of the
concentration dependenix~::
of diffusivity data, D,,,
for the systems p-xylenc
1ol' 41 0.2 03 94 45 96 47 Q@ or! MFI-(a) (A)and benzene
on MFI-(b) (H) and MFI-(c)
n/mmol (v),all at 363 K.
S u r p t i o n uptake experiments for o-xylene/MFI--
(a) did not allow
tn determine both equilibrium and intracrystalline diffusiuri
data. T h i s finding, cf. Fig. 7, corresponds to that already
described in (ref. 1 7 ) .

015 I

0.10
-n
mm0l (1'

0.05

Fig. 7 . Concentration vs.

time dependences for tho
'lh o-xylene/MFI-(a) system.

'11 NMR spectra of p-xylene-d4 sorbed on ZSM-5 (MFI-(b)) are

shown in F i g . 8. The spectrum obtained by simple 4 2 pulses
(Fig. 8a) exhibits a rectangular line shape with clear edges at;
3 7 0 kHa. As distinct from the spectra in Fig. 3 , this line shape
is not caused by motional processes but by a non-uniform excitn-
tion of the range of possible resonance frequencies (k140 kHe).
According to a relation given in (ref. 20), only 29 % of the truo
spectral intensity at (o - wo)/2n = * 7 0 kHe are obtained f o r the
applied rf power. Using composite pulses with much larger excita-
tion widths (ref. ll), one obtains a line shape characteristic o f
deuterons bonded to carbon in solid state. From the observed
quadrupole splitting of about 140 kHe it follows, that all mole-
512

kJ-4 F i g . 8. '€1 NMR s p e c t r a of

p-xylene -d4 s o r b e d
ZSM-5 (MFI-(b),
0t1

/ ,L
7 . 2 molecules p e r u . c . ,
T = 295 K ) ) o b t a i n e d by
(a) 5.0 P S J t / 2 p U l s C ? S
(16,000 s c a n s ) and
w 4 , (b) composite n/2 p u l s e s
of t h e same r f power
u l . . . , h . . I ( . . . . ' , . . . . ' " " (32,000 scans).
100000 0 - 100000 A p u l s e s p a c i n g of 40 p s
HERTZ was used i n both cases.

c u l a r mot,ions have a t room t e m p e r a t u r e c o r r e l a t i o n times much

l a r g e r than 1 p s . Taking i n t o account t h e p u l s e i n t e r v a l and t h e
d u r a t i o n of t h e composite sc/Z--pulse used ( 4 0 p s and 71 p s ,
r e s p e c t i v e l y ) , one can o b t a i n a more precise lower l i m i t f o r t h e
c o r r e l a t i o n time. A l l m o l e c u l a r motions t h a t change t h e o r i e n t a -
t i o n of t h e molecular p l a n e with respect t o t h e magnetic f i e l d
proceed a t rnaxirnirm s o r b a t e concentrat.ior-i w i t h time c o n s t a n t s
l a r g e r than 100 p s . A f a s t r o t a t i o n about t h e p a r a - a x i s of t h u
111 . l e c u l e , deduced from 13C NMR s p e c t r a ( 4 . 8 molecule:: per U . C . )
a t 310 K ( r e f . 1 8 ) , can be excluded. O u r f i n d i n g s are i n a c c o r
dance with t h o s e of a p r e v i o u s H' NMR stiidy ( r e f . 1 9 ) f o r a
c o n c e n t r a t i o n of 3 . 6 molecules p e r d e u t e r a t e d p-xylene per u. c .
Using p-xylene-d4 w e g o t r i d of t h e s t r o n g s i g n a l from CD3, which
is i n s e n s i t i v e t o a motion a b o u t t h e p a r a - a x i s and o b s c u r e s t h e
l i n e s h a p e of t h e a r o m a t i c d e u t e r o n s . The a d d i t i o n a l i n t e n s i t y i n
t h e c e n t r e of t h e spectrum i n F i g . Rb arises most probably from
r e s i d u a l methyl d e u t e r o n s . There i s a l s o no e v i d e n c e f o r a f a s t
180°-flip of t h e molecule. I n t h e l i m i t of h i g h exchange r a t e s ,
such a motion would r e s u l t i n t o a spectrum f o r a n o n - a x i a l l y
symmetric f i e l d g r a d i e n t t e n s o r w i t h s t r i k i n g s i n g u l a r i t i e s a t
( w - wo)/2n = i 1 7 kHz. Owing t o the e f f e c t o f motional p r o c e s s e s
d u r i n g t h e long composite p u l s e , t h e i n t e r p r e t a t i o n of spectra
f o r lower s o r b a t e c o n c e n t r a t i o n s is much more c o m p l i c a t e d .
 513

DISCUSSION
The i n t r a c r y s t a l l i n e c h a r a c t e r of t h e m o l e c u l a r m o b i l i t y d a t a
d e r i v e d from s o r p t i o n u p t a k e e x p e r i m e n t s f o r b e n z e n e a n d p-
xylene/MFI s y s t e m s i s e n s u r e d by t h e f o l l o w i n g :
( i ) experimental c o n d i t i o n s which s t r o n g l y f a v o u r i n t r a c r y s t a l
l i n e d i f f u s i o n under quasi--isothermal c o n d i t i o n s ( r e f s . 4,231;
( i i ) t h e s h a p e o f u p t a k e c u r v e s is t y p i c a l f o r a d i f f u s i o n -
1i m i t e d process ;
( i i i ) t h e t i m e c o n s t a n t s of s o r p t i o n u p t a k e s h o w t h e crystal s i z e
d e p e n d e n c e expected f o r i n t r a c r y s t a l l i n e d i f f u s i o n , i . e. t h e
d i f f u s i v i t i e s are i n d e p e n d e n t o f c r y s t a l s i z e ( a n d of t h e o r i g i n
o f t h e samples);
( i v ) t h e r e s u l t s o f s o r p t i o n u p t a k e a r e c o n s i s t e n t w i t h t h o s e of
‘11 and 13C NMR measurements w i t h respect t o b o t h t h e a b s o l u t e
v a l u e s and t h e i r d e p e n d e n c e s o t i t e m p e r a t u r e a n d c o n c e n % r a t i m
( c f . below);
( v ) t h e d i f f u s i v i t i e s agree w e l l w i t h d a t a o b t a i n e d i n o t h e r
l a h o r a t a r i e s ( c f . Table 2 f i x benzene) ;
( v i f o r b e n z e n e , t h e a c t i v a t i o n e n e r g y v a l u e s which arc: compa-
rable f o r t h e MFI s y s t e m s i n v e s t i g a t e d by v a r i o u s e x p e r i m e n t a l
techniques, agree w e l l w i t h r e s u l t s f r o m c o m p u t e r s i m u l a t i o n s
( r e f s . 12,131;
( v i i ) f o r p x y l e n e , t h e informat,iori d e r i v e d f r o m NMR mc~n~~urernerit,:;
and cnmputer sirnll1ati0ti work ( r e f , 2 6 ) do n o t c o n t r a d i c t thi:
f i n d i n g of a i:c-Jric!erit.ral.icrn-dependftril; e n e r g y of act,ivHt.irm.
The latLer p e c u l a r i t y mayl>e i n t e r c o n n e c t e d w i t h t h e phenomannn n P
hysteresis in sorption i snt.herms ( c o n c e n t r a t i on-dependent,
s o r p t i o n s t a t e s of p - x y l e n e ) repeatedly reported i n literature
( e . g . r e f s . 14,17,27).
Despit.t: t h i s c o n s i s t e n c y of d a t a , t h e i r general i n t e r p r e t a t i o n
meets s t i 11 d i f f i cu 1t i e ~. ; With cert a i n pre r e q u i s i tes der i ved f rrm
appropriatx l i t e r a t u r e , and s u p p o s i n g t h e t r a n s l a t i o n a l mot,ion of
aromatic compounds i n MFI t y p e z e o l i t e s to proceed v i a a c t i v a t e d
m o l e c u l a r jumps, t h e c o n s t a n t jump l e n g t h model ( r e f . 2 8 ) h a s
b e e n sjllg$ested f o r Lhe i n t e r p r e t a t i u n of t h e b e n z e n e d i f f i x l ; i o n
d a t a ( r e f . 2 9 ) . Assuming a jump l e n g t h e q u a l t o t h e tli:;t,uncr:
between two ad j a o e n t c h a t i n e l i n t e r s c c t i o n s , t h i s model describe:;
the b e n z e n e d i f f u s i o n f a i r l y we11 at. c:oric:oritrat.ioris C: 4 m c i l w x ~ l w
p e r u .1:. , I : i i ~ t , i L bei:orrie:; i n a d e q u a t e a t h i g h e r l o a d i n g s . For t h i ?
1 attxr ~ ~ ~ i r i ~ ~ ~ r i Ir e, g r~i o~n ~, i ~it.
. i rw~iiild
i fcil l o w t h a t , m u l t i p l t ! m o l t : -
c u l n r jumps a r e t-ieeilei-I %[.] ovt?rl:oriit: i:,he samc f iseci d i s t ; w ~ c t ? . M w : L
~ ~ i - c ~ h a t i l yt.ht+rc
, occur:; H uomplex process i n c : l u c l i n ~ r i o t rinly H

change o f t h e jump l e n g t h but, also .a v a r i a t i o n n f b o t h 1;tiF: .jum

p i n g frequency arid t h o number of ticcc2t;f;ible ocirpt-,iori si1.t.:;.
T a k i n g i n t o account, t h e a b o v e p e c u l a r i t i e s o f t h e p . - x y l e n a sorp -
t i o n , l.ht: i r i ~ i p p il c i r t i i 1i t.y (if t.tw (:~iri~t.iiril. jurnp 1t:ngt.h rncidel w i t h
t h e d i f f u s i o n ririta f o r p -sylene/MFI s y s t e m i n :i.t;1.;iightfi.)1.warrlI
514

Table 2
D i f f u s i v i t y d a t a for t h e benzene/MFI s y s t e m
-
MFI sample experimental concentra-- T D,xlO1' ref,
method tion
( s i z e ) /pm3 , ,-.
. a l./ A l molec. / I A . c. K c2-s-l

S i licalite-1 ~ E I - N M Rt r a c e r 6.0 293 0.5 22

( 3 0 x 2 5 ~ 1 5;)>lo3 deSOrptim
Silicalite-1 p = const. -3.5 303 0.7 23
( 1 0 b x 4 5 x 4 5 ) ; > 1 03 Cahn b a l a n c e -2.0 343 -2
Silicalite-l v = const. 4.0 323 1 this
(19Ox56x35);>1O3 p = var. 1.2 363 7 paper
S i 1ical i t e -1 p = const. -3.5 303 -6 4
( 3 0 x 2 5 ~ 1 5 )>; l o 3 spring balance
S i l ical i t e - 1 frequency 1.0 388 -10 24
( 1 ' 1 0 x 5 5 ~ 4 3;)> lo3 response
Silicalite 1 p = const,. 4.0 293 0.1 25
( 6 ~ 3 x )2; > 1 O3 microbalance
t 1-- ZSM - 5 p = const.
( 5 . 7 ~ 3 ~;235) 4.0 298 1 17
( 1 3 ~ 7 xj6;35 Cahn h a 1a n c e
(Na,E1) ZSM 5 v = const. -3.5 363 4 4
(35x15~10);135 p = var.

(Na,II)- ZSM 5 p = const. -3.5 363 4 4

( 3 5 x l 5 x 1 0 ) ; 135 s p r i n g balani:c
(Ma,E1)- ZSM 5 v = const.. 2.0 303 1 this
(55X12XlO) ; 5 0 p = var. 2.0 363 -6 paper

The cwnclusioris on m o l e c u l a r rnobi 1i t y uf s o r b e d b e n z e n e as

drawti from 8 o r p t ; i o n u p t a k e are s u p p o r t e d by t h e f i n r i i n g s of t h u
't1 firid I3C NMR. T h e i r r e s u l t s s u g g e s t t h e f o l l o w i n g model for t h e
iroleuulilr rnot;iori o f benzene i n MFI t y p e z e o l i t e s ( r e f s . 5 , 7 ) :
(i The s o r b e d b e n z e n e rric1lecules perfcmm fas 1. r.ec.JrieritAt.iunr;
abIJlAt, t h e i r C6 a x e s . E v e n at 125 K, t h e c o r r e l a t i o n t i m c o f t h i s
111 ' i o n is much s h o r t e r t h a n 1 p s .
( i i ) Superimposed upon t h i s C6 r e o r i e n t a t i o n , t h e r e are jumps of
.the benzene r r o l e o u l e s between a 1irnit,rsd number t r f sorpt.ic.m site:;
which a l l o w o n l y d i s t i n c t , o r i e n t a t i o n s of t h e hexad axis of tht:
lit?tizcrie mco1c:oul e with respcot. 1.0 the c r y s t a l :l;ysl,cm. Tho mean
r e s i d e n c e time '6 between t w o s u c c e e d i n g jumps decreases w i t h
j r i c r e a s i n g t e m p e r a t u r e arid d e c r e a s i n g l o a d i n g .
A m o t i o n a l b e h a v i o u r o f t h i s t y p e explain:: a l s o t h e i n i t i a l l y
u~lint,allibible strong H ' NMR s i g n a l r e d u c t i o n w i t h i n c r e a s i n g
t e m p e r a t u r e . .Jump m o t i o n s w i t h '6. i n t h e order of t h e p u l s c
J
 515

i n t e r v a l T of t h e q u a d r u p o l e e c h o s e q u e n c e g i v e r i s e t o "echo
d i s t o r t i o n s " accompanied by a s t r o n g d e c r e a s e o f t h e s i g n a l
i n t e n s i t y ( r e f s . 3 0 , 3 1 ) . The o b s e r v e d r e d u c t i o n of t h e e c h o
i n t e n s i t y beyond t h e d e t e c t i o n l i m i t i m p l i e s a v a l u e o f ' v j i n t h i :
o r d e r of 100 p s or less.
T h e o r e t i c a l c a l c u l a t i o n s o f 13C NMR spectra show t h a t i n t h e
casc of m o l e c u l a r jumps, t h e NMR l i n e s h a p e i s n o t s e n s i t i v e l y
d e p e n d e n t on t h e g e o m e t r i c a l a r r a n g e m e n t of t h e s o r p t i o n s i t e s
( r e f s . 3 2 , 3 3 ) . T h e r e f o r e , c o n c l u s i o n s on t h e jumping rate c a n be
drawn e v e n i f t h e r e is a l a c k of i n f o r m a t i o n on t h e genuirlc
s o r p t i o n s i t e s of benzene i n MFI s t r u c t u r e . S e m i - - e m p i r i c a l
p o t e n t i a l c a l c u l a t i o n s ( e .6 . r e f . 3 4 ) have shown t h a t t h e c h a n n e l
i n t e r s e c t i o n s as w e l l as t h e p o r e segments i n between car1 a c t OF;
s o r p t i o n s i t e s f o r benzene i n s i l i c a l i t e - 1 . From t h e e x p e r i m e n t a l
I3C NMR l i n e s h a p e s w e d e r i v e d a rnean r e s i d e n c e t i m e 'I . o f 20 pi;
J
and 150 pci f o r a c o n c c n t r a t i o n o f 6 m o l e c u l e s p e r U . C . arid a
t e m p e r a t u r e of 250 K and 200 K , r e s p e c t i v e l y .
Provided t h a t the jumps d e t e c t e d i n NMR s p e c t r o s c o p y arc
~ c ~ ~ ~ r n p a nby i e d a t r a n s l a t i o n a l motion ( J f t h e rnolecule, i t is
pos s i b 1e t o e:; t imate i n t rar r y s t a 11i n e s e 1f -d i f f us i v i t i es Do.
Assuming t h e d i f f u s i o n p a t h o f a m i g r a k i n g m o l e c u l e as a %urn o f
irld i v i dual a c t i v a t e d jumps I f o r i s o t r o p i r: s y s t e m s t h e re1 t i t i on
<12i = 6-Do-7 is v a l i d . < I 2 i d e n o t e s ' t h e mean s q u a r e jump
lerlgth. With t h e f u r t h e r a s s u m p t i o n t h a t o n l y jumps between
a d j a c e n t s i t e s t a k e p l a c e , one obi;ains a rnean s q u a r e jump l e n g t h
~ ~ f<Jr a l u c a l i z u . l , i o n of sorp-ticin si1.S::; i n the pore:
7 . 4 - 1 0 - - lc12
segments ( r e f . 3 5 ) . A p r e f e r r e d a r r a n g e m e n t o f t h e benzene mole
cule:; i n oklciriric.1 irit.ersec:tic.itis and the segments o f t h e si.,raighL
ctwmnele ( r e f s . ~ , 3 7 , 2 8 ) r e s u l t s i n a v a l u e o f 5 . 5 . 1 0 - - ' ~ in2.
Although the a h n i c e uf t h e a r r a n g e m e n t is a l i t - t l o a r t i i t r a r y , t h e
rnean d i s t a n c e t j c L w e e n ad jacent; sibs would he i n any case i n t k i c
urcler. U.f 1 rim. The c1iffusiviLie:; otitairied i n t h i s way are i n
reascjnal-ils agreament w i t h t h e dsLa f rom u p t a k e experirnents . With
Lhe c i t ~ c i v u value:; f o r Lhc r i i t w i rwidericx: Lime 'I and the c u r -
responding a c t i v a t i o n e n e r g y E = ( 1 7 t 4 ) k.J-mo1. l a s e l f
d i f f u s i v i t y D, = I . . . ~ - 1 0 - 1 0 cm2-;-- is o b t a i n e d at. 303 K f o r a
orti ti at.^: r:rincent.ratiori of 6 rnolecules per u . c. Furthermore, t-he:
d e c r e a s e of m o l e c u l a r rnrsbility w i t h i n c r e a s i n g s o r b a t e c o n c e n t r a -
t i o n i s c l e a r l y r e f l e c t m l i n t h e NMR s p e c t r a ( c f . F i g s . 3 arid 4 )
and i:;m be e x p l a i t i e d by at'i iricrea:;e of the mean resiiiwice t i m e I . .
3

p m~.:chttrii:xn i n t h o (:ase o f xylerie, t h e

EJ-

same procedure y i e l d s a t least a n u p p e r l i m i t f o r t h e s e l f -

d i f f u f i i v i i , y . T h e 1 1 - xylc?rv? mtile(;ules s o r b e d i n MFI a e u l i t e s w e r e
l o c a l i z e d b y Lhtwret.ica1 ( r e f . 3 6 ) a: well by XRD s t u d i e : ;
( r e f . 3 9 ) irr 1.ht: clinr~nt:l int.err;ec:t.icjris and thr? p o r e segmont.s of
% h e ~j i n u ~ ; u i i i a . lchannel::. WiLh L h i s arr;mgement of sot.pticxi r; i
516

and the d e r i v e d lower l i m i t f o r t h e mean r e s i d e n c e time

(> 100 p s ) , one o b t a i n s Do < lo-'' c m 2 - s - ' a t room t e m p e r a t u r e
and f o r a sorbate c o n c e n t r a t i o n of 7 . 2 m o l e c u l e s per U . C . This
v a l u e c o r r e s p o n d s w i t h t h e u p t a k e d a t a shown i n F i g . 5.
Thus, t h e NMR i n v e s t i g a t i o n s g i v e f u r t h e r e v i d e n c e t h a t the
d i f f u s i v i t i e s measured by s o r p t i o n u p t a k e are i n d e e d i n t r a -
c r y s t a l l i n e d a t a which depend on c o n c e n t r a t i o n . They a l s o allow
to d e r i v e a m i c r o p h y s i c a l model f o r t h e intracrystalline
molecu 1ar t r a n s p o r t .

ACKNOWLEDGEMENT
The a u t h o r s d e d i c a t e t h i s paper t o P r o f e s s o r H . Pfeifer, Karl
Marx l l n i v e r s i t y o f L e i p z i g , who s u p p o r t e d t h i s work i n v e r y rnat1y
w ~ y s ,a t t h e o c c a s i o n o f h i s 6 0 t h b i r t h d a y .

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34 J . Ramdas, J.M. Thomas, P.W. BetteridBe, A . K . Cheetham and
E.K. Davies, Angew. Chemie ( E n g l . ) , 23 (1984) 671-679.
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r'orous S o l i d s , E l s e v i e r , Amsterdam, 1988, pp. 109- 118.
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This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

DIFFUSION OF n-HEXANE AND 3-METHYLPENTANE I N H-ZSM-5 CRYSTALS OF VARIOUS S I Z E S

P. VOOGD and H. VAN BEKKUM

Department o f Organic Chemistry, D e l f t U n i v e r s i t y o f Technology,

J u l i a n a l a a n 136, 2628 BL D e l f t (The N e t h e r l a n ds)

ABSTRACT
A t temperatures below 373 K t h e d i f f u s i v i t i e s o f n-hexane and 3-methylpentane
i n z e o l i t e ZSM-5 were determined i n a c o n s t a n t volume v a r i a b l e p r e s s u r e system.
The ZSM-5 c r y s t a l l e n g t h was v a r i e d between 20 pm and 150 pm i n o r d e r t o st udy
i t s e f f e c t on u p t a k e r a t e s . The e x p e r i ment al r e s u l t s i n d i c a t e t h a t i n t r a -
c r y s t a l 1 i n e d i f f u s i o n determines t h e s o r b a t e upt ake r a t e p r o v i d e d t h a t c r y s t a l s
w i t h h e i g h t s l a r g e r t h a n 40 pm a r e used. Also, t h e e f f e c t o f t h e sorbed amount
on t h e d i f f u s i v i t y was s t u d i e d . Near s a t u r a t i o n an i n c r e a s e o f b o t h t h e
apparent and t h e i n t r i n s i c d i f f u s i v i t i e s o f n-hexane and 3-met hylpent ane w i t h
t h e degree o f p or e f i l l i n g was observed.

INTRODUCTION

S inc e the first applications o f zeolites the determination o f d i f f u s i o n a l

upt ak e r a t e s i n z e o l i t e c r y s t a l s has been a w i d e l y s t u d i e d s u b j e c t o f research.
A number o f re v ie w s have been p u b l i s h e d (I-4), c o n s i d e r i n g m a i n l y d i f f u s i o n i n
l o w - s i l i c a z e o l i t e s l i k e z e o l i t e A and X and i n n a t u r a l z e o l i t e s l i k e f a u j a s i t e
and mo rd enit e . However, the study o f m o l e c u l a r t r a n s p o r t i n t h e well-known
h i g h - s i l i c a z e o l i t e ZSM-5 appeared t o encounter some d i f f i c u l t i e s . F i r s t l y , t h e
synthesis of a w o r k a b l e amount o f l a r g e , w e l l - d e f i n e d ZSM-5 c r y s t a l s h a v i n g a
narrow particle size d i s t r i b u t i o n has o n l y become p o s s i b l e i n t h e l a s t few
years (e.g. 5,6), a l t h o u g h t h e c r y s t a l morphology i s as y e t r a t h e r d i f f i c u l t t o
c o n t r o l . Secondly, some doubt e x i s t s r e g a r d i n g t h e v a l i d i t y o f F i c k ' s e q u a t i o n
i n c o n n e c t i o n w i t h d i f f u s i o n i n z e o l i t e ZSM-5. F o r some adsorbates, l i k e
3-methylpentane and p-xylene, Riekert et a l . (7,8) s t a t e t h a t t h e s o r p t i o n
k i n e t i c s can r e s u l t f r o m a s u p e r p o s i t i o n o f i n t r a c r y s t a l l i n e d i f f u s i o n and a
rearrangement o f s o r b a t e i n t h e ZSM-5 c r y s t a l .
The need f o r applying large ZSM-5 c r y s t a l s can be e x p l a i n e d as f o l l o w s :
d u r i n g a s o r p t i o n u p t a k e experiment t h e g e n e r a t i o n o f h e a t o f s o r p t i o n causes a
tem p era t u re r i s e o f t h e sorbent, which may r e s u l t i n an u p t a k e c u r v e s e r i o u s l y
deviating f rom t h e t h e o r e t i c a l c u r v e f o r an i s o t h e r m a l system ( 9 ) . Because o f
520

the z e o l i t e ’ s h i g h t h e r m a l c o n d u c t i v i t y ( r a p i d e q u a l i z a t i o n o f t h e t emperat ure

thr o ughout t h e c r y s t a l ) t h e r a t e o f h e a t g e n e r a t i o n i s i n v e r s e l y p r o p o r t i o n a l
2
t o t h e c h a r a c t e r i s t i c d i f f u s i o n t i m e (tD=R /D, R = c r y s t a l radius, D =
d i f f u s i v i t y ) . Th e r e f o r e , l a r g e c r y s t a l s a r e p r e f e r a b l e t o small c r y s t a l s ,
e s p e c i a l l y when r a p i d l y p e n e t r a t i n g s o r b a t e s p e c i e s ( l a r g e 0) a r e considered.
Another phenomenon which may i n f l u e n c e a s o r p t i o n process i s s u r f a c e - b a r r i e r -
l i m i t e d d i f f u s i o n (7); sorbate uptake i s l i m i t e d by a t r a n s p o r t r e s i s t a n c e a t
the zeolite crystal surface. I f t h i s surface b a r r i e r completely c o n t r o l s the
s o r b a t e u pt a k e r a t e t h e c h a r a c t e r i s t i c d i f f u s on t i m e i s p r o p o r t i o n a l t o t h e
c r y s t a l r a d i u s (R), hence m a n i p u l a t i o n o f t h i s parameter i s a u s e f u l approach
i n t h i s r e s p e c t as w e l l .
An i n t e r e s t i n g i t e m i n z e o l i t i c d i f f u s i o n i s he c o n c e n t r a t i o n dependence o f
apparent as w e l l as i n t r i n s i c d i f f u s i v i t i e s . Th s dependence can be s t u d i e d by
p e r f o r m i n g u pt a k e measurements, i n t r o d u c i n g a small amount o f s o r b a t e i n t h e
system c o n t a i n i n g t h e s o r b e n t which m i g h t a l r e a d y c o n t a i n a c e r t a i n amount of
the sorbate (interval method). Thus the fractional coverage (0) w i l l , a t
most,change a few p e r c e n t s . The d i f f u s i v i t y t h e n d e r i v e d i s o f a d i f f e r e n t i a l
k i n d . It o b v i o u s l y can be d e t e r m i n e d a t v a r i o u s s o r b e n t coverages. T h i s i s i n
c o n t r a s t t o t h e i n t e g r a l d i f f u s i v i t y w h i ch i s det ermined f rom upt ake curves
measured ov er a l a r g e c o n c e n t r a t i o n i n t e r v a l , and has by t h a t a mean v a l u e ( 2 ) .
The purpose o f t h i s paper i s t w o f o l d . F i r s t l y , t h e i n f l u e n c e o f t h e c r y s t a l
r a d i u s on d i f f u s i o n was s t u d i e d ; f o r t h i s purpose we were a b l e t o s y n t h e s i z e
ZSM-5 c r y s t a l s o f l e n g t h s r a n g i n g f r o m 20 pm t o 150 pm. Also, t h e c o n c e n t r a t i o n
dependence of the diffusivity i n z e o l i t e ZSM-5 was det ermined. The sorbat es
s t u d i e d were n-hexane and 3-methylpentane. The z e o l i t e was used i n i t s p r o t o n
(H-ZSM-5) form. The e x p e r i m e n t s were p e r f o rmed i n a c o n s t a n t volume v a r i a b l e
pres s ure system a t t e m p e r a t u r e s below 373 K.
The s o rb at e s , n-hexane and 3-methylpentane, a r e i n t e r e s t i n g f rom a c a t a l y t i c
point o f view. Both compounds a r e commonly a p p l i e d i n t h e d e t e r m i n a t i o n o f t h e
so-called constraint index (ll),
i n w h i ch catalytic conversion o f t hese
compounds a r e used t o c h a r a c t e r i z e ( a c t i v e ) z e o l i t e s , such as z e o l i t e H-ZSM-5.
Diffusion o f t h e r e a c t a n t s i n t h i s c r y s t a l l i n e m a t e r i a l may be r a t e l i m i t i n g ,
especially when large c r y s t a l s a r e used. O b v i o u s l y i t i s v e r y i n t e r e s t i n g t o
det ermine the d if f u s i v it i e s at reaction t emperat ure. However, sorption
experiments at h i g h temperatures are. u n s u i t a b l e because o f r e a c t i o n s t a k i n g
pla c e . Rather, dependences of c a t a l y t i c c o n v e r s i o n s on c r y s t a l s i z e can, by
t r e a t i n g them w i t h t h e T h i e l e concept, r e s u l t i n d i f f u s i v i t i e s o f t h e r e a c t a n t s
under c o n s i d e r a t i o n . Some pioneering work i n t h i s f i e l d has been r e c e n t l y
pub1 ished (10,12).
 521

EXPERIMENT

1. Method o f S orD t i o n

The u pt a k e measurements were c a r r i e d o u t i n a c o n s t a n t volume v a r i a b l e pressure

system. A scheme of the apparatus is shown i n F i g u r e 1. The p r e s s u r e was
measured using a B a r a t r o n 170M-7 c a p a c i t a n ce manometer ( s e n s i t i v i t y 0.113 Pa)
and re c ord ed u s i n g a Kipp ED41 r e c o r d e r . The whole equipment system was
situated in a c o n s t a n t - t e m p e r a t u r e room (T = 295 K ) . Uptake r a t e s a t e l e v a t e d
temperatures were determined w h i l e t h e s o r p t i o n vessel was immersed i n a wat er
bat h w i t h t h e r m o s t a t . To a v o i d t h e p o s s i b i l i t y o f i n t e r c r y s t a l l i n e d i f f u s i o n -
c o n t r o l l e d s o r p t i o n , a small amount o f z e o l i t e (10-30 mg) was used i n each
experiment. The s o r p t i o n v e s s e l had a c y l i n d r i c a l shape (base s u r f a c e = 10
cm ) ,
2 wherein the zeolite sample was arranged i n t h e f o r m o f a monolayer o f
crystals. The volumetric (interval) method o f measuring z e o l i t i c d i f f u s i o n
permitted the st u d y o f t h e i n f l u e n c e o f t h e sorbed amount on t h e d i f f u s i v i t y .
In each d i f f u s i o n experiment a small percentage (<I%) o f t h e s a t u r a t i o n value
was sorbed. A sorption i s o t h e r m was d e t e r m ined by t h i s method as w e l l , w i t h
d i f f e r e n t sorbed amounts.

F i g . 1. Scheme o f t h e e x p e r i m e n t a l apparatus. 1, st andard volume (78.26 m l ) ;

2, v es s e l c o n t a i n i n g l i q u i d s o r b a t e ; 3, s o r p t i o n vessel (6.99 m l ) ;
4, c o nne c t i o n between s o r p t i o n v e s s e l and d o s i n g volume; 5 , v a l v e ;
6, r o t a r y o i l pump; 7 , p r e s s u r e gauge measuring t h e system
pre s s ure ; 8, P i r a n i 668 p r e s s u r e gauge; 9, Penning p r e s s u r e gauge;
10, o i l d i f f u s i o n pump. The c r o s s-hat ched s e c t i o n o f t h e scheme
r e p r e s e n t s t h e d o s i n g volume (23.66 m l ) .

The ranges of e x p e r i m e n t a l parameters were as f o l l o w s : prebsure = t 0 . 2 - 180

Pa; amount sorbed 3*10-3- 2*10-2 mmo1.g-l. The t emperat ures were 295 K and
=
348 K. I n b l a n k experiments t h e h a l f - t i m e s o f vapor p r e s s u r e expansions a f t e r
522

valve opening were determined. For n-hexane as w e l l as f o r 3-methylpentane and

at different temperatures o f the sorption vessel t h e h a l f - t i m e s were 0.2
seconds. These data were n o t assimilated i n t h e data evaluation, b u t they are
useful when applying t h e so-called method o f moments (18).

2. Z e o l i t e C h a r a c t e r i s t i c s and Treatment

Uniform samples of H-ZSM-5 crystals with various sizes were used. T h e i r

synthesis and f u l l p r o p e r t i e s w i l l be reported elsewhere. Some geometrical and
chemical characteristics are given i n Table 1. Figure 2 shows SEM (Scanning
Electron Microscopy) photographs o f f o u r c r y s t a l samples, where i t i s seen t h a t
all crystals have a similar morphology and, consequently, an equal surface
geometry. The c r y s t a l s are non-spherical and twinned. No gel remaining from
synthesis was detected during SEM analysis. Broadening o f peaks a t 28= 7.8O and
8.8O i n t h e XRD p a t t e r n s i n d i c a t e d t h a t the aluminium atoms a r e heterogeneously
d i s t r i b u t e d among t h e ZSM-5 c r y s t a l s .

Fig. 2. Scanning e l e c t r o n micrographs o f the f o u r ZSM-5 c r y s t a l samples

used i n the d i f f u s i o n experiments.
 523

Immediately before a s o r p t i o n experiment t h e sorbent was outgassed i n s i t u by

heating up t o 673 K i n vacuum o v e r a p e r i o d o f 10 h r . The sample was k e p t a t
t h a t t e mp era t u re f o r 10 h r and c o o l e d s l o w l y t h e r e a f t e r . The p r e s s u r e was t h e n
2.5*10-5 Pa.

TABLE 1

Geometrical and chemical c h a r a c t e r i s t i c s o f ZSM-5 z e o l i t e samples used i n

t h e d i f f u s i o n experiments.

sample no. 1 2 3 4

mean c r y s t a l l e n g t h ,
&
c - d i r e c t ion (pm) 26 61 102 150
sta ndard d e v i a t i o n
o f l e n g t h (pm) 2.1 3.5 24.9
+
mean c r y s t a l h e i g h t
#
a- o r b - d i r e c t i o n (pm) 19 39 56 65
standard d e v i a t i o n
o f height 2.7 5.7 13
Si/AIS 57 53 54 54
occurrence o f c r y s t a l
aggl omerates no no no Yes

*
) A l l f o u r samples were phase p u r e a c c o r d i n g t o X-ray a n a l y s i s ( G u i n i e r - De
Wol f f ) .
&) Mean c r y s t a l s i z e s and p a r t i c l e s i z e d i s t r i b u t i o n s o f a sample were
determined by image a n a l y s i s o f some 200 c r y s t a l s .
+) Not determined.
# ) C r y s t a l bre adt h s ( a - a x i s ) were equal t o h e i g h t s ( b - a x i s )
') As measured w i t h X - r a y f l u o r e s c e n c e .
524

THEORY

J . Data Evaluation

For the determination o f the diffusivities the measured sorption uptake curves
were fitted with a diffusion equation which is a solution of Fick's law in
spherical symmetry for a constant system volume (19),

with qn the nth positive root o f

tan qn =
qn
1 t
2 3.a
qn.

and with

a = > . K (3)
v9

The symbols used denote: 7 , relative uptake; t, time; 0, diffusivity; R,

crystal radius; V,, sorbent volume; Vg, gas volume; K , dimensionless
equi 1 i bri um constant.

Equilibrium constants (K) were determined from the sorption isotherms. For that
purpose the isotherms were fitted with a relationship derived from t h e Dubinin-
Polanij potential theory (20). The equation has the form

ca = c:. exp [ - _
k . (R.T.ln (p/p0))*] (4)
b2
with: ca, sorbate concentration in sorbed phase; ,:c saturation value o f ca;
k, constant, characteristic of sorbent; /I, affinity coefficient; R, gas
constant; T, temperature; p, vapor pressure of sorbate; po, saturation vapor
pressure o f sorbate.

The fit resulted in an estimation of the values o f the parameters c i and

k/b 2 . The equilibrium constant K was calculated from eqs. 4, 5 and 6.
 525

Ca
K = _ (5)
P P

K = K .R.Tv.pz
P

w i t h : Tv, t e m p e r a - i r e o f s o r p t i o n v e s s e l ; p, sorbent d e n s i t y ; K sorption

P’
e q u i l i b r i u m c o n s t a n t d e f i n e d i n terms o f s o r b a t e pressure.

I t i s c l e a r t h a t a i s a f u n c t i o n o f t h e s o r b a t e pressure. D e s p i t e t h e f a c t t h a t
i n the Henry region o f an i s o t h e r m K i s n o t b e l i e v e d t o be a f u n c t i o n o f
pres s ure p, the use o f t h e D u b i n i n - P o l a n i j p o t e n t i a l t h e o r y does cause a
pres s ure dependence. It s h o u l d be s t a t e d t h a t eq. 4 does n o t reduce t o Henry’s
law a t low pre s s u r e s (20). Conclusions c o n c erning d i f f u s i o n i n v a r i o u s l y s i z e d
z e o l i t e c r y s t a l s can o n l y be s a f e l y drawn i f t h e s o r p t i o n e q u i l i b r i a f o r t hese
d i f f e r e n t samples a r e i n s u f f i c i e n t agreement. I n o t h e r words, a l l samples must
be p h y s i c a l l y and c h e m i c a l l y comparable.

Because o f t h e n o n - s p h e r i c i t y o f t h e c r y s t a l s t h e d i f f u s i o n e q u a t i o n was f i t t e d
with t h e ex perim e n t a l c u r v e f o r 7 5 0.7. A t h i g h e r v a l u e s o f 7 d e v i a t i o n s f rom
the theoretical curve caused by a crystal-shape effect may become more
pronounced. The fit resulted in an estimation of DaPP/R2, w i t h DaPP t h e
apparent diffusivity. R was taken h a l f t h e h e i g h t (a- o r b - d i r e c t i o n ) o f a
c r y s t a l . R may be o t h e r w i s e approximated e i t h e r w i t h i n t h e c y l i n d r i c a l geometry
or by u s i n g t h e r a d i u s o f a h y p o t h e t i c a l sphere w i t h t h e s u r f a c e equal t o t h e
s u r f a c e o f t h e a c t u a l c r y s t a l s . However, d i f f u s i v i t i e s o b t a i n e d by means o f
the s e approaches p r o b a b l y do n o t d i f f e r more t h a n p o s s i b l e e r r o r s . E v i d e n t l y ,
because of changes in p r e s s u r e d u r i n g an uptake, Q and hence t h e e s t i m a t e d
diffusivities changed. Error analysis p r oved t h a t the pressure changes
comp let e ly determined the e r r o r i n the d i f f u s i v i t i e s . Finally, t o obtain the
intrinsic diffusivity, Dintr , a c o r r e c t i o n w i t h Darken’s e q u a t i o n was a p p l i e d
(20) :

2. A n a l y s i s o f Thermal E f f e c t s

I n o r d e r t o g a i n i n s i g h t i n t o t h e p o s s i b l e t hermal e f f e c t s a r i s i n g f r o m t h e
gen era t io n o f h e a t o f s o r p t i o n , c a l c u l a t i o n s analogous t o t hose perf ormed by
Lee e t a l . (9) have been made. I s o t h e r m a l s o r b a t e upt ake i s assumed, p r o v i d e d
that:
526

with:
2
h.a.R
‘T = (9)
P., Cs. D
n
L
a
-AH R.cn
B = (-1 * -. e.(i-e)
R.T cS

Explanation of symbols: h, heat t r a n s f e r c o e f f i c i e n t ; a, s p e c i f i c e x t e r n a l

surface area; cS, heat c a p a c i t y o f sorbent; AH, s o r p t i o n e n t h a l p y ; 8,
f r a c t i o n a l sorbent coverage. I n t h e o r i g i n a l e q u a t i o n f o r fl ( r e f . 9, eq. 11) a
simple Langmuir model equation was s u b s t i t u t e d i n o r d e r t o o b t a i n eq. 10. B
reaches i t s maximum v a l u e a t 0 = 0.5.
TABLE 2

Results o f thermal a n a l y s i s on n-hexane and 3-methylpentane d i f f u s i o n a t

295 K i n ZSM-5 c r y s t a l s o f v a r i o u s s i z e s .
~ ~~

compound c r y s t a1 spec. e x t . “T B Q,/B

height(pm) area (m-’)

n-hexane 19 4.4*105 1.3*104 4.2 3. 1*103

39 2.8*105 3.4*104 4.2 8. 1*103
56 1.8*105 4.5*104 4.2 1. 1*104
65 1.5*105 5.1*104 4.2 1. 2*104

3-methylpentane 19 4.4*105 1.8*105 1.2 1. 5*105

39 2.8*105 4.9*105 1.2 4. 1*105
56 1.8*105 6.4*105 1.2 5.3*105
65 1.5*105 7.2*105 1.2 6.0*105

I n Table 2 results a r e g i v e n from a thermal a n a l y s i s o f n-hexane and 3 -

methylpentane s o r p t i o n a t 295 K i n t h e f o u r s e l e c t e d ZSM-5 samples. Parameters
r e l e v a n t t o t h e c a l c u l a t i o n s have t h e f o l l o w i n g values:

n-Hexane: -AH = 8.6*10 4 (J .mol - )

D = l.O*lO-lo (cm2. s e c - l )
c: = 1.3*10-3 (mol . g - l )
3-Methylpentane: -AH = 6*10 4 ( J .mol-’)
D = 7*10-12 (cm2.sec-l)
 527

C: = 8.0*10- 4 (mol .g-')

- 1 -1
Z e o l i t e 2SM-5: cS = 0 . 8 (J.g * K 1
6
p, = 1.78*10 (g.m-3)
- f o r t h e c r y s t a l radius (R) i s taken h a l f the c r y s t a l
height
- the s p e c i f i c external surface area (a) has been
c a l c u l a t e d based on t h e c r y s t a l shapes shown i n Figure
2, assuming a roughness f a c t o r o f 2.

Furthermore, the heat transfer coefficient (h) has been estimated by

considering a r a d i a t i o n c o n t r i b u t i o n a t 295 K only. Using Stefan's law a value
for h o f 4.6 J.s'1.m-2.K-1 has been calculated. The thermal analysis presented
i n Table 2 rules out an i n f l u e n c e o f thermal e f f e c t s on the uptake curves.
However, caution should be exerted with regard to the values of the
diffusivities given above. I t i s n o t uncommon t h a t they show discrepancies
which amount t o several orders o f magnitude ( 2 0 ) . This problem diminishes t h e
clearness o f the c a l c u l a t i o n s shown i n Table 2, because aT s t r o n g l y depends on
the d i f f u s i v i t y (D).

RESULTS AND DISCUSSION

The r e s u l t s presented here concern the d i f f u s i o n o f n-hexane a t 295 K and o f

3-methylpentane a t 348 K. Some a d d i t i o n a l work on d i f f u s i o n o f these two
compounds w i l l be reported elsewhere. As can be seen i n Figure 3 the s o r p t i o n
isotherms o f n-hexane i n H-ZSM-5 are always i n s u f f i c i e n t agreement f o r t h e
various zeolite samples.
However, t h e e q u i l i b r i u m s o r p t i o n data o f 3-methyl-
pentane show some considerable s c a t t e r i n g ( c f . Figure 4). As t o the q u a l i t y o f
the fit when applying Dubinin-Polanij's equation (eq. 4) on the isotherms, i t
appears that the equilibrium data follow more c l o s e l y the simple Langmuir
model. Nevertheless, the latter model was not adopted to represent t h e
isotherms because most assumptions on which Langmuir's theory i s based, v i z .
the homogeneity o f s o r p t i o n s i t e s and t h e formation o f a mono-molecular sorbate
layer, do not meet r e a l i t y as f a r as s o r p t i o n i n z e o l i t e ZSM-5 i s concerned
(20) *
The concentration dependence of the apparent as well as the i n t r i n s i c
diffusivity is shown i n Figures 5 and 6 f o r n-hexane and 3-methylpentane, as
determined w i t h the sample having t h e longest c r y s t a l size, v i z . R
appears t h a t near s a t u r a t i o n both the apparent and t h e i n t r i n s i c d i f f u s i v i t i e s
- 33 pm. I t

o f n-hexane and 3-methylpentane increase w i t h t h e degree o f pore f i l l i n g .

Errors i n d i f f u s i v i t i e s appear t o amount t o about h a l f an order o f magnitude,
528

f
Fig. 3. Sorption isotherms of n-hexan6 Fig. 4. Sorption isotherms of 3-me-
in H-ZSM-5 type zeolites of three thylpentane in H-ZSM-5 type
crystal sizes at 295 K:
R-9.6/.ma, R.20 pm; 0, R-28 pm.
+, zeolites o f three crystal
sizes at 340 K: 0, R-9.6 p ;
+, R-20 pm; 0,R-33 jm.

c 1 2 3 4
Number n-h’exonc molecules Number 3 - Methy!?entonc molecules
per unit cel per uni: cel
Fig. 5. Concentration dependence of ap- Fig. 6. Concentration dependence of
parent (X) and intrinsic diffusi- apparent (x) and intrinsic
vities (m) of n-hexane at 295 K diffusivities (a) of 3-me-
thylpentane at 3 4 8 K

I I I
I I I
10.6 13-5 10.6 10-5 13-6
R ~ - 1cm21 R2- Icrn2)
Fig. 7. Characteristic diffusion time Fig. 8. Characteristic diffusion time of
o f n-hexane in H-ZSM-5 as a 3-rnethylpentane in H-ZSM-5 as a
function o f square o f crystal function of square of crystal
radlus at 295 K and at
fractional coverage 0 0.62 - radius at 348 K and at
fractional coverage 0 0.70
 529

viz. 5*10-11 cm2/s. The strong concentration dependence o f diffusivity, with

respect to zeolites, is not uncommon. Diverse dependences have been reported
earlier (2).
A simple criterion for intracrystalline diffusion is a linear relationship
between the characteristic diffusion time and the square o f the crystal radius
(R'), indicating diffusivity t o be independent of crystal size (10). If so, the
assumption that no thermal or surface-barrier effects affect the sorbate uptake
rate is justified. The possibility o f the intrusion of an intercrystalline
diffusion-limited process may then be excluded as well. However, a problem may
arise when serious deviations from the linear relation are t o be interpreted,
because it is not easy to decide which of the above-mentioned effects is mainly
responsible for a deviation. Solutions of extended differential equations (with
regard to the simple case of an isothermal, intracrystalline regime), which
take account of those phenomena, should then be used t o make proper selections
and estimations (20).
Figures 7 and 8 show characteristic diffusion times (R2/DaPP) o f n-hexane and
3-methylpentane as a function of the square o f the crystal radius. A linear
relationship between the characteristic diffusion time and the square of the
crystal radius is indeed observed. However, it appears that a deviation o f the
linear relationship occurs at R2= 9.1)*10-~ cm2 (crystal length = 2 6 pm), for
both n-hexane diffusion at 295 K and 3-methylpentane diffusion at 348 K.
Experiments with crystals having radii larger than 33 pm are planned t o confirm
this tentative conclusion. Moreover, in addition t o this approach it is
worthwhile to study zeolitic diffusion with equal samples but using different
techniques. Karger and Car0 compared results derived from sorption kinetics
with self-diffusivities obtained by an n.m.r. pulsed field gradient technique
(2, 21). Discrepant values, left unreconciled, have been obtained this way. On
the other hand, comparison o f the gravimetric with a chromatographic measuring
technique did result in agreeing values, e.g. the diffusivities of 2,2-
dimethylbutaan in H-ZSM-5 with a very high Si/A1 ratio at high temperatures
(448-563 K ) showed excellent agreement (10). As t o n-hexane and 3-methyl-
pentane diffusion in zeolite ZSM-5, in Table 3 a literature survey is given of
diffusivities measured with different methods and at various temperatures.
Comparison with the results presented here (Table 3) gives rise t o serious
contradictions as far as diffusion o f n-hexane is concerned. The results given
in Table 3 strongly point t o a need for more studies with different methods
using the same zeolite sample.
530

TABLE 3
Literature and present data on diffusion in zeolite ZSM-5 of n-hexane and
3-methylpentane.

Compound Data on Temp. D Measuring Ref.

ZSM-5* (K) (cm2/s) technique

3-Methyl - H-ZSM-5 296 6.6*10-11 Grav i me t ry , 8

pentane Si/A1-23 constant volume
c=6 pm, b=3 pm constant pressure
3-Methyl - H- ZSM-5 296 7.0*10-12 Gravimetric, 8
pentane Si/A1=23 constant volume
spherul i tes .. constant pressure
3-Methyl - H-ZSM-5 Constant volume this
pentane Si/A1=40 variable pressure work
c=26 - 150 pm
b=19 - 65 pm

n -Hexane H-ZSM-5 313 4*1oV9 Grav i met ry 13

S i/Al=17
0.5 and 14 pm
n -Hexane Na,H-ZSM-5 323 1*10-8- Const. volume 14
Si/A1=34 1*10-~ var. pressure
c=35 pm, b=lOpm
n-Hexane ? 303 7.5*10-12 ? 15
n -Hexane Na-ZSM-5 303 1 .31*10-1° Grav i me t ry , 16
Si/A1=66 const. volume
7 Pm const. pressure
n-Hexane sil ical ite 373 and 4.2*10-11 Gravimetry, 17
2 pm (sphere) 473 1 .33*10-1° const. volume
resp. const. pressure
n-Hexane H-ZSM-5 295 5*10-11- Const. volume this
Si/A1=40 1*10-l0 var. pressure work
c=26 - 150 pm
b=19 - 6 5 pm
*
c = crystal length, b = crystal height
 531

CONCLUSIONS

- Near s a t u r a t i o n the apparent as w e l l as t h e i n t r i n s i c d i f f u s i v i t i e s o f

n-hexane and 3-methylpentane i n H-ZSM-5 increase w i t h t h e degree o f pore
filling
- It appears that ZSM-5 crystals with a h e i g h t o f 20 pm are t o o small t o
measure the i n t r a c r y s t a l l i n e d i f f u s i v i t y o f n-hexane and 3-methylpentane a t
temperatures of K and 348 K r e s p e c t i v e l y . Experimenting w i t h samples
295
having crystal heights
l a r g e r than 40 pm probably ensures i s o t h e r m i c i t y o f
t h e sorbents and/or exclusion o f s u r f a c e - b a r r i e r 1i m i t e d sorbate uptake.

ACKNOWLEDGEMENTS

The authors would l i k e t o thank Prof. J. J. F. Scholten M r . N. van Westen and

M r . J. Teunisse o f the Laboratory f o r Chemical Techno ogy f o r t h e use o f the
experimental equipment and f o r h e l p f u l assistance. M r J . F. van Lent o f the
Laboratory o f Metallurgy i s acknowledged f o r t h e X-ray d f f r a c t i o n analysis.
M r . Th. W. Verkroost o f t h e Department o f Mining Engineering i s acknowledged
f o r c a r r y i n g out the X-ray fluorescence measurements.

REFERENCES

1. R. M. Barrer, Adv. Chem. Ser. "Molecular Sieve Z e o l i t e s " , 102 (1971) 1.

2. R. M. Barrer, " Z e o l i t e s and Clay Minerals as Sorbents and Molecular
Sieves", Academic Press, London, (1978), Chapter 6.
3. R. M. Barrer, "Zeolites: Science and Technology", F.R. Ribeiro, e t
al., Eds., Martinus N i j h o f f Publishers, The Hague, (1984), 261.
4. D. M. Ruthven, Am. Chem. SOC. Symp. Ser., 40 (1977) 320.
5. M. Ghamami and L. 6. Sand, Zeolites, 3 (1983) 155.
6. S. 2. Chen, K. Huddersman, D. K e i r and L. V. C. Rees, Zeolites, 8 (1988)
106.
7. K. Beschmann, G. T. Kokotailo and L. Riekert, Chem. Eng. Process., 22
(1987) 223.
8. D. P r i n z and L. Riekert, B e r . Bunsenges. Phys. Chem., 90 (1986) 413.
9. L. K. Lee and D. M. Ruthven, J. Chem. SOC. Faraday Trans. I , 75 (1979)
2406.
10. M. F. M. Post, J . van Amstel and H. W. Kouwenhoven, Proc. 6 t h I n t . Z e o l i t e
Conf. Reno, D. H. Olson e t al., Eds., Butterworths, Guildford, (1983), 517
11. V. J. F r i l e t t e , W. 0. Haag and R. M. Lago, J. Catal., u ( 1 9 8 1 ) 218.
12. W. . 0. Haag, R. M. Lago and P. 6. Weisz, Faraday Disc. Chem. SOC., 72
11982) 317.
13. J . Heering, M. K o t t e r and L. Riekert, Chem. Eng. Sci., 37 (1982) 229.
14. M. Bulow, H. Schlodder and P. Struve, Adsorpt. Sci. T e c F o l . , 3 (1986) 229
15. P. Wu, A. Debebe and Y . H. Ma, AIChE Winter Meeting, Orlando, FL, Paper
55a, (1981).
16. Y. H. Ma, T. D. Tang, L. 6. Sand and L. Y. HOU, Proc. 7 t h I n t . Z e o l i t e
Conf. Tokyo, Y. Murakami et a1 ., Eds., Elsevier, Amsterdam, (1986) 531.
17. P. Wu, A. Debebe and Y. H. Ma, Z e o l i t e s , 3 (1983) 118.
18. M. K o c i r i k and A. Zikanova, Ind. Eng. Chem. Fundam., 13 (1974) 347.
19. M. Biilow, P. Struve, G. Finger, C. Redszus, K. Ehrhardt and W. Schirmer,
J. Chem. SOC. Faraday Trans. I , 76 (1980) 597.
20. D. M. Ruthven, P r i n c i p l e s o f Adsorption and Adsorption Processes,
J. Wiley, New York, (1984).
21. J. Karger and J . Caro, J. Chem. SOC. Faraday Trans. I , 73 (1977) 1363.
This Page Intentionally Left Blank
H.G.Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science PublishersB.V., Amsterdam - Printed in The Netherlands

A COMPARATIVE STUDY BY DEUTERON SOLID STATE NMR SPECTROSCOPY OF THE DYNAMICS

OF BENZENE AND OLCFINS IN FAUJASITE- AND MORDENITE- TYPE ZEOLITES

B. BODDENBERG, R. BURMEISTER and G. SPAETH

Lehrstuhl fur Physikalische Chemie 11, Universitat Dortmund, Otto-Hahn-Str.,
D-4600 Dortmund 50 (Federal Republic of Germany)

ABSTRACT
From the lineshapes of the H' NMR spectra of benzene, ethene and propene
sorbed in X-type zeolites the anisotropic and isotropic rotations of these
molecules are assess9 and intracrystalline diffusion coefficients obtained.
For comparison, the H NMR spectra for these molecules in mordenite are pre-
sented.

INTRODUCTION
In recent years deuteron ( 2H) solid state NMR spectroscopy has proved
to be a very powerful tool for the investigation of the microdynamics of
molecules adsorbed on solid surfaces (refs. 1-9) as well as in the voids
of zeolites (refs. 10-17). This technique is used to study in which way and
how fast a deuterium-containing bond axis of a molecule is orientationally
moved in space, thus allowing conclusions to be drawn about internal rotations
as well as anisotropic and isotropic molecular reorientations.
The present contribution addresses the study by *H NMR of the anisotro-
pic reorientations as well as the site exchange motions of benzene, ethene,
and propene molecules sorbed in the supercages of X-type faujasites and in
the channel system of mordenite. The main emphasis is placed on the
molecule/faujasite systems, whereas the results obtained for the molecule/mor-
denite systems serve for comparison purposes.

THEORETICAL BACKGROUND
The LH-NMR spectrum exhibited by the deuterons (spin I = 1) in specified
carbon/hydrogen bonds of like molecules with random orientational distribu-
tion in space is displayed in Fig. 1. From the prominent edge splitting of
this Pake type powder pattern the deuterium quadrupole coupling constant
(DQCC) may easily be derived according to (ref. 18):

Av = (3/4) IDQCCI. (1)

The coupling constant defines the characteristic NMR time TNMR = IDQcCI-l.
534

I L

Generally, the shape and width of a H' spectrum depend on the type of
the rotational motion of the molecule a s well as on the correlation time
T of this rotation in relation to TmR. Actually, the Pake pattern shape
(Fig. 1) shows up under certain limiting conditions, of which two are of
importance in the following. (i) The rate of rotational motion is much lower
-1 .
than ( T ~ ~ , )1.e. T >XmR (rigid o r slow orientational exchange case).
2
Then DQcC in eqn. 1 represents the rigid coupling constant e qQ/h. With typi-
2
cal values of e qQ/h in the range 150 to 200 kHz for deuterons in carbon/hy-
drogen bonds (ref. 19) T~~ amounts to several microseconds. (ii) The molecu-
les rotate rapidly about an axis fixed in space, e.g. a molecular symmetry
axis. Rapid rotation means that the correlation time T of this rotation
meets the condition T ~ < < (fast
T ~ orientational exchange case). Under these
circumstances DQCC in eqn. 1 is given by the relation (refs. 18, 20)

2
DQCC = (1/2) (3 cos A-l)(e2qQ/h)
(2)
where A is the angle between the C-D bond direction and the axis of rotation.
It is, however, required that the potential energy as function of the angle
of rotation exhibits at least threefold symmetry. I n other cases such as
180' reorientational jumps quadrupole patterns of different shapes, in gene-
ral, result.
If the correlation time T~ of the previously considered uniaxial rotation
(and similarly T of any other type of rotation) becomes the order of T ~ ,
rather involved pattern shapes show up, the analysis of which requires much
computational effort based on detailed mechanistic models for the molecular
rotational processes involved. Pursuing this path with the presently studied
systems is hardly feasible because of the lack of criteria to differentiate
 535

between motional and heterogeneity effects on the spectrum shapes.

If the deuteron carrying molecules rotate isotropically and the corre-
lation time T~ of this motion meets the condition of fast exchange ('CR<<TNMR)
the 'H-NMR spectrum consists of a single line of, in general, Lorentzian
shape. The width at half height (6v) of this singlet is (ref. 20)
n

6v = (9n/20) (DQCC)L~R (3)

-1
under the constraint TR>>wo . DQCC is the rigid quadrupole coupling con-
stant. Eqn. ( 3 ) likewise is valid with DQCC given by eqn. ( 2 ) if the axis
around which the molecule is in rapid rotation is reoriented ra$idly and
isotropically in space, and the condition R >>.rP is
'I fulfilled (ref. 17).
The isotropy of the rotational motion is given if the potential energy as
function of the solid rotation angle exhibits spherical or cubic symmetry.

EXPERIMENTAL
The zeolites used for the present investigation were NaX (13X, Union Car-
bide) and Na-MOR (Zeolon 900, Norton). The partially (40%) silver exchanged
X zeolite (40AgNaX) was prepared from NaX according to standard procedures
(refs. 17, 2 1 ) . The zeolites were put into 10 mm 0.d. NMR glass tubes and
slowly heated under vacuum to 43OoC at which temperature they were kept for
-5
about 12 hrs. under a final pressure < 10 hPa. Separate samples were loaded
with calibrated amounts of benzene-d6 (99.5% D; Sigma, Geisenhofen, Germany),
ethene-d4 (99%; Merck, Sharp and Dohme (MSD), Montreal, Canada), and pro-
pene-dg (CD3CHCH2, 98%; MSD) to give well defined sorbate concentrations
in the range 1 to about 8 molecules/unit cell.
Using the equipment and the detailed procedure described elsewhere
2
(ref. 17) the H-NMR spectra were measured at the resonance frequency wo/2n
= 52.7 MHz by Fourier transformation of coherently added free induction decays

and solid state quadrupole echoes (ref. 22) detected in quadrature in cases
where isotropically averaged and solid state time domain spectra were ob-
served, respectively. Depending on the loadings of the zeolites and of the
widths of the spectra encountered, the number of accumulations was of the
order of 100 to 2500 with, in general, 0.5 to 1 s recycle delay time.

RESULTS AND DISCUSSION

Benzene in NaX, AgNaX and Na-MOR
Fig. 2 shows the H' NMR spectra of benzene sorbed in the zeolites NaX,
40AgNaX (1 molecule/supercage each), and Na-Mordenite (1 molecule/unit cell
(u.c.)) at several selected temperatures between 80 and 290 K. In each case
Pake powder patterns of AV = 70 kHz prominent edge splitting show up at low
536

T = 291 K
- ~~

T = 222 K
Jc K
T = 150
25 k n i

K
25 k h

T = 7 7 K

T = 292 K 1 = 222 K T = 100 K T = 7 7 K

T = 289 K
~~

T = 200 K
K 25 kHt

T = 9 8 K
Jc 25 knl

T = 7 7 K

"
Fig. 2. LH NMR spectra of benzene sorbed in (a) NaX, 1 molecule/supercage,
(b) 40 AgNaX, 1 molecule/supercage, and (c) Na-MOR, 1 molecule/unit cell.

temperatures. With increasing temperature the LH patterns of benzene in the

faujasites retain shape and width up to about 170 K (NaX) and 225 K(AgNaX),
but after crossing subsequent 30 K shape transition ranges become completely
transformed into Lorentzian-type singlets of halfwidths obeying an Arrhe-
nius-type law with activation energies of 22.5 (NaX) and 41 (4OAgNaX) kJ
mol-' (Fig. 3 ) . For benzene in mordenite, on the other hand, the patterns
remain practically unchanged up to ambient temperature.
The quadrupole coupling constant obtained from the powder patterns is
2
IDQCCI = 93 kHz (eqn. 1) which is just one half of e qQ/h in the range 184
to 187 kHz for the deuterons in the benzene molecule (refs. 23, 2 4 ) . From
eqn. (2) A = 90' is obtained, which proves that on the NMR scale ( 2 5 us)
the molecules rapidly reorient around the hexad axis with no other rotational
type of motion being feasible at temperatures where the quadrupole patterns
are observed. In mordenite it is, obviously, the geometric constraint imposed
by the 0.58 x 0,70 nm main channel cross section (ref. 25) which permits
a benzene molecule to reorient only around the sixfold symmetry axis. This
motion proceeds rapidly on the NMR time scale even at 77 K. This conclusion
agrees with the results of a recent neutron scattering study of benzene in
 537

l*t bvl Hz

Fig. 3. Temperature dependence of the widths at half height (6u) of the Lo-
rentzian singlets of molecules in NaX (open symbols) and lOAgNaX (filled
symbols) at 1 molecule/supercage loading. &A:Ethene. 0,O:Propene. 0,WBenzene.

Na-MOR performed at temperatures between 300 and 450 K (ref. 2 6 ) . The transla-
tional displacement of the molecules along the unidirectional channel axes
2
reported in that paper cannot, of course, be detected byH NMR because there
is no change of molecular orientation accompanying this motion.
The presently detected rapid C6 rotation motional state of benzene in
2
the faujasites deduced from the Pake shapes of the H patterns confirms pre-
vious findings (for NaX) from NMR line shape (ref. 11) and 1H NMR second
moment (ref. 27) studies. In NaX the anisotropically rotating benzene mole-
cules are considered to be bound to the cations located at the SII crystallo-
graphic sites (ref. 27) which are the apices of regular tetrahedra (ref. 21).
The collapse of the low temperature quadrupole patterns into singlets
(Fig. 2) indicates that a further motion moving the C6 axes of the molecules
isotropically in space is operative. The rate of this motion runs through
( TNMR)-l at some temperature within the previously mentioned shape transition
regions centered at 185 and 240 K for NaX and 40AgNaX, respectively. Applying
eqn. (3) to the line width data for benzene in Fig. 3 with IDQcC( = 93 kHz the
correlation times T~ for the isotropic motion are evaluated as T~ = 2*10-12
exp(2700/TK-l) s (ER = 2 2 . 5 kJ mol-l) for benzene in NaX, and ‘ I =
~ 1*10-14
exp( 49OO/TK-l) s for benzene in 4OAgNaX.
In NaX the isotropic motion being operative is most reasonably explained
(ref. 17) as consisting of the jumping of the molecules among the strongly
538

+
bonding Na ions on SII sites, thereby identifying T~ with the mean molecular
residence time on such a cation site. This notion implies that according
to the relationship

D = <12>/6'rR (4)
the intracrystalline diffusion coefficient D is accessible with <12> being
the mean square displacement per elementary site exchange jump. Putting as
an e s t i m a t e m = 1.1 nm (refs. 17, 28), which is the supercage distance
(ref. 21), diffusion coefficients are obtained that agree excellently with
respect to both the preexponential factor and the activation energy with
the data obtained with the aid of the proton ( 1H) pulsed field gradient (PFG)
technique (ref. 29). At 300 K the diffusion coefficient evaluated from the
present data is D(C6D6,NaX) = 1.3*10-11m2s-1. For comparison, the diffusion
coefficient of benzene at 300 K in Na-MOR is 7*10-11
m s * -'
(ref. 26). Notably
the present 2H NMR lineshape-derived diffusion coefficients are obtained
with commercially available zeolite materials of vm crystallite sizes where-
as the determination of D by means of the 'H PFG technique requires much
larger crystals (ref. 29).
The shift by about 60 K to higher temperature of the shape-transition
region of benzene in 4OAgNaX compared to NaX reflects the stronger a-bonding
t t
capability of Ag than Na ions. Accordingly, the previously derived expres-
sions for T~ of benzene in NaX and 4OAgNaX yield the relation 'rR(40AgNaX)
>>T (NaX) in the temperature range under study, suggesting the identification
R +
of T~ (40AgNaX) with the residence time of a molecule on a Ag site (ref.17).
Applying eqn. ( 4 ) with = 1.1 run as before, the intracrystalline diffu-
sion coefficient may be estimated. At 300 K the resulting value is D(C6D6,
4OAgNaX) = 1.5*10-12m2s-1, which is an order of magnitude lower than in NaX.

Ethene in NaX, AgNaX and Na-MOR

Fig. 4 shows the 2H NMR spectra of ethene in NaX ( 1 . 2 molecules/supercage) ,
40AgNaX ( 1 molecule/supercage) , and Na-MOR (1.4 molecule/u.c.) at several
selected temperatures between 80 and 290 K. Like benzene (Fig. 2b), ethene
in AgNaX exhibits Pake patterns at low temperatures with, however, 130 kHz
edge splitting, and singlets at high temperatures. The shape-transition region
is centered at about 230 K. For ethene in NaX and Na-MOR similar quadrupole
patterns of 130 kHz widths but of non-Pake shape are observed below about
80 K. Whereas in NaX the quadrupole patterns break down into singlets through
a shape-transition range centered at about 90 K, the development of the spec-
trum shapes for ethene in Na-MOR is much more involved. Characteristically,
 539

T = 289 K T = 222 K T = 119 K T = 7 8 K

T = 291 K T = 250 K T = 167 K T -77K

1'
1' XI
Lv
T = 284 K T = 220 K T = 125 K T = 8 1 K

Fig. 4. 2H NMR spectra of ethene in (a) NaX, 1.2 molecules/supercage,

(b)40AgNaX, 1 molecule/supercage, and (c) Na-MOR, 1.4 molecules/unit cell.

in the latter case the spectra continuously change shape and total width
but do not attain the Lorentzian singlet shape and rather narrow width
( < 100 Hz) of the NaX sample. The temperature dependence of the singlet line-
widths of the ethene/faujasite systems is shown in Fig. 3.
The splitting of the Pake pattern edges f o r ethene in 40AgNaX yields IDWC)
2
= 173 Idlz, in agreement with e qQ/h = 175 kHz for deuterons in the ethene
molecule (ref. 30). Hence, at these temperatures all rotational types of
motion conceivable proceed slowly on the NMR time scale in contrast t o benzene
where the hexad axis rotation is fast. Applying eqn. ( 3 ) to the corresponding
linewidth data of Fig. 3, the site-exchange correlation time rR is obtained
as TR = 7*10-12exp(2900/TK-1) s (ER = 24 kJ mol-l) for ethene in 40AgNaX.
The unusual temperature dependences both of the pattern shapes (Fig. 4)
and the linewidths 6v (Fig. 3) of the ethene/NaX system are the result of
the combined influence of the site exchange (T~) and of the reorientation
of molecules around the 7r-electron/cation bond axis (T~) (ref. 17). The more
detailed analysis of the low temperature pattern shapes as well as the singlet
linewidth temperature dependence going beyond the simple formula given in
540

eqn. ( 3 ) (ref. 17), yields the correlation times for both types of rota-
tional motion as follows: = 3*10-13exp(1700/TK-1)
'I~ s (ER = 14 kJ/mol),
'Ip = 2*10-11exp(850/TK-1) s (EP = 7 kJ mol) for ethene in NaX.
Identifying -rR in NaX and 40AgNaX with the mean residence time of an ethene
molecule on a Na
+ and Ag
+ cation site, respectively, and using the estimate
m= 1.1 nm as before, eqn. (4) yields diffusion coefficients the values
of which at 300 K are D(C2D4,NaX) = 2*10-9m2/s-1 and D(C2D4,40AgNaX) =
2*10-12 2 -1
m s .
The former value is in excellent agreement with the 'H PFG-de-
rived value (ref. 32); the latter is in the range of the values obtained
with the 1H PFG and adsorption kinetics techniques (ref. 31). The large diffe-
rences found for the diffusion coefficients at 300 K as well as for the acti-
vation energies between NaX and 4OAgNaX clearly reflect the much different
strengths of bonding of ethene t o the sodium and silver cations due to the
greater n-bonding capability of the latter (ref. 32). The clearest demonstra-
tion of this effect is the large shift of the pattern/singlet transition
range center from 90 to 230 K corresponding to the large shift of the line-
width curves of Fig. 3.
The results presently obtained indicate that the rate of site exchange
+
of ethene bound to Ag is much faster than the rate of anisotropic rotation
around the n-electron/cation bond. From T~ and T~ given previously for NaX
it is calculated that at about 210 K the rates of these two motions become
equal, and at 300 K the site exchange is the faster motion as in the case
of the silver-exchanged zeolite. These results support the conclusions from
'H NMR studies (refs. 33, 34) and can hardly be explained with the notion
of a free rotation around the a-electron/cation bond axis (ref. 32). In
addition, a Pake-pattern type spectrum with Av = 65 kHz should have shown
up at T < 80 K under these circumstances, which is not the case (Fig. 4).
A quantitative explanation of the spectra of ethene in Na-MOR is hardly
feasible at present mainly because the location of the molecules is not known.
The saturation capacity of ethene in Na-MOR was found (ref. 35) to be 7.7
molecules/u.c, (O°C adsorption isotherm) which requires the occupancy not
only of the main channels but also of the side pockets (refs. 21, 36).
Nevertheless, the similarity of shape of the 2H patterns of ethene in NaX
and Na-MOR at about 80 K indicates that in mordenite as in NaX the molecules
+
are bound to Na , with the rotation around the n-electron/cation bond axis be-
ing in the fast/slow transition regime. The further development with increas-
ing temperature of the mordenite spectra signify site-exchange processes
to be operative, the detailed nature of which is presently under study.
 541

T = 270 K T = 200 K
1207*r
'1 JY 20 L H I

T = 133 K
20 L H t

T = 105 K

I
T = 292 K
201-;IHr

T = 200 K
1JY 20

T = 167 K
knI 20 LHr

T = 133 K

n- L -KA
T = 292 K
20 LHr

T --
20 LHr

200 K
20 LHr

T = 132 K
20 LHr

T = 110 K

Fig. 5. *H NMR spectra of propene (CD3CHCH ) in (a) NaX, 1 molecule/super-

cage, ( b ) 4OAgNaX, 1 molecule/supercage, an% (c) Na-MOR, 3 . 3 molecules/unit
cell.

Propene in NaX, AgNaX and Na-MOR

2
The H NMR spectra of propene-dg at 1 molecule/supercage loading in NaX
and AgNaX (Fig. 5a and b) develop from Pake patterns with Av = 37 kHz edge
splitting at low temperatures into singlets at high temperatures with the
shape transition regions centered at about 115 K (NaX) and 145 K (40AgNaX).
The linewidths of the singlets as function of temperature are included in
Fig. 3 . In comparison to NaX the 2H spectra of propene in Na-MOR ( 3 . 3 mo-
lecules/u.c.) are the same at low temperatures up to about 135 K but exhibit
much more complex shapes at higher temperatures.
The quadrupole coupling constant IDQCCl = 49 H z derived from the pattern
edge splittings is typical for rapidly rotating methyl groups attached to
sp2-hybridized carbon atoms (ref. 18). At lower temperatures, therefore,
the molecules are seen in slow overall motion with rapidly rotating methyl
groups attached to them. Assigning again the breakdown of the quadrupole
patterns into singlets to the site-exchange motion, and analyzing the curves
in Fig. 3 according to eqn. 3 gives T~ = 2*10-12exp(1800/TK-1) s (ER = 15 kJ
mol-l) for propene in NaX, and TR = 8*10-12exp(2050/TK-1) s (ER = 17 kJ mol-l)
542

for propene in 4OAgNaX.

Inserting these expressions into eqn. (4), and again using the estimate
= 1.1 nm, intracrystalline diffusion coefficients are accessible which
at 300 K are calculated to be D(prop.. NaX) = 2.5*10-lo m2 s-' and D(prop.,
-'
4OAgNaX) = 2.7*10-11 m s.
The change of the temperature-independent Pake patterns into spectrum
shapes with temperature-dependent widths of propene in Na-MOR sets in at
.
considerably higher temperature (135 K) than in NaX (108 K ) Considering
the sodium cations as adsorption sites in both cases, this shift is an indica-
tive of a stronger bonding of propene in Na-MOR in comparison to NaX. The
change of spectrum shape and width observed for the propene/Na-MOR sample
at temperatures > 135 K is undoubtedly also due to site-exchange motions.
In order to obtain quantitative results, spectrum-shape calculations are
required which take account of the non-cubic symmetry of Na-MOR. Such work
is being undertaken at present.

ACKNOWLEDGEMENTS
The authors thank Prof. Dr. F. Fetting, Darmstadt, for the gift of the
mordenite zeolite. This work was supported by "Deutsche Forschungsgemein-
.
schaft" and "Fonds der Chemischen Industrie"

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22 J.H. Davis, K.R. Jeffrey, M. Bloom, M.I. Valic and T.P. Higgs, Chem.
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This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V.,Amsterdam - Printed in The Netherlands

PROBING THE HYDROGEN SORPTION STATES I N ZEOLITES A BY INFRARED SPECTROSCOPY

AND LOW-TEMPERATURE GAS CHROMATOGRAPHY SUPPLEMENTED BY THEORETICAL CALCULA-
TIONS

H. F o r s t e r , W . Frede’ and G. P e t e r s ’

I n s t i t u t e o f P h y s i c a l Chemistry, U n i v e r s i t y o f Hamburg, Bundesstr. 45,

P-2000 Hamburg 13, FRG
P r e s e n t Adress: Valvo A p p l i c a t i o n L a b o r a t o r i e s , V o g t - K o l l n - S t r . 30,
F-2000 Hamburg 54, FRG
P r e s e n t Adress: Reemtsma C i g a r e t t e n f a b r i k e n GmbH, L u r u p e r Chaussee 145,
D-2000 Hamburg 50, FRG

ABSTRACT
The s o r p t i o n s t a t e s o f hydrogen and d e u t e r i u m i n t h e sodium and mixed
sodium-calcium forms o f z e o l i t e A, c h a r a c t e r i z e d by t h e s i t e s o f i n t e r a c t i o n
and t h e microdynamics performed by t h e adsorbate, have been e x p l o r e d by I R
spectroscopy and low-temperature gas chromatography. Bonding t o t h e z e o l i t e i s
near t h e l i m i t o f pure p h y s i c a l i n t e r a c t i o n w i t h no e s s e n t i a l charge t r a n s f e r
i n e i t h e r d i r e c t i o n . Wells on t h e i n t e r a c t i o n p o t e n t i a l s u r f a c e a r e a t t r i b u t e d
t o d i f f e r e n t s u r f a c e compounds i n a c c o r d w i t h s p e c t r o s c o p i c and GC r e s u l t s .
The i s o s t e r i c h e a t o f a d s o r p t i o n i s e v a l u a t e d by a s t a t i s t i c - m e c h a n i c a l
t r e a t m e n t b e i n g i n good agreement w i t h t h a t e x p e r i m e n t a l l y o b t a i n e d f r o m t h e
isotherms.

INTRODUCTION
The application o f z e o l i t e s as d r y i n g agents, selective adsorbents and
catalysts is based on t h e i n t e r a c t i o n phenomenon i n s i d e the zeolite pore-
c a v i t y system, whose e x p l o r a t i o n forms t h e key o f u n d e r s t a n d i n g t h e processes
i n v o l v e d . S o r p t i o n s i t e s and microdynamics o f p h y s i s o r b e d molecules, b a s i c a l l y
described by the sorption state, are determinable from the interaction
potential. From t h e l a t t e r b o t h I R s p e c t r o s c o p i c and thermodynamic q u a n t i t i e s
can be calculated. Spectroscopic q u a n t i t i e s a r e band positions and band
pattern as well as band i n t e n s i t i e s c o r r e l a t e d t o the coverage and site
symmetries, while adsorbed amounts and h e a t s o f a d s o r p t i o n can be inferred
f r o m s o r p t i o n measurements. A measure on t h e r e l i a b i l i t y o f t h e s e t - u p o f t h e
interaction p o t e n t i a l and t h e c h a r a c t e r i z a t i o n o f t h e s o r p t i o n s t a t e is the
correspondence between c a l c u l a t e d and e x p e r i m e n t a l v a l u e s . The o b j e c t i v e of
our s t u d y was t o i n v e s t i g a t e d e t a i l s o f t h e b e h a v i o r o f s i m p l e molecules on
the z e o l i t e i n t e r n a l s u r f a c e by I R spectroscopy and gas chromatography, in
order to contribute t o the enlightenment o f the molecular sieve mode of
operation.
546

Some time ago, we r e p o r t e d f o r the f i r s t time N I R s p e c t r a o f the overtones

o f adsorbed H2 ( r e f . l), showing a weak band whose h a l f w i d t h and frequency
shift w i t h r e s p e c t t o the f r e e molecule pure v i b r a t i o n a l overtone transition
are t w i c e t h a t o f the fundamental. Comparing fundamental and overtone spectra,
the bond d i s s o c i a t i o n energy o f b o t h hydrogen and deuterium i s o n l y n e g l i g i b l y
changed i n the adsorbed s t a t e i n agreement w i t h quantum chemical c a l c u l a t i o n s ,
indicating no e l e c t r o n i c charge t r a n s f e r from t h e adsorbed molecule to the
zeolite skeleton, so t h a t a classical set-up o f the interaction potential
seemed t o be j u s t i f i e d .
A c q u i r i n g i n f r a r e d a c t i v i t y o n l y i f a d i p o l e moment i s induced by interac-
tion, homonuclear d i a t o m i c s p l a y a unique r o l e as adsorbates, while the f r e e
molecule does n o t c o n t r i b u t e t o the spectrum. Hydrogen and deuterium are
e s p e c i a l l y s u i t e d f o r these k i n d s o f experiments, as t h e i r molecular proper-
ties are most p a r t i c u l a r l y e x p l o r e d and t h e i r low mass augments the sensiti-
v i t y o f these i n v e s t i g a t i o n s . As adsorbent z e o l i t e A was chosen, s e r v i n g as a
model adsorbent due t o i t s simple composition and s t r u c t u r e .

TABLE 1
Band p o s i t i o n s , frequency s h i f t s w i t h r e s p e c t t o t h e gas phase v - v ( g a s ) and t o
the main band v-v(main) o f hydrogen and deuterium adsorbed i n z e o l i t e s Na,Ca,A
( a l l i n cm-’). Assignment o f t h e bands i s g i v e n i n t h e l e f t column (An means
the change o f t h e t r a n s l a t i o n a l quantum number n ) .

Species Band p o s i t i o n v-v(gas) v-v(main) Band p o s i t i o n v - v ( g a s ) v-v(main)

Hydrogen Deuterium

Fundamentals
Gas(O+l) 4161.2 2993.6

A,/Ca 408814092.5 -73168.5 0 2939.5 -54 0

A2/Na 411814124 -43137 t30 2964 -29.6 t24.5

Overtones
8087.1 5867.1

A,lCa 7940 -147 5760 -107

Sate1 1 it e s
Tang.
t r a n s l . 413114148 t43 2973 t33.5
(An=tl)

Tang.
transl. 4047 41 2909 -30.5
(An=- 1)

Radial 190
 547

EXPERIMENTAL
The experiments were c a r r i e d o u t on t h e z e o l i t e samples Na,,A, Na,Ca,A and
Na,Ca,A (A = A l 1 2 S i 1 2 0 2 , +t)h e l a t t e r b e i n g prepared f r o m t h e sodium form by
ion exchange w i t h aqueous CaC1, s o l u t i o n s a t room temperature. The infrared
spectra o f s e l f - s u p p o r t i n g w a f e r s ( 5 - 8 mg/cm2 t h i c k n e s s ) i n a c r y o g e n i c cell
were recorded on a D i g i l a b FTS 20E spectrometer a t 1 cw' r e s o l u t i o n between 20
and 80 K . D e t a i l s o f t h e p r e t r e a t m e n t and h a n d l i n g o f t h e samples have been
g i v e n elsewhere ( r e f . 2 ) . The chromatographic equipment m o d i f i e d f o r low-tem-
p e r a t u r e s t u d i e s has been d e s c r i b e d i n a d i f f e r e n t paper ( r e f . 3 ) .

INFRARED AN0 GAS CHROMATOGRAPHIC RESULTS

The bands observed a f t e r l o a d i n g z e o l i t e Na,Ca,A w i t h hydrogen o r d e u t e r i u m
and t h e i r assignment a r e summarized i n Table 1.
F o r i l l u s t r a t i o n a t y p i c a l low coverage IR spectrum o f H, adsorbed i n zeo-
l i t e Na,Ca,A a t 90 K i s d i s p l a y e d i n F i g . 1. S h i f t e d downscale by 73 cm' w i t h
respect t o t h e p u r e v i b r a t i o n a l Raman t r a n s i t i o n o f t h e free molecule, the
main band c o n s i s t s o f a sharp d o u b l e t w i t h a s e p a r a t i o n o f 5 cm-', approximate-
l y ( r i g h t s i d e ) . Another narrow a b s o r p t i o n appears a t s l i g h t l y h i g h e r frequen-
cies, with i n c r e a s i n g i n t e n s i t y as t h e temperature i s l o w e r e d t o 45 K (left
s i d e ) . The main band i s accompanied by two broad s a t e l l i t e s +42 CIT' apart.

90 K

i j
--.- . 1

F i g . 1. Low-temperature i n f r a r e d s p e c t r a o f hydrogen adsorbed

i n z e o l i t e Na,Ca,A a t d i f f e r e n t temperatures.

I s o s t e r i c heats o f a d s o r p t i o n were e v a l u a t e d f r o m GC d e s o r p t i o n experiments

r a n g i n g f r o m 50 K t o room temperature as w e l l as f r o m l o w - t e m p e r a t u r e s o r p t i o n
isotherms and w i l l be d i s c u s s e d i n connexion w i t h t h e s t a t i s t i c a l l y obtained
heats.
G e n e r a l l y , on a l l z e o l i t e s i n v e s t i g a t e d o r t h o - p a r a hydrogen i n t e r c o n v e r s i o n
was observed, so t h a t i n a l l e x p e r i m e n t s p e r f o r m e d an e q u i l i b r i u m m i x t u r e of
t h e n u c l e a r s p i n isomers must taken i n t o account, depending on t e m p e r a t u r e i n
t h e adsorbed s t a t e .

INTERACTION POTENTIAL
The aim of t h i s paper i s t o d e s c r i b e t h e s o r p t i o n s t a t e o f H, in zeolites
NaCaA. In case of s t r o n g chemical i n t e r a c t i o n i t i s u s u a l l y sufficient to
specify the s o r p t i o n s i t e , t h e e q u i l i b r i u m geometry o f t h e s o r p t i o n complex,
the s t r e n g t h of t h e s o r p t i o n bond and i t s i m p a c t s on t h e i n t r a m o l e c u l a r bond
of the adsorbed molecules. I f o n l y weak van d e r Waals f o r c e s are present,
however, the admolecules r e t a i n p a r t o f t h e i r dynamical degrees o f freedom.
Consequently, i n these cases ( a s f o r t h e H , / z e o l i t e NaCaA system) t h e dynamics
o f t h e adsorbed molecules have t o be t a k e n i n t o account.
The interaction potential o f the s o r p t molecules i n the field of the
sorbent is the key o f understanding the characteristics of adsorption:
Depending i n g e n e r a l on a l l s i x degrees o f freedom o f a d i a t o m i c , i t can be
expressed as a f u n c t i o n o f the three s p a t i a l coordinates o f the center of
interaction, t h e two o r i e n t a t i o n a l c o o r d i n a t e s o f t h e m o l e c u l a r a x i s i n space
and t h e i n t r a m o l e c u l a r s t r e t c h i n g c o o r d i n a t e . I n t h i s way t h e p o t e n t i a l minima
describe the equilibrium configurations o f the sorption complex, i.e. the
sorption sites and the o r i e n t a t i o n s o f the molecule with respect to the
surface. Furthermore, t h e i n t e r a c t i o n p o t e n t i a l p r o v i d e s t h e p o t e n t i a l energy
term o f t h e time-independent Schroedinger e q u a t i o n f o r t h e adsorbed molecule.
I n t h i s way i t determines t h e r o t a t i o n a l and t r a n s l a t i o n a l eigenvalues, i.e.
the m o l e c u l a r dynamics on one hand and t h e f r e q u e n c i e s o f I R transitions on
the other. Thus observed I R bands can be compared w i t h t h o s e c a l c u l a t e d from
the i n t e r a c t i o n p o t e n t i a l t o check t h e r e l i a b i l i t y o f e q u i l i b r i u m configura-
t i o n s and m o l e c u l a r dynamics o b t a i n e d .
As i t is, i n general, impossible t o determine t h e i n t e r a c t i o n potential
exactly, one i s dependent on (more o r l e s s ) rough a p p r o x i m a t i o n s for model
calculations. If l o n g range p h y s i c a l i n t e r a c t i o n s a r e p r e d o m i n a t i n g , i t i s u-
sually expressed as a sum o f coulomb and inductive electrostatic, of
d i s p e r s i v e and r e p u l s i v e f o r c e s :
'
= "coul '
"ind ''disp 'rep' (l)
F o r t h e e v a l u a t i o n o f t h e e l e c t r o s t a t i c terms, t h e m o l e c u l a r charge d i s t r i b u -
tion i s developed i n t o permanent and induced m u l t i p o l e moments t h a t interact
w i t h t h e e l e c t r o s t a t i c p o t e n t i a l o f t h e s o r b e n t and i t s d e r i v a t i v e s ( r e f . 4 ) .
The d i s p e r s i o n i s p u t up a c c o r d i n g t o London ( s e e r e f . 4), w h i l e an
e x p o n e n t i a l A*exp(-mr) e x p r e s s i o n i s chosen f o r t h e r e p u l s i v e term. Each term,
except the i n d u c t i v e one, i s r e p r e s e n t e d by a sum over the corresponding
 549

i n t e r a c t i o n w i t h t h e i n d i v i d u a l l a t t i c e atoms.
It is always a problem t o determine the parameters for the pairwise
interactions. Essentially, t h i s h o l d s f o r t h e r e p u l s i o n parameters R and m,
for t h e charges o f t h e l a t t i c e atoms ( i n t h e e l e c t r o s t a t i c term) as well as
f o r t h e i r p o l a r i z a b i l i t i e s ( i n t r o d u c e d by t h e London f o r m u l a ) .
I n e a r l i e r estimations o f physical i n t e r a c t i o n s i n z e o l i t e s A ( r e f . 5) the
c a t i o n s were g i v e n t h e i r nominal charges, balanced by -0.25 e l e m e n t a r y units
at each o f t h e 48 oxygens b e l o n g i n g t o one a-cage and n e g l e c t i n g t h e silicon
and aluminum atoms. This r e s u l t e d i n f a r too h i g h i n t e r a c t i o n energies at
s o r p t i o n s i t e s near c a t i o n s ( r e f . 6 ) . A l t h o u g h n o t y e t f i t t e d f o r t h e c a l c u l a -
tion of a b s o l u t e ( i n t e r a c t i o n ) energy values, t h e quantum chemical SCC-Xa
method is capable t o produce r e l i a b l e charge d i s t r i b u t i o n s and equilibrium
c o n f i g u r a t i o n s f o r t h e system under c o n s i d e r a t i o n , even i f as much as 50 atoms
are involved ( r e f . 7 ) . Consequently, a charge d i s t r i b u t i o n determined by SCC-
Xa calculations f o r unloaded NaA and CaA s t r u c t u r e s was finally introduced
i n t o t h e c l a s s i c a l i n t e r a c t i o n p o t e n t i a l , w h i c h a r e l i s t e d i n Table 2.

TABLE 2
Parameters and f o r m u l a s f o r t h e i n t e r a c t i o n p o t e n t i a l c a l c u l a t i o n s .
~~

Term Parameter 0 Na Ca A1 Si
A [ l o 7 Jmol-’I 13.25 16.39 8.55 11.79 12.63
m [ nm-‘] 34 44.7 35.6 41.4 35.6
vreP a 0.225 0.175 0.131 0.223 0.195

Vel q [ u n i t s of e l -0.725 0.7 1.4 1.0 1.2

Vrep = A [ l + 1 . 4 4 5 < v l ~ ~ ~ > ] e - ~ ~ [ l + a P , ( cOo) s] 5 = s t r e t c h i n g coordinate

Vdisp = C[a+yP,(cos o)/31/r6 P = Legendre p o l y n o m i a l a,y = p o l a r i z a b i l i t y

Vel = ( - l ) l q M 1 P l (cos O ) / r l t l r = d i s t a n c e m o l e c u l e - l a t t i c e atom
q = atomic charge M1 = l t h m o l e c u l a r moment 0 = a n g l e between m o l e c u l a r a x i s
and t h e j u n c t i o n o f m o l e c u l a r c e n t e r o f g r a v i t y w i t h t h e r e s p . l a t t i c e atom

D i s p e r s i o n and p a i r w i s e r e p u l s i o n parameters f o r t h e v a r i o u s l a t t i c e atoms

have been determined by a l e a s t square f i t t o sorption complex geometries
c a l c u l a t e d w i t h a quantum chemical ab i n i t i o method ( r e f . 8 ) and a r e g i v e n i n
Table 2 . The H,-specific parameters a r e m a i n l y t h e permanent m u l t i p o l e moments
and t h e d i p o l e moment p o l a r i z a b i l i t i e s , depending i n g e n e r a l on t h e i n t r a m o l e -
cular s t r e t c h i n g coordinate 6 . As the i n t r a m o l e c u l a r v i b r a t i o n i s v e r y fast
compared t o t h e e x t e r n a l m o t i o n s ( r o t a t i o n and t r a n s l a t i o n ) t h e latter only
e x p e r i e n c e t h e average o v e r a number o f p e r i o d s o f t h e f o r m e r . Now dependent
550

only on the v i b r a t i o n a l quantum number v, the molecular parameters are

represented by the corresponding expectation values over a v i b r a t i o n period,
which were t a k e n f r o m r e f . 9. A f i r s t and e s s e n t i a l l y q u i t e good a p p r o x i m a t i o n
to t h e v i b r a t i o n a l f r e q u e n c y s h i f t o f I R bands i s t h e d i f f e r e n c e between the
i n t e r a c t i o n p o t e n t i a l s i n t h e two s t a t e s covered by t h e t r a n s i t i o n , i.e. v=l
and v=O i n case o f t h e fundamental
AV = Vsorb-vfree = V(V=I)-V(V=O) (2)

THEORETICAL RESULTS AND DISCUSSION

In t h i s paper we w i l l c o n f i n e o u r s e l v e s t o t h e d i s c u s s i o n o f the results
o b t a i n e d on z e o l i t e Na,Ca,A. A pseudo 3-dimensional d i s p l a y o f t h e i n t e r a c t i o n
potential s u r f a c e i n t h e ( 1 1 0 ) - p l a n e o f z e o l i t e Na,Ca,A i s shown i n Fig. 2.

F i g . 2. I n t e r a c t i o n p o t e n t i a l s u r f a c e ( i n pseudo t h r e e - d i m e n s i o n a l
p r e s e n t a t i o n ) o f a (110) p l a n e i n t h e supercage o f z e o l i t e
Na,Ca,A ( l e f t ) c o n t a i n i n g two body d i a g o n a l s as w e l l as two
Na(S1) and Ca(S1) i o n s .

Each data p o i n t represents the (x,y)-position i n t h e p l a n e and t h e pertinent

energy v a l u e o f t h e most f a v o u r a b l e o r i e n t a t i o n o f t h e H, m o l e c u l a r a x i s .
Deep p o t e n t i a l minima o f a b o u t -920 cm-’ have been found on a s e c t i o n o f a
spherical s h e l l t h a t i s 256 pm a p a r t f r o m t h e Cazt-ions. The corresponding
minima i n f r o n t o f t h e sodium i o n s a r e o n l y v e r y s h a l l o w deepenings ( - 4 7 0 cnr’)
in an e q u i p o t e n t i a l s p h e r i c a l s u r f a c e (-435 cm-’) around t h e c e n t e r o f t h e a-
cage, 355 pm a p a r t . A d j a c e n t a-cages a r e s e p a r a t e d b y oxygen 8 - r i n g s o f a b o u t
400 pm diameter, g i v i n g r i s e t o a p o t e n t i a l w e l l o f V=-150 c d o n l y . The
p o t e n t i a l energy a t t h e c e n t e r o f t h e c a v i t y i s -120 cm-’.
Observed frequency s h i f t s f o r H, and 0, ( s e e Table 1 ) a r e compared with
those calculated according t o equation ( 2 ) f o r s o r p t i o n s i t e s in front of
Ca and Na i o n s and on t h e s p h e r i c a l s h e l l 355 pm a p a r t f r o m t h e c e n t e r o f the
 551

supercage, respectively, i n Table 3. H e r e i n energy v a l u e s a t t h e potential

minima have been a p p l i e d and t h e o n l y d i f f e r e n c e made between H, and D, was t o
use t h e i r i n d i v i d u a l m o l e c u l a r c o n s t a n t s . Experimental and t h e o r e t i c a l s h i f t s
o f t h e f o u r i n f r a r e d bands agree remarkably w i t h o u t any f u r t h e r a d j u s t m e n t of
t h e i n t e r a c t i o n parameters produced by t h e l e a s t square f i t f o r t h e H , - l a t t i c e
atom i n t e r a c t i o n s d e s c r i b e d i n t h e f o r e g o i n g s e c t i o n .
The n e x t s t e p i s t o ask f o r t h e e q u i l i b r i u m geometries o f t h e s o r p t i o n
complexes. I n f r o n t o f t h e c a t i o n s t h e m o l e c u l a r a x i s i s p e r p e n d i c u l a r t o t h e
c a t i o n - m o l e c u l e i n t e r s e c t i o n , w h i l e p o i n t i n g towards t h e oxygen atoms f o r
molecules on t h e sphere around t h e c e n t e r o f t h e c a v i t y .

TABLE 3
Observed and c a l c u l a t e d frequency s h i f t s o f t h e p u r e l y v i b r a -
t i o n a l t r a n s i t i o n s ( i n cm-I).

Species Av(eXp.) Av(ca1c.) Av(eXp.) Av(ca1c.)

Hydrogen Deut e r ium

A,/Ca - 73 -72 -54 -50

A,/Na + species C -43 -42 -29.6 -28.5

B u t t h e complexes a r e n o t expected t o be v e r y r i g i d . The p o t e n t i a l energy

of molecules e x a c t l y on t h e t h r e e f o l d symmetry a x i s i n f r o n t o f c a l c i u m ions
(V=-900 cm-'), f o r example, i s almost independent f r o m t h e o r i e n t a t i o n o f t h e
m o l e c u l a r a x i s i n t h e p l a n e p e r p e n d i c u l a r t o t h e symmetry axis. Consequently
the molecules a r e a b l e t o r o t a t e f r e e l y i n t h e p l a n e w h i l e p e r f o r m i n g o u t of
plane l i b r a t i o n s ( t o r s i o n a l v i b r a t i o n s ) .
On the symmetry a x i s mentioned t h e orientational potential is almost
exactly V,(r)P,(cos O), where r i s t h e d i s t a n c e f r o m t h e c a t i o n , 0 is the
a n g l e between t h e m o l e c u l a r and t h e symmetry a x i s . I n t h e p o t e n t i a l minimum V,
i s + l o 0 0 cm-', w i t h t h e p o s i t i v e s i g n f o r c i n g t h e p e r p e n d i c u l a r arrangement o f
t h e molecules. R o t a t i o n a l e i g e n v a l u e s have been c a l c u l a t e d f o r t h e v i b r a t i o n a l
ground and f o r t h e f i r s t e x c i t e d s t a t e (see r e f . 1). The p u r e l y vibrational
transitions from t h e two l o w e s t r o t a t i o n a l l e v e l s a r e s e p a r a t e d by 4.4 c d
with t h e low frequency t r a n s i t i o n b e i n g t h e more i n t e n s e one. The observed
main band s p l i t t i n g was 4.5 cm-' (see F i g . 1). I n case o f D, the calculated
s p l i t t i n g o f t h e d o u b l e t i s l e s s than 2 cm-' and o b v i o u s l y n o t r e s o l v e d .
The translational motion o f molecules i n f r o n t o f c a l c i u m ions can be
separated into a high frequency r a d i a l and a degenerate low frequency
t a n g e n t i a l one. While no a t t e m p t has been made t o c a l c u l a t e t h e l a t t e r , which
t h e two s a t e l l i t e s i n F i g . 1 a r e i m m e d i a t e l y assigned t o , t h e second radial
d e r i v a t i v e o f t h e p o t e n t i a l i n t h e minimum g i v e s a v i b r a t i o n a l c o n s t a n t o f 190
cm-'. Already i n 1980 we observed a weak FIR t r a n s i t i o n a t 190 c d and a l r e a d y
552

assigned i t t o a r a d i a l t r a n s l a t i o n a l v i b r a t i o n o f m o l e c u l e s adsorbed i n f r o n t
o f c a l c i u m i o n s (see r e f . 10).
From the foregoing d i s c u s s i o n i t i s o b v i o u s t h a t we have to deal with
s e v e r a l s p e c i e s o f adsorbed hydrogen
molecules localized in front of calcium ions, performing frustrated
translations, librations towards the cations and almost free planar
r o t a t i o n s ( s p e c i e s A),
molecules weakly bound t o t h e sodium i o n s , p e r f o r m i n g t h e same kinds of
motions ( s p e c i e s B),
molecules r o t a t i n g w i t h t h e i r c e n t e r o f mass on a sphere around t h e center
o f the cavity, simultaneously performing t r a n s l a t i o n a l v i b r a t i o n s towards
the center and v i c e v e r s a ( s p e c i e s C) ( T h e i r end-over-end rotations are
weakly h i n d e r e d . ) ,
molecules delocalized moving t h r o u g h t h e whole p o r e system from a-cage
t o a-cage ( s p e c i e s D ) , and
molecules c a p t u r e d w i t h i n a c e r t a i n a-cage and d e l o c a l zed t h e r e i n ( s p e c i e s
El.
An e l e c t r i c f i e l d s t r e n g t h o f 62 esu/cm2 on t h e s o r p t on s i t e i n f r o n t of
Ca(S1) i o n s was determined f r o m t h e i n t e n s i t y o f t h e main band, being larger
than that of 55 esu/cm2 o b t a i n e d f r o m t h e deuterium spectrum (ref. 10).
Furthermore, t h e r e l a t i v e l y h i g h i n t e n s i t i e s o f t h e h i g h - f r e q u e n c y bands may
be e x p l a i n e d by c o n t r i b u t i o n o f t h e two s p e c i e s B and C .
As the e x p e r i m e n t a l f r e q u e n c y s h i f t s and band p a t t e r n s agree remarkably
with the calculated ones, the rotational and translational eigenvalues
estimated from t h e i n t e r a c t i o n p o t e n t i a l a r e supposed t o be very re1i a b l e .
Thus i t i s i n p r i n c i p l e p o s s i b l e t o use t h e i n t e r a c t i o n p o t e n t i a l minima and
the eigenvalues f o r s t a t i s t i c a l c a l c u l a t i o n s .
Finding out t h e most p r o b a b l e c o n f i g u r a t i o n r e g a r d i n g either single or
multiple occupation immediately y i e l d s Fermi-Dirac o r Bose-Einstein statis-
t i c s . T h e r e f o r e we have a p p l i e d
- Fermi-Dirac statistics with a partition function G!ZN/(G-N) N! for the
l o c a l i z e d s p e c i e s ( A and B ) ,
- Bose-Einstein s t a t i s t i c s w i t h the p a r t i t i o n function ( G t N - 1 ! ZN/ (G- ) ! N !
f o r t h e d e l o c a l i z e d species and
- Maxwell-Boltzmann statistics for the gas phase.
G is the number o f p o t e n t i a l w e l l s , N t h e number o f p a r t i c l e s and 2 the
molecular p a r t i t i o n f u n c t i o n . Each s p e c i e s i s b r o u g h t s e p a r a t e l y i n t o e q u i l i -
b r i u m w i t h t h e gas phase.
W i t h t h i s method a p p l i e d t h e number o f adsorbed molecules, t h e i r d i s t r i b u -
t i o n o v e r t h e s e v e r a l species, and t h e i n t e r n a l energy o f t h e s e s p e c i e s can be
 553

c a l c u l a t e d . The a b s o l u t e amount o f gas adsorbed a t d i s t i n c t t e m p e r a t u r e s i s

w i t h i n t h e range o f e x p e r i m e n t a l accuracy (see F i g . 3), hence r e s u l t i n g i n g i n
a q u i t e good agreement between c a l c u l a t e d and measured h e a t s o f a d s o r p t i o n .

500 1000 1500 2000

p/Nl"-2

1 3 5 7
Moleculesluni t cell
F i g . 3 . Comparison o f s t a t i s t i c a l and e x p e r i m e n t a l r e s u l t s f o r hydrogen.
A) D i s t r i b u t i o n o f t h e hydrogen molecules o v e r t h e d i f f e r e n t adsorbed
species A,B,C,D and E.
B ) Comparison o f a d s o r p t i o n i s o t h e r m s a t 100 K s t a t i s t i c a l l y and expe-
r i m e n t a l l y obtained.
C) Coverage dependence o f c a l c u l a t e d energy o f a d s o r p t i o n AU, e n t h a l p y
o f a d s o r p t i o n AH and i s o s t e r i c h e a t o f a d s o r p t i o n Qst w i t h t h e ex-
p e r i m e n t a l l y achieved i s o s t e r i c h e a t o f a d s o r p t i o n .

As can be seen from Table 4, t h e r e i s good agreement o f t h e p r e d i c t e d w i t h

i s o s t e r i c heats o b t a i n e d by gas chromatography. Thermal d e s o r p t i o n experiment5
s t a r t i n g from 50 K prove a t l e a s t 3 o f t h e p r e d i c t e d s p e c i e s (see F i g . 4 ) .

TABLE 4
Comparison o f t y p e and i s o s t e r i c heats o f a d s o r p t i o n o f t h e d i f f e r e n t s o r p t i o n
complexes.

Spec ies Type QSt[kJmol 1 Type Q t[kJ/mol 1

predicted experimen t a f
A Langmui r 7.5-8 Langmui r 7-8
BtC l i n e a r isotherm 4- 5 symm. peak f o r m ca.5
DtE Volmer, concave i s o t h e r m 1.5 concave i s o t h e r m 1.2-1 8
554

F i g . 4 . Low-temperature thermal desorp-

t i o n o f deuterium from z e o l i t e
Na,Ca,A s t a r t i n g from d i f f e r e n t
l o a d i n g s . The CI peak i s a t t r i -
b u t e d t o s p e c i e s D+E, t h e B
peak t o s p e c i e s B+C and t h e y
peak t o s p e c i e s A.

I
0
, , , , ,

I00 200
T, K
100
.
CONCLUSIONS
- Physisorption of simple m o l e c u l e s i n z e o l i t e s may be described by an
e l e c t r o s t a t i c i n t e r a c t i o n model, p r o v i d e d a r e a l i s t i c charge distribution
o v e r t h e z e o l i t e s k e l e t o n , d e t e r m i n e d quantum c h e m i c a l l y , i s t a k e n as a ba-
sis.
- H e r e w i t h i n t e r p r e t a t i o n of I R s p e c t r a i s p o s s i b l e , even q u a n t i t a t i v e l y .
- T h i s method y i e l d s b e s i d e s l o c a l i z e d a l s o d e l o c a l i z e d s p e c i e s .
- Far-reaching e l e c t r o s t a t i c i n t e r a c t i o n s s h o u l d be included, additionally
r e g a r d i n g t h e dynamics o f t h e a d s o r b a t e .
- On the b a s i s of i n t e r a c t i o n p o t e n t i a l c a l c u l a t i o n s a statistical model
can be developed y i e l d i n g t h e thermodynamical p r o p e r t i e s o f the sorption
system, a l s o q u a n t i t a t i v e l y .

ACKNOWLEDGEMENT
We thank t h e Deutsche Forschungsgemeinschaft f o r c o n t i n u i n g s u p p o r t t o t h i s
work o v e r a number of y e a r s .

REFERENCES
1 H. Bose, H. F o r s t e r and W . Frede, Chem. Phys. L e t t . , 138 (1987) 401-404.
2 H. F o r s t e r and W. Frede, I n f r a r e d Phys., 24 (1984) 151-156.
3 H. F o r s t e r and G. P e t e r s , J. C o l l . I n t e r f a c e S c i . , i n p r e s s .
4 A . D . Buckingham, Adv. Chem. Phys., 12 (1967) 107-142.
5 E. Cohen de Lara and T. Nguyen Tan, J. Phys. Chem., 80 (1976) 1917-28.
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175 (1988) 195-201.
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Conf. Z e o l i t e s , Naples, 1980, Heyden, London, 1980, pp. 458-467.
H.G.Karge,J. Weitkamp (Editors1, Zeolites 0s Catalysts, Sorbents and Detergent Builders
Amsterdam - Printed in The Netherlands
0 1989 Elsevier Science PublishersB.V.,

FOURIER-TRANSFURM INFRA-RED PHOTOACOUSTIC SPECTROSCOPY, A USEFUL

TECHNIQUE FOR THE STUDY OF STRONGLY PHYSISOHBED MOLECULES.

J. Philippaerts. E.F. Vansant and Y. A. Yan.

Department of Chemistry, University of Antwerp (U.l.A.J,

Universiteitsplein 1 , 8-2610 Wilrijk, Belgium.

ABSTRACT
The pore-size moditication or Na-mordenite by implantation of
boron-nitrogen compounds is investigated by gas-volumetric
sorption experiments and by FTIH-photoacoustic spectroscopy
(FTIR-PASJ. The P A S spectra of a Na-mordenite after physical
sorption of diborane show the specific characteristics of the
physisorbed borane groups. These reactive species are further
treated with ammonia and methylamine at different reaction condi-
tions. The ultimate porosity is tested by adsorption of test
gases such as K r and X e tat 273 KJ, and the BN-compounds, formed
inside the channels of the substrate, can be characterized with
I . R. -spectroscopy.

INTRODUCTION
Structural modifications of the mordenite-type zeolite are the
subject of several investigations; even now the synthesis of new
zeolites with other pore sizes and other characteristics is
widely reported. In this work, a Na-mordenite has been used to
study the reactions between boron and nitrogen compounds inside
its channels. Much work has already been done in this field on
the H-form mordenite where the acidic OH groups are the reactive
sites. Modification reactions with the hydrides SiH. and BaH.
resulted in a controlled pure size reduction. Thjs knowledge
could be used for the preparation of substrates for gas separa-
tion and inclusion of gases (refs. 1-2).

+Si OH + SiH. - 2 jSi-O-SIHs + Ha (2)

The reactive silane or borane groups chemisorbed to the structure

cou d be further saturated with HzO, MeOH or amines, e.g. (refs.
i , 3 0 ):
+Si-O-BHa + NH, >- +Si-O-BHn+NHa

The implantation of these groups could even exclude small

molecules like A r from the structure. Recently, the modification
reactions were studied using FTIH-spectroscopy w i t h photoacoustic
detection (FTIR-PAS). This detector can be loaded i n a controlled
atmosphere which allows the study of all types of solid mate-
rials, especially zeolites, without the need for difficult sample
pretreatments. The time consuming techniques of grinding and
pressing self-supporting wafers are evaded. Spectral information
over the full l.R.-region can be obtained, even changes in the
lattice vibrations can be investigated without making use of KBr
disks. Scattering effects have no influence on the spectra so
that various sizes of crystallites can be investigated without
problems of baseline changes. Because of these properties, spec-
tral substractions yield difference spectra of very good quality.
W i t h this photoacoustic detection technique the reactivity of the
different types of structural OH groups towards the modifying
agents was demonstrated ( r e f . 4). The intermediate and final
products formed by hydroIysis and amination reactions could be
determined. The mechanisms of most of these modification reac-
tions are explained using troth the photoacoustic I.R. spectra and
the results of adsorption and chemisorption experiments, obtained
in a volumetric sorption apparatus.
The photoacoustic detection technique f o r solids can only be
used when the samples do not evolve gases that show an infrared
absorption such as H a O , CO,, NHa,... These evolved gases would
give a photoacoustic signal that is about 100 times more intens
than the signal of t h e solid material. Only gases such as He, Ne,
Ar, Nz, O a , . . . can be used inside the chamber of the detector. In
H-form zeolites, the modifying agents are irreversibly bound to
the structure by covalent bonds. In this work, P A S spectra are
shown of Na-mordenite successively treated with BaH. and amine
(NH, and CHaNH,). In Na-mordenite, only a physical sorption can
take place since no acidic OH-groups are present. A dissociation
of the diborane molecules into BHs groups occurs on the surface
of the Na-mordenite. Addition of BHa on the siloxane bridges
 557

results in a strong physical sorption t n d t can be measured with

F T I R - P h S without tne disturbance o t the signal b y aesorted dibo-
rane molecules.

The sorbed tarane groups can react further with Nh, or amines
(refs. 5 , 7 , . The free electron pair or the nitrogen competes with
the electrons or the siioxane oridges and boron-nitrogen com-
pounds are rormed inside the zeolite channels. These BN-compounds
are studied in detail by FTIR-PAS a s a function of the reaction
temperature. The amount o r evolved Hz and the intluence o t the
BN-compounds o n tne pore size of the zeolite are investigated.

EXPERIMENTAL
The Na-mordenite was supplied b y the Norton Co. and the modi-
fying agents (BzH., NH,) were from U C A H (Union Carbide Belgium,.
Diborane was diluted in H2 (95%) to prevent polymerisation reac-
tions. It was purified b y destillation in high vacuum. T h e test
g a s e s Ar. hr, Xe and Nz came from A i r Liquide (Belgium, and they
were used without further purirication. The adsorption experi-
ments were carried out in a volumetric sorption apparatus as
discribed in tref. 1).
The FTIR spectra were collected with a Nicolet 5 DXB FTIR-
spectrometer equipped with a prototype of the MTEC-100 photo-
acoustic detector designed b y J.F. McClelland. Different mirror
velocities were used (0.08 - 0.64 cmlsec.) to check t o r photo-
acoustic saturation effects. Data collection times of 20 to 50
minutes and averaging of 300 to 1000 scans, depending on the
signal intensitity, were necessary. Happ-Genzel epodization w a s
used, and the single beam spectra, obtained in this way, were
ratioed against the PAS spectrum of carbon black to correct for
the source characteristics. The samples t o r the 1 . R . analyses
were prepared in the volumetric sorption apparatus, transterred
to a glove b o x that was purged with ultra dry nitrogen and loaded
into the P A S detector. T h e detector was, in addition, purged with
dry He to increase the signal intensity.
658

R E S U L T S A N D DISCUSSION

Boranation reaction

The Na-mordenite (3 gram) w a s outgassed a t 723 K in vacuum

over 17 hours and a n a l y s e d for its original s o r p t i o n characte-
ristics with A r , K r and X e a t 273 K ( k i n e t i c r u n s ) and with N a at
77 K (isotherms). The s u b s t r a t e was t h e n equilibrated at 273 K
and brought into c o n t a c t with 300 Torr (40 k P a ) of diborane at
different contact periods. Outgassing was performed in a s t a t i c
way by freezing t h e weakly physisorbed B t H . in a c o o l i n g trap at
77 k;, or in a dynamic way by e v a c u a t i o n of the s a m p l e t h r o u g n a
cooling trap in which t h e d i b o r a n e is f r o z e n out.
The amount of d i b o r a n e could be d e t e r m i n e d by expanding the
frozen gas in the volumetric system. T h e amount of B o h b held by
the sample after various s o r p t i o n and o u t g a s s i n g periods is shLswn
in T a b l e 1 . In general t h e s o r p t i o n r a t e of BIH. is rather low so
that mostly overnight contact is applied. T h e a e s o r p t i o n method
and time is of great importance s i n c e the s o r p t i o n is based o n a
physical interaction. A s expected. t h e a p p l i c a t i o n of a d y n a m i c
vacuum ot only a tew m i n u t e s c a n reduce t h e amount or retained
B 2 H L drastically. After outgassing, t h e s a m p l e was cooled d o w n to
77 k to avoid turther a e s o r p t i o n o t BIH.. For t h e 1 . R . measure-
ments, the sample w a s saturated with dry lqI, equilibrated at room
temperature and loaded into the glove box. The l.k. spectra.
obtained a t 3 diiferent mirror velocities, a r e s h o w n i n i i g u r e la
to lc. A broad OH band (3100 - 36UO cm-'J is attriouted to water
around the exchangeable Na' cations. T h e d e r o r m a t i o n vibration ot
these molecules is located at LS.?O cm.' Atter a denydration at
this temperature, it is observed that s o m e a c l s o r b r d water mole-
cules. probably around t h e cations, a r e still present. T'his WAS

aiso confirmed b y the results of a DSC, a n a l y s e s of the lua-mor,de-

nite. The presence of water m o l e c u l e s was e v e n observed o n 14-form
mordenites where very small a m o u n t s ot Na'-cations were still
present d u e to incomplete ion-exchange. A boranation reaction or
these substrates revealed that the water m o l e c u l e s held bv the
carions did nut react with diborane. e v e n not at 425 k as
observed rrom the I.R.-spectra tref. 3 J . A l s o in the deuterium
lsutupe exchange procedure. t h e s e water molecules & r e not a t r s c ~

ted while all the o t h e f hvdroxvl g r o u p s are exchanged. Tnis

demonstraces their special proper ties ot s t r o n g ci~ooroination 1.0
TABLE 1 . Amount of BiHL sorbed as a function of sorption and
outgassing time
~~

sorption outgassing amount

time time Bi Hc
(minutes1
(hours) static dynamic mmol/g.
vacuum vacuum

1.5 30 0.091
17 180 3 0.255
17 10 5 0.244
17 60 0.344
20 240 0.318
60 180 0.345

the cations. Temperatures higher than about 800 K are necessary

to evacuate these water molecules.
In the photoacoustic spectra of Na-mordenite. treated with
aiborane. smal1 bands of B-H stretching vibrations ot chemisorbed
-BHn g r o u p s are seen at 2573 and 2492 c m - 1 due to the reaction or
B2Ha with silanol groups and water molecules. The B-0 stretching
vibrations of these chemisorbed groups can be seen at 1580 - 1400
cm-1. These assignments can be supported with the frequency of
the B-H vibration band in the 1 . R . spectrum of a boranated 0-
mordenite L . P . (figure 1 d ) (ref. 3-4). The 0 D bands at 2 7 6 0 and
li'v0 c m - ' are still present arter a reaction at room temperature
which illustrates their l o w reactivity (see also ref. 4J.

In the Na-mordenire, an additional broad B-H vibration band is

seen at 2L,:6i, c m - ' whicrl we assign to BHr groups at the silohanr
bridges. A comparabie rrequrncy is round for the mine-buranes
wnere EIH, is stabilized by the electron pair of tne nitrogen
srrr. 5 ! . In t h e spectra a. b and c. the shape or the I . f i . -bands
does not change with increasing scan speed wnicn means that no
spectral region i s photoacoustical ly saturated !ref. G). The
cnaracteristic structure vibrations or mordenite are iocateu
Letween auij t.o 13ilu i>m- ', and around 1 V W cm" a broad uoublet,
a u e to overtclrles or lattice vibrations, can De noticed. At about
I b ~ J Vc m - ! . a small and sharp vibration band can be observed which
560

u0
fm
5
0)
m
U
I
U
0

1
c

3900.0 3400.0 PSOO.0 P400.0 1000.0 1400.0 BOO.00 400.00

uAvtiwuseAs tcu-1)

Fig. 1. (a) t o (c) : PAS s p e c t r a of borrnated Na-mordonite a t

s c a n s peed 0.32 , 0.16 and 0.08 cm/reo r e s p e c t i v e l y ;
(d) : boranated H/D-mordmnitm a t ncalr s p e e d 0.08 cm/sec.

is attributed to desorbed diborane. Nevertheless, a very repro-

ducible spectrum can be obtained, even after several hours or
storage in the P A S detector. The data collection time t o r the 3
spectra in Figure 1 was more than Z hours and even atter that
time no changes i n the spectra were observed. From voiumetric
sorption measurements i t was calculated that only 0.1 2 u.u3 mmol
H?,y. was evolved due to the reactions with silanol groups. The
ii value, which is tna ratio ot H, evolved to k h . sorbed, was
smaller than 0.5 .
 561

Reactions with Amines

After equilibration of the boranated mordenite to room tempe-

rature, an amount of NH, equal to the amount of physisorbed
borane groups was brought into contact with the substrate. The
adsorption took place within a few seconds while only a very
small amount of HZ was evolved. This indicates that most or the
compounds tormed contain a dative bond trets. 4-51 :

\ \
/
I0 + BHj + NHj -> IUI
/
t HxBtNHj

Only a few groups reacted further according to :

H31u+Uh, -' H- N'EiH? t 1-13

W
94
rn
8111
m
4
I
a
a

1
I
I
V

3900.0 3400.0 2900.0 2400.0 1900.0 1400.0 900.00 400.00

WAVENUMBERS EM-1)

Fig. 2. FTIR-PAS spectra of Na-mordenite modified with B Z H L and

NH, at (a): 298 K . (b): 353 K , ( c ) : 382 K, (d): 423 K , te): 493 K
( f ) : 543 K, tg): 573 K , (h): 623 K .
662

Further reactions or these BN-compounds. tollowed b y a release

or H 2 . can be expressed in terms ot a relative k value 1 h 1 . 1 . This
vaiue. detined by rhe Jirrerrnce between the I? value artrr the
amination reaction and the value arter the Goranat ion reaction,
was determined to be V.16 2 L..ul. The 1.k. spectrum or tne
sample ox figure L a shows NH-stretching and oerclrmat ion vinra-
tions at 33-1 and 1616 cm-'. respectively. A new B-rl vibration
band at 2350 cm-l and a small 6-N vibration band at 13.65 - luUC3

cm-' can be noticed. however, the frequency and shape ot the m a i n

6-H vibration tiana does not crlanqe very much. This can oe
explained b y the type or bond : i t is an electron donor-acceptor
interaction in which the structural oxygen (the original donor)
is replaced b y the nitrogen. The compounds formed are called
amine-boranes. F r o m the adsorption ~ i n e t i c s it can be seen tnat
these boron-nitrogen compounds completely block the channels f o r
molecules such as Xe while for hr an adsorption capacicy CRti of
7 X of the original capacity is obtained atter 1 hour sorption
time (iigure 4).

Thermal treatment

After the reaction w i t h NHs at room temperature, the sample

was heated stepwise in order to follow the change of the I.H.
bands, the evolution of Ht and the variations or the sorption
properties. Figure 5 shows the increase of the relative I3 value
as a function of the temperature for both NH,- and CHINH1-
treated samples. T h e curves show a sharp increase ot the Hr vaiue
between 343 k: and 423 K for NHs and between 373 K and 423 I( for
CHsNH,. This indicates further reactions of the amine-boranes
into amino-boranes acoording t o :

The higher thermal stability of the methylamine-borane com-

pound can easily be explained by the inductive effect of the CH,
group on the dative bond ( r e f s . 5 , 7 ) .
The I . R . spectra of an NHs-treated sample shows that most of
the B-H and N-H vibrations decreased in intensity after heating.
A thermal treatment at 423 K caused a shift of the N-H vibration
band to 3440 cm-' and the B-H vibration was split into two broad
bands at 2 5 3 7 and 2 5 5 2 C I I I - ~ .During this treatment i t is clearly
 663

seen trom computed ditference spectra (figure 3 ) that the b-N

vibration band shirts to nigher rrequencies tup to 1500 ern-')

w h i c n indicates a higher bond order ( s e e reaction 9). but i t is

also noticed that a low-frequency k i - N vibration band appears, and
this is attributed to conjugation of B - N bonds. A polymerisation
has taken p l a c e which thermodynamically f a v o r s the stability of
the amino-boranes. This efrect prevents these products releasing
all tncir H atoms, and above 423 k only a small increase in the
relative k value is observed ( f i g u r e 51.
Arter a thermal treatment at 623 K . nearly R I I the N -H and B-H
vibration bands disappeared. Thus w e can conclude that a boron-
nitride type Of compound is formed inside tne channels.
krom trir s.arption kinetics it c a n be noticed that. the amino-

3900.0 3400.0 2900.0 2400.0 1900.0 1400.0 900.00 400.00

WAVENUMBERS (CM-1)

Fig. 3. Difference spectra of Na-mordenite modified with BzH6 and

NHs and thermally treated ( 1 ) t 382 K - 352 K ,
(2) : 423 K - 382 K , (3) : 493 K - 423 K .
564

borane polymers are less e f f e c t i v e in blocKing the z e o l i t e cnan-

nels since the r,r uptake increases with increasing reaction
temperature. This i s causea b y shortening ot t h e ti-lu bond d i s t a n -
ces a n a possibly b y reorientation ot t h o s e c o m p o u n d s inside the
z e o I i te pores.
It should be mentioned that a c h a n g e in the heating rate
drastically changes the a m i n a t i o n reactions. T n i s is illustrated
in tigure 1; where spectrum c a ~s h o w s t h e c h a r a c t e r i s t i c s ot the
mociiried zeolite atter a slow heating u p to 623 L.; in vacuum and
spectrum ( b l atter a thermal shock treatment a t the same t e m p e r a -
ture in vacuum. T h i s o b s e r v a t i o n indicates that porymerisation
c a n occur before H1 is split off. T h e s p e c t r u m is very similar t o
that o r a s a m p l e treated a t 423 li a t a IOU heating rate. These
effecrs are e v e n more pronounced when t h e s a m p l e is treated with
a thermal shock up to 675 I.; in a static vacuum a s shown in f i g u r e
6c. The t i - N stretching vibration shifts to higher f r e q u e n c i e s ( u p
to 1470 cm-', while still a significant a m o u n t ot 6 - H and N-H
groups a r e present a s indicated by their intense vibration bands.

Fig. 4. K r u p t a k e a t 273 K

0.8
P after
tion steps,
uptake
different

of
modifica-
relative to the
the original
sample (= outgassed Na-
mordenite)
0.8

0.4 * ORIGINAL
+ + BPH8 + NH3
-e
313 K
0.2 A 443K
-EJ- 513 K
-+ 688K
0.0 + HYDROLYSIS
0 1 2 3 4 5 6 7 8 9
time expV2
 565

ELATIVE R-VALUE
Fig. 5. Relative R
value of the reac-
tion between bora-
nated Na-mardenite
and amine as a
function of the
reaction tempera-
ture.

* NH3
CH3NH2
-A.
273 373 473 673 673 773
Temperature (K)

bl
0
z
4
:
0
VI
m
d
I
d
a'
1
I
I
v

SSOO.0 3400.0 2900.0 2400.0 1900.0 1400.0 900.00 400.00

WAVCNUMBERS (CM-1)

Fig. 6. FTIR-PAS spectra of ( a ) and ( b ) : Na-mordenite with

diborane and ammonia heated at 623 K respectively at low and high
heating rate in vacuum; ( c ) heated at 673 K at high heating rate
in static vacuum.
566

However, the formed EN-compounds c a n be partially hydrolyzed

at 298 K in contact with water. As shown in figure 4, the
adsorption capacity for K r is again 80 X of t h e original capacity
although the Xe-adsorption is still controlled by a diftusion
process.

CONCLUSION
Intra-red studies o n solid materials such a s eorbents, and
their interaction with gases, liquias or even other solids, are
very important when the samples can be characterized without
sample preparation. In this w o r k it is proven that F T I H - P A S can
be used to elucidate the mechanisms ot the reactions inside the
channels of a zeolite. It i s shown that sorbents with strong,
physicallv sorbed species d o not cause problems r o r signal gene-
ration, so that the sorbent-sorbate interactions c a n be studied
with PAS. The I.H. spectra or the Na-mordenite moditied with
various types of bN-compounds help t o explain the results ot the
s o r p t i o n ex per 1 men t s .
REFEkENC€S

1 A. 'Thijs. G. Peeters. E . F . Vansant and 1 . Verhaert. Journ.

Cnem. SOC.. Faraday Trans. 1. 1 9 W . 2821.
2 A. Thijs, G. Peeters. E.F. Vansant and I. Verhaert, Journ.
ihem. SOC.. Faraday rrans. 1 , 2,l Y t i . 3 . 28.35.
3 J. Fhilippaerts, E . F . Vansant, i;. Peeters and E. Vanderneydrn.
Anal. Chim. Acta, 165, 1967, 237.
4 J . Philippaerts, E .F. Vansant, in D . E . Levden (Editor,.
Silanes, Surfaces and lntertaces U o l . 2 . 1963 ( i n p r e s s ) .
5 W. Sawodny, J. Goubeau. Leitschr. Fur Phvsic. Chem. Neue
Folge, bd. 44, 1965, 227.
6 A . hosencwaig. Photoacoustics and Photoacaustic s p e c ~ r o s c o p ~ .
Wiley Interscience. New 'iork , 1680.
7 h.C. Taylor. A d v . in Chemistry 4.Z, 1964, 59.
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

ADSORPTION PROPERTIES OF LARGE CRYSTALS OF ZSM-5 ZEOLITE AS A FUNCTION OF THE

DEGREE OF DEALUMINATION

J. KORNATOWSKI, M. ROZWADOWSKI, A. G U T S Z E ~AND K.E. WISNIEWSKI

I n s t i t u t e o f Chemistry, Nicolaus Copernicus U n i v e r s i t y , Gagarina 7, 87-100 Torun
(Pol and)
'Department of Biophysics, Medical Academy, Karlowicza 24, 85-092 Bydgoszcz
(Pol and)

ABSTRACT
Large c r y s t a l s o f ZSM-5 z e o l i t e o f mean length o f about 300 pmwere grown.
The z e o l i t e samples were dealuminated t o various extents by both hydrothermal
and chemical a c i d and s a l t s o l u t i o n s treatments. Their adsorption isotherms f o r
benzene and methanol were examined as a f u n c t i o n o f the degree o f dealumination.
The benzene isotherms were described w i t h equations o f t h e Polanyi-Dubinin po-
t e n t i a l theory. Using the determined parameter values, the f u n c t i o n s c h a r a c t e r i -
z i n g the adsorption p o t e n t i a l s were p l o t t e d .

INTRODUCTON
Presentation o f a c o r r e c t mechanism f o r an adsorption process i s one o f t h e
most important aims o f adsorption theory. An explanation o f t h e mechanism o f ad-
s o r p t i o n on ZSM-5 z e o l i t e s i s s t i l l an unsolved t h e o r e t i c a l problem. The few pa-
pers dealing w i t h the adsorption on ZSM-5 ( r e f s . 1-3) are fragmentary and they
show e x p l i c i t l y t h e considerable d i f f i c u l t i e s w i t h i n t e r p r e t a t i o n o f t h e adsorp-
t i o n measurements.
I n adsorption investigations, the Pol anyi -Dubi n i n p o t e n t i a1 theor
' (PO)
( r e f s . 4, 5), developed by Dubinin ( r e f . 6) as the theory o f volume f i l i n g o f
micropores, (TVFM) i s p a r t i c u l a r l y important. I t s fundamental equation i s t h e
Dubinin-Astakhov equation (DA) ( r e f . 7):

= Wo exp I - k(AIP)"/
W = W oexp I-(AIPEU)nI
where W represents the volume o f the l i q u i d - l i k e adsorbate present i n micropores
a t temperature T and r e l a t i v e presssure p/ps; Wo i s the t o t a l volume o f t h e m i -
cropores, A i s t h e d i f f e r e n t i a l molar f r e e enthalpy o f adsorption, P i s the sim-
i l a r i t y f a c t o r r e f l e c t i n g the nature o f the adsorbate, Eo i s the c h a r a c t e r i s t i c
energy o f adsorption o f standard vapour f o r which p= 1, k i s the s t r u c t u r a l pa-
rameter c o r r e l a t e d w i t h the micropore dimensions, and n i s the parameter charac-
t e r i z i n g the shape o f the adsorption p o t e n t i a l d i s t r i b u t i o n i n microporous ad-
sorbent.
568

The volume filling of micropores in A and X zeolites during adsorption of

different vapours of relatively small molecules, e.g. water, n-pentane etc. was
already proved experimentally (refs. 8, 9). Recently, the applicability of eqn.
(1) for studies of adsorption on zeolites was proven in the papers of refs.
10-13.
ZSM-5 and the other zeolites of the pentasil family are still intensively
studied because of their adsorptive and catalytic properties (ref. 14). However,
to date only little attention was paid in the literature to the dealumination of
those zeolites (refs. 15-20),
In 1984, Scherzer (ref. 21) presented an extensive review of both the prepa-
ration of aluminium-deficient zeolites and their characterization including
structural and physico-chemical characteristics (adsorption, thermal stability,
NMR, IR, acid and catalytic properties) for Y and mordenite zeolites. The prepa-
ration methods were divided into three groups: a) thermal and/or hydrothermal
dealumination, b) chemical dealurnination (reactions with acids, salts, chelating
agents and volatile compounds), and c) combination of thermal and chemical
dealumination. Each of them can produce a different dealumination effect.
The dealurnination of zeolites influences significantly the behaviour of the
zeolite structures (refs. 15-21). Furthermore, the properties of zeolites depend
on the dimensions of zeolite crystals (refs. 22-25) due to the role of diffusion
of adsorbate molecules. Therefore, we decided to search for a correlation be-
tween adsorption properties and the degree of dealumination in large ZSM-5 cry-
stals where the extraction of aluminium ions from the lattice forms aluminium-
deficient centers of a disturbed structure.

EXPERIMENT
Large crystals of ZSM-5 zeolite were grown according to the procedure des-
cribed in ref. 26. Their crystallinity was examined by XRO techniques (Soviet-
Union-made ORON) and by scanning electron microscopy (NOVOSCAN 30). The amount
of aluminium in the samples was determined from both the elemental analysis and
the titration of solutions after dealumination treatment with 0.002 M EDTA solu-
tion, using chromazurol S as the indicator (ref. 27).
The parent sample (K4) was prepared by calcination of as-prepared ZSM-5 zeo-
lite in a quartz tube at about 830 K first under flowing air for 24 hrs and next
under flowing oxygen for 72 hrs. Samples A02 and A05 were dealuminated by lea-
ching of the K4 with 1.25 M HCl at the boiling point for 2 and 5 hrs, respec-
tively, and fivefold washing with water at the boiling point for 15 minutes. The
sample US2 was prepared by leaching of the K4 with 1.25 M HC1 followed by
steaming in a quartz tube at about 1070 K for 6 hrs; the flow rate of water va-
.
pour was about 70 g h-l. After a final leaching with 1.25 M HNO3 at the boi-
ling point for 5 hrs the samples were washed as before. The sample US3 was pre-
pared from the K4 by ion exchange in 2 M NH4N03 solution at room temperature for
 569

70 hrs followed by steaming at about 990 K for 65 hrs, leaching with HNO3 and
washing as with the US2 sample. The SD sample was prepared by threefold leaching
of the K 4 with 0.3 M AlCl3 solution for 10 hrs at room temperature and intensive
agitation.
Adsorption isotherms for spectroscopically pure benzene and methanol vapours
were determined at a temperature of 298.2 K in a vacuum device equipped with a
McBain balance. The pressure within the range to 5 * kPa was measured
with a resistance vacuum meter rescaled for the adsorbates studied by means of
the compensation method (McLeod vacuum meter). Higher pressures were determined
with a differential vacuum meter. Before the adsorption measurements, the zeo-
lite samples were heated under stationary vacuum of about kPa at 700 K to
constant mass (about 8 hrs) .
Thermogravimetric analyses (TGA) were carried out for 100 mg samples within
the temperature range 295-1273 K at a heating rate of 5 K/min, under flowing air
atmosphere. The equipment was from the company MOM, Hungary.

RESULTS AND DISCUSSION

The synthesized zeolite was fully crystalline and a pure ZSM-5 phase
(ref. 26). X-ray spectra of the zeolite exhibited lines in positions typical for
ZSM-5. SEM photomicrographs showed a regular columnar habit of the crystals with
very rare twins and intergrowths. Most of the crystals had a mean length of
about 300 pm within the range 280-320 pm. The full range of dimensions was 200
to 350 pm.
The results of dealumination are listed in Table 1. Isotherms of benzene ad-
sorption on the samples studied are presented in Fig. 1.

1.5

-
UI
-
'L

-p
n'
1.0

u
'
W
4
a
0.5
0
U

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
R E L A T I V E P R E S S U R E , P/PI

Fig. 1. Isotherms of benzene adsorption on dealuminated samples of large ZSM-5

zeolite crystals: 1 - K4, 2 - AD2, 3 - AD5, 4 - US2, 5 - US3, 6 - SD.
570

The applicability of eqn. 1 (DA) for description of benzene isotherms (Fig.

1) is supported by the values of the determination coefficients OC (ref. 28)
presented in Table 2. The determination coefficients are defined by

N
c (Y,-$P
i=l
DC=?=l
N
2 (yl -yP
i=l

where r represents the correlation coefficient, yi the dependent variable, ji

the value of the dependent variable approximated by the method of least squares,
..
y the arithmetic mean value of the dependent variable, and N is the number of
pairs of experimental data.

TABLE 1
Characteristics of dealuminated samples of large ZSM-5 crystals.
- - -- - - . -_
Sample Composition. wt % Deal umi nat ion, % Si02
Fi02 A1203 Nap0 e 1 ement a1 *l2O3
analysis
-_ _ -- - . - . ... .. -
K4 97.7 2.10 0.200 - 79.1
AD2 98.9 0.90 0.020 57 186.8
AD 5 99.1 0.70 0.020 67 240.7
us2 99.3 0.60 0.005 71 281.4
us3 98.7 1.05 0.030 50 159.8
SD 98.5 1.25 0.020 40 134.0

TABLE 2
Values of the determination coefficients (DC) for the descriptions of the iso-
therms of benzene adsorption on dealuminated ZSM-5 samples calculated with use
of eqns. 1, 3, 4 (see below).

Sample Determination Coefficients for

eqn. 1 eqn. 3 eqn. 4

K4 0.98031 0.99908 0.99992

AD2 0.981 39 0.99933 0.99939
AD 5 0.94265 0.99998 0.99998
us2 0.95640 0.99988 0.9999 1
us3 0.92834 0.99981 0.99982
SD 0.98976 0.99989 0.99990
 571

A more general equation resulting from the PD theory is the Dubinin-Radushke-

vich-Stoeckli equation (ref. 29) which for zeolites, where the parameter n from
the DA equation i s usually greater than 2, can be written in the following form
(ref. 28):

where A is the half-width o f the distribution function f (k) and ko repre-

sents the maximum of the function of micropore volume distribution with respect
to k.
When the value o f parameter k is included, which corresponds to the maximum
dimension o f the micropores, i.e. kmax (ref. 30), eqn. 3 is transformed into the
following isotherm equation:

where Y =
The data from Table 2 show that eqns. 3 and 4 are applicable to describe the
isotherms of benzene adsorption on the studied zeolites. In accordance with the
PD theory, the adsorption is determined by the adsorption potential. As is in-
ferred from refs. 13. 31-33, the distribution of the adsorption potential is
closely connected with the heterogeneity of microporous adsorbents. This distri-
bution has the following forms, corresponding to eqns. 1, 3 and 4, respectively.

X ( A ) = - dW/dA = ( n W , k An-'/ 0") expl- k (AIflPI (5)

where v = e r f l k , / A m + erflk,,,, -kOlAm.

572

The functions of the adsorption potential distribution X(A) for the iso-
therms of benzene adsorption (Fig. l ) , obtained from eqns. 5 and 7, are presen-
ted in Figs. 2 and 3, respectively.

Fig. 2. Functions of the adsorption Fig. 3. Functions of the adsorption

potential distribution obtained from potential distribution obtained from
-
eqn. 5: 1 - K4, 2 AD2, 3 - AD5, eqn. 7: 1 - K4, 2 - AD2, 3 - AD5,
4 - US2, 5 - US3, 6 - SD. 4 - US29 5 - US3, 6 - SD.

The curves demonstrate a pronounced effect of the ZSM-5 zeolite dealumina-

tion on the adsorption potential. Short acid treatment (sample AD2, Table 2,
Figs. 2, 3) causes relatively small dealumination and decreases the adsorption
without a change of the potential. This can be caused by leaching o f A1 atoms
from the center of the crystal and deposition close to the outer shells, which
finally hinders benzene molecules from penetrating the channels. Longer acid
treatment (sample AD5, Table 2, Figs. 2, 3) causes much higher dealumination and
increases adsorption with parallel increase of the adsorption potential. This
indicates that new micropores through Al-vacancies are created and the mentioned
hindrance for benzene penetration is removed. Acid leaching followed by steaming
and a second acid leaching (sample US2, Table 2, Figs. 2, 3) causes the highest
dealumination and the greatest decrease of the adsorption potential. This might
suggest a considerable increase of the adsorption volume of micropores. Steaming
without prior acid leaching (sample US3, Table 2, Figs. 2, 3) leads to lower
dealumination, which does not change the adsorption potential but increases the
 573

adsorption at lower relative pressures. This could indicate very easy penetra-
tion of benzene molecules. Salt dealumination (sample SO, Table 2, figs. 2, 3)
leads to the lowest dealurnination. resulting in effects similar to but lower
than the short acid deal umi nat ion.
Investigations of methanol adsorption did not show any significant influence
of the dealumination on the adsorption properties of the zeolite. The above
equations did not provide a correct description of the isotherms.
XRD analysis of the series of differently dealurninated ZSM-5 zeolite samples
revealed complete maintenance of the crystal 1 ine structure. The dimensions of
the crystals remained also unchanged. TGA measurements supported the conclusions
derived from the adsorption data about changes of micropore structure. The
detailed XRD and TGA investigations will be published separately.

ACKNOWLEDGEMENT
The work was partially supported by the Polish Ministry of National Educa-
tion within the Project CPBP 01.06.

REFERENCES
1 Y.H. Ma, T.D. Tang, L.B. Sand and L.H. HOU, Proc. 7th Int. Zeolite Conf.,
(Y. Murakami et al, Eds.), Kodansha, Tokyo, 1986, pp. 531-538 and refs. 2-6
therei n.
2 Y.H. Ma. Proc. Eng. found Conf. 1983, (A.L. Myers and G. Belforz, Eds.), New
York. 1984. pp. 315-324.
3 A.N. Kotasthane, V.P. Shiralkar, S.G. Hegde and S.B. Kulkarni, Zeolites 6
(1986) 253.
4 M.M. Dubinin, Chemistry and Physics of Carbon, (P.L. Walker, Jr., Ed.),
Marcel Dekker, New York, 1966, Vol. 2, pp. 51-120.
5 M.M. Dubinin, Progress in Membrane and Surface Science, (D.A. Cadenhead,
Ed.), Academic Press, New York, 1975, Vol. 9, pp. 1-70.
6 M.M. Dubinin, Zh. Fiz. Khim. 39 (1965) 1305.
7 M.M. Dubinin and V.A. Astakhov, Izv. Akad. Nauk SSSR, Ser. Khim (1971) 5.
8 M.M. Dubinin, J.G. Zhukovskaia and K.O. Murdmaa, Izv. Akad. Nauk SSSR, Ser.
Khim (1966) 620.
9 M.M. Dubinin, J.G. Zhukovskaia and K.O. Murdmaa, Izv. Akad. Nauk SSSR, Ser.
Khim (1966) 802.
10 U. Lohse, 6. Engelhardt and V. Patzelova, Zeolites 4 (1984) 163.
11 U. Lohse, G. Engelhardt, E. Alsdorf, P. Kolsch, M. Feist and V. Patzelova,
Ads. Sci. Technol. 3 (1986) 149.
12 U. Lohse, J. Richter-Mendau and V. Patzelova, Ads. Sci. Technol. 3 (1986)
173.
13 M. Jaroniec, J. Piotrowska, M. Bulow and 6. Finger, Adsorption in Micropo-
rous Adsorbents-Workshop 111, Academy of Sciences of the GDR, 1987, Vol. 2,
pp. 41-48.
14 M. Bulow, H. Schlodder, L.V.C. Rees and R.E. Richards, Proc. 7th Int. Zeo-
lite Conf., (Y. Murakami et al., Eds.), Kodansha, Tokyo, 1986, p. 579 and
refs. therein.
15 P.A. Jacobs, M. Tielen, J.B. Nagy, 6. Debris, E.G. Derouane and 2. Gabelica,
Proc. 6th Int. Zeolite Conf., (D.H. Olson and A. Bisio, Eds.), Butterworth,
Guildford, 1984, p. 783.
16 J.A. Lercher, 6. Rumplmayr and H. Noller, Proc. Int. Symp. on Zeolite
Catalysis, Siofok, 1985, p. 71.
17 R. von Ballmoos, Dissertation, Verlag Sauerlander, Aarau, 1981, pp. 155-177.
18 S. Namba, A. Inaka and T. Yashima, Zeolites 6 (1986) 107.
19 6. Engelhardt, H.G. Jerschkewitz, U. Lohse, P. Sarv, A. Samoson and E Lipp-
maa, Zeolites 7 (1987) 289.
20 H. Hamdan and J. Klinowski, Chem. Phys. Lett. 139 (1987) 576.
21 J. Scherzer, Catalytic Materials, ACS Symp. Series 248 (1984) 157-200.
22 L.B. Sand, Proc. 5th Int. Zeolite Conf.,(L.V.C. Rees, Ed.), Heyden, London.
1980. p. 1.
23 A. Nastro and L.B. Sand, Zeolites 3 (1983) 57.
24 R. Mostowicz and L.B. Sand, Zeolites 3 (1983) 219.
25 P. Ratnasamy, G.P. Babu, A.J. Chandwadkar and S.B. Kulkarni, Zeolites 6
(1986) 98.
26 J. Kornatowski, Zeolites 8 (1988) 77.
27 M. Theis, Z. anal. Chem. 144 (1955) 106.
28 M. Rozwadowski and R. Wojsz, Carbon 22 (1984) 363.
29 M.M. Dubinin and H.F. Stoeckli, J. Colloid Interface Sci. 75 (1980) 34.
30 M. Rozwadowski, R. Wojsz, K.E. Wiiniewski and J. Kornatowski. Zeolites,
submitted for publication.
31 H. Marsh and B. Rand, J. Colloid Interface Sci. 33 (1970) 101.
32 J. Choma, M. Jaroniec and J. Piotrowska, Carbon 26 (1980) 1.
33 M. Jaroniec, Langmuir 3 (1987) 795.
H.G. Karge, J. Weitkamp (Editors),Zeolites (IS Catalysts, Sorbents and Detergent Builders
-
0 1989 Elsevier Science Publishers B.V., Amsterdam Printed in The Netherlands

SELF-CONSISTENT-CHARGE Xa CALCULATIONS ON SORPTION COMPLEXES OF NITROUS OXIDE

ATTACHED TO T R A N S I T I O N METAL OCCUPIED ZEOLITE CLUSTERS

0. Zakharieva-Pencheva', M. G r o d z i c k i ' and H. F o r s t e r 3

' P h y s i c a l F a c u l t y , U n i v e r s i t y o f S o f i a , S o f i a 1126, B u l g a r i a
'1. I n s t i t u t e o f T h e o r e t i c a l Physics, U n i v e r s i t y o f Hamburg,
0-2000 Hamburg 36, West Germany
3 1 n s t i t u t e o f P h y s i c a l Chemistry, U n i v e r s i t y o f Hamburg,
D-2000 Hamburg 13, West Germany

ABSTRACT
Quantum chemical SCC-Xa MO c a l c u l a t i o n s were c a r r i e d o u t on an a l u m i n o s i -
l i c a t e s i x - r i n g c l u s t e r occupied by n i c k e l o r copper i o n s , approached by a
n i t r o u s o x i d e molecule i n N- o r 0 - f a c e d i n t e r a c t i o n i n o r d e r t o f a c i l i t a t e t h e
assignment o f i n f r a r e d bands. I n a l l cases s t a b l e s o r p t i o n com l e x e s a r e found
w i t h s t r o n g e r bonding i n t h e case o f n i c k e l and t h e M +-NNO s p e c i e s . R
E l e c t r o n i c s t r u c t u r e and charge d i s t r i b u t i o n a r e analyzed, r e v e a l i n g an N-N t o
N-0 bond charge r e d i s t r i b u t i o n f o r b o t h o r i e n t a t i o n s on n i c k e l , w h i l e a loss
o f e l e c t r o n i c charge f o r t h e copper species r e s u l t s . The s p l i t t i n g o f t h e wI
and t h e frequency s h i f t o f t h e w 3 fundamental band o f N20 on n i c k e l i o n -
exchanged z e o l i t e A may be e x p l a i n e d by t h e d i f f e r e n t o v e r l a p p o p u l a t i o n s o f
t h e bonds.

INTRODUCTION
The a n a l y s i s o f i n t r a z e o l i t i c compounds can be c o n s i d e r a b l y f a c i l i t a t e d by
quantum chemical c a l c u l a t i o n s y i e l d i n g i n f o r m a t i o n on i ) the stability of
assumed d i f f e r e n t a d s o r p t i o n geometries, i i ) the constitution of molecular
orbitals i n v o l v e d i n t h e a d s o r p t i o n process, and i i i ) t h e strengthening or
weakening o f t h e adsorbate i n t e r n a l bonds i n comparison t o t h e f r e e molecule.
The s p e c t r a l changes upon a d s o r p t i o n become i n c r e a s i n g l y complex w i t h a grow-
i n g number o f atoms i n t h e adsorbate. Even w i t h t r i a t o m i c s such as C02 and N20
the i n t e r p r e t a t i o n o f t h e r e c o r d e d s p e c t r a t u r n s o u t t o be r a t h e r difficult.
Thus, f o r an u n d e r s t a n d i n g o f t h e s p e c t r a l changes, quantum chemical i n v e s t i -
g a t i o n s a r e compulsory due t o t h e a m b i g u i t y o f t h e e x p e r i m e n t a l results. The
o b j e c t i v e o f t h i s paper was t o g i v e some a s s i s t a n c e t o t h e assignment o f bands
observed i n t h e i n f r a r e d s p e c t r a o f t r a n s i t i o n - m e t a l ion-exchanged z e o l i t e s A
when t h e y were exposed t o N20 as a probe.

PROCEDURE
SCC-Xa c a l c u l a t i o n s were performed on a z e o l i t e s i x - r i n g c l u s t e r , occupied
by e i t h e r a Ni2+, Cu2' o r Cut i o n , approached by a n i t r o u s oxide molecule
either by i t s t e r m i n a l n i t r o g e n o r oxygen atom (see F i g . l ) , as has been
576

described i n d e t a i l i n r e f s . 1 and 2. A c c o r d i n g t o o u r p r e v i o u s r e s u l t s ( r e f .
2) a l i n e a r arrangement w i t h t h e c a t i o n was assumed. This c l u s t e r models a
sorption complex i n f r o n t o f S1 cations i n zeolite A o r S2 cations in
faujasites. The free N20 molecule and t h e b a r e c l u s t e r a r e calculated for

2-M-NNO 2-M-ONN

F i g . 1. SCHAKAL drawing o f t h e z e o l i t e s i x - r i n g w h i c h i s o c c u p i e d by a t r a n s i -
t i o n metal i o n and used as a model c l u s t e r f o r quantum chemical c a l -
c u l a t i o n s . The c l u s t e r i s approached by an N20 m o l e c u l e i n -NNO o r
-0" end-on o r i e n t a t i o n .

THEORETICAL RESULTS
Quantum chemical calculations a l l o w c o n c l u s i o n s t o be drawn about the
s t r u c t u r e o f the molecular o r b i t a l s , t h e charge d e n s i t y d i s t r i b u t i o n and the
a d s o r p t i o n geometry by comparing r e l a t i v e t o t a l e n e r g i e s . Our f i n d i n g s can be
summarized as f o l l o w s .

Table 1. Percentage o f a t o m i c c o n t r i b u t i o n s t o t h e 30, 40 and 2n o r b ' t a l s o f

N20, f r e e and adsorbed on t h e model c l u s t e r o c c u p i e d w i t h N i E+ .
30 Ni-NNO Ni-ONN NNO 40 Ni-NNO Ni-ONN NNO
E(eV) 25.54 27.46 20.30 E(eV) 19.13 17.02 17.46
........................... --_-_--_-__________________
Nc 2s - 1 5 Nc 2s 3 2
2P - 4 3 2P 3 1 2
N t 2s 31 3 6 N t 2s - 46 38
2p 56 1 2P 2 49 52
0 2s 3 26 42 0 2s 40 1
2P - 57 43 2p 52 1 7
N i 4s - 1
4P 1 2
3d 6 5
1. The strongest i n t e r a c t i o n s i n a l l c o n f i g u r a t i o n s take place v i a the HOMO
(symmetry 2n) o f N20 ( c f . Table 1). I n the gas phase this MO has
predominantly oxygen c h a r a c t e r , whereas i n t h e adsorbed s t a t e oxygen and
the terminal n i t r o g e n (Nt) c o n t r i b u t e a l m o s t u n i f o r m l y to this MO. In
a d d i t i o n , oxygen atoms f r o m t h e z e o l i t e s k e l e t o n as w e l l as 3dxz and 3dyz
o r b i t a l s o f N i 2 + p a r t i c i p a t e s i g n i f i c a n t l y i n t h i s MO, leading t o a s l i g h t
d e s t a b i l i z a t i o n of t h e r e s p e c t i v e N i 3d l e v e l s (see F i g . 2). The la MO
shows a s i m i l a r b u t l e s s pronounced s t r u c t u r e .

E 4'.

-10,:

- 11.0

-11.j

Ni-zodite Ni-zeolite Ni-zeolite

cluster -NNO cluster Cluster-ONN

F i g . 2. N i c k e l 3d o r b i t a l s i n t h e b a r e zeo-
l i t e c l u s t e r and t h e i r change upon i n t e r a c -
t i o n w i t h n i t r o u s o x i d e i n a l i n e a r -NNO
and -0" arrangement.

The p a r t i c i p a t i o n o f 3dxz and 3dyz o r b i t a l s i n t h e case o f a d s o r p t i o n via

nitrogen i s considerably higher than i n the reversed o r i e n t a t i o n . This i s a
h i n t t o a s t r o n g e r Ni-adatom i n t e r a c t i o n i n Z-Ni-NNO compared w i t h Z-Ni-ONN
i n t e r a c t i o n and w i l l be confirmed by subsequent charge d e n s i t y a n a l y s i s .
2. I n f r e e n i t r o u s oxide, f r o m t h e two h i g h e s t occupied a MOs, 30 and 4a, t h e
f i r s t one i s an almost i d e a l oxygen sp h y b r i d , w h i l e t h e second one i s an
approximate sp h y b r i d o f t h e t e r m i n a l n i t r o g e n atom ( c f . Table 1). A s t r o n g
r e o r g a n i z a t i o n o f these l e v e l s , depending on t h e o r i e n t a t i o n o f N20, o c c u r s
in t h e adsorbed s t a t e due t o t h e s t r o n g i n t e r a c t i o n with N i 3dZz. Accor-
d i n g l y t h e N i 3dZ2 l e v e l i s d e s t a b i l i z e d by a p p r o x i m a t e l y 1 eV f o r adsorp-
578
 579

t i o n v i a b o t h Nt and 0. However, f o r m a t i o n o f an N-bound s p e c i e s s t a b i l i z e s

the nitrogen sp h y b r i d (40 i n t h e f r e e m o l e c u l e ) by 8 eV due to this
interaction, r e s u l t i n g i n an i n t e r c h a n g e w i t h t h e ( s l i g h t l y destabilized)
oxygen sp hybrid (3u i n t h e f r e e molecule). The analogous effect is
observed w i t h t h e 0-bound species, s t a b i l i z i n g t h e 30- MO by 7 eV w h i l e t h e
40 l e v e l remains p r a c t i c a l l y u n a f f e c t e d . Hence, t h e 3a o r b i t a l i s always
p a r t o f t h a t atom f a c i n g t h e n i c k e l i o n .
In t h e n e x t s t e p t h e charge d i s t r i b u t i o n f r o m SCC-Xa c a l c u l a t i o n s w i l l be
analyzed. The most i m p o r t a n t r e s u l t s a r e d i s p l a y e d i n Tables 2 and 3 and can
be expressed as f o l l o w s :
1. D i f f e r e n c e s i n t h e e l e c t r o n i c s t r u c t u r e o f t h e Ni2' i o n are simultaneously
caused by 4s, 4p and 3d e l e c t r o n s . In particular, a transfer of 0.13
e l e c t r o n s f r o m 3d t o 4p s h o u l d be mentioned due t o t h e h i g h e r coordination
i n t h e s o r p t i o n complex.
2. The t o t a l charge Qmol o f t h e N20 m o l e c u l e becomes more p o s i t i v e i n t h e 0-
bound compound.
3. P o s i t i v e o v e r l a p p o p u l a t i o n s between n i c k e l and t h e a d j a c e n t atom a r e q u i t e
w e l l pronounced i n b o t h cases o f o r i e n t a t i o n and a r e l a r g e r compared t o ad-
s o r p t i o n i n f r o n t o f c a l c i u m (see r e f . 3 ) . Moreover, t h e N i - N t o v e r l a p po-
p u l a t i o n exceeds t h a t o f N i - 0 by 20%, p r o v i n g a s t r o n g e r bonding v i a n i t r o -
gen. Correspondingly, t h e p o t e n t i a l c u r v e s show t h e same t r e n d , i . e . the
minimum t u r n s o u t t o be deeper f o r t h e Ni-NNO c o n f i g u r a t i o n ( c f . T a b l e 2 ) .
4. A bond-bond charge t r a n s f e r t a k e s p l a c e w i t h i n t h e adsorbed m o l e c u l e from
t h e Nt-Nc t o t h e Nc-0 bond i n b o t h cases o f attachment. This f i n d i n g dif-
f e r s from t h a t found w i t h t h e Ca c l u s t e r , i n which case a charge trans-
f e r was observed always f r o m t h e a d j o i n i n g t o t h e t e r m i n a l bond.
Concerning the copper-exchanged z e o l i t e s t h e v a r i o u s molecular . o r b i t a l s
with predominant N20 p a r t i c i p a t i o n show e s s e n t i a l l y t h e same f e a t u r e s as in
the case o f n i c k e l . Compared t o n i c k e l t h e r e a r e s i m i l a r i t i e s b u t a l s o some
differences i n t h e charge d i s t r i b u t i o n s ( c f . Table 4 and 5), yielding the
following results:
1. Approaching t h e Cut s i x - r i n g c l u s t e r b y N20 two s t a b l e s o r p t i o n complexes
i n a Z-CU-NNO and Z-CU-ONN a l i g n m e n t may be formed, as can be d e r i v e d f r o m
t h e minima o f t o t a l energy a t Cu-Nt and Cu-0 d i s t a n c e s o f 1.64 i.
2. I n accordance w i t h t h e Ni2'-exchanged c l u s t e r the larger charge transfer
f r o m N20 t o Cu t a k e s p l a c e i n t h e Z-CU-ONN complex.
3. I n b o t h species t h e adsorbed molecules a r e p o s i t i v e l y charged, more pro-
nouncedly f o r Z-CU-ONN where a l l adsorbate atoms lose e l e c t r o n i c charge;
while i n case o f t h e Z-Cu-NNO t h e l o s s o f charge on t h e 0 and Nc atoms is
p a r t l y compensated by t h e g a i n o f charge on t h e Nt atom.
580

TABLE 4
E f f e c t i v e atomic and m o l e c u l a r charges Q, e l e c t r o n o c c u p a t i o n numbers of
AOs xs and x o v e r l a p p o p u l a t i o n x and t o t a l e n e r g i e s E o f 2-CU-NNO.
P'
 581

4. F o r b o t h s o r p t i o n complexes p o s i t i v e o v e r l a p charges were o b t a i n e d between

Cu and t h e a d j a c e n t atom of N20. The o v e r l a p charge i s l a r g e r i n t h e case
o f Z-CU-NNO i n accordance w i t h a s l i g h t l y deeper minimum o f t o t a l energy.
5. The c r u c i a l d i f f e r e n c e i s t h e m i s s i n g bond-bond charge t r a n s f e r w i t h i n the
adsorbate m o l e c u l e . The o v e r l a p popu a t i o n s o f b o t h N20 bonds decrease in
comparison w i t h t h e gas phase values F o r t h e N-N bond a more pronounced
r e d u c t i o n i s observed.

INTERPRETATION AND D I S C U S S I O N
On t h e b a s i s of t h e quantum chemical r e s u l t s and normal c o o r d i n a t e a n a l y s i s
we attempted t o i n t e r p r e t t h e observed i n f r a r e d s p e c t r a o b t a i n e d (see r e f . 4),
applying the f o l l o w i n g strategy:
- F i r s t we t r i e d t o f i n d quantum c h e m i c a l l y s t a b l e s o r p t i o n complexes o f N-
and O-bound n i t r o u s o x i d e .
- Next we examined which v i b r a t i o n a l c o o r d i n a t e s and f o r c e constants i n f l u -

75

1350 1230 2300 21 50

Frequency /cm- 1
F i g . 3. I R s p e c t r a o f n i t r o u s o x i d e adsorbed i n z e o l i t e s Nii.,NatefA
and Cu3 1Na5 8A i n t h e r e g i o n s o f t h e u, and v3 f u n amen a s.
582

ence most s t r o n g l y t h e v i b r a t i o n a l mode under c o n s i d e r a t i o n .

- F i n a l l y we sought t o f i n d t h e e x t e n t o f change i n t h e o v e r l a p p o p u l a t i o n o f
t h e i n v o l v e d bonds upon a d s o r p t i o n compared t o f r e e N20.
Analyzing at first t h e u 1 band o f n i t r o u s o x i d e in the Ni2+-exchanged
z e o l i t e , one peak i s observed a t 1304 cni' and t h e second as a s h o u l d e r a t 1290
cm-' (see F i g . 3 ) , compared w i t h t h e gas phase v a l u e o f 1285 c d . The s p l i t t i n g
of the vl band may be due t o t h e two sorption complexes in different
o r i e n t a t i o n o f t h e adsorbate (Z-Ni-NNO and Z-Ni-0"). I n t h e L modes o f t h e v1
fundamental v i b r a t i o n t h e h i g h e s t p a r t i c i p a t i o n c o e f f i c i e n t i s t h a t o f t h e N-0
s t r e t c h i n g coordinate, which i s more t h a n t w i c e as l a r g e as t h e c o r r e s p o n d i n g
participation coefficient o f t h e N-N stretching coordinate. The Jacobian
elements i n d i c a t e t h a t aXl/aFNo i s about f o u r times h i g h e r than the correspon-
ding aX,/aF" and a l s o t h a t ahl/aFNiN i s n e a r l y t w i c e as h i g h as aX,/aF".
Therefore t h e h i g h - f r e q u e n c y band a t 1304 cm-' must be a s s i g n e d t o t h e Ni-NNO
and t h e 1290 cni' a b s o r p t i o n t o t h e N i - O N N species, a l t h o u g h i n t h e case o f t h e
latter no i n n e r charge r e d i s t r i b u t i o n i s observed as i s f o u n d w i t h Ca (see
ref. 2). I n b o t h o r i e n t a t i o n s t h e v a l u e s o f t h e o v e r l a p charges 0-N and N-N
are almost i d e n t i c a l , hence t h e d i f f e r e n c e i n t h e r e s p e c t i v e f r e q u e n c i e s may
be due t o t h e d i f f e r e n t N i - 0 and N i - N o v e r l a p c h a r g e s . Here we have t o take
i n t o account t h e l a r g e e i g e n v e c t o r o f t h e Ni-adatom i n t e r n a l c o o r d i n a t e t o t h e
L mode o f this vibration, as w e l l as t h e l a r g e v a l u e o f the corresponding
Jacobian element.
The u p s c a l e f r e q u e n c y s h i f t o f t h e v 3 band w i t h i t s main peak a t 2257 CN'
may be i n t e r p r e t e d o n l y by t h e N i - N o v e r l a p p o p u l a t i o n . I n t h e L mode o f the
v 3 v i b r a t i o n t h e p a r t i c i p a t i o n c o e f f i c i e n t o f t h e N-N s t r e t c h i n g c o o r d i n a t e i s
t h e l a r g e s t , f o l l o w e d b y t h a t o f t h e N-0 c o o r d i n a t e . O n l y i n t h e case o f Z - N i -
NNO configuration does t h e Ni-adatom c o o r d i n a t e p a r t i c i p a t e i n t h e L mode.
Furthermore, this i s c o n f i r m e d by t h e c a l c u l a t e d d i s p l a c e m e n t s o f t h e atoms
from their equilibrium positions. I n t h e case o f t h e Z-Ni-ONN species the
displacement o f t h e t e r m i n a l 0 atom i s small w h i l e t h a t o f N i i s n e a r l y zero.
This i s a l s o r e f l e c t e d i n t h e J a c o b i a n elements o f t h e v 3 v i b r a t i o n . In the
case of t h e Z-Ni-ONN complex t h e v 3 mode i s n e a r l y i n s e n s i t i v e t o the FNiO
force element (aX3/aFNio = 0). Furthermore the v 3 v i b r a t i o n turns o u t t o be
i n s e n s i t i v e t o t h e mode o f a t t a c h m e n t t o t h e c a t i o n , i.e. v i a the nitrogen or
the oxygen atom, as t h i s v i b r a t i o n r e p r e s e n t s e s s e n t i a l l y t h e m o t i o n o f the
central n i t r o g e n w i t h r e s p e c t t o t h e t e r m i n a l atoms, w h i l e f o r the v 1 mode
just t h e o p p o s i t e i s t h e case. Compared t o v l t h e h i g h e r f r e q u e n c y s h i f t of
t h e v 3 mode i n b o t h o r i e n t a t i o n s o f N20 a d s o r p t i o n can be u n d e r s t o o d f r o m the
l a r g e v a l u e s o f t h e c o r r e s p o n d i n g e i g e n v e c t o r s and t h e J a c o b i a n elements.
The s i t u a t i o n w i t h t h e copper-exchanged z e o l i t e s i s r a t h e r complex, as it
 583

was found by CO probing t h a t the primarily exchanged Cu2' during the

p r e t r e a t m e n t i s e s s e n t i a l l y auto-reduced t o Cut and Cuo ( s e e r e f . 5 ) . This i s
in accordance w i t h t h e c a l c u l a t e d r e s u l t s on t h e Cu2+-loaded cluster which
cannot c o n s i s t e n t l y e x p l a i n t h e e x p e r i m e n t a l s p e c t r a . T h e r e f o r e an a t t e m p t was
made t o t e n t a t i v e l y a s s i g n t h e d o u b l e t a t 1289 and 1282 cm-' t o t h e v 1 bands o f
n i t r o u s o x i d e adsorbed i n f r o n t o f a Cut i o n i n -NNO and -0" alignment, and
the d o u b l e t a t 2245 and 2223 cm-' t o t h e v j fundamental mode, while adjacent
overlapping subbands under the envelope were attributed to N20 species
i n t e r a c t i n g w i t h Na' cations. The s p l i t t i n g o f t h e v1 i n t o two bands without
appreciable shift of t h e c e n t e r may be e x p l a i n e d by t h e existence of two
opposite e f f e c t s :
- d i m i n i s h i n g o f t h e N-0 o v e r l a p p o p u l a t i o n and
- p a r t i c i p a t i o n o f t h e Cu-0 or CU-N i n t e r n a l c o o r d i n a t e i n t h e L mode o f the
v 1 fundamental.
Concerning t h e v g mode, o n l y f o r t h e Z-Cu'-NNO species can t h e b a n d s h i f t t o
a h i g h e r frequency (2245 cm-') be reasonably understood f r o m t h e l a r g e v a l u e o f
the CU-N overlap population i n combination w i t h the eigenvectors of this
vibration. (Only in the Cu-NNO o r i e n t a t i o n does the Cu-adatom internal
coordinate participate in t h e L modes o f v g . ) F o r the Cu+-ONN complex a
downscale s h i f t compared t o t h e gasphase f r e q u e n c y s h o u l d o c c u r .
The h i g h e r i n t e n s i t y o f t h e v, HF band may be e x p l a i n e d by t h e l a r g e r N-0
bond d i p o l e moment i n t h e case o f t h e Z-M-NNO s o r p t i o n complex.

CONCLUSIONS
Quantum chemical calculations supplemented by vibrational analyses on
sorption complexes o f t r i a t o m i c s i n z e o l i t e s o f f e r a h e l p f u l guide for the
assignment of the complex overlapping bands usually observed. As
demonstrated by t h e copper example, success i s n o t guaranteed - which should
give impetus t o more r e f i n e d experiments, s i n c e more s o p h i s t i c a t e d calcula-
t i o n s do n o t seem p o s s i b l e a t p r e s e n t .

ACKNOWLEDGEMENT
This work was supported b y t h e U n i v e r s i t i e s o f Hamburg and S o f i a and the
Fonds d e r Chemischen I n d u s t r i e .
584

REFERENCES

1. 0. Zakharieva-Pencheva, H. Bose, H. F o r s t e r , W. Frede and M. G r o d z i c k i , J .

M o l . S t r u c t . , 122 (1985) 101-114.
2. M. Grodzicki, 0. Zakharieva-Pencheva and H. F o r s t e r , J. M o l . S t r u c t . , 175
(1988) 175-201.
3. M. Schumann, M. Grodzicki, H. Bose, H. F o r s t e r and 0. Zakharieva-Pencheva,
i n D. Shopov e t a l . (Eds.), Heterogeneous C a t a l y s i s , Proc. S i x t h I n t . Symp.
S o f i a , 1987, Volume 2, P u b l i s h i n g House o f the B u l g a r i a n Academy o f S c i -
ences, Sofia, 1987, pp. 193-198.
4. H. F o r s t e r and M. Remmert, 3. M o l . S t r u c t . ,174 (1988) 357-362.
5. H. F o r s t e r and U. Witten, Z e o l i t e s , 7 (1987) 517-521.
H.G. Karge, J. Weitkamp (Editors), Zeolites [IS Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

I R STUDY OF THE ADSORPTION OF BENZENE ON HZSM5

Andreas J e n t y s and Johannes A. Lercher

I n s t i t u t f u r P h y s i k a li s c h e Chemie, Technische U n i v e r s i t a t Wien
Cetreidemarkt 9, A-1060 Vienna, AUSTRIA

ABSTRACT
The a d s o r p t i o n o f benzene on a s e r i e s of HZSM5 samples (1-4.5 aluminum atoms
p e r u n i t c e l l ) was s t u d i e d by means o f i.r. sp ec roscopy. The sam p l es were
e x p o s e d t o b eq ze n e v a p o r a t p r e s s u r e s b e t w e e n lo-’ a n d 1 mbar. Benzene was
adsorbed on Na c a t i o n s and on hydroxyl groups l e a d i n g t o f o u r d i f f e r e n t f o r m s
of hydrogen-bonded molecules: adsorbed on SiOHAl groups, hydrogen-bonded SiOH
i n s i l a n o l n e s t s , f r e e SiOH g r o u p s , and t w o m o l e c u l e s a d s o r b e d p e r SiOHAl
group. The s t r e n g t h o f t h e i n t e r a c t i c g o f benzene d ecr eased i n t h i s sequence.
The s p e c t r a a f t e r e q u i l i b r a t i o n a t 10 mbar b e n z e n e p r e s s u r e w e r e co m p ar ed
q u a n t i t a t i v e l y f o r a l l samples s u g g e s t i n g t h e a d s o r p t i o n s t o i c h i o m e t r y b ei n g
s t r i c t l y one f o r a l l s i t e s and samples. The a d s o r p t i o n e q u i l i b r i u m c o n s t a n t o f
benzene and, hence, t h e a c i d s t r e n g t h s of a l l a c i d s i t e s d o n o t v ar y w i t h t h e
aluminum c o n t e n t p e r u n i t c e l l .

INTRODUCTION
Benzene i s a f r e q u e n t l y proposed and used probe molecule f o r t h e e v a l u a t i o n
of t h e a d s o r p t i v e p r o p e r t i e s o f z e o l i t e s ( 1 - 5 ) a n d , i n p a r t i c u l a r , f o r t h e
s t r e n g t h of t h e hydroxyl groups (6-8) by means o f v i b r a t i o n a l spectroscopy. Re-
c e n t l y , adsorbed benzene was used f o r e v a l u a t i o n o f t h e b ase s t r e n g t h o f a l k a l i -
e xch an g ed z e o l i t e Y (9-11). A s a c o n s e q u e n c e , s i g n i f i c a n t i n f o r m a t i o n on t h e
l o c a t i o n o f b en ze n e i n z e o l i t e s , e s p e c i a l l y i n X a n d Y t y p e (12-14) a n d ZSM5,
exists.
For HZSMS, Mentzen (15) r e p o r t s benzene t o r o t a t e on a n axis a t t h e m i r r o r
plan e and/or t o be p r e s e n t i n two symmetric l o c a t i o n s a t t h e channel i n t e r s e c -
t i o n s , t h e l a t t e r p o s s i b i l i t y s u p p o r t e d by h i s own X-ray powder d i f f r a c t i o n
m e a s u r e m e n t s o f p - x y le n e on b o r a l i t e , a b o r o n - c o n t a i n i n g a n a l o g u e o f HZSM5
(16,17). S i m i l a r c o n c lu s io n s , i.e., t h e l o c a t i o n o f a p a i r o f benzene molecules
a t t h e c h a n n e l i n t e r s e c t i o n and o n e s i n g l e b en zen e m o l e c u l e i n t h e s t r a i g h t
c h a n n e l , were r e a c h e d by T a y l o r on t h e b a s i s o f p o w d er n e u t r o n d i f f r a c t i o n
measurements of deuterobenzene i n HZSM5 (18,19). The i m p o r t an ce o f c a t i o n s as
l o c a l i z e d a d s o r p t i o n s i t e s was emphasized by Thamm (20) and F o e r s t e (21) sug-
g e s t i n g a d s o r p t i o n a t t h e c h a n n e l i n t e r s e c t i o n o n B r o n s t e d an d L e w i s a c i d
s i t e s , respectively. Similarly, t h e a u t h o r s u s i n g v i b r a t i o n a l sp ect r o sco p y as
586

a n a l y t i c a l means s t r o n g l y suggest t h a t a t l e a s t a t low and moderate coverages

d i r e c t l o c a l i z e d a d s o r p t i o n of benzene predominates (1-11).
I n t h i s p a p e r we i n t e n d ( i )t o d e s c r i b e t h e i n t e r a c t i o n s o f benzene w i t h
HZSM5 (1 t o 4.5 A 1 per u n i t c e l l ) a t e q u i l i b r i u m p r e s s u r e s ranging from
t o 1 mbar benzene, ( i i ) t o d e s c r i b e t h e changes of t h e a d s o r b a t e s a s a f u n c t i o n
of the aluminum content a t an e q u i l i b r i u m p r e s s u r e of benzene a t which i n t e r -
a c t i o n s of benzene w i t h s i l i c a i m p u r i t i e s can be neglected and (iii)t o charac-
t e r i z e t h e v a r i a t i o n of t h e a c i d s i t e s of HZSM5 a s a f u n c t i o n of t h e aluminum
c o n t e n t . T i m e - r e s o l v e d i.r. s p e c t r o s c o p y i s u s e d t o check w h e t h e r t r a n s p o r t
phenomena a f f e c t t h e i.r. s p e c t r a measured.

EXPERIMENTAL
Materials
The ZSM5 samples were synthesized according t o t h e method o f I n u i e t a1 (22)
using w a t e r g l a s s (28 mol% s o l u t i o n i n water), aluminumsulfate and t e t r a p r o p y l -
ammoniumbromide as reagents. ZSM5 was t h e o n l y c r y s t a l l i n e phase d e t e c t e d by
XRD. Subsequently, t h e samples were ion-exchanged w i t h ammoniumnitrate solu-
t i o n . The c o m p o s i t i o n o f t h e HZSM5 s a m p l e s , t h e c o n c e n t r a t i o n of s t r o n g and
weak Bronsted a c i d s i t e s and t h e concentration of t e t r a h e d r a l l y and octahedral-
l y coordinated aluminum a r e compiled i n Table 1.

TABLE 1
Unit c e l l composition and a c i d i t y of HZSM5 samples

Sample Unit cell strong weak tetr. oct.

composition H'1U.C. H'1U.C. Si/A1 Na'1U.C. A13+/U.C.
H A1 Si 0
HZSM5-1 4.5 4.5 91.5 192 3.28 0.27 20.2 0.4 3-28 1-22
HZSM5-2 3.7 3.7 92.3 192 1.70 0.18 25.2 0.4 1-70 2.0
HZSM5-3 2.1 2.1 93.9 192 1.64 0.23 45.8 0.3 7-64 0.46
HZSM5-4 1.5 1.5 94.5 192 1.39 0.16 63.0 0.4 1.39 0.11
HZSM5-5 1.3 1.3 94.7 192 0.78 0.42 73.6 0.6 0.78 0.52
HZSM5-6 1.0 1.0 95.0 192 0.97 0.09 101.0 0.3 0.97 0.03

1.r. and temperature-programmed desorption (t.p.d.) measurements

Self-supporting d i s c s of t h e HZSM5 samples were analyzed by t r a n s m i s s i o n -
a b s o r p t i o n i.r. s p e c t r o s c o p y (BRUKER IFS 88, 4 cm-l r e s o l u t i o n ) . The d i s c was
p l a c e d i n a s a m p l e h o l d e r i n t h e c e n t e r o f a small f u r n a c e i n t h e i.r. beam.
The bands of t h e l a t t i c e v i b r a t i o n s b e t w e e n 2090 and 1740 cm-l w e r e used as
s t a n d a r d s t o normalize t h e i n t e n s i t i e s of all bands. For a c t i v a t i o n and t.p.d.;
 581

t h e sample was heated i n s i t u w i t h a r a t e of 10 K.min-’ t o a temperature of

873 K a t pressures lower than mbar. The p r e s s u r e changes were determined
by means of a Balzers 311 quadrupole mass spectrometer. The amounts desorbed
were q u a n t i f i e d using a reference sample o f HZSM5 (23).

RESULTS
Adsorption of benzene
HZSM5 a c t i v a t e d a t 873 K e x h i b i t e d f i v e bands due t o OH v i b r a t i o n s a t 3745
(SiOH), 3726 ( f r e e SiOH a t d e f e c t s i t e s ) , 3698-3670 (water on e x t r a l a t t i c e

c-.
m a t e r i a l ) , 3610 (SiOHA1, b r i d g i n g h y d r o x y l g r o u p ) and a r o u n d 3500 cm-l ( p e r -
t u r b e d SiOH a t d e f e c t s i t e s ) . These bands w e r e o b s e r v e d w i t h a l l s a m p l e s i n -
v e s t i g a t e d ; t h e i r r e l a t i v e i n t e n s i t i e s , however, v a r i e d s i g n i f i c a n t l y .

0.0325 A

v! \i’

L
35bo 3000 2500 2000 moo mo 3000 2wo 2000 id0

(7
y
vEHy
B E
R B CM-1 M A V W B E R S MI-i

10

Fig. 1. D i f f e r e n c e between t h e i.r. s p e c t r a o f t h e a d s o r b a t e w i t h benzene a t

t h e equilibrium pressure i n d i c a t e d and t h e spectrum of t h e a c t i v a t e d HZSM5.
588

The d i f f e r e n c e between t h e adsorbate s p e c t r a and t h e spectrum of a c t i v a t e d

HZSM5-1 a r e compiled i n Fig. 1. The d i f f e r e n c e s p e c t r a between two subsequent
equilibrium p r e s s u r e s a r e compiled i n Fig. 2. Bands p o i n t i n g upwards increased,
t h o s e p o i n t i n g downwards d e c r e a s e d i n i n t e n s i t y compared t o t h e s u b t r a c t e d
spectrum.
Increasing t h e benzene p r e s s u r e up t o mbar caused t h e OH band a t 3610
cm-' t o d e c r e a s e , i n d i c a t i n g i n t e r a c t i o n w i t h t h e bridging hydroxyl groups. A
broad band o f p e r t u r b e d OH g r o u p s a p p e a r e d a t 3350-3250 cm-l, w h i l e bands o f
adsorbed benzene were observed a t 3093, 3074, 3039 (CH s t r e t c h i n g v i b r a t i o n s ) ,
2000, 1973, 1892, 1832 (combination bands of out-of-plane CH deformation vibra-
t i o n s ( 4 and r e f e r e n c e s t h e r e i n ) ) and a t 1477 cm-' (C-C stretching vibration).

I T ' 1

II T 0.Om A

Fig. 2. Changes i n t h e i.r. s p e c t r a i n d u c e d by t h e s t e p w i s e i n c r e a s e of t h e

benzene equilibrium pressure.
 589

At and mbar b e n z e n e p r e s s u r e , t h e b an d s a t 1971 a n d 1 8 3 2 cm-l

i n c r e a s e d i n I n t e n s i t y . P r i m a r i l y , t h e band a t 3610 cm-l d ecr eased i n i n t e n s i t y
and o n l y a v e r y small f r a c t i o n o f t h e i n t e n s i t y o f t h e h y d r o x y l band a t 3 7 2 6
cm-l d e c r e a s e d . Two o v e r l a p p i n g b a n d s o f p e r t u r b e d h y d r o x y l g r o u p s w e r e ob-
se r v ed a t 3350 cm-l and 3240 - 50 cm-
1
.
We n ot ed a somewhat h i g h e r wavenumber
f o r t h e l a t t e r band i n a r e c e n t s t u d y o v e r HZSM.5 ( 2 4 ) , a n d we t h i n k t h a t t h e
d i f f e r e n c e may be due t o s u b t l e s t e r i c d i f f e r e n c e s a t t h e benzene a d s o r p t i o n
site. The presence of two p e r tu r b e d bands s u g g e s t s two t y p e s o f hydrogen bond-
i n g an d / o r t w s t y p e s o f a c i d s i t e s (25). After e q u i l i b r a t i o n a t a p r e s s u r e o f
10-1 mbar benzene, t h e OH band 3726 cm-l d e c r eased i n i n t e n s i t y and new bands
appeared a t 3612, 3250 w i t h a s h o u l d e r a t 3174 cm-l and a t 1954 and 1811 cm-
1
.
Upon i n c r e a s i n g t h e b e n z e n e p r e s s u r e t o 1 mbar t h e b a n d s a t 3 6 1 2 , 3 1 7 4 , 1 9 5 4
and 1811 cm-l f u r t h e r i n c r e a s e d i n i n t e n s i t y . The b an d s a t 3350 cm-l a n d a t
1971 a n d 1832 cm-l d e c r e a s e d s l i g h t l y i n i n t e n s i t y . W i t h i n c r e a s i n g b e n z e n e
p r e s s u r e t h e bands a t 3093, 3074, 3039 and 1477 cm-l d i d n o t change i n wavenum-
b e r s , b u t i n c r e a s e d i n i n t e n s i t y . The i n t e g r a l i n t e n s i t y o f t h e band a t 1 4 7 7
-1
cm , p l o t t e d as a f u n c t i o n o f t h e e q u i l i b r i u m p r e s s u r e (see Fig. 31, seems t o
f o l l o w a Langrnuir-type isotherm. The a d s o r p t i o n of benzene i s co m p l et el y r e v e r -
s i b l e a t ambient temperature.
No(*uuzEDA88Q118ANQ. B€"E 1 8 0 1 2 an4 URB. U
Nm
0.x)
I

prwure [rnbar]
Fig. 3. I n t e g r a l i n t e n s i t y of t h e band a t 1477 cm-l of benzene on HZSM5-1 as a
function of the equilibrium pressure.

The t i m e d e p e n d e n c e o f t h e i.r. a d s o r b a t e s p e c t r a o f b en zen e o n HZSM5-1

a f t e r a s t e p up o f t h e p r e s s u r e f r o m to mbar b e n z e n e i s p l o t t e d i n
Fig. 4. Note t h a t a l l b a n d s i n c r e a s e d i n p a r a l l e l . S u ch b e h a v i o u r s u g g e s t s
t h a t l o c a l ad s o r p t io n - d e s o r p t io n e q u i l i b r i u m e x i s t s durbng t h e t r a n s i e n t , much
like the situation prevailing i n
s i t u a t i o n d es cr i b e d by Rieck and
590

TIE [el
1000

0.12

0.085 500

5
0.05

f 0.015

-
-0.02 1
3500 3000 2500 2000 1500
WAVENUMBERS CM-1

F i g . 4. 1.r. d i f f e r e n c e s p e c t r a d u r i n g e q u i l i b r a t i o n o f b e n z e n e o n HZSM5-1
a f t e r a s t e p w i s e i n c r e a s e o f t h e benzene p r e s s u r e f r o m to mbar. The
i.r. spectrum o f t h e a c t i v a t e d sample i s s u b s t r a c t e d f r o m each o f t h e s p e c t r a .
0.019

0.01C5

v)
I-
H
z
3
W
y 0.002
a
rn

I-
U
0
v)
m
4

-0.006

1 :
I
I I

-0.015
3500 3000 2500 2000 1500
WAVENUMBERS CM-1

Fig. 5. Benzene on tIZSF15-3 mbar).

.... s p e c t r u m measured; - s i m u l a t e d b a n d s a t 3350 and 3240 cm-’;
____ sum o f b o t h bands
 591

Influence of t h e Si/A1 r a t i o
We i n v e s t i g a t e d benzene a d s o r p t i o n a t a p r e s s u r e o f mbar o f b e n z e n e ,
because under t h i s condition t h e bands of SiOH v i b r a t i o n s a r e h a r d l y a f f e c t e d
by t h e presence of benzene. The most s i g n i f i c a n t d i f f e r e n c e s between a l l samples
a r e t h e v a r i a t i o n of the r e l a t i v e i n t e n s i t i e s of t h e perturbed OH band and t h e
decrease of t h e i n t e n s i t y of t h e bands due t o adsorbed benzene w i t h decreasing
concentration of aluminum. Typical d i f f e r e n c e s b e t w e e n t h e i.r. s p e c t r u m of
t h e a d s o r b a t e and t h a t of t h e a c t i v a t e d s a m p l e t o g e t h e r w i t h t h e two decon-
voluted perturbed OH bands a r e compiled i n Fig. 5. Fig. 6 shows t h e v a r i a t i o n s
1
of t h e i n t e g r a t e d i n t e n s i t i e s of t h e bands a t 3350 and a t 3240-50 cm- Fig. 7 ,
t h e concentration of strong and weak Bronsted a c i d sites determined by t.p.d.
of pyridine as a f u n c t i o n of t h e aluminum content of t h e u n i t c e l l . The average
c o n t r i b u t i o n of t h e a c i d s i t e s f o r a d s o r p t i o n o f benzene on t h i s s e r i e s of
HZSM5 s a m p l e s i s b e s t i l l u s t r a t e d i n Fig. 8. I t shows t h e dependence o f t h e
concentration of adsorbed benzene upon t h e concentration of aluminum and sodium
p e r u n i t c e l l . The l i n e a r f u n c t i o n p a s s e s t h r o u g h t h e o r i g i n , s u g g e s t i n g t h a t
indeed we account f o r a l l p o s s i b l e adsorption s i t e s .

DISCUSSION
I t i s accepted (4-11) t h a t two groups of i.r. bands can be used t o character-
i z e a d s o r b e d benzene: ( i )bands of u n p e r t u r b e d and p e r t u r b e d OH g r o u p s and
( i i )bands of c o m b i n a t i o n s of CH out-of-plane d e f o r m a t i o n v i b r a t i o n s b e t w e e n
2100 and 1800 cm-l, t h e i r wavenumber d i f f e r e n c e (25,271 and t h e i r wavenumber
i n c r e a s i n g with t h e i n t e r a c t i o n strength.
I n t o t a l , four perturbed hydroxyl bands were observed (3612, 3350, 3250 and
3170 cm-l).At low pressures (up t o mbar) only those a t 3350 and 3250 cm-’,
a t h i g h p r e s s u r e s , i n a d d i t i o n , t h o s e a t 3612 and 3170 cm-l. Below mbar
benzene two pairs of CH out-of-plane deformation bands were observed a t 2000,
1892 and 1973, 1830 cm-l. The f i r s t p a i r o f bands i n d i c a t e s t h e s t r o n g e s t
adsorption on H E M 5 and was a t t r i b u t e d t o benzene on r e s i d u a l Na
+ c a t i o n s (10).
The h i g h s t a b i l i t y o f t h i s a d s o r b a t e i s a l s o r e f l e c t e d i n t h e h i g h e r t h e r m a l
s t a b i l i t y of benzene on NaZSM5 a s compared t o benzene on HZSM5 (27). The
i n t e n s i t y of t h e o t h e r two bands i n c r e a s e d i n p a r a l l e l w i t h b o t h p e r t u r b e d
h y d r o x y l bands (3350 and 3240-50 cm-l). We a t t r i b u t e t h e s e bands t o benzene
adsorbed on Bronsted a c i d i c hydroxyl groups.
From t h e CH out-of-plane d e f o r m a t i o n v i b r a t i o n s o f benzene, t h e r e i s no
i n d i c a t i o n of t h e p r e s e n c e o f two t y p e s of B r o n s t e d a c i d s i t e s , i n d i c a t i n g
r a t h e r similar s t r e n g t h s of i n t e r a c t i o n . The s e p a r a t i o n of t h e two perturbed OH
bands ( a p p r o x i m a t e l y 100 cm-l; J a c o b s r e p o r t i n g a A Y o f 50 cm-I (8)) i s ,
however, v e r y l a r g e compared t o t h e d i f f e r e n c e s i n t h e s h i f t s (rnax. 17 ern-')
592

NORMAUZEDABSORBANCE OFTHE
PERTURBEDy OH We. UNITS) SITES I U.C.

31
sT:wl
SITES

b
0.1 . *.."
,,~3250,
0.0 -
*.._':,
0 1 2 3 4 5 0 1 2 3 4 5
Al I UNIT CELL Al I UNIT CELL
Fig. 6. Normalized i n t e g r a l i n t e n s i t y Fig. 7. Concentration of t h e s t r o n g and
of t h e perturbed OH bands a s a func- weak Bronsted a c i d s i t e s as a f u n c t i o n
t i o n o f A13'/U.C. of Al3'/U.C.

OAOO 0.006 OXHO 0x116 0.020

NORMALIZED ABSORBANCE, BENZENE, 1516-1412 UII~
(ARB. UNITS)

Fig. 8. Normalized i n t e g r a l i n t e n s i t y of t h e band a t 1477 cm-' of benzene a s a

f u n c t i o n of t h e sum of t h e t o t a l amount of A13' and Na'.

reported (7). I f t h i s s p l i t t i n g were due t o two hydroxyl groups w i t h i d e n t i c a l

p o s i t i o n s of t h e u n p e r t u r b e d OH g r o u p s , t h e d i f f e r e n c e i n t h e s t r e n g t h of
these hydroxyl groups should be extremely high. I n t h a t c a s e one expects two
experimental observations: ( i )t h e r e should be a p r e f e r e n t i a l a d s o r p t i o n on t h e
s i t e o f t h e h i g h a c i d s t r e n g t h a t low e q u i l i b r i u m p r e s s u r e s and ( i i )a more
 593

b a s i c m o l e c u l e (e.g. t o l u e n e ) s h o u l d p r o d u c e a l a r g e r wavenumber d i f f e r e n c e
between t h e two p e r t u r b e d OH bands. N e i t h e r e x p e c t a t i o n was f u l f i l l e d by o u r
experiments. We d i d not observe a s i g n i f i c a n t p r e f e r e n t i a l a d s o r p t i o n a t low
equilibrium pressures, o r a l a r g e r wavenumber d i f f e r e n c e of t h e two perturbed OH
bands i n p r e l i m i n a r y experiments of toluene adsorption.
If t h e two perturbed OH bands indeed o r i g i n a t e from Briinsted a c i d s i t e s of
comparable s t r e n g t h , t h e bands of t h e f r e e hydroxyl groups must have a spacing
i n wavenumbers similar t o t h e perturbed ones, Thus, we propose t h a t t h e band a t
3350 cm-’ stems from t h e OH band a t 3610 cm-l and that a t 3250 cm-l from t h a t a t
3500 cm-l , t h e former possessing strong, t h e l a t t e r weak Briinsted a c i d i t y (28).
S u p p o r t f o r t h i s a t t r i b u t i o n i s g i v e n f r o m t h e t h e p a r a l l e l i n c r e a s e of t h e
concentration of t h e s t r o n g BrBnsted a c i d s i t e s and t h e i n t e g r a l i n t e n s i t y of
t h e band a t 3350 cm-l and t h e c o n s t a n t v a l u e s f o r t h e c o n c e n t r a t i o n o f weak
Bronsted a c i d s i t e s and f o r t h e i n t e n s i t y of t h e band a t 3240-50 cm-’ (see Figs.
6 and 7).
The two perturbed OH bands a t higher equilibrium p r e s s u r e s of benzene can be
a t t r i b u t e d t o t h e i n t e r a c t i o n of benzene with S i O H groups (3612 cm-’) ( 4 ) and t o
t h e adsorption of a second benzene molecule on a s t r o n g Bronsted a c i d i c hydroxyl
group. The l a t t e r adsorbate s t r u c t u r e was a l s o suggested by Taylor (18,191 and
i s supported by t h e s l i g h t decrease i n i n t e n s i t y of t h e bands a t 1971 and 1832
cm -1 c h a r a c t e r i s t i c f o r adsorption on BrBnsted a c i d s i t e s . I n both forms of ad-
s o r p t i o n benzene e x h i b i t s CH o u t - o f - p l a n e d e f o r m a t i o n v i b r a t i o n s similar t o
l i q u i d b e n z e n e , s u g g e s t i n g o n l y weak i n t e r a c t i o n s w i t h t h e s u r f a c e .
The i d e n t i c a l wavenumbers of t h e perturbed OH bands a f t e r benzene a d s o r p t i o n
on a l l HZSM5 samples suggest e i t h e r t h a t t h e s i t e s do n o t vary i n s t r e n g t h as a
f u n c t i o n of t h e aluminum c o n t e n t o r t h a t benzene i s t o o i n s e n s i t i v e a probe
molecule t o d i f f e r e n t i a t e . Because of t h e l i n e a r dependence of t h e concentration
of adsorbed benzene upon t h e sum of t h e concentration of t o t a l aluminum and Na’,
we c o n c l u d e t h a t t h e a d s o r p t i o n s t o i c h i o m e t r y i s s t r i c t l y one a t mbar
benzene, T h i s s u g g e s t s t h a t even s i l a n o l n e s t s c r e a t e d by d e a l u m i n a t i o n o n l y
adsorb one benzene molecule per s i t e . Extrapolation of t h e concentrations ad-
t
sorbed t o zero aluminum content and Fig.8 demonstrate t h a t Na a r e not located
t
a t t h e c a t i o n exchange p o s i t i o n o f t h e z e o l i t e . Note t h a t t h e s e Na cations
c o u l d n o t be removed by r e p e a t e d i o n exchange. Because of t h e s t r i c t l i n e a r
dependence of t h e amount of benzene adsorbed per u n i t c e l l on t h e concentration
of aluminum, w e f u r t h e r conclude t h a t t h e a d s o r p t i o n e q u i l i b r i u m c o n s t a n t f o r
a l l samples i s i d e n t i c a l and hence t h e a c i d s t r e n g t h of t h e s i t e s i s independent
of t h e u n i t c e l l composition.
I n c o n c l u s i o n , we have shown t h a t benzene i s a d s o r b e d on l o c a l i z e d s i t e s
1
which can be i d e n t i f i e d and q u a n t i f i e d up t o an equilibrium p r e s s u r e of 10-
594

mbar. A t lower p r e s s u r e s p r e f e r e n t i a l a d s o r p t i o n on Na' t a k e s p l a c e followed by

a d s o r p t i o n on Bronsted a c i d s i t e s . Only a t p r e s s u r e s of lo-' mbar benzene and
h i g h e r do s i g n i f i c a n t a d s o r p t i o n on SiOH groups and m u l t i p l e a d s o r p t i o n on one
s i t e o c c u r . While b e n z e n e i s n o t a v e r y good p r o b e m o l e c u l e t o d i f f e r e n t i a t e
between s u b t l e d i f f e r e n c e s of Bronsted a c i d s t r e n g t h , i t i s w e l l s u i t e d t o
c h a r a c t e r i z e a d s o r p t i o n on z e o l i t i c m a t e r i a l q u a n t i t a t i v e l y and t o d i f f e r e n t i a t e
between c l a s s e s o f a c i d s t r e n g t h .

ACKNOWLEDGEMENT
This work was supported by t h e ttFonds zur Forderung d e r W i s s e n s c h a f t l i c h e n
F o r s c h u n g " u n d e r p r o j e c t P5757. We a r e g r a t e f u l t o Dr. H. Mayer f o r t h e X R D
measurements.

REFERENCES
1 L. H. L i t t l e , I n f r a r e d S p e c t r a o f Adsorbed S p e c i e s , Academic P r e s s ,
London, New York (1966) and r e f e r e n c e s t h e r e i n .
2 J.J. Freeman, and M.L. Unland, J. C a t a l . 54 (1978) 183.
3 M.L. Unland, and J.J. Freeman, J. Phys. Chem. 82 (1978) 1036.
4 M. P r i m e t , E. G a r b o w s k i , M.V. M a t h i e u and B. I m e l i k , J. Chem. SOC.
Faraday Trans. I 76 (1980) 1942.
5 B. Coughlan, W.M. C a r r o l l , P. O'Malley and J. Nunan, J. Chem. SOC.
Faraday Trans. I 77 ( 1 9 8 1 ) 3037.
6 P.G. Rouxhet and R.E Semples, J. Chem. SOC. Faraday Trans. I 77 (1972) 2021.
7 P.A. Jacobs, C a t a l . Rev. S c i . Eng. 24 (1982) 415.
8 P.A. J a c o b s , J . A . M a r t e n s , J. Weitkamp and H.K. B e y e r , D i s c u s s .
Faraday SOC. 72 (1981) 353.
9 A. de Mallmann and D. Barthomeuf, J. Chem. SOC. Chem. Comm. (1986) 476.
10 A. d e Mallmann a n d D. B a r t h o m e u f , S t u d . S u r f . S c i . C a t a l . 2 8 (1986) 609.
11 D. Barthomeuf and A. d e Mallmann, S t u d . S u r f . S c i . C a t a l . 3 7 ( 1 9 8 8 ) 365.
1 2 A.N. F i t c h , H. J o b i c a n d A. Renouprez, J. Phys. Chem. 9 0 ( 1 9 8 6 ) 1311.
1 3 A.N. F i t c h , H. J o b i c a n d A. R e n o u p r e z , J. Chem. SOC. Chem. Comm. ( 1 9 8 5 ) 284.
14 V.Yu. Borovkov, W.K. H a l l and V.B. K a s a s a n s k i , J. C a t a l . 51 ( 1 9 7 8 ) 439.
1 5 B.F. Mentzen, Mater. Res. Bull. 22 (1987) 337.
1 6 B.F. Mentzen, F. B o s s e l e t a n d J. Bouix, C.R. Acad. S c i . P a r i s , t. 305, S e r i e
I1 (1987) 581.
17 B.F. Mentzen, F. B o s s e l e t and J. Bouix, C.R. Acad. S c i . P a r i s , t. 306,
S e r i e I1 (1988) 27.
18 J.C. Taylor, J. Chem. SOC. Chem. Comm. (1987) 1186.
I 9 J . C . Taylor, Z e o l i t e s 7 (1987) 311.
20 H. Thamm, H.G. Jerschkewitz and H. S t a c h , Z e o l i t e s 8 (1988) 151.
21 C. F o e r s t e , A. Germanus, J. K a e r g e r , H . P f e i f e r , J. C a r o , W. P i l z a n d
A. Zikanova, J. Chem. SOC. Faraday Trans. I 8 3 (1987) 2301.
22 T. I n u i , 0. Yamase, K. Fukuda, A. I t h o , J. Turumoto, N. M o r i n a g a , T.
H a g i w a r a and Y. Takegami, Proc. 8 t h I n t . Congr. Catal., B e r l i n , ( 1 9 8 4 ) 569.
23 C. H a l i k , J.A. L e r c h e r and H. Mayer, J. Chem. SOC. F a r a d a y T r a n s . I ,
84 (1988) i n p r e s s .
24 A. J e n t y s , G. Warecka and J . A . Lercher, J. Mol Catal. submitted.
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26 J.S. Rieck and A.T. B e l l , J. C a t a l . 85 (1984) 143.
27 M. Derewinski, J. Haber, J. Ptaszynski, J.A. Lercher and G. Rumplmayr, Stud.
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H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

ADSORPTION SEPARATION OF METHYLNAPHTHALENE ISOMERS ON X AND Y ZEOLITES

1 1 2
V. SOLINAS , R. MONACIl, E. ROMBI and M. MOREIDELL1
'Dipartimento d i Scienze Chimiche, Universita d i Cagliari, V i a Ospedale 72,
09124 C a g l i a r i ( I t a l y ) .
L
Dipartimento d i Ingegneria Chimica e M a t e r i a l i , U n i v e r s i t a d i C a g l i a r i , Piazza
d'Armi, 09124 C a g l i a r i ( I t a l y ) .

ABSTRACT
The separation o f 1-methylnaphthalene (1-MN) and 2-methylnaphthalene (2-MN)
was studied on X and Y z e o l i t e s exchanged w i t h a l k a l i n e and a l k a l i n e - e a r t h
c a t i o n s , i n a l i q u i d phase a t 293 K.
The t o t a l adsorbed amount depends on t h e volume o f t h e c a t i o n i n t h e
z e o l i t e framework.
The z e o l i t e s exchanged w i t h t h e l a r g e r c a t i o n s showed h i g h e r s e l e c t i v i t y .
The system e x h i b i t s a non-ideal behaviour showing a s t r o n g dependence o f selec-
t i v i t y on composition.

INTRODUCTION
The z e o l i t e adsorbents a r e commercially used i n v a r i o u s s e p a r a t i o n pro-
cesses, such as n- p a r a f f i n , and i n xylene isomers separation processes ( r e f .
1 ) . I n t h i s work we a r e seeking s u i t a b l e z e o l i t e s on which one o f two methyl-
naphthalene isomers i s s e l e c t i v e l y adsorbed i n t h e c o m p e t i t i v e a d s o r p t i o n o f
t h e isomeric mixture, with t h e aim o f developing a separation process. The tech-
nique o f c o m p e t i t i v e adsorption i n l i q u i d phase u s i n g an i n e r t s o l v e n t has
been r e p o r t e d by Namba e t a l . ( r e f . 2 ) .
The separation o f 1-methylnaphthalene (l-MN) and 2-methylnaphthalene (2-MN)
was s t u d i e d on X and Y z e o l i t e s exchanged w i t h a l k a l i n e and a l k a l i n e - e a r t h
c a t i o n s . The molecular dimensions o f MN, as maximal c r o s s - s e c t i o n a l s i z e , were
0

6.2 A f o r 1MN and 5.8 A f o r 2MN ( r e f . 3). These c r i t i c a l dimensions o f aroma-

0

t i c molecules a r e comparable w i t h 7 A C a u j a s i t e nominal pore openings.

EXPEHIMENT
Absorbents
X- and Y-zeolites v a r i o u s l y exchanged were prepared from commercially
596

a v a i l a b l e powder (Nal3X and LZY-52 from Union Carbide). The exchange was
c a r r i e d out by t r e a t i n g 10 g o f the commercial z e o l i t e w i t h 150 cm3 o f a
b o i l i n g aqueous s o l u t i o n o f a l k a l i n e o r a l k a l i n e - e a r t h c h l o r i d e (1M) f o r 2 h.
The procedure was repeated f i v e times. The exchanged z e o l i t e was then washed,
d r i e d a t 373 K f o r 3 h and calcined a t 773 K f o r 12 h.
The adsorption runs were performed on zeolite as powder. The main
c h a r a c t e r i s t i c s o f the z e o l i t e s employed are summarized i n Table 1.

Adsorbates and solvents

1- and 2-methylnaphthalene and n-octane were obtained from a commercial
source. They were high-purity reagents and were used without further
purification.

Methods
A l l t h e runs were performed i n a closed vessel i n which 0.5 g o f z e o l i t e ,
degassed a t 773 K f o r 5 h, were contacted w i t h 2 m l o f the s o l u t i o n o f 1- and
2-methylnaphthalene i n a-octane. The i n i t i a l concentration o f each isomer was
4 wt%. The amount o f each isomer adsorbed was obtained from t h e concentration
o f each isomer i n l i q u i d phase, which was determined by gas chromatographic
analysis.
The e f f i c i e n c y o f t h e z e o l i t e s i n separating the methylnaphthalene isomers
was measured by t h e s e l e c t i v i t y (S
2MN/ 1MN
1 defined by t h e f o l l o w i n g formula:

2-MN adsorbed on z e o l i t e 1-MN i n s o l u t i o n

%/1 = 1-MN adsorbed on z e o l i t e
X
2-MN i n s o l u t i o n (11

RESULTS AND DISCUSSION

I n t h e competitive adsorption o f methylnaphthalene isomers on X and Y
zeolites, the amount o f each isomer adsorbed increased monotonously w i t h
adsorption time (Fig. 1 ) .
 597

Fig. 1. Amount o f methylnaphthalene isomers adsorbed ( r ) on KY vs. time o f

adsorption; ( A 1 1-MN, ( 0 I 2-MN.

The adsorption e q u i l i b r i u m was a t t a i n e d w i t h i n 24 h. The e q u i l i b r i u m was

confirmed by the coincidence o f the amounts o f each isomer adsorbed a f t e r 24
and 48 h o f adsorption.
Table 1 shows the t o t a l amount o f methylnaphthalene isomers and t h e selec-
t i v i t y (S J , determined a f t e r 24 h o f adsorption.
2/1
I t can be seen t h a t t h e t o t a l q u a n t i t y o f isomers adsorbed i s u s u a l l y
higher i n the Y z e o l i t e s than i n the corresponding X z e o l i t e s . This may be due
t o the higher value o f the S i / A l r a t i o o f t h e Y z e o l i t e s , and thus t o a smaller
population o f c a t i o n i c s i t e s .
I I
From a comparison o f the s e l e c t i v i t y values f o r t h e Me X and Me Y z e o l i t e s
I
( w i t h Me = L i , Na, K, Rb, CsJ i t can be seen t h a t they vary i n q u i t e a small
range, between 1 and 2 and between 0.9 and 2.4, respectively.
598

TABLE 1
Adsorption of methylnaphthalene isomers on X and Y exchanged zeolites.

Adsorbent % exchangeda Amount of methyl naphthalene

s2/ I
isomers adsorbed (mg/g zeolite)
Li X b 71 141.81 1.16
NaX / 122.42 1.18
KX 92 b3.40 1.60
RbX 64 69.07 1.61
csx 82 81.98 1.98
M9X 72 173.32 U.8b
CaX 98 167.93 1.28
Bax 96 50.71 2.38
Li Yc 61 207.66 0.93
NaY / 206.91 0.94
KY 89 143.5b 2.23
RbY 73 116.22 2.30
CSY 75 99.95 2.37
76 169.36 0.73
CaY 91 168.66 0.74
Bay 78 153.01 2.45
a
Ion-exchange degree with respect to the original form;
b13X powaer, Si/Al = 1.4;
'LZY-52 powder, Si/A1 = 2.4.
Amount o f adsorbent = 0.5 g., amount of adsorbate = 2 ml of solution
(4% W/W of both 1MN and 2-MN).

I1 I1
On examining the Me X and Me Y zeolites (with ME" = Mg, Ca, Ba) the
tollowing considerations can be made:
the selectivity increases about threefold from Mg to Ba; it is affected by the
acidity in the structure caused by the exchange of the bivalent cations; it is
similar for BaX and BaY zeolites.
I1
Particularly for Me Y, an inversion of the selectivity (S ) for the
2/ I
more acid zeolites (Mg and Ca) can be observed, with values approaching 0.7.
This inversion was confirmed when using a totally decationated HY zeolite,
which presents a low adsorption capacity (50 mg/g) and a selectivity of S =
2/ 1
u.5. The high selectivity found for the BaY zeolite may be due to the fact that
the Ba introduced comes out of the channel wal I (ref. 2).
figure 2 (a and b) shows the amount of methylnaphthalene isomers adsorbed
3
versus the volume (r ) of cations in the zeolite structure.
X- and Y- zeolites show a similar trend: the total adsorbed amount decreases
generally, on increasing the volume of the cations. It can be noticed that the
 599

amounts adsorbed on Mg-X, Ca-X versus L i - x , Na-X a r e d i f f e r e n t and i n c o n t r a s t

w i t h t h e c o r r e s p o n d i n g s e r i e s on z e o l i t e Y .

\
200 250 1
r
160 2oo'.
150
I Li Na
b

120 -. Mg

80 100 '.
cs

40 Ba

O*'
0 1 2 (r3) 3 4 5 o 1 ~ ( ~ 33 ) 4 5

F i g . 2 . Amount of methylnaphthalene isomers adsorbed ( r 1 vs. volume (r3 1 o f

t h e exchanged c a t i o n . ( a ) X - z e o l i t e s , ( b ) Y - z e o l i t e s .

On t h e o t h e r hand, t h e s e l e c t i v i t y i n c r e a s e s on i n c r e a s i n g t h e volume o f
t h e c a t i o n s i n F i g u r e 3 ( a and b ) .

2.5 2.5

I--
b

2.0 2.0
s2/1
1.5

1 .o

0.5
%/1
1.5

1 .o

0.5
4
Li

Mg
N

Ca

0 1 2 (r3) 3 4 5 0 1 2 (r3) 3 4 5

3
F i g . 3. S e l e c t i v i t y (S2,,) vs. volume ( r 1 of t n e exchanged c a t i o n . (a)
x-zeol i tes, (b) Y-zeol it e s .
600

Selectivity can also be correlated with the Sanderson electronegativity of

the framework in Figure 4 (a and b).

2.1
a

2*I

%/1
2.1

1 .I

1.

0.
3 3.3 Sint 3.6 3.3 3.6 Sint 3.9

Fig. 4. Selectivity (S2/1 1 vs. intermediate Sanderson's electronegativity (S.

I nt
1
(a) X-zeolites, (b) Y-zeolites.

It can be seen that the selectivity increases when Sint decreases, i.e. when
the structure becomes more basic. There are two sets ot results, one for the Y
and one for the X zeolites. For each of these types the correlations are very
simi 1 ar.
Unsaturated hydrocarbons, which have II electrons capable o t a strong in-
teraction with the surface, can cause changes in the surface field properties.
The difference noted between the X and Y zeolites may be related to non-
identical charge densities (linked to the aluminium atom content) in the two
materials, producing dissimilar fields.
Barthomeuf (ref. 4) shows that the specific field of the cations has a
 601

small i n f l u e n c e a t h i g h coverage. The o n l y changes o r i g i n a t e f r o m t h e d i f -

ference i n aluminium atom content, which m o d i f i e s t h e t o t a l number o f charges
i n t h e framework and hence t h e z e o l i t e f i e l d . Ihe n i g n e r t h e aluminium content,
t h e lower t h e i n t e r a c t i o n energy between c a t i o n s i t e and adsorbed molecule.
I t i s known t h a t t h e e f f e c t o f t h e z e o l i t e f i e l d due t o A10- on a d s o r p t i o n
4
i s b e t t e r s t u d i e d a t h i g h s u r f a c e coverage, w h i l e t h e s p e c i f i c c a t i o n i n f l u e n c e
i s b e t t e r s t u d i e d a t low coverage.
The above f e a t u r e s reveal a complex v a r i a t i o n o f t h e separation f a c t o r ,
showing no obvious c o r r e l a t i o n w i t h t h e charge, volume and p o l a r i z i n g power o f
t h e exchangeable c a t i o n s o r t h e d i p o l a r moments o f t h e aromatic molecules. A t
h i g h loadings i n t h e l i q u i d phase, t h e s e l e c t i v i t y i s determined by t h e e t f e c t s
o f sorbate-sorbate i n t e r a c t i o n s ( r e f . 5).
I n order t o v e r i f y t h i s hypothesis, runs were c a r r i e d o u t w i t h d i f f e r e n t
r e c i p r o c a l concentrations o f t h e two isomers. Table 2 shows t h e s e l e c t i v i t i e s
obtained. The s e l e c t i v i t y changes s i g n i f i c a n t l y w i t h t h e c o n c e n t r a t i o n o f t h e
i n i t i a l s o l u t i o n , and t h i s f a c t confirms t h e n o n - i d e a l i t y o f t h e b i n a r y m i x t u r e
o f methylnapnthalene isomers.

Table 2
S e l e c t i v i t y and amount adsorbed on KY a t 293 K upon changing t h e c o n c e n t r a t i o n
o f methylnaphthalene isomers
1-MN 2-MN s2,, r r. r
(%w/wJ (%w/w)
1 z total x1 x2
2 6 .I .50 36.3 95.0 131.3 0.277 0.723
3 5 1.63 42.8 82.3 125.1 0.342 U.658
4 4 2.23 63.6 80.0 143.6 U.443 0.557
6 2 2.80 90.9 39.2 130.1 0.69Y 0.301

Adsorption E q u i l i b r i a
I n order t o b e t t e r understand t h e e q u i l i b r i u m behaviour o f t h e system under
examination, a more d e t a i l e d a n a l y s i s o f t h e adsorption e q u i l i b r i u m isotherms
was developed i n t h e case o f z e o l i t e KY. The pure-component e q u i l i b r i u m d a t a a t
293 K are shown i n F i g u r e 5 t o r both 1- and 2-methylnaphthaiene, i n terms o f
c o n c e n t r a t i o n i n t h e adsorbed phase r as a t u n c t i o n o f c o n c e n t r a t i o n i n the
b u l k l i q u i d pnase C. I n t h e same t i g u r e , t h e experimental d a t a a r e compared
w i t h curves c a l c u l a t e d through t h e Langmui r equi 1ibrium model
r / r" = KC/l+KC (2)
602

1 6 0 1

0.01 0.05 0.10 c 0.18

Fig. 5. Experimental data o f concentration i n t h e adsorbed phase, r (mg/g), vs.

concentration i n the bulk phase, C(mol/l); ( 0 ) 1-MN, ( A 2-MN.

using t h e f o l lowing values o f the equi 1ib r i um parameters, as obtained through

t h e usual 1east-squares-estimati on tecnni que ,
1-MN 2-MN
K (l/mol) 37.2 86

rm (mg/g) 168 166

The observation t h a t two pure components e x h i b i t almost i d e n t i c a l values
m
f o r the amount adsorbed a t s a t u r a t i o n conditions, r , seems t o i n d i c a t e t h e
p o s s i b i l i t y o f d e s c r i b i n g b i n a r y e q u i l i b r i u m data through t h e multicomponent
Langmuir e q u i l i b r i u m model, which i n t h e case o f two adsorbable components
reduces as f o l l o w s :
r
- i-
r
- KiCi
1+K.C.+K2C2
1 1
,i= 1,2 (3)

Such a model would p r e d i c t t h e f o l l o w i n g composition-independent expression

f o r the binary s e l e c t i v i t y ( 1 )

which i n the case under examination leads t o S = 2.31.

2/1
However, t h i s conclusion does n o t agree w i t h experimental f i n d i n g s , which,
as shown by t h e data summarized i n Table 2, i n d i c a t e a strong dependence of
s e l e c t i v i t y upon composition.
 603

This behaviour i n d i c a t e s t h e presence o f s t r o n g i n t e r a c t i o n s among ad-

sorbate molecules, which are r e s p o n s i b l e t o r t h e observed d e v i a t i o n s f r o m i d e a l
aehaviour.
Thus, t h e m o d e l l i n g o f b i n a r y e q u i l i b r i u m data r e q u i r e s e x p l i c i t accounting
f o r d e v i a t i o n s from i d e a l i t y i n t h e adsorbed phase. l o t n i s aim t h e t h e o r y o f
adsorption from r e a l s o l u t i o n s , as f i r s t developed by Myers and P r a u s n i t z ( r e f .
6 ) i n t h e c o n t e x t o f gaseous m i x t u r e adsorption and subsequently extended t o
l i q u i d mixtures ( r e f s . 7, 81, o f t e r s t h e most convenient framework.
A t e q u i l i b r i u m c o n d i t i o n s t h e f u g a c i t i e s o f each i - t h component i n t h e l i q -
u i d and i n t h e adsorbed phase ( i n d i c a t e d w i t h a prime symbol) a r e equal
- -
f. = f
1 1
’.
w i t h o u t going i n t o t h e d e t a i l s o t t h e e v a l u a t i o n o f t h e above f u g a c i t i e s ,
and r e c a l l i n g t h a t t h e system under examination i s a t low pressure, one can
w r i t e as t o l l o w s ( r e f . I ) :
T O ’ ’ ( T ) Y1. X1. = foYa(T,O)y;x;
i (5)
i
where Y. i n d i c a t e s t h e a c t i v i t y c o e f f i c i e n t , foYa(T,o) t h e pure-component
1 1
f u g a c i t y i n t h e adsorbed phase a t t h e same temperature, and 0 f r e e energy o f
immersion values as i n t h e b i n a r y mixture. When t h e e q u i l i b r i a o f t h e pure
components a r e described through t h e Langmuir model , t h e q u a n t i t y foYa(T,o) can
1
be r e a d i l y evaluated from t h e tiibbs isotherm. This leads t o t h e f o l l o w i n g r e l a -
t i onshi p:
K .x
x = - Y;X; c. -
J j (61
i K.
1 J yj
where i d e a l behaviour f o r t h e l i q u i d phase i s assumed ( i . e . y = 1). From
i
eq(6) t h e f o l l o w i n g new expression f o r t h e b i n a r y s e l e c t i v i t y can be obtained:

(7)

which depends on t h e composition o f t h e adsorbed phase through t h e a c t i v i t y

c o e t f i c i e n t s . Such a f u n c t i o n can be q u a n t i t a t i v e l y evaluated by t h e use o f a
model f o r t h e excess f r e e energy o t t h e adsorbed phase. F o r example, w i t h t h e
n i l d e b r a n d model ( r e f . 91 t h e f o l l o w i n g expressions are obtained:
604

where the parameter A i n d i c a t i n g t h e i n t e r a c t i o n between the two adsorbed

12’
species, can be considered as an adjustable parameter and estimated by d i r e c t
comparison w i t h the experimental data.
This i s achieved through the f o l l o w i n g l i n e a r i z a t i o n r e l a t i o n s h i p :
,2 2
I n Y;/Y; = A l p (x, x; 1 - (Y)

This leads t o t h e l i n e a r p l o t shown i n F i g . 6, when t h e experimental values o f

Table 2, the Langmuir constant values estimated above and eq(7) are used. From
F i g . 6 the value A12 = 143 i s obtained.

I
I n Y;/Yi

-0.5
0 ( x i 2 - x i2) t0.5
-0.5

Fig. 6. C o r r e l a t i o n o f experimental data from equation (9).

Tnus, i n conclusion, the binary s e l e c t i v i t y can be obtained by s u b s t i t u t i n g

eq(8) i n t o eq(71, as f o l l o w s :
2
exp(A12x; /r-1
=
K2
- 2
(10)
K1 exp(A12x; /P)
The values obtained by t h i s r e l a t i o n s h i p are compared w i t h experimental
data i n Figure 7.
As f u r t h e r support f o r t h e conclusion t h a t non-ideal adsorbate-adsorbate
interactions are dominant in tne system under examination, the binary
e q u i l i b r i u m data may be r e p l o t t e d according t o the s t a t i s t i c a l approach r e p o r t -
ed by Ihm and Lee ( r e f . 10). I n p a r t i c u l a r , t h e f o l l o w i n g r e l a t i o n s h i p i s con-
sidered :
- I n S2,1 = KO t (1 - 2xi)cw/2kT (I11
 605

where K" i s a c o n s t a n t r e l a t e d t o t h e s u r f a c e t e n s i o n o f t n e p u r e component, c

is t h e number o f t h e n e a r e s t neighbour s i t e , w h i l e w r e f e r s t o t h e v a r i o u s i n -
v o l v e d m o l e c u l a r i n t e r a c t i o n e n e r g i e s as f o l l o w s :
w = U' (12)
1-1

0 0.5 xi I
F i g . 7. C o r r e l a t i o n o f e x p e r i m e n t a l d a t a f r o m e q u a t i o n ( 1 0 )

The s e l e c t i v i t y S and t h e s u r f a c e coverage X ' can be c a l c u l a t e d f r o m t h e

2/ 1 1
s o r p t i o n data. The c o n s t a n t K O and cw/EkT can be o b t a i n e d f r o m t h e i n t e r c e p t
and s l o p e o f t h e l i n e a r p l o t s o f - l n S vs.(l-2xi).
2/ 1
The e s t i m a t e d v a l u e cw/2kT = 0.75, which i s s i g n i f i c a n t l y d i f f e r e n t f r o m
zero, c o n f i r m s t h a t t h e system e x h i b i t s a n o n - i d e a l behaviour, w i t h U i 2 + Uilor

F u r t h e r s t u d i e s a r e i n p r o g r e s s along t h e s e l i n e s , w i t h d i f f e r e n t z e o l i t e s
and temperatures, i n o r d e r t o b e t t e r understand t h e n a t u r e o f a s e l e c t i v e
a d s o r p t i o n process. However some h i g h s e l e c t i v i t y values, determined i n t h e
p r e s e n t study, suggest c l e a r l y t h a t t h e s e p a r a t i o n of t h e s e two isomers i s
p o s s i b Ie .
ACKNOWLEDGEMENTS

We w i s h t o thank Mr. A. R i v o l d i n i f r o m t h e I s t i t u t o d i G i a c i m e n t i M i n e r a r i ,
U n i v e r s i t i d i C a g l i a r i , f o r t h e atomic a d s o r p t i o n analyses on t h e z e o l i t e s .
606

REFERENCES

1 O.M. Ruthven, i n P r i n c i p l e s o f Adsorption and Adsorption Processes, John

Wiley and Sons ( t d i t o r s ) , New r o r k 1984.
z S. Namba, Y. Kanai, H. Shoj and T. Yashima, Z e o l i t e s , 4 (1984) 77.
3 D. Fraenkel, M. Cherniavsky, 8. I t t a h , M. Levy, J. Catal., 101 (1986) 273.
4 D. Barthomeuf, B.H. Ha, J. Chem. SOC. Farad. Irans. I , 7 (1913) 2158.
5 D.M. Ruthven, i n Olson and B i s i o ( E d i t o r s ) , Proceedings o f t h e s i x t h I n t e r -
n a t i o n a l Z e o l i t e s Conference, Butterworths, 1983, p. 31.
6 A.L. Myers, J.M. Prausnitz, A.I.Ch.E.J., 11 (1965) 121.
7 C. Minka, A.L. Myers, A.I.Ch.E.J., 19 (1973) 453.
8 O.G. Larionov, A.L. Myers, Chem. Eng. Sci., 26 (19/1) 1025.
9 J.H. Hildebrand, J.M. Prausnitz, R.L. Scott, i n r e g u l a r and Related Solu-
t i o n ; Van Nostrand Rheinhold ( E d i t o r ) , New York, 1970.
10 S.K. Ihm, H.S. Lee, i n Murakami, L i j i m a , ward ( E d i t o r s ) , New Oevelopments
i n Z e o l i t e s Science and technology, E l s e v i e r Amsterdam 1986, p. 571.
H.G. Karge,J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V.. Amsterdam - Printed in The Netherlanda

GEXwlRD REISS
Bayer AG, PK-A Zeolithe, D-5090 Leverkussen, F.R.G.

ABSTRACT
Pressure swing systems for direct adsorptive production of oxygen
from air are described and the costs of production are calculated and
compared.

INTRODUCTIOK
In the past ovygen production from air was mainly carried out by means of
cryogenic systems. Since 1970 a new technique has been developed whereby
ovygen is separated from air by the adsorption process using molecular sieve
zeolites. Up to now the main fields of application of oxygen produced by these
adsorption separation plants have been for water treatment and in the smel-
ting of scrap metal. In some areas it has replaced over 50 % of the original
oxygen market "(ref. 1)". Comparison of the adsorption system with conven-
tional oxygen supply shows that the former has distinct advantages.

Adsorptive production of oxygen from air

The separation of oxygen from air with ?IS zeolites is based on the fact
that nitrogen (quadruple moment) has a higher affinity to MS zeolites than
oxygen. Ca-Zeolite A, .ha-Zeolite X and Ca-Zeolite X are normally used. There-
fore H,O, CO, and N, are preferentially adsorbed and the required product,
oxygen (plus argon), less so (see Fig. 1).
Two different adsorption processes are usually applied in the market:
pressure swing adsorption (PSA) with ail adsorption pressure of 3 - 6 bar
and a desorption pressure of 1 bar (ref 2 ) and vacuum swing adsorption
(VSA) with adsorption at 1.0 to 1.5 bar and desorption at 200 - 300 mbar
(ref 3 ) .
In both processes the H,O, CO, and nitrogen in the air are adsorbed
Y

in one step. Desorption is carried out b? purging the bed with the oxygen
produced or by evacuating the ?IS zeolite.
Oxygen
- -. .
produced
- by PSA/VSA has already been used in various fields e.g.
-S
medicine ( 0 . 2 Nm3 02/h) (ref 4 ) and steel lancing (3.000 Nm O,/h) (ref 5)
608

Pressure, mbar

Fig. 1. Adsorption isotherms Fig. L . Two-bed PSA u n i t ( a ) a i r

of Ca-Zeolite !
I compressor, (b) 0, product, (c)
purge, ( d ) pre ssufe e q u i l i z a t i o n

Adsorption urocesses
Pressure swing adsorption systems mainly d i f f e r i n the number of ad-
sorberbeds used. Depending on t h e required oxygen r a t e , u n i t s with two,
th r e e o r , l e s s common, four beds a r e used. The key t o the best pe rfor-
mance is maximum oxygen product recovery which reduces t h e s i z e of the
a i r rompressor needed. T h i s is achieved by using small beds and pre ssure
e q u i l i z a t i o n a f t e r t h e adsorption period. The simplest PSA process, and
hence a l s o tho most favourable from t h e point of view of investment, is a
two-bed u n i t with cy cl es of between 10 and 80 seconds per bed and a maximum
adsorption pressure of 6 bar ( a b s ) .

After adsorption, pressure is equalized a t the O2 product end of the u n i t .

Air i s used f o r r ep r es s u r i zat i o n . A t t h e desorption s t a g e the nitrogen adsorbed
is desorbed or displaced by some of t h e 0, product. In orde r t o obta in a
constant 0, product stream, a b u f f er must be used (se e F i g . 2 ) .
 609

Since 0 , recovery capacity is limited in a two-bed unit, three-bed PSA

systems are used for larger quantities of 02. The higher investment costs are
offset by the lower energy consumption of the air compressor. All three-bed
PSA systems are based on an old patent (ref 2) from Feldbauer (see Fig. 3 ) .
In more advanced processes, the oxygen yield is increased by producing part
of the 0 , during air repressurization and co-current pressure release
il

(ref. 6 ) . Here the cycle should last 3 x (45-60) seconds.

d
a

Fig. 3 . Three-bed PSA unit Fig. 4 . Three-bed VSX

(a) 0,-product, (b) repressurization (a) air blower, (b) vacuim
+ equflization, (c) purge, (d) air, pump, (c) 0,-product, (d)
(el waste repressurization

Vacuum swing adsorption plants generally consist of three adsorbent beds

and have a process sequence of adsorption, evacuation and repressurization
with the oxygen produced. The aim of this process is to ensure low energy
consumption of the vacuum pump. The cycle lasts 3 x 60 seconds (see Fig. 4 ) .
The energy consumption of the vacuum pump depends on the adsorption-desorption
properties of the zeolite and the process data.

In the last few years, we have made improvements in commercial zeolites f o r

the 0, VSA process. The nitrogen adsorption capacity of the selected Ca-
Zeolite A has been increased by 100 8 . We noticed that i n the 0 , VSA process
-
the O2 rate and hence also the energy consumption of the vacuum purr~p decrease
as N2 adsorption increases.
610

The energy consumption shown in Fig. 5 was measured on comniercial VSX

plants. A further reduction in energy consumption was achieved !)y optimizing
the vacuum pumps (ref. 7) and by a purge-and-filling step after evacuation
(back-fill purge process = BFP process) (ref. 8).

Il2,
160

* 140

ii 100
d
80
7 8 9 10 11 12 13 14
q//
$O

1 0
10 100
/*

1000
N i t r o s e n load, Nlhg

Fig. 5 . Performance of an 0, vsa Fig. 6 . (a) Staff and ( 0 )

plant to N, capacity (at 1 000 maintenance costs of PSA/VSA
mbar, 25OCf of Ca-Zeolite A . oxygen plants
(a) 0 production rate, (b)
0, yigld, (c) horsepower of
vacuum pump

Comparison of adsorptive separation processes

PSA/VSA processes can be compared from the point of view of capital cost,
operation costs, flexibility of capacity turn-down and tinally oxygen pro-
duction costs. From the market survey and experience it has to be concluded
that two-bed PSA systems are limited to approximately 100 3m3 O,/h, three-bed
PSA units are built for gas rates of between 100 - 500/600 Nm3 -O,/h for one
3
train and VSA plant with capacities up to 2 000 UI O,/h per train.
Y

We have endeavoured to calculate the production costs or the price of oxygen

produced by the three adsorptive processes described above. Personnel and
repair costs are estimates (see Fig. 6 ) . The electricity requirements of the
two- and three-bed PSA system are based on a medium adsorption pressure of
3 bar (abs) and a 2 9 % and 39 % oxygen yield.
 611

The energy consumption of 3-bed PSA systems shown in Fig. 7 agrees with the
ialues given in the literature (ref. 9 ) . The specific. energy consumption for
inygen produced hy t h e VS4 process was determined with existing plants, taking
into account the BFP process. The costs of investment in oxygen PSA/VSA plants
(see. Fig. 8) a r e based on our experience of the market.

2-O:
*fi
PII
\ d

I
2
0.5 .
13 100 1000
'
I

02-capacity, Nn'/h (93 %)

Fig. 7. Energy consumption (T!

of oxygen PSA/VSA systems

( a ) ?-bed PSA, ( b ) 3-bed PSA,

(c) 3-bed VSA, (d) cryogenic
systenls

I - L ' ' I . ' ' '

10 100 1000
02-capacity, Nn3/h (93 %)

Fig. 8. Capital cost (DM/!h3

O J h ) of 0, PSAIVSA systems
(93 % 0,)
( a ) ?-b6d PSA, ( h ) 3-bed PSA,
(c) 3-bed VSA

The price of oxygen produced by adsorptive processes can be seen from the
calculations in table 1.
612

Table 1. Calculation of the costs of producing oxygen (93 % vol.)

from air using the PSAIVSA proyess.
Example: VS.4 process, 1 000 Nm /h 0,
-; electricity: 0.1 DM/KW

Investment : DM 2.8 x 106

Quantity of MS zeolite : 75 000 kg
Engergy consumption : 0.48 KWh/Nm 0, Annual operation: 8.200 h
Personnel and repair costs: DY 2 9 000 ” Depreciation : 10 years
DM 17 000
7 MS service life: 10 years

Tied-up capital
Calculation of net assets required f o r operations,
consisting of electricity costs, investnients, repairs,
MS zeolites.

Electricity : 0.48 x 1 000 x 0.1 N 8 200 = DM 393 600

Capital spending: = DM 2 800 000
Repairs = DM 17 000
Idsorbent = DM 525 000
= Net assets DM 3 735 600

Calculation of production costs

DM/h
Energy 48.0
a Depreciation 34.1
+ Repairs 2.07
+ Personnel 2.68
-
= Production costs 86.85 DM/h

Calculation of operating c o s t s
DM/h
Production costs 86.85
+ 13 % of net assets/operations/8 900 h 59.22
+ 30 % of production costs 17.38

= Operating costs 163.51 DM/h

 613

Production costs can be reduced greatly as the s ~ L \ . of the plant increases

(see Fig. 9). The most cost-effective adsorptive method of producing oxygen
is the V S A process. This h a s been confirmed by our knowledge of the market.
Using the VSA, 100 to 2 000 Xm 3 oxygen per hour and per train is alieadl twiiig
produced, with several plants in Europe, Japan, Korea, India and Taiwan.

0.6 k
0.5
fi
0.4

tI
10
I 1 I I

100
-& I I I I

1000
f

Fig. 9. Costs of oxygen, supplied by PSA/VSA

Electric current price (1): 0,15 DM/KW
( 2 ) : 0,l DM/KW
(a): 2-bed PSA, (b): 3-bed PSA
(c): 3-bed VSA

Comparison of adsorptive separation processes with cryogenic plants

Small oxygen adsorption systems producing up to 300 N I3 /h can compete with
liquid oxygen, depending on the standard required. Typical applications
include welding, fish-farming, glass-blowing and small waste-water treatment
plants,
With larger quantities of O 2 gas, oxygen produced in VSA systems can com-
pete with cryogenic plants. The energy consumption of cryogenic plants
(ref. 101, shown in Fig. 7, reverts the advantage of the VSA process as far as
energy is concerned. Other advantages are ease of operation, the possibility
of an u p to 10 - 20 % turn-down in nominal load and the availability of oxygen
a few minutes after start-up of the plant.
614

REFERENCES

Gas Review Nippon, No. 143

US Patent 3.338.030
G. ReiB, Chem. Ind., 35 (1983), 689-693
Brochure of Buderus AG, Wetzlar
Gas Review Nippon, Summer 1985, pp. 6-7
US Patent 3.636.679
DOS 3.413.895
DOS 3.144.012
Leaflet of Linde AG, Werksgruppe TVT Mtinchen, Sauerstoffverbrauch
durch PSA-Anlagen
10 H. Springmann, Wirtschaftlichkeitsgrenzen fkr den Bau von Luftzer-
legungsanlagen, 3. Arbeitstagung der Linde A G , Oct. 14.-16., 1975
in Munich
H.G. Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science PublishersB.V., Amsterdam - Printed in The Netherlands

ADSORPTION AND DIFFUSION OF DIFFERENT HYDROCARBONS IN MFI ZEOLITE OF VARYING

CRYSTALLITE SIZES
D.H. LIN, V. DUCARME, G. COUDURIER and J.C. VEDRINE(*)
Institut de Recherches sur la Catalyse, C.N.R.S., ConventionnO B 1'UCB. LYON I,
2 Avenue Albert Einstein, 69626 - Villeurbanne (France)

ABSTRACT
MFI zeolite samples have been synthesized with a crystallite size varying
in a range of 1 to 220 um and with aluminum, boron or silicon as substituting
elements for silicon in the framework. The rate of hydrocarbon adsorption at
temperatures from 18 to 120°C has been measured gravimetrically with a
micro-balance. N-hexane and para-xylene have been observed to adsorb too rapidly
for small crystallites to give reliable information with such a technique.
3-methyl-pentanehas been on the contrary, found to be suitable, over the whole
range of sizes. The rate of 3-methyl-pentane adsorption has been observed to
decrease with increase of the particule s i y i , wtp.. allows us to calculate a
diffusion coefficient equal to ca 1.1 x 10 cm s .
The chemical feature of
the materials, mainly the presence of more or less strong Bronsted acid sites,
has been shown to have an effect on the adsorption rate, but only of minor
importance.

INTRODUCTION
The importance of zeolitic-type materials is well established and need not
be emphasized in terms of sorptive and catalytic properties. The concept of
shape selectivity has also been widely discussed and assigned to a particular
fitting between the reactant and/or product molecules and the zeolite
geometrical aspects : pore size, interconnecting channel structure, etc. The
role of adsorption and diffusion of molecules within the pores is obviously
important for shape-selectivity properties. Several review papers have already
been devoted to the subject, particularly by Barrer (ref. 1) and Ruthven (ref.
2). The article by Palekar and Rajadhyaksha (ref. 3 ) reports interesting results
with special emphasis on catalytic reactions.
Various experimental techniques have been employed in trying to measure
diffusivities. The most commonly used method is conventional gravimetry, where
sorption kinetics is measured by means of a microbalance. The most serious
limitation is in terms of the response time of the equipment and the heat
transfer effect. Other techniques include chromatography (ref. 4 ) . tracer
diffusion (ref. 51, neutron diffusion (ref. 6 ) and pulse field gradient NMR

(*) to whom queries should be sent

616

spectroscopy (ref. 7 ) . The former two involve adsorption and diffusion with a
concentration gradient (driving force) whiie the latter two involve motion of
the adsorbates within the pores. This difference results in large discrepancy in
diffusion coefficient values, by 2 to 4 orders of magnitude.
More recently Ruthven et al. (ref. 8) have tried to eliminate the intrusive
effects of adsorption heat and mass transfer by using a chromatographic
technique (ZLC zero-length column). It consists of analyzing by gas
chromatography the desorption of an adsorbate under sudden purge with an inert
carrier.
To try to provide some insight to the difficult problem of adsorption and
diffusion we have studied gravimetrically the adsorption of hydrocarbons on
samples exhibiting a large domain of crystallite sizes (1 up to 220 pm) and
Bronsted acid sites of different strength and concentration. Special care was
taken to synthesize well crystallized samples. Note that we have chosen only
samples with well defined shape (usually parallelepipedic twinned single
crystals) and narrow size distribution.

EXPERIMENT
A Sartorius microbalance was used for measuring the adsorption and
desorption rates. The samples (ca. 10 mg) were outgassed at 400°C overnight down
to torr (1.3 x 10-2Pa) and then cooled down to room temperature for 10 to
15 minutes. The samples were placed at the desired temperature and further
contacted with the hydrocarbon vapor at a given pressure measured by a Barocell
gauge. The adsorbate molecules were outgassed by the freeze-pump-thaw technique
several times. The weight changes were directly recorded with a Sefram recorder.
MPI-type materials were synthesized either in our laboratory in the
classical way in basic medium or in professor R. Wey's laboratory in Mulhouse in
fluoride medium (ref. 9).
Chemical analyses of the samples were performed in our laboratory by atomic
absorption of the elements other than Si, namely aluminum, boron and sodium. The
morphology of the crystallites was determined by scanning electron microscopy
from CAMECA with the aim of measuring the size distribution.

EXPERIMENTAL RESULTS AND DISCUSSION

The chemical composition of the samples is given in table 1.
All samples are well crystallized as evidenced by IR spectroscopy (ref.
10). X-Ray diffraction and adsorption capacity values ( 8 0.5 mol per U.C. for
n hexane, 6 0.5 for 3-methyl-pentaneand 8 2 0.5 for p-xylene).
 617

TABLE 1
Chemical composition of the various samples calculated from chemical analysis of
Al, B and Na assuming 96 TO per U.C. the proton content is calculated assuming
tetrahedral framework for A? and B.

Samples Composition (per u.c.)

~

A Silicalite 05 A1O. 06 si95.94 0192

B H-A1, ZSM-5 H0.3 A1O. 32 si95.68 '192
C H-B, ZSM-5 B1.38 si94.6 '192
H1.4 A10.02
D H-A1, ZSM-5 H3.56 Na0.05 A13.61 si92.39 '192
E H-B, ZSM-5 H3.2 A10.02 B3.18 si93.4 '192
F H-A1, ZSM-5 H4.a3 A14.80 B0.03 si91.17 '192
G H-A1, ZSM-5 H3. 14 A13.11 BO. 03 si92.86 '192
H Silicalite
A10.11 Na0.11 si95.89 '192
I H-A1, ZSM-5 H3.8 3 A14.1 si91.9 '192

TABLE 2
Average crystallite sizes of the various samples calculated from SEM data

Samples Size (urn> A/V* (pm-')

~~

A 220 x 40 x 40 0.11
B 75 x 40 x 30 0.14
C 90 x 15 x 15 0.29
D 38 x 20 x 12 0.32
E 30 x 12 x 8 0.48
F 17X7X5 0.80
G 2.5 x 0.8 x 0.6 6.6
H 5 x 1 x 0.3 9.0
I 1 x 0.6 x 0.35 11.0

fc A and V correspond respectively to the surface and volume of the crystallites

deduced from SEM data (shape and size of crystallites). The accuracy in A/V
values obviously decreases with decreasing crystallite size. The average size
was determined by analysis of 20 to 30 particles for homogeneous size
distribution and more than 200 for slightly heterogeneous size distribution.

The adsorption of n-hexane, 3-methyl-pentane and p-xylene was studied at

room temperature for all samples. The rate of adsorption was observed to
decrease sharply with increasing crystallite size (ref. 11). The rate was too
fast for n-hexane and para-xylene in the case of small crystalite sizes to give
reliable information by the gravimetry technique (adsorption within a few
seconds for sample I, for instance). On the other hand, the adsorption rate
618

appeared to be reliably measurable for 3-methyl-pentane within the whole

crystallite size range (fig. 1).
The adsorption rate may be expressed using the Crank relationship (ref. 12):

m
-t-- 1 - -
m,
6

n2
- 1
E - 2 exp
n=l n
[- 4nnADt

2V2
2 2 I
For small adsorption time this relationship may be written :

m
- =
3
.
c
m
2 -
V n
[-]
A D 112
t1/2 = kt1l2

where A is the total external surface, V the total volume of the cristallites,
and mt and m, the weight gain at time t and at equilibrium. Figure 2 gives the
variations of k values for 3-methyl-pentane adsorption at room temperature
versus A/V for the various samples within the whole crystallite size range.

Several conclusions may be drawn :

(i) We were unable to synthesize samples with intermediate crystallite
sizes (A/V between 1 and 7 pm-').
(ii) For large crystallite sizes (A/V < 1 Vm-') a linear relationship
between k and A/V exists (Fig. 2B). For small crystallite sizes (A/V > 7 prn-')
one may also consider a linear relationship. However, for the whole range of
crystallite size some curved relationship appears to exist, as shown in Fig. 2A,
which may correspond to some surface barrier phenomenon for small crystallite
sizes, as discussed below.
(iii) For large crystallite sizes it seems that A1-ZSM-5 samples correspond
to a smaller SlOp8, i.e. lower adsorption rate than for B-ZSM-5 and to a larger
extent than for Si-ZSM-5. This trend also exists for smaller crystallite sizes,
but the effect is not very important.
It is known (ref. 13) that Bronsted acid site strength follows the'relation
Si < B << Al. It may thus be suggested that Bronsted acid sites hinder
3-methyl-pentane adsorption commensurate with the strength of the sites. The
effect is not very important but does exist.
The adsorption rate depends on the adsorbate concentration (ref. 14-17).
The diffusion coefficient can then be corrected using Darken's equation :
D = Do (dLn p/dLn 9).
Using different concentration gradients, i.e. different partial pressures,
it was possible to calculate D Experimental data are given in Fig. 3 for
0'
sample A for three different adsorption temperatures.
 619

8
E
\
c,
E

0 2 6 10
I /2)
t (s

Figure 1. 3-methyl-pentane uptake at room temperature for different crystallite

sizes (in urn) of MFI-type samples.
D : 38 x 20 x 12 um E:30x12x8um F : 1 7 x 7 x S u m
G : 2 . 5 x 0.8 x 0 . 6 um

A B
A
e 0.4.
N
\
-I 0.3.
v)
v
0.2.

0.1.

Figure 2 . Variations of k values versus A/V for the different samples.

A : Within the total crystallite size range,
B : Enlargement of the part corresponding to large crystallite sizes.
The symbols correspond to samples in tables 1 and 2, and the elements in
parentheses refer to the substituting element for Si in the framework.
620

20 1

0
m t x I 02 (9.9- II
2
Figure 3. Variations of k versus the amount of 3-m
hyl-pentane adsorbed at 40

80 (0) and 120 ( x ) " C

('0).
J
for sample A with k2 = 2 - .
D
V n

Figure 4. Variations of the m,/moo values as a function of t1l2 at 18 (0).40

(o), 80 (t) and 120 ( x ) " C for sample H.
 62 1

Diffusion coefficient Do values were found to be equal to

0.5 -
1.1 x cm’s-l in the whole range of crystallite sizes at 4OOC. The
adsorption of 3-methyl-pentane was studied as a function of temperature from 18
to 120°C. as shown in Fig. 4 for sample H. The activation energy value could
-1
therefore be determined and was found in the range 10 to 21 kJ.mol for
3-methyl-pentane, the larger values corresponding to the larger crystallite
sizes.
Catalytic properties are known to be influenced by diffusion features (ref.
la), particularly for shape selectivity. The catalytic behaviour involves
several steps :
(i) Adsorption at the crystallite surface. Its probability is rather low
since the surface is mainly composed of pore openings in MFI structure.
(ii) Entrance through the pore openings which may involve a surface barrier
phenomenon. This should increase when the crystallite size decreases since the
number of openings increases sharply.
(iii) Diffusion of reactant molecules within the pores.
(iv) Adsorption of reactant molecules on active sites and desorption of
product molecules. It depends obviously on the number and density of active
sites and on the space available with respect to intermediate species size.
(v) Diffusion of the product molecules.
(vi) Exit of the product molecules.
Catalytic properties have been studied for A1-ZSM-5 samples for methanol
conversion at 370°C and toluene alkylation with methanol at 400°C. Si- and B-
ZSM-5 are inactive under the same conditions. The selectivity in para-xylene
with respect to the other two isomers has been observed to increase noticeably
with crystallite sizes. For instance, it varies from 55-60 X up to 95 Z when the
crystallite size increases from 1 to 220 pm. However. the deactivation rate in
such reactions was found to increase greatly with increasing crystallite size
(ref. 19). This presumably stems from the corresponding sharp lowering of the
number of pore openings, deactivation being primarily due to pore blocking.

CONCLUSION
Adsorption rate measurement appears to be a good way to elicit information
about diffusivity phenomena in zeolite matrice insofar as an appropriate
adsorbate is chosen. Mass transfer and heat transfer consecutive to adsorption
are two serious limitations one has to take into consideration when using the
thermogravimetry technique.
3-methyl-pentane turns out to be a suitable adsorbate for studying
diffusivity in MFI zeolite over a large range of crystallite sizes ; n-hexane
622

and p-xylene are suitable only for large crystallite sizes in order for the
adsorption rate to be low enough for meaningful measurement.
Strong Bronsted acid sites associated with A1 are observed to slightly
hinder diffusion of the adsorbate molecules by comparison with weak or non-acid
sites associated with B and Si respectively.
A limitation to diffusion due to a surface barrier effect, as often
suggested (e.g. ref. 20, 211, does not appear to be very efficient for
3-methyl-pentane,at least for large crystallite sizes. As a matter of fact, the
fast initial adsorption involves many more molecules of adsorbate than the
number of surface pore openings. Such an effect may explain Fig. 2A for low
crystal size, particularly because the number of pore openings is then not
negligible. Nevertheless, we are of the opinion like Ruthven (ref. 8) that it is
possible to implicate this effect in the behaviour between crystallites of small
size in regard of crystallites of large size and perhaps it is also a limiting
step even for crystallites of large size but to a lower extent.
In fact, if the diffusivities so calculated are not actually representative
of the true intracrystalline diffusion, as compared to values obtained by field
gradient N.M.R. or neutron diffraction studies, they may be more representative
of the catalytic activity, since both adsorption and diffusion phenomena are
involved.

REFERENCES
1 R.M. Barrer, Zeolites and Clay Minerals as Sorbents and Molecular Sieves,
chap. 6, Academic Press, London, 1978, pp. 256-337.
2 D.M. Ruthven, Principles of Adsorption and Adsorption Processes, Wiley, New
York, 1984.
3 M.G. Palekar and R.A. Rajadhyaksha, Catal. Rev. Sci. Eng. 28 (1986)
371-429.
4 D.M. Ruthven, K.F. Loughlin and R.I. Derrah, Molecular Sieves, Adv. Chem.
Ser., Vol. 121, W.M. Meier and J.B. Uytterhoeven, Ed., Washington (1973)
330-344.
5 L. Forni, C.F. Viscardi and C. Oliva, J. Catal. 97 (1986) 469-479.
L. Forni and C.F. Viscardi, J. Catal. 97 (1986) 480-492.
6 A.N. Pitch, H. Jobic and A. Renouprez, J. Phys. Chem. 90 (1986) 1311-1318.
D.L. Hasha, V.W. Miner, J.M. Garces and S.C. Rocke. Catalyst
Characterization Science, ACS Symp. Ser., Vol. 288, M.L. Deviney and J.L.
Gland, Ed., Washington, (1988) 485-497.
7 J. Karger, H. Pfeifer, E. Ride1 and H. Winkler, J. Colloid Interf. Sci. 44
(1973) 1870.
8 D.M. Ruthven and M. Eic, Perspectives in Molecular Sieve Science, ACS Symp.
Ser. Washington, Vol. 368, W.H. Flank and T.E. Whyte, Ed., (1988) 362-375.
9 J.L. Guth. H. Kessler and R. Wey, Proceed 7th IZC, Tokyo, Y. Murakami et
al.. Ed., Elsevier, Amsterdam, 1986, p. 121.
10 G. Coudurier, C . Naccache and J.C. Vedrine, J. Chem. SOC., Chemical Corn.
1982. pp. 1413-1415.
11 J.C. Vedrine, G. Coudurier and B.P. Mentzen, Perspectives in Molecular
Sieve Science, ACS Symp. Ser., Vol. 368. W.H. Flank and T.E. Whyte. Ed.,
1988, pp. 66-84.
12 J. Crank, The Mathematics of Diffusion, Clarendon Press, Oxford, 1976.
 623

13 G. Coudurier and J.C. Vedrine, Pure and Appl. Chem. 58 (1986) 1389- 396.
14 M. Goddard and R.M. Ruthven. Zeolites 6 (1986) 283-289.
15 A. Cointot, G. Joly and V. Perperas, J. Chirn. .Phys. 80 (1983) 213-2 8.
16 A.P. Vavlitis. D.M. Ruthven and K.F.J. Loughlin, J. Colloid Interf. Sci. 84
(1981) 526.
17 M. Biilow, P. Struve and Ch. Redsus, Proceed 5th IZC, Napoli, L.V.C. Rees,
Ed., Heyden, London, (1980) pp. 580-591.
18 W.O. Haag, R.M. Lago and P.B. Weisz, Discussion Faraday SOC. 72 (1981)
317-330.
19 V. Ducarme and J.C. Vedrine. Appl. Catal. 17 (1985) 175-184.
20 J. Karger and H. Pfeifer, Perspectives in Molecular Sieve Sciences, ACS
Sympos. Ser., Vol. 368, W.H. Flanck and T.E. Whyte, Ed., Washington (1988)
pp. 376-396.
21 E.G. Derouane, J-M. Andre and A.A. Lucas, J. Catal. 110 (1988) 58-73.
This Page Intentionally Left Blank
H.G.Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
Amsterdam - Printed in The Netherlands
0 1989 Elsevier Science Publishers B.V.,

HIGH RESOLUTION SORPTION STUDIES OF ARGON AND NITROGEN ON LARGE CRYSTALS

OF ALUMINOPHOSPHATE A1P04-5 AND ZEOLITE ZSM-5

u. MULLER', K.K. UNGER', DONGFENG PAN^, A. MERSMANN'

Y. GRILLET', F . ROUQUEROL3, J. ROUQUEROL3
'Institut fur Anorganische Chemie und Analytische Chemie, P. 0. Box 3980,
Johannes Gutenberg-Universitat, D-6500 Mainz, F.R.G.

21nstitut fur Verfahrenstechnik der Technischen Universitat, Lehrstuhl B,

Arcisstr. 21, D-8000 Miinchen 2, F.R.G.

3Centre de Thermodynamique et de Microcalorimetrie du C.N.R.S.,

26 Rue du 141e R.I.A., 13003 Marseille, France

ABSTRACT
High resolution adsorption (HRADS) with argon and nitrogen at 77 K in the
pressure range of c p/po < 0.5 were performed on large crystals of zeolite
ZSM-5 (180 pm) and aluminophosphate AlP04-5 (150 pm) using a novel volumetric
device. Multi-step isotherms of both adsorptives on ZSM-5 could be observed for
the first time. The adsorption followed by low temperature microcalorimetry re-
sulted in distinct exothermic signals at the steps in the adsorption isotherms.
Based on the results of atom-atom potential energy calculations (AAP) as well as
independent model building it was shown that 24 'kinetic' adsorbate molecules can
be filled into a ZSM-5 unit cell. Experimental results are reasonably interpreted
assuming a primary filling of narrow channels and a secondary adsorption in the
wider channel intersections. Localized adsorption is understood as a possible
filling mechanism. In ZSM-5 and nitrogen as adsorbate there is evidence for a
transition of fluid-like to solid-like adsorbate phase.
AlPOq-5 behaves as a homogeneous sorbent with a micropore capacity of four
molecules per unit cell for argon and nitrogen. For both adsorptives in the mole-
cular sieves under investigation the initial isosteric heat of adsorption for
nitrogen was found to give values comparable to the enthalpies of adsorption
derived from the temperature dependence of experimentally determined HENRY
constants. HENRY constants and the initial isosteric heat of adsorption are indi-
cative of a stronger adsorption of nitrogen compared to argon which is thought
to be due to additional interactions between the nitrogen quadrupole moment and
the crystalline molecular sieve framework.

INTRODUCTION
Zeolite ZSM-5 and aluminophosphate AlP04-5 have attracted considerable inte-
rest as microporous model adsorbents. Both materials are crystalline molecular
sieves with strictly regular pore systems, viz. intersecting straight and zig-
zag 10-membered ring channels (ultramicropores) connected by larger cavities
(micropores) in ZSM-5 111, and unidimensional 12-membered ring tubes (micropores)
in A1POq-5 12 1 . Based on novel synthesis concepts 13,41 the growth of large uni-
form crystals at high yields and with narrow particle size distribution has been
achieved. Employing large monocrystals in sorption investigations, no erroneous
contributions by interparticle vapour condensation and external surface area
626

effects to adsorption occur as on polycrystalline powders. Thus, the intrinsic

sorptive properties can be reliably determined with high precision over a wide
range of coverage 8 . Gravimetric sorption experiments with nitrogen at 77 K on
large ZSM-5 crystals led to the discovery of a sharp hysteresis loop at low
pressures of p/po = 0.15 15-71. Furthermore, in contrast to the BDDT-model 181
which predicts a LANGMUIR-type of isotherms for microporous adsorbents, both
argon and nitrogen revealed distinct multi-step isotherms on large ZSM-5 crystals
whereas no deviation from type-I isotherms was seen for AlP04-5.
This study presents experimental results obtained by combining high resolution
adsorption techniques (HRADS) with low temperature microcalorimetry. The calcu-
lated thermodynamic properties like HENRY constants, heats of adsorption and
atom-atom approximation for adsorbate-adsorbent interactions strongly suggest
localized adsorption on energetically enhanced crystallographic sites. In addi-
tion, a transition of the adsorbate to a denser phase at higher coverage is
assumed to explain the sorption behaviour of nitrogen on large ZSM-5 crystals.

EXPERIMENTAL
Large crystals, 600 pm, of AlPO4-5 131 were prepared by optimization of a
procedure described elsewhere 191. A sample consisting of 150 pm hexagonal rods
was used in this study. Monocrystals of HZSM-5 (180 pm with Si/A1 = 1000) were
synthesized according to a process described in the literature 141. The products
were characterized by scanning electron microscopy SEM. x-ray diffraction, ther-
mal analysis and electron microprobe analysis. Additionally the HZSM-5 crystals
were analyzed by IR and 29Si-MAS-NMR spectroscopy. Adsorption isotherms with
argon and nitrogen at 77 K were recorded on a novel dynamic volumetric device
(Omnisorb 360, OMICRON Corp., U.S.A.). Data acquisition started at a relative
pressure of p/po = and was continued up to p/p" = 0 . 5 , thus collecting se-
veral hundred quasi-equilibrium points of the adsorption isotherm. Nitrogen ad-
sorption isotherms at 303 to 430 K were determined gravimetrically at a relative
sensitivity of lo6 (ultramicrobalance 4433, Sartorius, F.R.G.) . Continuous calori-
metric measurements were performed on a reversible isothermal microcalorimeter
of Tian-Calvet type (C.N.R.S. Thermodynamique et Microcalorimetrie, Marseille,
France). A detailed description of the microcalorimeter is given in the litera-
ture 1101. Prior to all experiments samples calcined at 823 K were degassed for
12 hours at 473 K and at a vacuum of mbar.

CALCULATIONS
Calculations of the intermolecular interactions of argon adsorbed on ZSM-5
and AlP04-5 respectively, were performed using atom-atom approximation for the
potential energy (AAP) and Lennard-Jones 6:12 potentials. Only contributions
of the framework oxygen atoms were taken into account, based on determinations
of the refined structures of ZSM-5 111,121 in space group Pnma and P6cc for
 627

A1P04-5 121. V a l u e s f o r t h e p o l a r i z a b i l i t y of a r g o n (1.63.10-3 nm3) a n d n i t r o g e n

(0.88-10-3 nm3) a s w e l l a s t h e i r r a d i i were t a k e n from l i t e r a t u r e d a t a 131. Cov-
e r a g e s €I were c a l c u l a t e d from t h e e x p e r i m e n t a l i s o t h e r m s as m o l e c u l e s of a d s o r -
bate per n i t c e l l ( m o l e c / u c ) , u s i n g STP v a l u e s f o r a r g o n (1.784.10-3 g/cm3) a n d
nitrogen 1.251.10-3 g/cm3). D a t a d e r i v e d by g r a v i m e t r y were c o r r e c t e d f o r buoy-
ancy w i t h t h e s o r b a n t c r y s t a l l i n e d e n s i t i e s . I s o s t e r i c h e a t s o f a d s o r p t i o n , qST,
a r e t a k e n from t h e e x p e r i m e n t a l h e a t f l u x 4 by t h e equation:
V(dp/dt) -4
qST = (1)
dn/dt
w i t h d n / d t as c o n t i n u o u s a d s o r b a t e u p t a k e r a t e a n d a c o r r e c t i o n V ( d p / d t ) f o r t h e
h e a t l o s s d u r i n g t h e e x p a n s i o n o f gas i n t o t h e s a m p l e b u l b . The i s o s t e r i c h e a t
of a d s o r p t i o n , qST, c a n b e compared w i t h t h e v a l u e of t h e d i f f e r e n t i a l e n t h a l p y
of a d s o r p t i o n , q d i f f s ( q d i f f = qST - R T ) . From t h e i n i t i a l s l o p e of t h e i s o t h e r m s
t h e HENRY c o n s t a n t s KH were c a l c u l a t e d a c c o r d i n g t o €I = K H - p. The h e a t of ad-
s o r p t i o n , -AH, was d e r i v e d from HENRY c o n s t a r i t s u s i n g KH = Kfi e x p (-4H/RT).

RESIJLTS and DISCUSSION

I s o t h e r m s a n d isosteric h e a t of a r g o n a n d n i t r o g e n on AlP04-5
Type-I i s o t h e r m s o f a r g o n a n d n i t r o g e n (see F i g . 1, shown f o r N2) on large
A1P04-5 c r y s t a l s w e r e o b s e r v e d f o r b o t h gases a t 77 K. A p p l y i n g LANGMUIR-plots
as w e l l as t h e method of DUBININ-RADUSHKEVICH, a m i c r o p o r e f i l l i n g c a p a c i t y of
3.9 0.2 molec/uc f o r n i t r o g e n a n d 3 . 8 2 0 . 2 molec/uc f o r a r g o n w a s c a l c u l a t e d .
Dense a d s o r b a t e p h a s e s f o r n i t r o g e n a n d a r g o n i n AlP04-5 were assumed. I s o s t e r i c
h e a t of a d s o r p t i o n , qST, r e a c h e d a maximum a t a c o v e r a g e o f a b o u t 3.5 m o l e c / u c
( 1 4 . 5 kJ/mol N2 and 1 3 . 2 kJ/mol A r ) a n d d e c l i n e d when t h e s a t u r a t i o n c a p a c i t y was
e x c e e d e d . W i t h i n t h e e x p e r i m e n t a l e r r o r t h e i n i t i a l i s o s t e r i c h e a t , qST, f o r ad-
s o r p t i o n o f n i t r o g e n (13 f 0.6 kJ/mol a t 0 e O . 1 ) c a n b e compared t o t h e h e a t o f
adsorption, -AH, c a l c u l a t e d from t h e t e m p e r a t u r e d e p e n d e n c e o f t h e HENRY c o n s t a n t
KH ( 9 . 9 2 3.3 k J / m o l ) . A t 77 K t h e l i n e a r s l o p e o f t h e n ' i t r o g e n i s o t h e r m a t
p / p o c 10-5 y i e l d e d v a l u e s of KH = 13.1 molec/uc'mbar a n d KH = 1 4 . 2 molec/uc.mbar
r e s p e c t i v e l y . The l a t t e r was c a l c u l a t e d u s i n g t h e v i r i a l e q u a t i o n of BARRER 1141.

F i g . 1. High r e s o l u t i o n a d s o r p -
t i o n (HRADS) i s o t h e r m s a t 77 K
of a r g o n a n d n i t r o g e n o n large
c r y s t a l s of a l u m i n o p h o s p h a t e
A1P04-5 ( 1 5 0 pm) a n d z e o l i t e
ZSM-5 ( 1 8 0 bm a n d S i / A 1 = 1000).
628

Isotherms and isosteric heat of argon and nitrogen on ZSM-5

Multi-step isotherms were observed for nitrogen on ZSM-5 at 77 K. Steps in the
adsorbate uptake were monitored at coverages of 20, 22, 24 and 30.5 molec/uc,
respectively (see Figs. 1,2). Standard deviations amounted to 0.8 molec/uc in the
uptake values, based upon statistical certainties of 95%. The initial isosteric
heat of adsorption of nitrogen was calculated to 16.5 kJ/mol. The exothermic
peaks of 6.4 kJ/mol clearly coincide with the observed steps in the isotherm as
illustrated in Fig. 2. The exothermic contributions at coverages of 20 to 22 and
24 to 30.5 molec/uc respectively, were comparable to the sum of the heats of
condensation (5.56 kJ/mol) plus solidification (0.72 kJ/mol) being required for
phase transitions in tridimensional bulk nitrogen. At low coverage (0e0.1) values
of qST (16.8 2 0.2 kJ/mol) equal the enthalpy change derived from van't HOFF plots
(18.2 1.7 kJ/mol). HENRY constants for nitrogen on ZSM-5 at 77 K were computed
to KH = 830 molec/uc'mbar, using the virial equation at p/po* this value was
decreased to KH = 594 molec/uc.mbar.

Fig. 2. Nitrogen isotherm and isosteric heat of adsorption on large ZSM-5

crystals at 77 K.

The argon adsorption on ZSM-5 occurred in steps of 20 and 24 molec/uc (Fig. 1).
At these steps in the isotherm an exothermic increase (1.7 kJ/mol) of the iso-
steric heat of adsorption, qST, (see Fig. 3)occurred; however, the heat curve as
well as the isotherm were less pronounced compared to the N2/ZSM-5 system.

Potential energy distribution in A1P04-5 and ZSM-5

Results of atom-atom approximation (AAP) calculations for argon atoms adsorbed
on A1P04-5 are summarized in Fig. 4. Six minima of the potential energy were found
above the evenly distributed TO4 6-rings in the channel walls. Model-building
with localized 'kinetic' gas molecules (0.38 nm diameter) at these minima, in-
dicated a preferred population of three argon atoms per radial TO4 six-ring
 629

channel segment. This represents a micropore filling of 4 molec/uc and is in

close agreement with the experimentally observed data from sorption isotherms
and enthalpy curves.

1 -7

.. .- . ... .,

Fig. 3. Argon isotherm and isosteric heat of adsorption on large ZSM-5

crystals at 77 K.

From AAP-calculations and independent model-building 24 minima of the potential

energy in an unit cell of ZSM-5 were registered. Eight minima are situated at the
channel wall 6-rings in the straight tubes (see Fig. 6) and twelve in the zig-
zag channels (see Fig. 7). Additional four ones are located at the wider chan-
nel intersections, thus giving a total of 24 rninima/uc. Note that in the argon
and nitrogen isotherms steps occur at fillings of 20 and 24 molec/uc, respec-
tively.

Fig, 4. Potential energy distribution (AAP approximation) for argon across

a channel in A1P04-5.
630

Sorptive properties of large AlP04-5 crystals

Adsorption studies of microcrystalline AlPOq-5 have been described in the
literature 115-181. Unusual type-V isotherms of the system H*O/AlP04-5 have been
reported and were attributed to crystal hydrate formation 1161. Studies of
STACH and coworkers I17 I at ambient temperatures identified A1P04-5 as energe-
tically homogeneous sorbent. At low temperatures type-I isotherms f o r oxygen and
nitrogen are reported by WILSON et a1 1151 and BOND et a1 1181, respectively.
However, these isotherms showed 30 to 40% of the final uptake in a relative
pressure range of 0.05<p/po<l.0 which seems unlikely for homogeneous purely
microporous systems. The occurrence of a nitrogen hysteresis (p/p0+0.4) was
assumed to be caused by capillary condensation in the mesopores 1181. Application
of preadsorption of n-hexane on AlP04-5, previously investigated 131, clearly
showed that the observed hysteresis was not caused by micropores in AlPO 5.
4-
The comparatively low heats of adsorption of argon and nitrogen obtained in
this study (see Fig. 5) support the view that AlP04-5 exhibits a mildly hydro-
philic sorbent character. At low pressures the micropore filling capacity for
kinetic gas molecules (4molec/uc) is reasonably predicted by theoretical AAP-
calculations and model-building.

0.1
AlP04-5 I77 K1
-I
I¶ P/OO
kd-1
0.4
I¶

0.a

10

0.1

¶
0.1

0 0.0
l a a 4 1

Fig. 5. Nitrogen isotherm and isosteric heat of adsorption of argon and

nitrogen on large AlP04-5 crystals at 77 K.

Sorptive properties of large ZSM-5 crystals

Data for nitrogen adsorption on polycrystalline powders of ZSM-5 habe been
already reported in the literature 119,201. In general, the overall sorption
capacities agree fairly well with this study. However, most of these measure-
ments collected only few isothermal points (5 to 20) and were not extended into
the low pressure range p/poe A geometrical model of JACOBS et al. 1201 pro-
poses a closest-possible packing of nitrogen molecules in the larger channel in-
tersections of ZSM-5. In contrast to this model, theoretical calculations of gas-
 631

solid interactions by EVERETT and POWL 1211, recently adapted to zeolites by

DEROUANE I22 I , clearly indicate an enhancement of adsorption energy in smaller
pores of molecular diameter (e.g. 0.55 nm channels in ZSM-5). According to
DUBININ 123 I these channel 'ultramicropores' are primarily filled due to over-
lapping force fields from opposite walls of the narrow micropores. With increase
of the pore size up to 2-3 molecular diameters (i.e. 0.8 to 1.0 nm for argon and
nitrogen and close to the space available in a ZSM-5 channel intersection) the
superimposed enhanced adsorption energy deciines, and cooperative secondary
rnicropore filling might occur 1241.

Fig.' 6. Potential energy distribution for argon in a straight channel of ZSM-5

(arrows: channel minima; asterix: minima at the intersection).

I
,-,,
,o..B/..-ciIl

Fig. 7. Potential energy distribution for argon in a zigzag channel of ZSM-5

(arrows: channel minima; asterix: minima at the intersections).

For argon and nitrogen AAP calculations and model-building yielded a channel po-
pulation of 20 molec/uc which is in full agreement with the first step in the
adsorption isotherms (see Fig. 1). Further filling of the four larger intersec-
tions with one argon atom in each site is attributed to the second plateau in
the argon isotherm, giving a final coverage of 24 molec/uc. At this stage all
channels and intersections are occupied by kinetic gas molecules. The exothermic
increase (1.7 kJ/mol) during the intersection filling (20 up to 24 molec/uc)
might be due to adsorbate-adsorbate interactions (e.g. the heat of fusion for
bulk liquid argon amounts to 1.21 kJ/mol).
As already shown (figs. 1-3) the situation is more complex for the nitrogen

in ZSM-5. Although the kinetic molecular diameter of argon (0.35 nm) and nitrogen
(0.38 nm) are quite similar, nitrogen as a diatomic molecule offers a considerable
quadrupole moment which permits additional adsorbate-adsorbent interactions.
Hence, the steps in the nitrogen isotherms are more pronounced and the isosteric
heat of adsorption is enhanced (1.8 kJ/mol) compared to argon. After initial up-
take of 20 molecules in the channels (i.e. first step in the isotherm) a further
coverage up to 22 molec/uc follows. The latter connects the channel adsorbate
(2 nm) to the overall crystal adsorbate macroscopic phase (at least 30,000 nm,
as taken from the crystal dimension along the (100) or (010) axis). At this
point, monitored as a small substep in the isotherm, the adsorbate phase loses
significantly in kinetic energy and mobility, as is obvious from Fig. 2.
At a coverage of 24 molec/uc, corresponding to a filling of all channels and
intersections, the largest step in the isotherm up to 30.5 molec/uc takes place.
This unusual behaviour is known to be correlated with a sharp type-A hysteresis
loop between the adsorption and desorption branch of the isotherm 15,61. It has
independently been observed even on smaller ZSM-5 crystals 171. The energy
which is dissipated when tridimensional nitrogen is transformed from a gaseous
to a solid phase is close to the value of 6.3 kJ/mol which has been experimen-
tally observed during the densification of the fluid adsorbate in ZSM-5. The
uptake ratio of 24/30.5 molec/uc before and after the inflexion of the isotherm
at p/po = 0.15 is identical with the ratio of the density of liquid (0.808g/cm3)
to solid nitrogen (1.027 g/cm3). Freezing of adsorbed 2D nitrogen at 77 K is a
well documented phenomenon occurring on homogeneous graphite or boron nitride as
adsorbents 110,251, and complex phase diagrams have been calculated 1261. Abrupt
transitions of dense fluid-like to solid-like adsorbate in slit-shaped pores was
theoretically predicted over a range of 1 - 2 up to 3 - 4 adsorbate layers
1271. Adapted to ZSM-5, this situation occurs at the completion of fluid filling
in the wider intersections, where the 2D channel adsorbate is contacted with a
3D adsorbate phase. Furthermore this result can be explained by the 'site-and-
bond' network hypothesis of MAYAGOITIA, which assumes cooperative filling pro-
cesses when half of the network sites (i.e. intersections in ZSM-5 at N = 22
molec/uc) are filled 1281. Monte Carlo simulations of gases in narrow pores sug-
gest that phase transitions and metastable states are formed which should show
up in experimental sorption isotherms as hysteresis effects 1291. This is con-
 633

sistent with earlier observations on the existence of a hitherto unknown low-

pressure hysteresis loop in the nitrogen ZSM-5 system 15-71.

CONCLUSION
The results of both high resolution adsorption and microcalorimetry at low
temperatures provide clear evidence that the stepped isotherms of argon and
nitrogen on large ZSM-5 crystals can be rationally explained by localized ad-
sorptive molecules at the channel walls and the channel intersections. The find-
ings are consistent with theoretical predictions. Heats of adsorption on A1P04-5
are lower compared to ZSM-5. Further investigations on unidimensional zeolitic
materials (e.g. high silica ZSM-12) should show whether this behaviour is caused
by different surface force fields of aluminophosphates and zeolites or if it is
due to the different pore sizes of 10-membered and 12-membered micropore chan-
nels. At least nitrogen adsorbed at higher loadings in the ZSM-5 network should
be considered as an immobile dense phase. Low temperature NMR and neutron dif-
fraction experiments are in progress to further elucidate the adsorbate struc-
ture of gases in microporous adsorbents.

ACKNOWLEDGEMENTS
We are grateful to Dr. G. Engelhardt, Konstanz, and Dr. H.-G. Karge, Berlin,
for 29Si-MAS-NMR and IR-spectroscopic characterization of the ZSM-5 sample. This
work is financially supported by Deutsche Forschungsgemeinschaft.

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0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

A NEW POTENTIAL LARGE-SCALE APPLICATION OF ZEOLITES AS FIRE-RETARDANT MATERIAL

H. K. BEYER', G. BORBiLY', P. MIASNIKOV' and P. RbZSA3

'Central Research I n s t i t u t e f o r Chemistry o f the Hungarian Academy o f Sciences,

P.O. Box 17, 1525 Budapest (Hungary)
' I n s t i t u t e o f B u i l d i n g Science, P.O. Box 71, 1502 Budapest (Hungary)
3Department o f Mathematics, Technical U n i v e r s i t y o f Budapest, Muegyetem rkp. 3-9,
1111 Budapest (Hungary)

ABSTRACT
The heat f l u x i n systems c o n s i s t i n g o f coaxial l a y e r s o f f i r e - r e t a r d a n t mate-
r i a l s and b u i l d i n g structures has been simulated and mathematically modelled.
The f i r e - p r o t e c t i v e e f f e c t o f z e o l i t e s was calculated and experimentally deter-
mined. Compared w i t h conventional f i r e - r e t a r d a n t m a t e r i a l s z e o l i t e s are more
e f f e c t i v e i n the temperature range up t o 570 K, thus applicable e s p e c i a l l y f o r
the p r o t e c t i o n o f heat-sensitive b u i l d i n g s t r u c t u r e s and goods against the
effect of fire.

INTRODUCTION
The o b j e c t i v e o f f i r e - r e t a r d a n t m a t e r i a l s i s t o i n h i b i t as e f f e c t i v e l y as
possible the f l o w o f heat towards the p a r t o f the b u i l d i n g o r b u i l d i n g s t r u c -
t u r e t o be protected. I n s t a l l e d i n f i r e - p r o t e c t i v e constructions such as f i r e -
-doors, movable o r f i x e d f i r e - w a l l s , f a l s e c e i l i n g s , etc., they slow down the
flow o f heat through these b u i l d i n g s t r u c t u r e s and thus a l s o the spread o f f i r e
w i t h i n the b u i l d i n g . Covering the surface o f b u i l d i n g structures, f i r e - r e t a r d a n t
m a t e r i a l s p r o t e c t them against the e f f e c t o f f i r e . This p r o t e c t i o n i s of g r e a t
s i g n i f i c a n c e i n the case o f supporting constructions, e.g. p i e r s , beams and
s t r u t s , since they lose t h e i r s t a t i c a l s t a b i l i t y and load-bearing capacity a t a
c e r t a i n temperature. Last b u t n o t l e a s t , the enclosure o f storage containers
w i t h f i r e - p r o t e c t i v e m a t e r i a l may p r o t e c t heat-sensitive goods (e.g. valuable
papers, magnetic records, f i l m materi a1 ) against damage from f i r e .
Heat i n s u l a t i o n and absorption o f heat by the p r o t e c t i n g m a t e r i a l i t s e l f p l a y
a d e c i s i v e r o l e i n f i r e r e t a r d a t i o n . A l a r g e heat capacity o f the s t r u c t u r e t o
be protected may be achieved by making i t heavy. However, weight and dimensions
o f b u i l d i n g s t r u c t u r e s are generally l i m i t e d by constructional considerations.
Moreover, increasing the bulk density o f f i r e - r e t a r d a n t m a t e r i a l s g e n e r a l l y
r e s u l t s i n a d e t e r i o r a t i o n o f t h e i r h e a t - i n s u l a t i o n properties. Therefore tech-
niques have been developed t o apply m a t e r i a l s which by phase i n v e r s i o n from
s o l i d t o l i q u i d s t a t e (e.g. Glauber's s a l t ) o r by an endothermic chemical r e -
a c t i o n (e.g. dehydroxylation o f g i b b s i t e ) "absorb" heat energy i n l a t e n t form.
The o b j e c t i v e of the present paper i s t o i n v e s t i g a t e whether z e o l i t e s may be
applicable as f i r e - r e t a r d a n t m a t e r i a l due t o t h e i r endothermic dehydration
636

process. Heat f l u x and temperature p r o f i l e s i n l a y e r s o f f i r e - p r o t e c t i v e m a t e r i -

a l s and constructions are simulated and mathematically modelled i n order t o com-
pare the p r o t e c t i n g e f f e c t s o f z e o l i t e s and conventional m a t e r i a l s . Heat conduc-
t i v i t y c o e f f i c i e n t s were experimentally determined and heat capacity data needed
f o r these c a l c u l a t i o n s were taken from the l i t e r a t u r e . Temperature p r o f i l e s i n
z e o l i t e layers were measured and compared w i t h c a l c u l a t e d ones.

METHODS
Mathematical model l i n g o f temperature p r o f i l e s i n f i r e - r e t a r d i n g m a t e r i a l s

I n order t o describe t h e heat t r a n s f e r through f i r e - r e t a r d a n t l a y e r s and

implement the p r o t e c t i o n o f c o n s t r u c t i o n s against the e f f e c t o f f i r e , the homo-
geneous problem o f heat conduction i n a composite medium c o n s i s t i n g o f L l a y e r s
o f coaxial c y l i n d e r s being i n contact i s considered ( r e f . 1). The c o n s t r u c t i o n
i s assumed t o be o f i n f i n i t e length, thus the heat i s t r a n s f e r r e d i n r a d i a l d i -
r e c t i o n only. L e t the thermal c o n d u c t i v i t y o f t h e 1 - t h l a y e r be denoted by
kl(T), the d e n s i t y by pl(T), and the s p e c i f i c heat by cl(T) expressing t h e f a c t
t h a t they are dependent on the temperature T. The temperature d i s t r i b u t i o n
T ( r , t ) has t o be determined as a f u n c t i o n o f t h e r a d i a l coordinate r and the
time t, thus t h e one-dimensional coupled system o f heat conduction equations

a aT1 ( r , t ) kl ( T I aT1 ( r , t ) aT1 ( r , t )

- (kl(T) )+- = P1(T)C1(T) (1)
ar ar r ar at
has t o be solved i n the domains

rl-l 6 r 2 r , t > 0 , 1=1,2,...,L (ro=O)

s a t i s f y i n g the conditions o f coupling

1=2,3, ...,L
t h e boundary conditions

Tl(o.t) < m , TL(rL,t) = T L ( t )

and the i n i t i a l conditions

Tl(r,o) :0 , rl-l s r s rl , 1=1,2,...,L (ro=o) .

 637

The c o n d i t i o n s ( 2 ) imply t h e c o n t i n u i t y o f temperature o r p e r f e c t thermal

c o n t a c t between two consecutive l a y e r s . The c o n d i t i o n s (3) s t a t e t h a t t h e h e a t
f l u x i s continuous a t t h e i n t e r f a c e s .
For the numerical s o l u t i o n o f the system o f p a r t i a l d i f f e r e n t i a l equations
(1) t h e method o f f i n i t ; d i f f e r e n c e s w i l l be a p p l i e d . Making use of t h e Crank-
-Nicolson i m p l i c i t method ( r e f . Z), a system o f a l g e b r a i c equations w i l l be
obtained. Since t h e c o e f f i c i e n t s kl, p1 and c1 depend on t h e temperature, the
c o e f f i c i e n t s o f t h e a l g e b r a i c system a r e f u n c t i o n s o f t h e unknown values o f t h e
temperature as w e l l , thus t h e system o f equations w i l l be s o l v e d by i t e r a t i o n .
I n o r d e r t o o b t a i n t h e a l g e b r a i c system, l e t t h e v a r i a b l e s t and r b e
d i s c r e t i z e d by s u b d i v i d i n g them i n t o i n t e r v a l s A t and Arl, respectively,
according t o

t ( n ) = nAt, n=1,2,3,. .. and

1-1
r(i) = C m (Ar - Arl) t iArl in rl-l 5 r 5 r
1
p=l p p

f o r i = m, m t l , . . . , mtml where

1. - 1-
m = C m l=l,Z, ...,L
m=l P

i s i n t r o d u c e d f o r s i m p l e r n o t a t i o n (m=O i f 1=1).
F o r t h e d i s c r e t e values o f t h e f u n c t i o n s t o b e determined l e t us i n t r o d u c e

T,( r ( i ) , t ( n ) ) = Ti ( ’ I n for i=m, m t l , . . . , mtml , 1=1,2 ,... ,L

I n a s i m i l a r way t h e corresponding values o f heat c o n d u c t i v i t y and t h o s e o f
t h e product o f d e n s i t y and s p e c i f i c h e a t w i l l b e denoted as

i=m, mtl,.,., mtml

The values o f h e a t c o n d u c t i v i t y corresponding t o t h e m i d d l e o f t h e i n t e r v a l s

[ r ( i ) , r ( i t 1 ) l w i l l be denoted as

Making use of these n o t a t i o n s , t h e i m p l i c i t method o f Crank-Nicolson l e a d s t o

t h e f o l l o w i n g system o f a l g e b r a i c equations:
638

L
For i=0,mlymltm2,mltm2tm3,.. ., C m
p= I P'
the boundary c o n d i t i o n s ( 4 ) and the

conditions o f coupling (2) and ( 3 ) have t o be taken i n t o consideration.

S u b s t i t u t i n g the d i s c r e t i z e d form o f these c o n d i t i o n s and a f t e r rearranging
t h e system (5), i t can be w r i t t e n i n t h e f o l l o w i n g concise form:

where Dn = <d?> i s a diagonal m a t r i x , t h e elements o f which a r e

 639

K(p)= [a. .I 1.I

i s a t r i d i a g o n a l m a t r i x o f t h e thermal c o n d u c t i v i t i e s w i t h
elements

a.i,i kl;hn f o r i=O

1-1 1
ai,i
=
(’1’ (’In
ki-1/2 + k i t 1 / 2
for m = c m < i < c m = m t ml I=I,Z, ...,L
p=l p=l

1-1
n n f o r i = ~m = m 1=2,3, ...,L
ai,i ‘i-1 ‘it1 p=l p

1-1
a.1 ,i-1 = - u ? - ~, ai,i+l = -u?+~ for i =Z m = m 1=2,3, ...,L
p=l

where
640

Tn i s a column vector o f the unknown temperature,

where
L L
q-1 = C m -1 and 9-1/2 = C m -1/2,
p=l p=l

and E i s the q - t h u n i t vector.

q- 1
Since elements o f t h e c o e f f i c i e n t m a t r i x i n (6) depend on t h e unknowns

T,!')"', t h e system (6) can be solved by the f o l l o w i n g i t e r a t i o n :

Assuming the i t e r a t i o n t o be convergent, we get

l i m rtl(j) = T"+'
j-

S t a r t i n g w i t h t h e i n i t i a l c o n d i t i o n , i . e . f = 0, the i t e r a t i v e s o l u t i o n
o f equation ( 7 ) gives temperature d i s t r i b u t i o n s T1.T2.. .
. ,Tn f o r the
d i s c r e t i z e d time v a r i a b l e n.

Determination o f m a t e r i a l - s p e c i f i c c o e f f i c i e n t s needed f o r t h e c a l c u l a t i o n o f
temperature p r o f i1es

Density, heat capacity and thermal c o n d u c t i v i t y of s t a i n l e s s s t e e l , mineral

wool, z e o l i t e 13X and g i b b s i t e considered i n t h e present study as c o n s t r u c t i o n
and f i r e - p r o t e c t i v e materials, resp., a r e sumnarized i n Table 1. The thermal
c o n d u c t i v i t y o f z e o l i t e 13X (extrudates, diameter: 2 mm, water adsorption capa
c i t y : 260 rng-g-' dehydrated product) , g i b b s i t e (commercial pel l e t s , diameter:
2-4 nun) and y-A1203 (obtained from the g i b b s i t e sample by heat treatment a t
870 K) was determined by measuring t h e e l e c t r i c energy needed t o m a i n t a i n a
temperature g r a d i e n t of 12 K.cm..' i n a 5 cm t h i c k l a y e r o f t h e m a t e r i a l . The
t e s t device i s described i n r e f . 3.
 641

TABLE 1
Values of coefficients used f o r t h e c a l c u l a t i o n o f temperature p r o f i l e s

mater ia 1 therma 1 conduct iv i ty heat capaci ty bulk d e n s i t y

W. m- 1. K-1 .
J kg-1. K-1 .
kg m-3
stainless 0.22.T t 401
steel 0.135 + 14.8 f o r 293<T<650 K 7830
A I S I 347 1.118.T -
146
( r e f . 4) f o r Tz650 K
0.00017.T 0.001 - 0.67-T + 700
mineral wool f o r 293<T<373 K f o r 293<T<573 K 150
(ref. 3) 0.00033.T 0.061 - 0.04.T t 900
f o r T2373 K f o r T2573 K

hydrated 13' 0.047 ( a t 360 K)* see Fig. 1 832

gibbsite 0.32 ( a t 363 K)* see Fig. 1 1150

0.75.T + 462
y-A1203 0.075 ( a t 360 K)* f o r 293<T<373 K 725
0.09.T t 706
f o r T2373 K
( r e f . 5)
0.000072.T t 0.004 0.000036.T t 0.995
air f o r 293<T<573 K f o r 293<T<410 K
( r e f . 3) 0.000053.T + 0.016 0.000022.T t 0.822 353.T-1
f o r T2573 K f o r Tz410 K
*regarded as independent o f T
The c o n t r i b u t i o n o f t h e s p e c i f i c heat t o
the o v e r a l l heat capacity a t d i f f e r e n t

h
temperatures were c a l c u l a t e d t a k i n g i n t o
d
I consideration t h e temperature dependence
Y
b-4 o f the s p e c i f i c heat o f the i n i t i a l mate-
I
cn
Y r i a l and the product formed as w e l l as
T
v conversion degree c a l c u l a t e d from the

.r
3
U 10 - thermogravimetric curve. The c o n t r i b u t i o n

xm of dehydration and r e a c t i o n heat was

U obtained i n t h e f o l l o w i n g way. I n t h e
c,
m case o f gibbsi t e t h e DTA curve was
aJ
c 6 t
g r a p h i c a l l y integrated, q u a n t i f i e d using
-1 I\
I t h e value o f 1890 kJ.kg-l ( r e f . 6 ) f o r

2
I
?
a

heats o f water desorption reported by

Fig. 1. Temperature dependence o f
the o v e r a l l heat capacity o f g i b b s i t e D z h i g i t e t a]. ( r e f . 7). I n F i g . 1 the
( f u l l line) and z e o l i t e 1% (dashed sum of both c o n t r i b u t i o n s i s p l o t t e d .
line).
642

The f i r s t maximum a t about 590 K i n t h e g i b b s i t e curve i s due t o a p a r t i a l

conversion t o boemithe, the decomposition o f which i s revealed by t h e endo-
thermic peak a t about 830 K.

Test device
The t e s t device used consists o f a s t a i n l e s s s t e e l tube ( i n n e r diameter
45 mm, length 20 cm) i n which a second tube ( i n n e r diameter 15 mm, l e n g t h 14 cm,
w a l l thickness 2 . 5 mm) i s centred. Heat f l u x i n a x i a l d i r e c t i o n i s prevented
by a l a y e r o f mineral wool f i l l i n g o u t t h e space between the ends o f both tubes.
I n t h e middle, mantled thermocouples a r e brazed onto both these tubes. The ma-
t e r i a l s t o be tested a r e contained i n space A i n s i d e the i n n e r tube and/or
space B between t h e tubes. The device i s placed i n a t u b u l a r furnace heated up
t o a temperature between 770 and 900 K and t h e temperatures o f both tubes a r e
registered.

RESULTS AN0 DISCUSSION

Heating curves o f the o u t e r (a) and inner (b) tube of the t e s t device con-
t a i n i n g z e o l i t e 13X i n space A a r e shown i n F i g . 2. Curve ( c ) represents t h e
temperature increase o f the i n n e r tube as a f u n c t i o n o f time f o r t h e same case
c a l c u l a t e d according t o the numeric method described i n the previous section.
I n c o n t r a s t t o the c a l c u l a t e d data (curve c), t h e temperature experimental
determined approaches 373 K a f t e r a s h o r t time and remains constant over a
r e l a t i v e l y long time i n t e r v a l . This
d e v i a t i o n can be explained by prog-
r e s s i v e desorption o f water vapour
the z e o l i t e l a y e r and i t s recondensa-
t i o n a t t h e cooler i n n e r tube. This
h
Y
v
process contributes t o the heat f l u x
W
L through the z e o l i t e l a y e r o n l y i n t h e
=I
CI
m temperature range up t o 373 K regard
L
a
W l e s s of the f i r e r e t a r d a t i o n aspect
E
F and, therefore, has n o t been taken
i n t o consideration i n the mathema-
t i c a l model. A t higher temperatures
both the experimentally determined
30(
and t h e c a l c u l a t e d curve a r e i n sa-
10 20
t i s f a c t o r y agreement. The s l i g h t
Time (min) d e v i a t i o n may be due t o a minor h e a t
F i g . 2. Measured (a,b) and calcu ated f l u x i n a x i a l d i r e c t i o n . Experimental
( c ) temperature of the o u t e r ( a ) and and c a l c u l a t e d r e s u l t s were a l s o i n
i n n e r (b,c) tube of the t e s t dev ce
described i n the t e x t . good agreement when space A and/or B
 643

c o n t a i n e d m i n e r a l wool, z e o l i t e 13X and g i b b s i t e i n v a r i o u s c o m b i n a t i o n s .

Since c a l c u l a t i o n s gave r e 1 i a b l e r e s u l t s , temperature p r o f i l e s o f d i f f e r e n t
v a r i a n t s of a s i m p l e model c o n s i s t i n g o f a h e a t - i n s u l a t e d s t e e l t u b e have been
c a l c u l a t e d i n o r d e r t o compare t h e e f f e c t i v e n e s s o f z e o l i t e s and c o n v e n t i o n a l
f i r e - r e t a r d a n t m a t e r i a l s . Some t y p i c a l r e s u l t s o f such c a l c u l a t i o n s a r e i l l u s -
t r a t e d i n F i g s 3-5. Only t h e temperature o f t h e t u b e i s given, w h i c h i s p r a c t i -
c a l l y c o n s t a n t i n r a d i a l d i r e c t i o n because o f t h e h i g h h e a t c o n d u c t i v i t y . The
i n n e r space of t h e t u b e i s empty o r c o n t a i n s m a t e r i a l s consuming h e a t i n l a t e n t
form. A c o n s t a n t ambient temperature o f 1073 K i s supposed.
Curve b i n F i g . 3 i l l u s t r a t e s t h e h e a t - r e t a r d i n g e f f e c t o f z e o l i t e 13X com-
pared t o t h e e f f e c t o f a m i n e r a l wool l a y e r ( a ) o f t h e same t h i c k n e s s . S i n c e t h e
weight o f structures i s generally t h e l i m i t i n g f a c t o r i n b u i l d i n g , curve c rep-
r e s e n t s t h e temperature i n c r e a s e o f t h e s t e e l t u b e surrounded b y g i b b s i t e , t h e
w e i g h t o f which corresponds t o t h a t o f t h e z e o l i t e l a y e r . Up t o a b o u t 570 K
z e o l i t e p r o v i d e s t h e b e s t p r o t e c t i o n ; however, a t h i g h e r temperatures g i b b s i t e
i s more e f f e c t i v e . F i g . 4 demonstrates t h e e f f e c t o f combined a p p l i c a t i o n of
z e o l i t e and h e a t - i n s u l a t i n g m a t e r i a l s . The t u b e i s assumed t o b e i n s u l a t e d w i t h
a 3 cm t h i c k l a y e r t h e i n n e r s h e l l o f which c o n s i s t s o f z e o l i t e 13X ( t h i c k n e s s
r z ) and t h e o u t e r one o f m i n e r a l wool ( t h i c k n e s s rm). Heat r e t a r d a t i o n approaches
a maximum when r z / ( r z t r m ) = 0.66. Combined a p p l i c a t i o n o f z e o l i t e and a conven-
t i o n a l f i r e - i n s u l a t i n g m a t e r i a l r e s u l t s n o t o n l y i n a s l i g h t improvement o f t h e
e f f e c t i v e n e s s b u t a l s o i n a decrease o f w e i g h t .

h
E
.r
E
v

P
ir

L
0.5
1

Time (min) rz/(rz+rmw)

F i g . 3. Temperature o f a s t e e l t u b e F i g . 4. Time r e q u i r e d t o h e a t an i n s u -
( o u t e r 0 9, i n n e r 0 7 cm) vs t i m e . l a t e d s t e e l t u b e ( o u t e r 0 9, i n n e r 0 8
Ambient temp.: 1073 K. I n s u l a t i o n : cm) a t 1073 K ambient temp. up t o t h e
(a) 3.9 cm m i n e r a l wool, ( b ) 3.9 cm i n d i c a t e d temperature vs r Z / ( r Z + r m ) .
z e o l i t e 13X, ( c ) 3 cm g i b b s i t e .
644

The e f f e c t o f heat-consuming m a t e r i a l s i n
t h e inner p a r t o f the tube i n s u l a t e d o u t s i d e
w i t h a 3 cm l a y e r o f mineral wool i s i l l u s -
t r a t e d i n F i g . 5 (curves a-c). Compared t o
t h e empty tube (a) a z e o l i t e f i l l i n g consider-
a b l y r e t a r d s the temperature increase (b);
however, a t higher temperature again g i b b s i t e
i s more e f f e c t i v e ( c ) . The most e f f e c t i v e
p r o t e c t i o n provides a g i b b s i t e f i l l i n g com-
bined w i t h z e o l i t e 13X ( 2 cm) and mineral
wool ( 1 cm) surrounding the tube (curve d ) .
Curve ( e ) represents the heating curve when
i n the combination (d) z e o l i t e i s replaced
40 80 120 by g i b b s i t e on weight basis.
Time (min)
Fig. 5. Temperature o f a s t e e l tube
(outer 0 9, i n n e r 0 8 cm) vs time.
Ambient temp.: 1073 K. For f u r t h e r
d e t a i l s see t e x t .

CONCLUSIONS
Z e o l i t e s a r e more e f f e c t i v e i n f i r e r e t a r d a t i o n than conventional heat-insu-
l a t i n g m a t e r i a l s . Enclosi’ng b u i l d i n g s t r u c t u r e s o r constructions t o be protected
against damage from f i r e , they e x h i b i t an e x c e l l e n t e f f e c t i v e n e s s i n the temper-
a t u r e range up t o about 570 K. Thus they e s p e c i a l l y provide p r o t e c t i o n f o r i n -
flammable and heat-sensitive b u i l d i n g s t r u c t u r e s and goods. F i l l e d i n t o e x i s t -
i n g o r created hollow p a r t s w i t h i n s t r u c t u r e s t o be protected, z e o l i t e s e x h i b i t
an a d d i t i o n a l p r o t e c t i v e e f f e c t . However, g i b b s i t e proved t o be more e f f e c t i v e
as f i r e - r e t a r d a n t m a t e r i a l i n t h e temperature range above 600 K. Combined a p p l i -
c a t i o n o f z e o l i t e s , g i b b s i t e and conventional h e a t - i n s u l a t i n g m a t e r i a l s ensures
the b e s t p r o t e c t i v e e f f e c t . Mathematical modelling o f simple f i r e - p r o t e c t e d
s t r u c t u r e s provides t h e p o s s i b i l i t y t o c a l c u l a t e the optimum choice o f m a t e r i a l
and l a y e r thickness i n c o n f o m i t y with constructional considerati ons.

REFERENCES
1 M.N. Ulzisik, Heat Conduction, Wiley, New York, 1980.
2 D.M. Young and R.T. Gregory, A Survey o f Numerical Mathematics, Addison-
Wesley, Reading, Massachusetts, 1972.
3 R. Doring, Koch und H. Zeltner, Wametechnische I s o l i e r u n g , VEB Fachbuch-
verlag, Leipzig, 2nd ed., 1981.
4 H.Y. Wong, Heat Transfer f o r Engineers, Longman, London, 1977.
5 C.H. Shomate and ELF. Naylor, J. Am. Chem. SOC. , 67 (1945), 72-75.
6 Tran-huu Th’e, i n P. Pascal ( E d i t o r ) , Nouveau T r a i t 6 de Chimie Minerale,
Vol. 6, Masson, Paris, 1961, p. 582.
7 O.M. Dzhigit, A.V. Kiselev, K.N. Mikos, G.G. M u t t i k and T.A. Rahmanova, JCS
Trans. Far. SOC. I, 67 (1971), 458-467.
111. ION EXCHANGE AND DETERGENT BUILDING
This Page Intentionally Left Blank
H.G.Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

INDUSTRIAL PRODUCTION OF ZEOLITES

E. ROLAND
Degussa AG, Inorganic Research Department,
Rodenbacher Chaussee 4,6450 Hanau 11, FRG

ABSTRACT

The manufacture of zeolites is exemplified by the industrial synthesis of NaA zeolite, NaY
zeolite and ZSMJ. Chemical, technical and economic factors are considered. Dealumination
using Sic14 and a shaping process are described as additional steps in the zeolite product design.

INTRODUCTION

The beginning of the industrial production of zeolites dates back to the year 1954, when Union
Carbide Corporation first commercialized Linde molecular sieves. However, much pioneering
work was still necessary at that time to scale-up the syntheses. A report by MiZton (ref. 1) gives
an impression of the many difficulties that had to be overcome before the first manufacturing
plant could be put into operation later in 1957: "Major problems solved before this plant was
constructed were: filtration of the fine particle zeolite, continuous drying and activation, reduced
crystallisation times and raw material utilisation efficiency."
Since then, zeolites have been developed into key materials in the chemical industry for a wide
field of applications ranging from ion exchange to the catalysis of petrochemical processes. In
1987, the production of synthetic zeolites had grown to an estimated 460,000 metric to& world-
wide, and this from not much more than a few hundred tons per year in the late fifties and about
60,000tons in 1975 (refs. 2-4). The manufacturing technology had to reach a high standard to
make possible the extensive use of zeolites indicated by these figures. However, in spite of the
importance of this aspect of zeolite chemistry, it has been'only rarely reviewed (refs. 5-7).
It cannot be the purpose of this contribution to provide a comprehensive treatise on the indu-
strial production of zeolites, due space limitations. Rather, an attempt is made to describe some
typical zeolite production processes on the basis of the experience reported in the patent litera-
ture. Since the commercial importance of the zeolite material was a criterion for its choice as an
example, a brief survey covering the economic situation of different types is provided, followed
by a technical discussion of their industrial synthesis.
646

COMMERCIALA S P E W OF ZEOLllT PRODUCTION

As a result of vigorous research programs in academia as well as in industry, more than three
hundred types of zeolites or related molecular sieves (ref. 8) based on about sixty different struc-
tures are known at the moment. However, only few of these types are actually produced. Table
1gives an estimation of zeolites manufactured in amounts of more than one hundred tons per
year. The figures in this table are based on published data (refs. 3,4). For example, the amount
of zeolite Y was estimated from the quantity of FCC catalyst sold worldwide (ref. 4).

TABLE 1

Synthetic Zeolites Produced in Bulk Amounts

type estimated annual major fields

usage worldwide -
1987 of application
(thousands of metric tons)

zeolite A 400 detergents

adsorption
zeolite Y 50-60 FCC
zeolite X 2 adsorption
ZSM-5 and 1 catalysis of petro-
analogues chemical processes
mordenite 0.3 C, /CI isomerization
dewaxing

The zeolites listed in Table 1 can be divided in two groups:

- The "commodity" zeolites A, X and Y
First introduced in the chemical industry between 1954 and 1960, these zeolites now represent
more than ninety-nine percent of all the zeolites produced. Much development work has been
invested in adjusting these zeolites to the requirements of the different applications.
This inlcudes:
- chemical modifications, for instance by ion exchange and dealumination procedures;
- variations in particle size and crystal morphology;
- forming.
Even after more than thirty years of development,many patent applicationsare filed every year
dealing with the synthesis and the modifications of these zeolites. This clearly shows that im-
provements are still possible.
- The "specialty" zeolites ZSM-5 and large-port mordenite
Because of their great potential for catalysis in petrochemistry and for the synthesis of organic
 647

intermediates, industrial research programs mainly focus on these and similar materials at the
moment. The production capacities are still comparativelylow for two reasons:
- Applications requiring bigger quantities are still under development.
- Manufacturingprocesses are more complicated than for the "commodity"zeolites, as the
syntheses have to be done under elevated pressure and often in the presence of structure-
directing agents.

PRODUCTION TECHNOLOGY OF ZEOLKES

The manufacturing of zeolite powders is only one step in a sequence of processes by which
materials for very specific applications are designed. In many cases additional treatments are
necessary to modify the properties of the zeolite by changing the cations located in the pore
systems, or even the frameworkcomposition.Finally, a formingprocedure is included,since most
applicationsrequire shaped materials.
It is essential that the different steps are specifically matched according to the properties of
the desired product. Thus, the sequence of these steps can be varied. In particular, shaping can
be done before an ion exchange. In some processes for the preparation of binderless pellets, the
starting materials are shaped and converted to a zeolite afterwards.
The different parts of the industrial product design - synthesis of zeolite powders, modifica-
tion and shaping - are discussed below, taking specific examples for illustration.

Molecular sieve zeolites are produced in industry either from aluminosilicatehydrogels or by

conversion of clay minerals. The hydrogels can be prepared from various sources of silica and
alumina, which are listed in Table 2. Depending on the choice of these starting materials as well
as on the requirements of the synthesis, bases or mineral acids have to be added. For some pre-
parations a structure-directingagent is needed as well.
The kinds of starting materials, the method of mixing them, determine the structure of the re-
sulting gel. The nature of the gel, in turn, influences the rate of the subsequent crystallization,
the particle size distribution, and the formation of impurities.
Production processes for NaA zeolite, NaY zeolite and E M - 5 are discussed to demonstrate
how the synthesis of a zeolite can be directed by the conditions of the gel preparation and the
crystallization to afford materials for the applications envisaged, and how it can be done in an
economical way at the same time.
648

TABLE 2
Silica and Alumina Sources
in Zeolite Manufacturing Processes

sodium silicate solutions sodium aluminate solutions

amorphous solid silica: aluminium salts
various precipitated silicas, (sulfate, chloride)
blast furnace slag,
fly ash from the production
of silicon
silica sol colloidal alumina

c Iays
(raw kaolin, metakaolin, halloysite)
volcanic glasses

By far the greatest amount of NaA zeolite is consumed in the manufacturing of detergents,
since it was decided in many countries to replace phosphate as the builder component respon-
sible for the reduction of the water hardness: in 1987, 375,000metric tons of NaA zeolite were
produced worldwide only for the detergent industxywith a forecast of 500,000 metric tons in 1990
(ref. 3). This commercial success of zeolite chemistry could only happen because it was possible
to develop a zeolite with properties which are expected of a detergent builder:
- high Ca binding capacity and rate;
- good dispersability;
- low sedimentation tendency;
- low abrasiveness.
Translated into the language of a zeolite chemist, this means: A NaA zeolite suited as a deter-
gent builder should be free of impurities (in this case, hydroxysodalite is a possible impurity, if
the reaction conditions are not chosen properly); it should have a small average particle size
(approximately4 q~ and less) and a narrow particle size distribution. In addition, the zeolite cry-
stals must not have sharp edges or comers.
Fig. 1shows an electron micrograph picture of a zeolite meeting these requirements. It will
be outlined how such a zeolite can be synthesized on an industrial scale by reaction of a sodium
silicate and a sodium aluminate solution.
This combinationof educts is the most commonly used for the manufactureof detergent-grade
NaA zeolite, as in the processes of HENKEL, DEGUSSA and PQ, for instance. Sodium silicate
solutionsare easily handled and inexpensivestarting materials. For the synthesisof NaA zeolite,
 649

Fig. 1. Electron micrograph showing crystals of detergent NaA zeolite.

various technical qualities are available, which differ in the content of Na2O and Si02:
- a sodium silicate solution prepared by the fusion of selected sands with soda ash, having a
content of 8 percent Na2O and 27 percent Si02 (Na2O/SiOz = 1 :3.4);
- a sodium silicate solution synthesized via hydrothermal decomposition of sand by caustic,
containing 14 percent Na2O and 26 percent Si02 (Na2O/SiOz = 1 : 1.9).
For the preparation of the sodium aluminate solution, hydrated alumina is usually digested by
caustic.
The clay route (HUBER, ETHYL)is less often applied. There can be a disadvantage of this
method, in that iron impurities in metakaolin cause a coloring of the product zeolite. By addi-
tion of iron complexingagents (ref. 9) or by special grinding of the metakaolin (ref. 10) the bright-
ness can be improved. The MIZUSAWA process, which starts from an acid-treated clay, has
been described elsewhere (ref. 11).
The reaction mixture for the synthesis of zeolite NaA (Na2OA1203'2Si02'4.5H20) can be
varied within wide boundaries of the overall composition. For the efficiency of the industrial
process, however, it is necessary to find the best composition in terms of product quality, yield
and synthesis time. A possible composition for the production of NaA zeolite meeting these re-
quirements is represented by the ratios 1 (ref. 12). An excess of alumina is employed in this
example.

2.11 Na2O :A1203 : 1.74 Si02 :77.6 H20

I

As mentioned above, the average particle size is avery critical parameter of the zeolite product.
It is mainly influenced by
- the Na20/H20 ratio in the reaction mixture: high basicity favors the formation of small
particles (ref. 13);
650

- the mixing sequence and the addition rate of the different components;
- the temperature of the gel precipitation;
- the stirringhhearingenergy applied during the gel preparation;
- seeding (ref. 6).
Considering these factors, it becomes quite clear that the gel preparation is the crucial step with
regard to the particle size in the synthesis of a detergent zeolite.
In Fig. 2, the flow diagram for the preparation of detergent NaA zeolite is shown as an example
(refs. 14, 15). Usually, the gel precipitation temperature is between 50 and 80 "C, the tempera-
ture during the crystallizationbeing slightly higher (80-90 "C).The time required for the gel pre-
paration may vary from 0.5-1.5 hours, whereas 1.0-2.0 hours are necessary for the zeolite crystal-
1ization.

Fig. 2. Process for the production of NaA zeolite.

As indicated in Fig. 2, after the crystallization the zeolite suspension is filtered with a filter
press, a rotary filter or a band filter. The filtrate containingthe mother liquor and the wash water
is usually characterized by low concentrations of sodium hydroxide. It can be used for the neu-
tralization of acidic effluents. If the reaction mixture contained an excess of Al203,as in compo-
 651

sition 1,there is also some sodium aluminate present. In this case, the filtrate is concentrated
and recycled to the digestion of the hydrated ,4203, for example (ref. 15). For economic and en-
vironmental reasons, complete utilization of the mother liquor is essential in the manufacturing
of zeolites.

Many detergent manufacturers prefer a zeolite slurry instead of a zeolite powder. Water and
a suspension stabilizer, which prevents rapid sedimentation, are then added to the filtered
zeolite. Otherwise, the zeolite is spray-dried.
It should be stressed that in most cases the entire process is run semi-continuously. Whereas
it is possible to prepare the gel in a continuous way in zeolite syntheses (ref. 16), the crystal-
lization is usually carried out batch-wise in reaction vessels having a size of sometimes more than
100 m3. The typical zeolite yield obtained this way is about 120 kg/m3 (ref. 7).

Zeolite Y is mainly employed as a component of FCC catalysts in a proportion of 15 to 40

percent. For this application, the "standard" NaY zeolite is subjected to rare earth and ammo-
nium ion exchanges as well as to calcination steps. This process has been discussed in detail in
the literature (refs. 17,18).
The following properties are expected of a NaY zeolite suited as a starting material for the
zeolite component of a FCC catalyst:
- high purity: the presence of the zeolites P,gmelinite and phillipsite, which are thermodyna-
mically more stable and are possibly formed as byproducts, is to be avoided;
- good crystallinity;
- high surface area;
- high thermal and hydrothermal stability, which correlates with a high SiWAl2O3 ratio in the
zeolite.
The enhancement of the SiOdAl203 ratio has been the subject of intensive research efforts.
High-quality NaY zeolites obtained by direct synthesis are characterized by si02/A1203 ratios
between approximately 5.0 and 5.6. Values up to 7.8 are mentioned in the literature (ref. 19),
but the corresponding materials are difficult to obtain:

It has been found that the SiOdAl203 ratio in the zeolite product is highly sensitive to the
excess alkalinity in the batch, which is defined as [(NaOH)-(NaAlO2)ySiO2 (ref. 20). Lower
values of this excess basicity result in higher SiodAl203 ratios in the zeolite prepared (ref. 21).
Concurrently, however, the crystallization time has to be multiply prolonged. A tendency to the
formation of more siliceous Y zeolites can also be observed, if the SiOdAl203 ratio in the reac-
tion mixture is increased considerably: to raise the SiodAl203 ratio in the zeolite from 4.2 to
6.5, it has to be enhanced by a factor of 5 in the gel (ref. 22). Thus, the direct synthesis of Si02-
rich Y zeolites is not economical. Zeolites of this kind are better manufactured by dealumina-
tion of a "standard" NaY zeolite.
652

Fig. 3. Process for the production of NaY zeolite (ref. 24).

It is evident from a comparison of the patent literature that most of the reaction mixtures yiel-
ding NaY zeolites with SiOdAl203= 5.0-5.6have the compositions2. Various combinations of
the starting materials mentioned in Table 2 are used as reactants.

(2.5-3.5) Na2O : A1203 : (8.0-10.0)Si02 : (120-180) H20

2

In the first syntheses of NaY zeolite the gel slurry had to be aged for a day or more at ambient
temperature. Seed crystals (of zeolite X, for instance) could be added to the ready gel instead,
but at the moment the addition of various seeding mixtures is in common use. The latter pre-
sumably contain particles having at least partially a zeolite structure (ref. 23).The chemical com-
positions of these nucleation center slurries, which are described in the examples of the patent
literature, are specified by the ratios 1.The exact way these seeding mixtures are prepared and
aged strongly influences the rate of the NaY zeolite crystallization.
 653

Depending also on the synthesis mixture and the kind of gel prepared, the time necessary to
obtain a well crystallizedNaY zeolite varies from 12 to 30 hours. The reaction temperatures are
in the range 90 and 100 "C.Vigorous stirring may cause some problems, as it often results in the
formation of gmelinite and phillipsite as impurities. A problem can also arise from sequential
crystallizationyielding mainly zeolite P.This can be avoided by dilution of the zeolite slurry to
reduce the temperature or by quick filtration.
Fig. 3 shows a process published in a GRACE patent (ref. 24) as an example for the synthesis
of NaY zeolite. A characteristicof this process is the utilization of the mother liquor. In the pre-
paration of NaY zeolite, this is a weak sodium silicate solution. By addition of an aluminium
sulfate solution a silica-alumina hydrogel is formed, which is used as a starting material in the
next synthesis. It is also possible to precipitate amorphous silica from the mother liquor. A direct
recycling of unprocessed crystallization filtrate is critical, however, because the mother liquor
possibly contains nucleation centers of impurities.

Whereas zeolite Y is synthesized for one major catalytic application, ZSMJ can act as a cata-
lyst for petroleum refining as well as for many different petrochemical processes (Table 3), in
which it shows the unique property of shape selectivity(refs. 25,26).Several additionalprocesses
are currently in the development stage.

TABLE 3
Major Commercialized Processes
Catalyzed by ZSM-5

FCC (Octane Enhancing)

Xylene lsomerization
Dewaxing
MTG (Methanol to Gasoline)
Ethylbenzene Synthesis (Mobil-Badger)
p-Methylstyrene Synthesis

Each of these processes requires a speciallydesigned catalyst:the zeolite component may vary
in the siOz/A1203ratio, the number and strength of acid sites, the crystal size and morphology.
In addition, for the final molded catalyst, the nature and amount of binder, the size and the po-
rosity of the agglomerates are important. The result is a catalyst with very special properties re-
garding catalytic activity and life-time.This also means that for each application a very special
type of ZSM-5 has to be synthesized.The ability to select the kind of ZSMJ best suited for a
654

certain process is part of the know-how of the catalyst manufacturer.

The development of a ZSM-5 type zeolite in this way becomes all the more difficult as the
number of synthesis parameters is substantially increased compared to the preparation of the
"commodity" zeolites by the need for a structure-directing agent ("template"). Some template-
free laboratory preparations are described in the literature (ref. 27), but this author is not aware
that a corresponding industrial production process has been realized so far.
Among the many possible templates the tetrapropylammonium cation is the most favored
(ref.27). According to the the targeted zeolite, the syntheses are performed in autoclaves having
volumes from 0.5 m3 (pilot plant size) up to about 10m3at temperatures between 100and 180"C,
corresponding to an autogenous pressure of 1-10 atm. If high concentrations of tetrapropylam-
monium salts and high temperatures are used, decomposition to amine and propene occurs,
effecting a rise of the pressure and increasing the number of possible templates present. The
time necessary for the synthesisvaries from 20 hours to several days, depending on the gel com-
position and the reaction conditions. Especially the choice of the silica source has a great influ-
ence on the crystallization rate (ref. 27).
After crystallizationand drying, the zeolite is calcined in air or oxygen at approximately 600°C
to remove the organic template from the pore systems. The effluent air contains C02 and NOx,
which can cause pollution problems. This is one of the reasons why the production of ZSM-5 in
the absence of templates is highly desirable.

As indicated above, the as-synthesizedzeolite can be subjected to additional treatments,which

change its properties. The methods for the chemical modification can be classified in two groups
of reactions:
- those, which leave the zeolite framework unchanged (exchange of non-framework cations,
silanation), and
- those, which affect the framework composition (dealumination).
In the chemical industry, four dealumination methods are currently practiced (refs. 28-31):
- acid treatment;
- high-temperature steam treatment (ultrastabilization) of NH4Y zeolite with optional
subsequent acidification;
- reaction of NH4Y zeolite with an aqueous solution of (NH4)zSiFa ;
- reaction of NaY zeolite with gaseous Sic14
Dealurninationprocedures were originally developed to improve the thermal and hydrother-
mal stability of zeolite Y in FCC catalysts. More recently, however, the hydrophobic properties
of Sia-rich Y zeolites have attracted much interest for the removal of organic components from
humid effluent air or fromwater. The followingproperties are expected of a Y zeolite suited for
this purpose:
 655

- excellent crystallinity to ensure high adsorption capacities: the framework must not under-
go partial destruction during dealumination;
- high hydrophobicity: Si02/&03 ratios > 50 are requisite.
Dealumination using Sic14 is the best method for reaching this goal, as very high SiWAl2O3
ratios can be obtained from NaY zeolite in one step without loss of crystallinity. A process based
on this reaction (equation 1) is under development at the moment.

A flow chart (Fig. 4) shows the different steps of this procedure. The most critical part is de-
finitely the reaction between Sic14 and calcined NaY zeolite at temperatures higher than 300 OC,
as reaction (1)is very exothermic. In the next step the formed NaAlC14 must be carefully washed
out, before the product can be filtered and dried.

Fig. 4. Process for the dealumination of NaY zeolite with SiC14.

656

ShaDine
Zeolites are commerciallyavailable in a variety of different shapes: microgranulates, spheroi-
dal agglomerates, extrudates and molded bodies with a honeycomb-like structure, for instance.
The different forming procedures applied constitute a science in itself (ref. 32).
Here the forming of NaA zeolite into a granulate, which can be used as a desiccant in insula-
ting glass, is given as an example. The world market for such a zeolite product is about 8000
metric tons per year at the moment. A product best suited for this purpose would have the fol-
lowing characteristics:
- high adsorption capacity for water, but exclusion of gases, which are components of air or
which are applied for insulating (SF6 for instance);
- narrow agglomerate size distribution (diameter: 1-2 mm);
- high attrition resistance.
The first of these requirements can be met by a zeolite A having a pore size of 3 k As a con-
sequence, NaA zeolite is partially potassium-exchanged and granulated. Possible binders are
clays, such as a bentonite. At DEGUSSA, a more direkt method is used, which is based on the
choice of sodium silicate as a binder for 4 A NaA zeolite (ref. 33). By this "molecular glue" the
pores of the NaA zeolite are partially plugged, creating the 3 A characteristics required. The
shaping process is illustrated in a simplified way in Fig. 5: In a mixer a sodium silicate solution
is sprayed onto NaA zeolite powder. The resulting mixture, which contains the agglomeration
nuclei, is transferred to a balling pan. There, the particles are enlarged in size and attain a sphe-
roidal shape of high strength. Afterwards the green pellets are classified, dried and calcined.

Fig. 5. Process for the production of a NaA zeolite granulate having 3 A Characteristics.
 657

CONCLUSION: Future Developments

There is no doubt that in the next years the production technology of zeolites will concentra-
te mainly on highly sophisticated materials. For example, the growing demand for ZSM-5 and
related zeolites (for instance borosilicates) will be an incentive to improved manufacturing pro-
cesses. In particular, it will be necessary to produce these materials in a more inexpensive way.
In this context it would be a major achievement if the manufacturingcould be done in the absence
of structure-directingagents. Lower prices for these zeolites will make them competitive for ap-
plications still covered by other materials which are less expensive at the moment.

Besides these topics, the modificationof the "commodity"zeolites to refined materials for new
applications will continue to be the subject of development efforts. In addition, other molecular
sieves, which were for a long time neglected and stored on the laboratory shelves, will be re-dis-
covered for new applications. For instance, there is - more than twenty years after its first pre-
paration - currently a growing interest in zeolite Beta as a catalyst in oil refining (ref. 34).
In the long run, some members of the Alp0 family, where by now a whole variety of new ma-
terials is available on the laboratory scale (ref. 8), could open totally new areas of application for
molecular sieves. A spectacular example in this regard is the recently discovered alumino-
phosphate-based molecular sieve VPI-5,which has a free-pore-sizediameter of more than 10 A
(ref. 35).
Economic success, however, will mostly depend on the prolific interaction of research, deve-
lopment, application engineering, manufacturing and commercialization, which has been so
efficient in the past.

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658

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This Page Intentionally Left Blank
H.G.Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

CALCIUM AND MAGNESIUM EXCHANGE I N Na-A, Na-X AND THEIR PRECURSOR GELS

LOVAT V.C. REES

P h y s i c a l Chemistry L a b o r a t o r i e s , I m p e r i a l C o l l e g e o f Science and Technology,
London SW7 2AY ,(England)

ABSTRACT
Na-Ca and Na-Mg b i n a r y and Na-Ca-Mg t e r n a r y exchange i s o t h e r m s have been
determined i n z e o l i t e A . The e f f e c t o f t e m p e r a t u r e and n o r m a l i t y o f t h e
s o l u t i o n phase on t h e exchange e q u i l i b r i u m has been s t u d i e d . Standard f r e e
e n e r g i e s , e n t h a l p i e s and e n t r o p i e s have been c a l c u l a t e d f r o m t h e b i n a r y
i s o t h e r m data. The b i n a r y isotherms have a l s o been determined i n samples o f
z e o l i t e A and X g e l s as a f u n c t i o n o f c r y s t a l l i z a t i o n t i m e and t h e s t a n d a r d
f r e e e n e r g i e s o f exchange have been c a l c u l a t e d . The k i n e t i c s o f t h e b i n a r y
exchange r e a c t i o n s have been measured i n t h e s e amorphous g e l samples and
compared w i t h t h e k i n e t i c s i n t h e c o r r e s p o n d i n g c r y s t a l l i n e z e o l i t e s .

I O N EXCHANGE I N ZEOLITE A
C r y s t a l l i n e z e o l i t e A i s used ( r e f . l ) , w h i l e z e o l i t e X has been suggested
( r e f . 2 ) as a b u i l d e r i n d e t e r g e n t f o r m u l a t i o n s t o r e p l a c e phosphates which a r e
banned, o r whose c o n c e n t r a t i o n s a r e s e v e r e l y 1i m i t e d , i n many c o u n t r i e s through-
out t h e world. Z e o l i t e b u i l d e r s exchange t h e Ca2+ and Mg2+ i o n s p r e s e n t i n
hard waters w i t h t h e Na' i o n s r e s i d e n t i n t h e z e o l i t e s . The s e l e c t i v i t y o f
Na-A towards t h e i n g o i n g d i v a l e n t i o n i s v e r y l a r g e as can be c l e a r l y seen i n
t h e exchange isotherms i n F i g . 1 where Ca, and Mg, and Ca, and Mg, represent
the respective equivalent cation fractions o f the ingoing divalent ions i n the
z e o l it e phase, z, and s o l u t i o n phase, s ( r e f . 3 ) . The c o r r e c t e d s e l e c t i v i t y
c o e f f i c i e n t , Kc, can be expressed i n a c o n v e n i e n t f o r m f o r use w i t h t h e i s o t h e r m
d a t a by eqn.1. 2 4
Ca, (Na,)
K C z-2. - 2N . YtNaC1
.. r
(Naz) Ca, Y+CaC1
where N i s t h e t o t a l n o r m a l i t y o f t h e s o l u t i o n phase and Y+- i s t h e a c t i v i t y
~

c o e f f i c i e n t o f t h e i n d i c a t e d s a l t i n t h e m i x e d s a l t s o l u t i o n phase. The
c o r r e c t i o n i n t r o d u c e d by t h e l a s t two terms i n eqn.1 removes t h e s e l e c t i v i t y o f
t h e exchange i n t r o d u c e d by t h e s o l u t i o n phase. Thus, t h e c o r r e c t e d s e l e c t i v i t y
c o e f f i c i e n t i s a q u a n t i t a t i v e r e p r e s e n t a t i o n o f t h e s e l e c t i v i t y o f t h e exchange
a s s o c i a t e d w i t h t h e z e o l i t e phase o n l y . Eqn.1 q u a n t i f i e s t h e c o n c e n t r a t i o n -
v a l e n c y e f f e c t which i s c l e a r l y demonstrated i n Fig.1. Decreasing s o l u t i o n
phase n o r m a l i t y r e s u l t s i n i n c r e a s i n g s e l e c t i v i t y i n the exchange r e a c t i o n
towards t h e i n g o i n g d i v a l e n t i o n .
662

EXPERIMENTAL
The chemical a n a l y s i s o f t h e z e o l i t e A used i n these s t u d i e s gave an almost
i d e a l u n i t c e l l composition o f
Nal 112. O O A l O2 . 12 .08Si02] 26 .8H20
A t l e a s t 5 days were allowed f o r each p o i n t t o come t o e q u i l i b r i u m i n t h e
isotherms a t 65OC and 10 days a t 25OC.

RESULTS
The c o r r e c t e d s e l e c t i v i t y c o e f f i c i e n t s , Kc, were c a l c u l a t e d f r o m t h e
i s o t h e r m data i n Fig.1 u s i n g eqn.1 and f r o m these t h e loglOKc vs Ca, o r Mg,
p l o t s i n Fig.2 and 3 r e s p e c t i v e l y were constructed. As i n d i c a t e d above these
p l o t s i n d i c a t e t h e s e l e c t i v i t y o f t h e z e o l i t e phase f o r t h e r e s p e c t i v e i n g o i n g
d i v a l e n t i o n as a f u n c t i o n o f l o a d i n g . Logl0KC values g r e a t e r than z e r o
i n d i c a t e preference f o r t h e d i v a l e n t i o n over t h e Nat i o n by t h e z e o l i t e phase.
Fig.2 and 3 show t h a t Na-A p r e f e r s Ca2' i o n s up t o l o a d i n g s g r e a t e r t h a n 90%
and Mg2' i o n s up t o %40%. Thus Na-A i s a b e t t e r b u i l d e r towards Ca2+ t h a n
2t
Mg . These f i g u r e s , a l s o show t h e enhancement i n s e l e c t i v i t y f o r b o t h
d i v a l e n t i o n s as t h e temperature increases because o f t h e endothermic n a t u r e
o f t h e exchange r e a c t i o n .
The experimental p o i n t s i n Fig.2 and 3 were f i t t e d t a polynomial
equation o f t h e form

(2)
(where A, = Ca, o r MgZ). The r e s u l t i n g polynomials a r e g ven i n Table 1 and
t h e isotherms c a l c u l a t e d from these polynomials a r e drawn as continuous l i n e s
i n Fig.1 which c l e a r l y show t h e g o o d n e s s - o f - f i t o f t h e polynomial i n r e p r e s e n t -
i n g t h e experimental isotherms.
TABLE 1
Polynomial Equations o f loglOKc vs A,

Exchange Reaction Temp( O C ] Polynomi a1 Eqn

Nat + $Ca2 t 25 loglOKc = 2.83 - 6.03Caz t 11.5CaZZ - 9.11CaZ 3

65 = 3.41 - 5.28CaZ t 6.32CaZ2 - 4.01Caz 3

Nat -+ 3Mg2' 25 loglOKc = 1.46 - 2.66MgZ - 6.34MgZ2 + 5.08Mgz 3

65
= 2.61 - 7.74Mgz + 3.57MgZ 2

From these polynomials t h e c o r r e c t e d s e l e c t i v i t i e s , Kc, a r e 676 and 2570 f o r

Ca, = 0 and 28.8 and 407 f o r Mg, = 0 a t 25 and 65OC r e s p e c t i v e l y . These values
i n d i c a t e t h e v e r y h i g h i n i t i a l s e l e c t i v i t i e s f o r Ca2+ a t 25 and 65OC r e s p e c t i v -
ely.
 663

Fig. 1. Na/Ca and Na/Mg

b i n a r y exchange isotherms
0 0.2N; X 0.1N; 0 0.05N;
0 0.01N; 0.005N

1.6

\
0.0
20
b%K,
0
1.5

-0.8
1.0
00 '

-1.6
0.5

- 0 . 5
0

L
- 2.4
0.2 0.4 0.6 0.8 0.2 0.4 a6 08

Fig. 2 . Loglo Kc v s Ca, Fig. 3. Log10 K, vs Mg,

(Symbols same as i n Fig. 1 ) (Symbols same as in F i g . 1)
664

From these loglOKc p l o t s o r t h e polynomials i n Table 1 i t i s p o s s i b l e t o

c a l c u l a t e t h e standard f r e e energies, e n t h a l p i e s and e n t r o p i e s o f these exchange
reactions (ref.3). The standard q u a n t i t i e s so o b t a i n e d a r e l i s t e d i n Table 2.
TABLE 2
Standard Thermodynamic Q u a n t i t i e s f o r Exchange i n Z e o l i t e A

Exchange Reaction Temp('C) A G ~ AH& TA S~

kJ(g equiv)-l
t
Nat -+ 4Ca2 25 -2.68 12.2 14.9
65 -4.69 16.9
Nat +. $Mg2' 25 3.26 18.6 15.5
65 1.20 17.4

The TAS* values a r e very s i m i l a r f o r a l l f o u r exchanges l i s t e d i n Table 2.

The n e g a t i v e AG& values f o r t h e Ca2' exchange and t h e corresponding p o s i t i v e
values f o r t h e Mg2+ exchange a r i s e , t h e r e f o r e , from t h e l a r g e r endothermic
e n t h a l p i e s f o r t h e Mg2+ exchange. The d i v a l e n t i o n s have t o shed water molecul-
es associated w i t h t h e i r h y d r a t i o n s h e l l b e f o r e t h e y can e n t e r t h e channel
network o f z e o l i t e A . The endothermic d e h y d r a t i o n energy must be some 50%
g r e a t e r f o r Mg2' i o n s t h a n f o r Ca2' i o n s and i t i s t h i s i n c r e a s e i n d e h y d r a t i o n
enthalpy which produces t h e p o s i t i v e f r e e energy t o t h e Mg2' exchange r e a c t i o n .
When z e o l i t e A i s used as a b u i l d e r i n detergency, one i s d e a l i n g , a t
i t s s i m p l e s t concept, w i t h a t e r n a r y exchange r e a c t i o n . A l l such t e r n a r y
exchange r e a c t i o n s behave i n a manner s i m i l a r t o t h a t shown by Fig.4. Ternary
isotherms d i s p l a y a h i g h s e l e c t i v i t y f o r b o t h d i v a l e n t i o n s a t l o w Mg, and Ca,
loadings and i n t h i s r e g i o n o f t h e i s o t h e r m l i t t l e o r no d i v a l e n t i o n s remain
i n t h e s o l u t i o n phase a t e q u i l i b r i u m . A l l divalent ions, i n i t i a l l y i n the
s o l u t i o n phase a r e exchanged i n t o t h e z e o l i t e which r e s u l t s i n a s t r a i g h t l i n e
z e o l i t e phase composition curve, as seen i n Fig.4, a t low d i v a l e n t i o n l o a d i n g s .
When t h i s l i n e i s e x t r a p o l a t e d t o Na, = 0 i t i n t e r s e c t s t h e Ca-Mg a x i s a t a
value equal t o t h e Ca:Mg r a t i o i n t h e i n i t i a l s o l u t i o n phase. The c o n c e n t r a t i o n
o f d i v a l e n t i o n i n t h e s o l u t i o n phase g r a d u a l l y b u i l d s up w i t h i n c r e a s i n g
d i v a l e n t i o n l o a d i n g o f t h e z e o l i t e phase u n t i l , f i n a l l y , t h e Na, v a l u e
approaches zero and t h e Cas/Mgs r a t i o approaches t h a t o f t h e i n i t i a l s o l u t i o n
phase. The Mg, value a t t a i n s i t s i n i t i a l s o l u t i o n phase value l o n g b e f o r e
t h e Ca, value a t t a i n s i t s i n i t i a l value.
Mg, passes through a maximum i n a l l t e r n a r y isotherms measured i n our
laboratories. The magnitude o f MgZ a t t h e maximum depends on t h e Ca/Mg r a t i o
o f t h e i n i t i a l s o l u t i o n phase b u t t h e maximum always occurs a t a Na, v a l u e o f
a 0.33. The value o f Mg, i s found t o i n c r e a s e from . ~ 0 . 1 9 f o r a Ca/Mg r a t i o
o f 2 : l t o ~ 0 . 3 8f o r a Ca/Mg r a t i o of 1:2. It i s a l s o i n t e r e s t i n g t o n o t e
t h a t Mg, never increases above a value o f a0.4, t h e maximum found i n t h e b i n a r y
 665

Ca

Na 5 6
\,-4
0.2 0.4 0.6 0.8

Fig. 4. Na/Ca/Mg ternary exchange isotherm at 65OC. Initial solution phase

0.05N and Ca/Mg ratio o f 1:l. 0 Zeolite phase 0 Solution phase
Equilibrium compositions in each phase have the same number.

m
3

R e a c t i o n Tlme(hours)

Fig. 5. Ion exchange and water capacities o f zeolite A and X gels as a function
o f crystallization time.
666

exchange o f Ca-A w i t h Mg2' ions (ref.3) confirming t h e great d i f f i c u l t y o f

loading z e o l i t e A w i t h more than 2Mg2+ ions per u n i t c e l l when there are Ca2'
ions a v a i l a b l e t o the z e o l i t e .
The rates o f exchange o f t h e Na' i o n s i n Na-A by Ca2', Mg2' and b i n a r y
mixtures o f these ions have been determined. The d i f f u s i o n c o e f f i c i e n t s
c a l c u l a t e d from these r a t e s are given i n Table 3. This t a b l e shows t h a t t h e
r a t e o f pure Ca2' exchange i s 10 f o l d f a s t e r than the corresponding Mg2'
exchange r a t e ( r e f . 4 ) . The presence o f Mg2' ions i n t h e b i n a r y mixtures does
n o t decrease t h e r a t e o f exchange found w i t h pure Ca2+ s o l u t i o n s when the
s o l u t i o n phase contains an i n i t i a l Ca/Mg r a t i o o f 2 : l . However, when t h i s
r a t i o decreases t o 1:2 the r a t e o f d i v a l e n t exchange i s considerably reduced.
Mg2+ ions, i n t h i s l a t t e r case, must block t h e eight-membered windows c o n t r o l l -
i n g access t o the channel network o f z e o l i t e A and slow down the ingress o f
the more r a p i d l y d i f f u s i n g Ca2' ions.
From these r a t e measurements the time constants f o r 50% exchange o f lpm

radius Na-A c r y s t a l s ( t h e s i z e o f c r y s t a l used i n detergent formulations) by

Ca2' and Mg2' ions could be calculated. They were found t o be 9s and 250s
respectively. The slowness o f the big2' exchange must be ascribed, once again,
t o the need t o s t r i p water molecules from the h y d r a t i o n s h e l l before access t o
the channel network o f z e o l i t e A can be achieved. The slowness o f t h e exchange
r e a c t i o n allows the Mg2' ions t o r e a c t w i t h o t h e r species present i n the
detergent formulation.
TABLE 3
K i n e t i c s o f I o n Exchange i n Z e o l i t e A

I n i t i a l S o l u t i o n Phase
Pure Ca Ca:Mg Ca:Mg Ca:Mg Pure Mg
2:l 1 :1 1 :2
Diffusion Coefficient 1.67 1.70 1.38 0.62 0.18
0/1 0-1 5m2s-1

I O N EXCHANGE I N PRECURSOR GELS

I n the above studies c r y s t a l l i n e z e o l i t e A has been shown t o be an
e x c e l l e n t b u i l d e r f o r t h e removal o f Ca2' ions. However, t h e performance o f
the z e o l i t e as a b u i l d e r f o r t h e removal o f Mg2' ions i s poor e s p e c i a l l y when
Ca2' ions are present i n the s o l u t i o n phase. This poor performance towards
Mg2' i s associated w i t h need t o reduce t h e e f f e c t i v e s i z e o f t h e hydrated
Mg2' i o n before i t can e n t e r t h e channels o f z e o l i t e A. We decided, therefore,
t o study the exchange behaviour o f t h e precursor gels o f z e o l i t e s A and X as
a f u n c t i o n o f c r y s t a l l i z a t i o n time ( r e f . 5 ) . P r i o r t o c r y s t a l l i z a t i o n the g e l s
should have more open s t r u c t u r e s w i t h l a r g e r water contents than the f i n a l
c r y s t a l 1i n e product.
 667

EXPERIMENTAL
The z e o l i t e A g e l s had m o l a r compositions o f Si02/A1203 o f 2 . 0 0 ;
Na20/Si02 o f 2.50 and H20/Na20 o f 40 w h i l e t h e z e o l i t e X g e l s had c o r r e s p o n d i n g
r a t i o s o f 3.0, 1.2 and 40 r e s p e c t i v e l y . The g e l s were d i v i d e d e q u a l l y between
t e n s e a l e d p o l y p r o p y l e n e b o t t l e s which were t h e n heated i n an oven a t 8OoC.
The t e n samples were a l l o w e d t o c r y s t a l l i z e o v e r r e a c t i o n t i m e s o f 0 t o 14 hours
f o r t h e z e o l i t e A g e l s and 0 t o 24 hours f o r t h e z e o l i t e X g e l s . R e a c t i o n was
stopped by f i l t r a t i o n f o l l o w e d by washing w i t h c o l d , d i s t i l l e d w a t e r u n t i l t h e
pH o f t h e washings f e l l below 9. The samples were exchanged t w i c e w i t h
c o n c e n t r a t e d NaCl s o l u t i o n s , washed w i t h d e i o n i s e d w a t e r a t pH 10 (pH a d j u s t e d
w i t h NaOH) u n t i l c h l o r i d e f r e e and t h e n a i r d r i e d .
The exchange c a p a c i t i e s o f t h e s e a i r d r i e d samples were determined by
i s o t r o p i c d i l u t i o n u s i n g 0.1 N NaCl s o l u t i o n s tagged w i t h 22Na. The w a t e r
c a p a c i t i e s o f t h e samples were o b t a i n e d f r o m t h e w e i g h t l o s s on h e a t i n g o v e r -
n i g h t a t 50OoC. The c a l c i n e d samples were r e h y d r a t e d i n a d e s i c c a t o r o v e r
s a t u r a t e d NaCl s o l u t i o n and t h e i r w a t e r c a p a c i t i e s r e d e t e r m i n e d as above.
I o n exchange i s o t h e r m s were determined u s i n g “Na tagged samples and, a l s o by
atomic a b s o r p t i o n a n a l y s i s . E q u i l i b r a t i o n t i m e s o f 10 days p e r p o i n t were
used i n a l l cases.

RESULTS
The samples were d e s i g n a t e d A o r X t o i n d i c a t e z e o l i t e A and X g e l s
r e s p e c t i v e l y and t h e number f o l l o w i n g t h e l e t t e r i n d i c a t e s t h e c r y s t a l l i z a t i o n
t i m e i n hours, e.g. A4 i n d i c a t e s a z e o l i t e A g e l heated a t 8OoC f o r 4 hours.
Xray a n a l y s i s showed t h a t samples AO, A1 and A2 were amorphous w h i l e A3
was p a r t l y c r y s t a l l i n e . Samples A4 t o A14 were c o m p l e t e l y c r y s t a l l i n e w i t h
much sharper d i f f r a c t i o n l i n e s t h a n sample A3. Samples XO t o X4 were amorphous,
X6 p a r t l y c r y s t a l l i n e w h i l e samples X8 t o X24 were c o m p l e t e l y c r y s t a l l i n e w i t h
sharp d i f f r a c t i o n l i n e s .
The w a t e r c a p a c i t i e s o f t h e t e n , as-synthesised, z e o l i t e A and X samples
a r e g i v e n i n F i g . 5 and, a l s o a f t e r r e h y d r a t i o n f o l l o w i n g c a l c i n a t i o n a t 50OoC.
The severe decrease i n w a t e r s o r p t i o n c a p a c i t y a f t e r c a l c i n a t i o n o f t h e
amorphous Ad), A1 and A2 samples and t h e c o r r e s p o n d i n g XO t o X4 samples c l e a r l y
demonstrates t h e l a c k o f thermal s t a b i l i t y o f t h e amorphous samples. Fig.5
a l s o i n c l u d e s t h e i o n exchange c a p a c i t i e s o f t h e s e samples based on b o t h
h y d r a t e d and dehydrated mass o f t h e samples. The exchange c a p a c i t y o f t h e
z e o l i t e A g e l s i n c r e a s e w i t h i n c r e a s i n g c r y s t a l l i n i t y whereas t h e c a p a c i t i e s
o f t h e z e o l i t e X g e l s a r e l e s s dependent on c r y s t a l l i n i t y . The enhanced
exchange c a p a c i t y o f c r y s t a l l i n e z e o l i t e A compared w i t h z e o l i t e X i s c l e a r l y
seen i n Fig.5.
668

I n Fig.6 the Na/Ca and Na/Mg exchange isotherms o f samples AO, A1 , A2 and
A14 are presented and i n Fig.7 the corresponding isotherms o f samples XO, X1,
X2, X3 and X24. A l l f o u r sets o f isotherms c l e a r l y demonstrate the decreasing
s e l e c t i v i t y f o r the ingoing d i v a l e n t i o n w i t h increasing c r y s t a l l i z a t i o n time,
This t r e n d continues i n the case o f z e o l i t e A gels up t o the c r y s t a l l i n e product.
However, an i n t e r e s t i n g reversal o f t h i s trend occurs w i t h z e o l i t e X gels on
going from sample X3, which i s s t i l l amorphous t o Xrays, t o X24 which i s 100%
crystalline. Secondly, the change i n s e l e c t i v i t y w i t h c r y s t a l l i z a t i o n time i s
greater w i t h the z e o l i t e X samples than w i t h the z e o l i t e A samples.
I n Fig.8 and 9 the respective logl0KC p l o t s f o r Na/Ca and Na/Mg exchange
i n the z e o l i t e A gel samples a r e presented. The corresponding p l o t s f o r t h e
z e o l i t e X gel samples are given i n Fig.10 and 11. These p l o t s q u a n t i f y the
s e l e c t i v i t y trends seen i n the isotherms as a f u n c t i o n o f c r y s t a l l i z a t i o n time.
I n Fig.8 and 10 the much higher s e l e c t i v i t i e s f o r Ca exchange, i n both types
o f z e o l i t e gels, compared w i t h the s e l e c t i v i t i e s f o r Mg exchange i n Fig.9 and
11 can be seen. The change i n s e l e c t i v i t y w i t h c r y s t a l l i E a t i o n time i s s l i g h t l y
more pronounced i n the case o f the Mg exchanges.
The experimental p o i n t s i n the above logloKc p l o t s were f i t t e d t o eqn.3
and the r e s u l t i n g set o f polynomials are l i s t e d i n Table 4. The f l u c t u a t i o n s
i n the Co values ( i . e . t h e value o f loglOKc a t AZ = 0) w i t h c r y s t a l l i z a t i o n
time a r e due t o the s p a r c i t y and s c a t t e r o f t h e experimental p o i n t s i n these
loiloKc p l o t s as AZ * 0. However, the standard f r e e energies o f exchange,
AG , i n d i c a t e (a) the preference f o r Ca2' over Na' i n both z e o l i t e systems
( b ) the opposite r e s u l t f o r Mg2' and ( c ) a decreasing s e l e c t i v i t y f o r the
d i v a l e n t i o n w i t h increasing c r y s t a l l i z a t i o n time a p a r t from t h e reversal i n
t h i s t r e n d w i t h the X24 sample.
Preliminary k i n e t i c s t u d i e s have been c a r r i e d o u t w i t h the amorphous A2
sample. This sample had a spread i n p a r t i c l e s i z e over t h e range 1.9 t o
23.7~11w i t h an average o f 8.2um. Because o f t h e amorphous nature o f t h e
sample and the wide d i s t r i b u t i o n o f p a r t i c l e s i z e i t i s d i f f i c u l t t o o b t a i n
accurate d i f f u s i o n c o e f f i c i e n t s f o r Ca and Mg exchange i n t h i s sample. I f
t h e p a r t i c l e s are assumed t o be spheres o f 4.lum r a d i u s then the d i f f u s i o n
c o e f f i c i e n t f o r Mg exchange i s the same as t h a t given i n Table 3 f o r Mg
exchange i n c r y s t a l l i n e z e o l i t e A w h i l e t h e d i f f u s i o n c o e f f i c i e n t f o r Ca
exchange i s a t h i r d o f t h a t given i n Table 3 f o r Ca exchange i n c r y s t a l l i n e
z e o l i t e A. Thus, i n t h e amorphous samples the r a t e of exchange w i t h Ca2+ i o n s
i s only three times f a s t e r than t h a t f o r Mg2' ions compared w i t h the t e n f o l d
d i f f e r e n c e w i t h c r y s t a l l i n e z e o l i t e A.
 669

CALCIUM MAGNESIUM

Ca

Fig. 6. Na/Ca and Na/Mg binary exchange isotherms of zeolite A gels a t 25OC.
Solution phasg 0.05N. AO, A l , A2 and A 1 4 represent gels which had been
reacted a t 80 C f o r 0, 1 , 2 and 14 hours respectively.

CALCIUM MAGNESIUM

F i g . 7. Na/Ca and Na/Mg binary exghange

isotherms of zeolite X gels a t 25 C.
Solution phase 0.05N. XO, X1, X2, X3 and
X 2 4 represent gels which had been reacted
a t 8OoC f o r 0, 1, 2 , 3 and 24 hours
respecti ve ly .

Fig. 8. LoglO Kc vs Ca, plots for z e o l i t e A

gels. (Symbols and conditions as defined
in Fig. 6 )

-1.0 J
670

3.0

2.0

1 .o

1 .c

Y,
m
0
-1
0.C
0.c .o

0 x2
x3
0 ex24
0
2
-1.c

F i g . 10. Loglo Kc v s Ca, plots for zeolite X

- 1 .I
gels. (Symbols and conditions as defined
i n Fig. 7 )

F i g. 9. Log K vs MgZ p l o t s for z e o l i t e A

10 c
gels. (Symbols and condit ions as def ined
i n Fig. 6 )

F i g . 11. LoglOK v s Mg, plots for z e o l i t e X

C
gels. (Symbols and condit ions as def ined
i n Fig. 7 )
 671

TABLE 4
LoglOKC polynomials and Standard Free Energies o f Exchange
Zeol it e A Samples
Na-Ca Exchange
Sample A0 : LoglOKc = 2.20-3.29Cazt7.30Caz2-5.17Caz3 AG8 = -3.61kJ/g e q u i v .
Sample A1 : LoglOKc = 2.47-5.55Cazt11.91Ca 2-8.09Ca AG* = -3.45kJ/g equiv.
Sample A2 : LoglOKc
= 2.48-5.07Caztll .31CaZz2 -8.37Ca:3 AG* = -3.38kJ/g equiv.

Sample A14 : LoglOKc = 2.95-10. 12Cazt23.93Caz2-17.61CaZ3 AG* = -2.94kJ/g equiv.

Na-Mg Exchange
Sample A0 : LoglOKc = 1 .30-2.15Mgzt2.90Mgz2-3.5OMg A& = 0.33kJ/g equiv.
Sample A1 : LoglOKc = 1 .72-4.82Mgzt7.43Mgz2-5.80Mg:3 A G ~= 0.28kJ/g equiv.
Sample A2 : LoglOKc = 0.93t4.46Mgz-17.45Mgz 2+10.53Mg AG* = 1.30kJ/g equiv.
= 1 .59-0.06MgZ-10.83Mgz 2t7.74MgZ3 AG* = 1.57kJ/g equiv.
Sample A14 : LoglOKc

Z e o l i t e X Samples
Na-Ca Exchange
Sample XO : LoglOKc = 1 .97-5.15Caztll .91Ca 2-8.75Caz3 AG* = -2.14kJ/g equiv.
Sample X1 : LoglOKc 2.19-7.13Cazt16.81Ca~2-12,38Ca *GO = -1.99kJ/g equiv.
Sample X2 : LoglOKc = 1 .90-5.56Cazt14.23Ca 2-11 .60CaZ3 AG* = -1.5lkJ/g equiv.
Sample X3 : LoglOKc = 1 .70-5.07Cazt13.66Caz2-12.07Ca:3 AG* = -0.76kJ/g equiv.
= 2.04-5.72Cazt14.28Caz z2-11.51CaZ3 A& = -1.81kJ/g equiv.
Sample X24 : LoglOKc
Na-Mg Exchange
Sample XO : LoglOKc = 0.82t0.64Mgz-1 .75Mg '-2.19MgZ3 AG* = 1.23kJ/g equiv.
Sample X1 : LoglOKc = 0.92-0.17Mgzt1 .17Mg:2-6.18Mgz3 AG*
= 2.16kJ/g equiv.
= 0.76t3.87Mgz-15.00Mgz 2+5.45Mgz3 A G ~= 3.92kJ/g equiv.
Sample X2 : Logl0KC
Sample X3 : LoglOKc = 0.30t8.98MgZ-39.10Mg 2+27.16Mg AG* = 5.40kJ/g equiv.
Sample X4 : LoglOKc
= 0.88t1 .16Mgz-6.42Mgz f t0.19Mgz3z AG* = 3.04kJ/g equiv.

CONCLUSIONS
These s t u d i e s show t h a t t h e s e l e c t i v i t y f o r Ca2' and Mg2+ i o n s i s g r e a t e r
i n t h e more open and more h i g h l y hydrated amorphous a l u m i n o - s i l i c a t e gel
samples than i n t h e z e o l i t e A and X products which f i n a l l y c r y s t a l l i z e o u t
from these gels. The exchange c a p a c i t i e s o f these g e l samples a r e q u i t e l a r g e
and n o t g r e a t l y d i f f e r e n t from those o f t h e corresponding c r y s t a l 1i n e z e o l i t e .
The d i f f e r e n c e in t h e r a t e s o f exchange o f Ca2+ and Mg2+ i s much reduced i n
t h e amorphous z e o l i t e A gel samples compared w i t h t h e t e n f o l d d i f f e r e n c e found
i n c r y s t a l l i n e z e o l i t e A. Thus, amorphous z e o l i t e A and X gel samples seem
t o have e x c e l l e n t b u i l d i n g p r o p e r t i e s f o r b o t h Ca2+ and MgZt ions.

REFERENCES

1 A.C. Savitsky, Soap Cosmet. Chem. Spec., 53 (1977) 29.

2 G.H. Kuhl and H.S. Sherry, "Proc. F i f t h I n s t . Conf. Z e o l i t e s " (Ed. L.V.C.
Rees) Heyden, London, 1980, p.813.
3 S . A . I . B a r r i and L.V.C. Rees, J. Chromatog., 201 (1980) 21.
672

4 D. Drummond, A. De Jonge and L.V.C. Rees, J. Phys. Chem., 87 (1983)

1967.
5 V.C. Mole and L.V.C. Rees, "Recent Developments i n I o n Exchange" (Ed. P . A .
W i l l i a m s and M.J. Hudson), E l s e v i e r Appl. Science, London, 1987, p.264.
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

FUNDAMENTALS OF PHOSPHATE SUBSTITUTION I N DETERGENTS BY ZEOLITES

- c o b u i l d e r s and o p t i c a l b r i g h t e n e r s

M.J. Schwuger, M. Liphard

Henkel KGaA, P.O. Box 1100, 4000 Dusseldorf 1
(Federal Republic o f Germany)

ACSIP_ncI
This study i s concerned w i t h the physico-chemical background t o t h e s u b s t i -
t u t i o n o f phosphates i n laundry detergents, w i t h s p e c i a l emphasis on combina-
t i o n s o f z e o l i t e A w i t h other detergent i n g r e d i e n t s , e s p e c i a l l y water-soluble
c o b u i l d e r s and o p t i c a l b r i g h t e n e r s . The most important a c t i o n mechanisms o f
z e o l i t e A / c o b u i l d e r systems were i n v e s t i g a t e d f o r a v a r i e t y o f washing con-
d i t i o n s . I t i s shown t h a t the b u i l d e r performance o f z e o l i t e A i s o f t e n r e i n -
forced by small amounts o f water-soluble substances such as p o l y c a r b o x y l a t e s .
These detergents a r e a b l e t o compete, i n terms o f performance, w i t h products
c o n t a i n i n g a h i g h p r o p o r t i o n o f phosphate. F u r t h e r , the i n t e r a c t i o n o f z e o l i t e
A w i t h f l u o r e s c e n t whitening agents i n detergent powders was s t u d i e d . I t i s
shown t h a t the photophysical p r o p e r t i e s o f a t y p i c a l o p t i c a l b r i g h t e n e r are
n e g a t i v e l y i n f l u e n c e d by i o n i c b u i l d e r s and s u r f a c t a n t s . I n c o n t r a s t t o sodium
triphosphate, z e o l i t e A can enhance t h e appearance o f powders even i n t h e p r e -
sence o f a n i o n i c s u r f a c t a n t s .

1._ -_INTRODUCTION
A t the beginning o f t h e 60's the l a r g e p a r t played by phosphates i n the
e u t r o p h i c a t i o n o f staynant and s l o w l y f l o w i n g s u r f a c e waters l e d t o worldwide
research i n t o the problem o f f i n d i n g s u i t a b l e s u b s t i t u t e s f o r phosphates i n
detergents. The s o l u t i o n t o t h i s problem was complicated by the f a c t t h a t such
a s u b s t i t u t e not o n l y had t o measure up t o s i g n i f i c a n t e c o l o g i c a l and t o x i -
cological c r i t e r i a , i t a l s o had t o s a t i s f y p u r e l y p r a c t i c a l c o n s i d e r a t i o n s o f
use and performance, as w e l l as be economically v i a b l e , o f course. Z e o l i t e A,
a w a t e r - i n s o l u b l e , f i n e l y dispersed, i o n exchanger, met a l l these r e q u i r e -
ments. By now, z e o l i t e A has been incorporated i n t o detergents i n many coun-
t r i e s , e s p e c i a l l y i n those where e x i s t i n g o r planned l e g i s l a t i o n r e g u l a t i o n s
o r v o l u n t a r y agreements r e q u i r e a r e d u c t i o n or t o t a l ban on phosphates i n
laundry detergents. I n 1983, t h e f i r s t phosphate-free, powdered detergent con-
t a i n i n g z e o l i t e A was launched on the market i n the Federal Republic o f Ger-
many. I n 1986 the percentage o f z e o l i t e A-based products increased markedly,
and i n March 1988 t h e i r share o f the heavy-duty laundry detergents had reached
70%.
When z e o l i t e A i s t o be incorporated i n t o detergent f o r m u l a t i o n s i n s t e a d
o f sodium triphosphate, i t i s necessary t o i n v e s t i g a t e the common and the
674

d i f f e r e n t properties o f both b u i l d e r s . Subsequently the differences i n t h e i r

i n t e r a c t i o n s w i t h other detergent ingredients have t o be taken i n t o account,
both i n s o l u t i o n , f o r a v a r i e t y o f washing conditions, and i n the powder
itself.
The use of sodium aluminium s i l i c a t e s i n the washing process has been exa-
mined i n a series o f basic investigations ( r e f s . 1-10). This study i s concer-
ned w i t h the physico-chemical background t o two p r a c t i c a l aspects o f z e o l i t e
A-based laundry detergents: combination o f z e o l i t e A w i t h o p t i c a l brighteners
and w i t h water-soluble cobuilders, w i t h special emphasis on polycarboxylates.

2. EXPERIMENT
Most o f the methods have been described elsewhere ( r e f s . 1, 9). Concentra-
t i o n determination o f polycarboxylates was c a r r i e d o u t w i t h a microprocessor
ion-analyzer 901 (Orion Research) by potentiometric t i t r a t i o n w i t h c e t y l -
benzyl-dimethyl ammonium chloride, which forms water-insoluble complexes w i t h
long-chain polycarboxylates. The t i t r a t i o n curve was obtained v i a a surfac-
t a n t - s e n s i t i v e electrode ( r e f . 11).
Fluorescence spectra of the o p t i c a l brightener were made w i t h a ZMF4 / PMQ
I 1 1 Spectralfluorimeter (Zeiss). The degree o f whiteness (Berger) was obtained
w i t h a spectroreflectometer RFC 3-24 ( Z e i s s ) . The composition o f the powders
used was i n accordance w i t h the composition o f t y p i c a l laundry detergents. The
powders were produced by d i s s o l v i n g or dispersing the ingredients i n water,
then mixing and subsequently d r y i n g them. For easier handling the powders were
ground.
The f o l l o w i n g substances were used:
Industrial-grade z e o l i t e A ( S a s i l Q f r o m Henkel KGaA, DUsseldorf), w i t h an
ion-exchange capacity o f 162 mg CaO/g. Other b u i l d e r s and cobuilders: N a - t r i -
phosphate (STP), hydroxyethane-1,l-diphosphonic a c i d (HEDP), ethylene diamine
t e t r a k i s (methylene phosphonic acid)(EDMP), Na-salt o f maleic a c i d / a c r y l i c
acid copolymer (AC) w i t h a mean molecular weight of 70.000 g/mol ("Sokalan
CP 5" from BASF AG, Ludwigshafen). Optical brightener: b i s - t r i a c i n y l deriva-
t i v e of 4,4'-diaminostilbene-2,2'-disulfonic a c i d (BM, "Blankophor MBBH" from
Bayer AG, Leverkusen).

3 * RESU_L_TS-!N_Q -QI_ScUs_s_!ON_
Ll.,Dete_r-gen_cy p e r f ormance of bu i1ders ...-~e_ne_rrl-a~e_c~~L
Builders i n laundry detergents are o f great importance f o r detergency per-
formance, which includes s o i l removal i n a s i n g l e washing cycle, as w e l l as
long-term e f f e c t s such as i n h i b i t i o n o f t e x t i l e i n c r u s t a t i o n s . Table 1 gives
the c h a r a c t e r i s t i c functions o f water-soluble and water-dispersible b u i l d e r s
 675

i n t h e washing process. Sodium triphosphate i s the most important water-

s o l u b l e b u i l d e r , b u t t y p i c a l c o b u i l d e r s l i k e phosphates, NTA, EDTA and
other complexing agents, as w e l l as polycarboxylates, belong t o t h i s type.
Z e o l i t e A i s a r e p r e s e n t a t i v e example o f a w a t e r - d i s p e r s i b l e b u i l d e r .

Water-soluble b u i l d e r s Water-dispersible b u i l d e r s
(ex.: sodium triphosphate) (ex.: z e o l i t e A )
~~ _____ ~~ ~~

Binding o f m u l t i v a l e n t I o n exchange o f m u l t i v a l e n t c a t i o n s ,
c a t i o n s (complexation, e s p e c i a l l y Ca2+
counter-ion condensation)

Inhibition of precipitate Reduction i n p r e c i p i t a t e

formation (concentration and formation (mainly k i n e t i c a l l y
temperature dependent) controlled)

Dispersion o f s o i l and C r y s t a l l i z a t i o n surface f o r

p r e c i p i t a t e s by s p e c i f i c s p a r i n g l y s o l u b l e compounds
adsorption

Heterocoagulation w i t h s o i l
particles

One o f the main f u n c t i o n s o f b u i l d e r s i s t h e i r a b i l i t y t o s o f t e n t h e

washing l i q u o r , i . e . they s t r o n g l y lower t h e calcium and magnesium concentra-
t i o n . Table 1 shows how t h i s laads t o an increase i n s o i l removal. A proper
detergent b u i l d e r softens by processes such as i o n exchange o r complexation,
and n o t by p r e c i p i t a t i o n , l i k e calcium carbonate i n soda-based laundry d e t e r -
gents.
I n a d d i t i o n , s p a r i n g l y s o l u b l e compounds should not form d e s p i t e t h e
s o f t e n i n g by the b u i l d e r . P r e c i p i t a t e s may o r i g i n a t e from t h e r e a c t i o n o f
calcium o r magnesium ions w i t h detergent i n g r e d i e n t s such as a n i o n i c
surfactants, soda, phosphate and water glass. CaC03 can a l s o be formed from
tap water t h a t contains hydrogen carbonate, due t o an a l k a l i n e r e a c t i o n w i t h
the detergent i n t h e washing l i q u o r (Table 2 ) .
Most o f these s p a r i n g l y s o l u b l e p r e c i p i t a t e s are deposited on f i b r e s and
the h e a t i n g elements o f washing machines, which shortens t h e l i f e t i m e o f
machines and c l o t h e s . E a r l i e r detergents c o n t a i n i n g a h i g h concentration o f
676

phosphate solved t h i s problem by p r o v i d i n g a s u f f i c i e n t l y h i g h concentration

of triphosphate anions i n the washing l i q u o r . These q u i c k l y formed strong,
water-soluble calcium and magnesium complexes. When z e o l i t e A i s incorporated
i n t o detergents there are two main differences: the e l i m i n a t i o n o f d i v a l e n t
cations from the washing l i q u o r by insoluble i o n exchangers i s somewhat slower
than by water-soluble b u i l d e r s , and due t o the pore s i z e o f z e o l i t e A, Mg2' is
exchanged more slowly than Ca2+, e s p e c i a l l y a t low temperatures ( f i g . 1)
( r e f . 1 ) . I f both types of ions are present, Ca2* w i l l be exchanged preferen-
t i a l l y (ref. 12).

TABLE 2
Main sources o f p r e c i p i t a t e s leading t o deposits
on f i b r e s and machine elements

tap water HCO -

Ca2', Mg2'

detergent soda
anionic surfactants,soap
water glass
phosphates (low dosage)

1.0
0.8
0.8

0.6

01.
1',..'
/-•
,ARo-
AIM**

0.2p
0.2

I
10 20 30 50 60 70 LO
t Iminl

Fig. 1. Ion exchan e by z e o l i t e A as a function o f time.

5.36*10-3 mol/l Caq+ or Mg2', 1 g / l z e o l i t e A, 25 OC
Q t = amount exchanged a t time t,
Q70 = amount exchanged a f t e r I 0 minutes.
 677

I n order t o compete w i t h triphosphate, z e o l i t e A i s t h e r e f o r e v e r y o f t e n

used i n combination w i t h small amounts o f water-soluble c o b u i l d e r s ( r e f s . 9,
13, 1 4 ) . Reinforcenent o f s o i l removal as w e l l as i n h i b i t i o n o f t e x t i l e
i n c r u s t a t i o n i n these systems w i l l be discussed.

3.2. Zeal it e ...A.. -.cqbu i,ldr.__s~stemsl-

S~L!.-r:~sx.al
The h i g h s e l e c t i v i t y o f z e o l i t e A f o r calcium ions can be considered a
p o s i t i v e f a c t o r i n s o i l removal, F i r s t , the concentration o f magnesium i n tap
water i s g e n e r a l l y much lower than t h a t o f calcium. Secondly, a c e r t a i n r e s i d -
u a l concentration o f magnesium i o n s can increase t h e detergency o f a n i o n i c
s u r f a c t a n t s by counter-ion e f f e c t s , as f o r instance i n the s o l u b i l i z a t i o n o f
o i l and dyes ( r e f . 7 ) .
Table 1 shows t h a t s o i l d i s p e r s i o n can be an important f u n c t i o n o f co-
b u i l d e r s , i n combination w i t h z e o l i t e A, i n s o i l removal. I n a d d i t i o n , as
water-soluble compounds, they are able t o b i n d calcium ions f a s t e r than
z e o l i t e A.

O / t ImJ/sl

61

Fig. 2. Heat evolved o r absorbed d u r i n g t i t r a t i o n o f z e o l i t e A (1.5 g / l ) and

z e o l i t e A/AC mixtures w i t h a CaC12 s o l u t i o n . T i t r a t i o n range: 10 min, f i n a l
Ca2+ concentration 3 . 1 3 ~ 1 0 - m ~ o l / l . Curves were corrected f o r heat o f d i l u t i o n .
( 1 ) no AC, ( 2 ) 60 mg/l AC, ( 3 ) 120 mg/l AC, ( 4 ) 180 mg/l AC, ( 5 ) 240 mg/l AC

F i g . 2 shows t h a t i n z e o l i t e A / AC mixtures, f o r instance, Ca2+ i s f i r s t

bound t o the polycarboxylate. (Nowadays AC i s an important c o b u i l d e r f o r
z e o l i t e A i n European detergents.) I n t h i s c a l o r i m e t r i c measurement, the i o n
exchange by z e o l i t e A was observed v i a t h e corresponding heat e f f e c t d u r i n g
678

t i t r a t i o n o f a z e o l i t e A d i s p e r s i o n w i t h a CaC12 s o l u t i o n ( c u r v e 1 ) . When
d i f f e r e n t concentrations o f AC were added t o the z e o l i t e A s l u r r y , t h e i o n
exchange was delayed by t h e time necessary t o p r o v i d e the maximum amount o f
Ca2+ ions t h a t cart be bound t o the c o b u i l d e r (curve 2 - 5 ) . The o v e r a l l heat
e f f e c t i n the mixtures, however, d i d n o t depend on t h e amount o f AC added
( t a b l e 3 ) . This means, t h a t calcium ions f i r s t become bound t o AC and a f t e r -
wards most o f t h e calcium ions are exchanged by z e o l i t e A. I n t h i s way the
p r e c i p i t a t i o n o f AC i n the presence o f excess calcium ions i s suppressed and
the s o l u b l e Na o r mixed Na/Ca s a l t s o f the p o l y c a r b o x y l a t e s a r e l e f t . This can
be shown by c o n c e n t r a t i o n measurements o f w a t e r - s o l u b l e AC i n the presence and
absence o f z e o l i t e A i n hard water ( t a b l e 4 ) . S i m i l a r r e s u l t s have been ob-
t a i n e d i n soda / z e o l i t e A / AC systems ( s e c t i o n 3.3.2.. fig. 7).

zeolite A (g/l) AC (mg/l) dH/J

60 0.15
- 120 0.20
- 180 0.31
- 240 0.45
1.5 0 1.87
1.5 60 1.86
1.5 120 1.81
1.5 180 1.83
1.5 240 1.a4

TABLE 4
E f f e c t o f z e o l i t e A on t h e r e s i d u a l c o n c e n t r a t i o n o f AC.

i n i t i a l c o n c e n t r a t i o n AC r e s i d u a l c o n c e n t r a t i o n AC
(ma/l) (ma/ll
AC o n l y +29/1 z e o l i t e A
(precipitation)
300 0 280
200 0 180
100 0 100
40 0 40

water hardness: 3.75.10-3mol/l Ca2+, 2 5 V

The s o l v a t e d AC s a l t s a r e thus now a v a i l a b l e f o r a d s o r p t i o n on

s o l i d surfaces such as pigments o r f i b r e s , and can t h u s support t h e
removal o f s o i l i n z e o l i t e A-containing systems ( f i g . 3 ) . The same
holds f o r other s o l u b l e c o b u i l d e r s l i k e the phosphonates EDMP and
 679

1 2 3 6 5 6
builder 19/11

Fig. 3 . Detergency performance o f b u i l d e r systems. S o i l i n g : clay/sebum on

cotton, washing conditions: 95'C. 30min., 285ppm water hardness,
launderometer. ( 1 ) z e o l i t e A, ( 2 ) z e o l i t e A/AC 9:1, ( 3 ) z e o l i t e A/EDMP 9:1,
( 4 ) z e o l i t e A/HEOP 9:1, ( 5 ) STP

reflectance 1%1

75-

73-

71-

nlln
0 l0 15

Fig. 4. Detergency performance o f laundry detergents w i t h 4% AC and d i f f e r e n t

z e o l i t e A content. S o i l i n g : clay/sebum on cotton, washing conditions: 90eC,
450 ppm water hardness (Ca:Mg=5:1), 8g/l detergent, European drum-type washing
mach ine
HEOP, and f o r small amounts o f STP i n combination w i t h z e o l i t e A ( r e f . 1 ) .
This may happen by dispersion o f s o i l by s p e c i f i c adsorption on the s o i l
p a r t i c l e or by subsequent desorption o f the soluble Ca/Na s a l t or complex, and
consequent loosening o f calcium bridges between s o i l and f i b r e .

Fig. 3 shows that by p a r t i a l l y s u b s t i t u t i n g z e o l i t e A w i t h a cobuilder,

almost the same l e v e l o f detergency as w i t h sodium triphosphate can be
reached. This holds not only f o r model systems but a l s o f o r a complete deter-
gent formulation. Fig. 4 shows how the detergency of z e o l i t e A i s r e i n f o r c e d
by AC i n a heavy-duty laundry detergent. I t a l s o shows t h a t the improvement i n
detergency cannot be a t t a i n e d by the cobirilder alone. The more complex calcium
binding processes and the mode of a c t i o n o f AC i n complete washing l i q u o r s
w i l l be discussed below.

3.3. Z e o l i t e A - cobuilder
.__.______..___I-___.__.__..__.._.__ systems / Textile incrustation
As the a c t i o n mechanism o f phosphonates has already been discussed
( r e f s . 9, 13), t h i s study i s confined t o polycarboxylates, namely copolymers
o f maleic and a c r y l i c acid. A t present these polymers are widely used i n zeo-
l i t e A-based detergents because of t h e i r good ecotoxicological p r o p e r t i e s
( r e f s . 15-17). The mechanisms o f i n h i b i t i o n o f t e x t i l e i n c r u s t a t i o n s are s t i l l
under discussion by manufacturers o f detergents and polymers ( r e f . 16, 18-22).
This i s a r e s u l t o f t h e i r manifold possible modes o f action. Small amounts o f
polycarboxylates can r e t a r d the p r e c i p i t a t i o n o f sparingly soluble calcium
s a l t s such as CaC03 ("threshold e f f e c t " ) . As anionic p o l y e l e c t r o l y t e s they are
able t o bind cations (counter-ion-condensation) where m u l t i v a l e n t cations are
s t r o n g l y preferred ( r e f . 23). Whereas the pure calcium s a l t o f the polymer i s
nearly i n s o l u b l e i n water, mixed Ca/Na-salts are soluble, i . e . only over-
stoichiometric amounts o f calcium ions can cause p r e c i p i t a t i o n . Polycarboxyl-
ates are also able of dispersing many s o l i d s i n aqueous s o l u t i o n . Both
dispersion and threshold e f f e c t s r e s u l t from the adsorption o f the polymer on
p a r t i c l e surfaces.

The predominant mode o f a c t i o n i n a detergent thus depends on many f a c t o r s .

To understand the mechanisms, i t i s therefore necessary t o take the various
laundering conditions, such as water hardness, b u i l d e r composition o f the
detergent, dosage and washing temperature, i n t o account. Table 5 shows the
t y p i c a l b u i l d e r composition o f a German z e o l i t e A-based laundry detergent and
the corresponding conditions f o r a t e x t i l e i n c r u s t a t i o n t e s t . The study con-
centrates on t h i s p o i n t o f emphasis.
 681

TABLE 5.
B u i l d e r composition of a t y p i c a l German z e o l i t e A-based heavy-duty laundry
detergent, and concentration ranges i n the washing l i q u o r

composition concentration ranae*

zeolite A 20 -
25 % 1.2 -
2.5 g/1
polycarboxylates 2 - 4 % 0.12 -
0.40 g/1
water glass 1.5 - 4 %
soda 5 -10% 0.3 - 1.0 g/1
(HCO3- from
tap water)"" 0.374 g / l (as soda)
typical t e s t conditions:
dosage* 6 - 10 g / l , medium HC03- concentration i n tap water: 215 mg/l**,
25 wash cycles, 90°C, water hardness: 2.28 - 5.38 m o l / l Me2+, Ca2+: Mg2+ = 5 : l

3.3.1. Threshold e f f e c t
The s t a b i l i z a t i o n o f s p a r i n g l y s o l u b l e s a l t s such as CaC03 i n a c o l l o i d a l
s t a t e i s one o f t h e p o s s i b l e mechanisms discussed f o r polycarboxylates i n
detergents. The advantage o f such a mode o f a c t i o n i s t h e f a c t t h a t , i n con-
t r a s t t o i o n exchange o r complexation, t h e concentration o f t h e c o b u i l d e r can
be much lower than t h e calcium concentration i n t h e washing l i q u o r . This means
t h a t , i n p r i n c i p l e , small amounts o f t h r e s h o l d - a c t i v e compounds c o u l d be used
as cobuilders even i n soda-based laundry detergents.

F i g . 5. P r e c i p i t a t i o n i n h i b i t i o n ( " t h r e s h o l d e f f e c t " ) o f CaC03 by AC as a

f u n c t i o n o f temperature and soda concentration. 3.04*10-3mol/l Ca2+,
( 1 ) 105 mg/l AC, ( 2 ) 210 mg/l AC
682

The e f f e c t , however, i s s t r o n g l y dependent on the experimental ( o r washing)

conditions, i.e. temperature, soda and cobuilder concentration. Fig. 5 shows
washing t e s t r e s u l t s i l l u s t r a t i n g the range o f effectiveness o f AC i n a
carbonate-containing system f o r t y p i c a l c e n t r a l European conditions o f water
hardness (3.04 * mol/l Ca2+). The r e s u l t s are based on t u r b i d i t y measure-
ments. The appearance o f CaC03-particle larger than aproximately 0.2 pm within
30 minutes was taken as an i n d i c a t o r o f whether or n o t the polycarboxylate ex-
h i b i t e d a threshold e f f e c t under the various conditions. The soda concentra-
t i o n s i n the t e s t include the hydrogen carbonate content o f the tap water as
well as the soda content o f the detergent ( t a b l e 5 ) . The r e s u l t s show that,
f o r t y p i c a l German, phosphate-free, heavy-duty detergents, AC i s no longer
threshold-active a t temperatures above 40 OC. This holds even more so f o r
higher carbonate concentrations, 4.e. purely soda-based detergents.

0.8-
2

0.6-

0.L -
0.2-

0-

Fig. 6. Temperature dependence of the influence of AC on the formation of pre-

c i p i t a t e s > 0 , q m i n soda and soda/zeolite A systems. Z e o l i t e A 1.5g/1, soda
0.6/1, AC 0.3g/1, 3.75*10-3 mol/l Ca2+ ( 1 ) soda, ( 2 ) soda + AC, ( 3 ) soda +
z e o l i t e A, ( 4 ) soda t z e o l i t e A t AC

For z e o l i t e A and soda-containing products the p a r t i c i p a t i o n o f z e o l i t e A

i n the e l i m i n a t i o n of calcium ions during the washing process has t o be taken
i n t o account as shown i n f i g . 6. For t y p i c a l t e s t concentrations, the amount
of coarsely dispersed CaC03 i s reduced i n the presence of z e o l i t e A over the
 683

whole washing temperature range. The e f f e c t o f AC on the t o t a l amount o f pre-

c i p i t a t i o n i s s t r o n g l y dependent on whether or not the system contains zeo-
l i t e A. When only soda i s used, p r e c i p i t a t i o n i s i n h i b i t e d o n l y below 40 OC as
would be expected from the range o f threshold a c t i v i t y shown i n f i g . 5. With
increasing temperature, p r e c i p i t a t i o n increases strongly and exceeds the maxi-
mum possible formation o f CaCO3. I n t h i s case, on a d d i t i o n o f CaC03, AC i s
p r e c i p i t a t e d as i t s calcium s a l t , as can be seen from the respective measure-
ments o f the residual concentrations o f water-soluble AC ( f i g . 7 ) . I n con-
t r a s t , the amount o f p r e c i p i t a t i o n which occurs i n the presence o f z e o l i t e A
-
and AC i s n e g l i g i b l y low, and the residual concentration o f water-soluble AC
i s as high as i n z e o l i t e A / AC systems without soda ( f i g s . 6 / 7 ) . These
r e s u l t s can be explained by the binding o f calcium by z e o l i t e A and AC i n i t s
water-soluble form.
The polycarboxylate i s able t o function l i k e t h i s because the calcium ion
concentration of the water i s lowered by z e o l i t e A. Thus, Ca2+ i s no longer i n
excess of AC and the formation o f the insoluble calcium s a l t o f the
polycarboxylate i s no longer possible.

AC I

300

Fig. I. Residua
200

100

Z e o l i t e A 1,5g/
o f AC: 300 mg/l
!
Ii 1 2 :

concentration of AC i n soda and soda/zeolite A systems.

, soda 0.6g/1, 3.15 * mol/l Ca2+, i n i t i a l concentration
( 1 ) soda, ( 2 ) z e o l i t e A t soda, ( 3 ) z e o l i t e A.
 I t has been assumed t h a t c o l l o i d a l CaC03 i s forned even i n the case o f
understoichiometric amounts o f Ca2+ r e l a t i v e t o the number o f carboxylate
groups i n the polymer, due t o the low s o l u b i l i t y product o f CaC03. The mode o f
action o f the polymers i s then c a l l e d "CaC03 dispersing capacity" ( r e f . 9 ) .
Corresponding c a l c u l a t i o n s are based on the assumption o f a "complexation con-
stant", defined j u s t as a normal complexing agent. This does not apply f o r
polycarboxylates, not o n l y because o f the inhomogeneity i n molecular weight o f
the products used, but also because o f the d i f f e r e n t mechanism o f calcium
binding (Counter-ion condensation, r e f . 23).

I f , however, the polymer has t o compete w i t h carbonate f o r the calcium

ions, i t s effectiveness i n the washing process should depend on i t s a b i l i t y t o
bind calcium, i.e. on degree o f counter-ion condensation o f the p o l y e l e c t r o -
l y t e s . This o n l y depends on the distance between the anionic ( i . e . carboxy-
l a t e ) groups ( r e f . 2 4 ) , i f the polymer i s s u f f i c i e n t l y long. The shorter the
distance, the higher the degree o f counter-ion condensation. I f the molecule
i s too short, i t loses p a r t o f i t s p o l y e l e c t r o l y t i c character and behaves more
l i k e a low-molecular-weight e l e c t r o l y t e , i . e . i t dissociates more strongly,
Corresponding r e s u l t s have been obtained f o r z e o l i t e A-based laundry deter-
gents ( r e f . 20). T e x t i l e i n c r u s t a t i o n decreases w i t h increasing molecular
weight (most s t r o n g l y i n the low-molecular-weight range) and w i t h increasing
share o f maleic acid i n acrylic/maleic a c i d copolymers. I t i s worth n o t i n g
t h a t the same sequence i s obtained f o r the so-called "CaC03 dispersing
capacity" .
Two more aspects have t o be taken i n t o consideration , i . e . which kinds o f
deposits on f i b r e s can be reduced, and t o what degree can t o t a l t e x t i l e i n c r u -
s t a t i o n be reduced. An important p r e c i p i t a t e i s CaC03, which leads t o a high
percentage o f CaO i n the ashes o f laundered t e x t i l e s . This share, i n turn, de-
pends on the amount o f CaC03 p r e c i p i t a t e formed under the s p e c i f i c washing
conditions. Fig. 8 shows the amount o f coarse CaC03 i n z e o l i t e A-containing
systems a t 90 OC f o r two d i f f e r e n t calcium concentrations and two d i f f e r e n t
dosages. Both can be considered t o be t y p i c a l t e s t conditions f o r heavy-duty
laundry detergents ( t a b l e 5 ) . A t lower calcium concentrations and lower dosa-
ges ( f i g . 8, curve l b ) , the amount o f CaC03 i s low. I n view o f the carbonate
concentration r e s u l t i n g from tap water only, i t can be concluded t h a t no CaC03
i s formed i n t h i s case. Only when the detergent i t s e l f contains soda i s CaC03
formed. This has been proved by washing t e s t s . Using a heavy-duty laundry
detergent w i t h 25 % z e o l i t e A, no CaO ash was formed f o r 6 g / l detergent dos-
age (corresponds approximately t o curve 1 b ) . When 5 % soda was put i n t o the
detergent, CaO ash was observed under i d e n t i c a l t e s t conditions. This could be
 685

reduced by 88 % i n turn, when the product was given an AC content o f 3%. How-
ever, the ( r e l a t i v e l y low) amount o f MgO ash o n l y dropped by about 4 %.

i 2
Na,co, 19/11

Fig. 8. P r e c i p i t a t i o n of CaC03 (>0.2/~m) i n the presence o f z e o l i t e A as a

function of soda concentration. Conditions: 90°C, 2Omin. ( l b ) 1.75g/l
z e o l i t e A, 3.04~10-3mol/l Ca2+; (2b) 2.40g/l z e o l i t e A, 5.36.10-3mol/l Ca2+;
(la,2a) no z e o l i t e A, calculated maximum amounts o f CaC03

The higher the water hardness, the greater the amount o f CaC03 formed, even
i f the dosage o f the detergent i s increased ( f i g . 8, curve 2 b ) . I t has t o be
taken i n t o account t h a t higher dosage means an increase i n both z e o l i t e A and
soda concentration.

Fig. 9 shows the reduction of t o t a l ash by 4 91 AC under conditions closer

t o those given i n curve 2b. AC i s very e f f e c t i v e against CaC03 i n the presence
of 25 9; z e o l i t e A, considering t h a t a large p a r t o f the non-reduced ash does
not contain CaO. The measurements ( r e f . 13) a l s o show t h a t i f the amount o f
p r e c i p i t a t e i s increased by lowering the z e o l i t e A content o f the detergent,
the polycarboxylate loses i t s e f f i c i e n c y , as has been shown previously
( f i g . 6). The p o s i t i v e e f f e c t o f AC as a cobuilder i s o n l y found i n combina-
t i o n w i t h z e o l i t e A, not w i t h soda only.
686

n 25
L -zeolite A [%I
AC 1%1

F i g . 9 . E f f e c t o f z e o l i t e A and AC on i n h i b i t i o n o f d e p o s i t s on c o t t o n i n a
heavy d u t y laundry detergent. Conditions: 25 wash c y c l e s , 90°C, 450ppm water
hardness, Ca : Mg = 5 : 1 , 8g/1 detergent w i t h 5% soda content, European drum-
type washing machine.

4. OPTICAL BRIGHTENERS I N DETERGENT POWDERS

This chapter i s concerned w i t h t h e i n f l u e n c e o f z e o l i t e A on t h e w h i t e n i n g
o f detergent powders by a t y p i c a l c o t t o n whitener (EM). T h i s was s t u d i e d by
measuring the fluorescence spectra and the degree o f whiteness o f powders con-
t a i n i n g d i f f e r e n t b u i l d e r s as w e l l as combinations o f b u i l d e r s and s u r f a c t a n t s .
F i g 10 shows t h e fluorescence emission spectrum o f t h e pure, o p t i c a l b r i g h t e -
ner i n comparison t o those o f powders c o n t a i n i n g z e o l i t e A, STP and Na2S04.
The water-soluble, i o n i c b u i l d e r s l e a d t o a bathochromic s h i f t i n t h e spectrum
whereas z e o l i t e A leads t o a hypsochromic s h i f t . Though t h e i n t e n s i t y o f t h e
emission i s h i g h e r i n the case o f STP and Na2S04, t h e w h i t e n i n g e f f e c t o f BM
i s stronger i n t h e z e o l i t e A-based powder. Table 6 shows t h a t t h e degree o f
whiteness c o r r e l a t e s w i t h t h e p o s i t i o n o f t h e maximum i n t h e emission spec-
trum. A s h i f t t o higher wavelengths causes t h e powder t o a c q u i r e a y e l l o w i s h
t i n g e , and t h e degree o f whiteness decreases.
 687

XInml

F i g . 10. I n f l u e n c e o f b u i l d e r s on the fluorescence spectra o f BM i n powders.

( 1 ) O M , ( 7 ) BM + zeci:ite A, ( 3 ) BM t Na2S04, ( 4 ) BM + STP

Table 6 .
I n f l u e n c e of b u i l d e r s and t a l l o w f a t t y a l c o h o l s u l f a t e (TA) on the s h i f t o f
the maximum i n the fluorescence spectrum o f EM, and r e l a t i v e degree o f w h i t e -
ness o f powders

powder i n g r e d i e n t rel.degree
o f whiteness
I A h a x ( nm)

zeol it e A
z e o l i t e A t TA
100 %
91 %
I _.
t o
-
STP a7 % - 5
STP t TA 73 % - 5
Na2S04 91 % - 5
Nags04 + TA 80 % - 10

The p o s i t i v e i n f l u e n c e o f z e o l i t e A on t h e photo-physical p r o p e r t i e s o f t h e
o p t i c a l b r i g h t e n e r can be supported by n o n i o n i c s u r f a c t a n t s , whereas a n i o n i c
s u r f a c t a n t s may lead t o negative e f f e c t s ( f i g . 1 1 ) . As can be seen from t a b l e 6
the r e s p e c t i v e bathochromic s h i f t and the decrease i n whiteness depend on the
type o f a n i o n i c s u r f a c t a n t used and are more pronounced i n t h e presence o f STP
and Na2S04. The r e s u l t s can be discussed on the b a s i s o f an aggregation model
which i s a l s o used f o r the e x p l a n a t i o n o f whitening e f f e c t s on f i b r e s ( r e f s .
25, 2 6 ) . I n s o l u t i o n , a n i o n i c f l u o r e s c e n t b r i g h t e n e r s can be present i n t h r e e
d i f f e r e n t forms: d i s s o c i a t e d , as i o n p a i r s and as aggregates.
688

The e q u i l i b r i u m i s influenced by the other solvated substances i n the solu-

t i o n . Whereas i n water w i t h low e l e c t r o l y t e concentration s i n g l e molecules o f
the o p t i c a l brightener are preferred ( d i s s o c i a t e d or ion p a i r s ) , high e l e c t r o -
l y t e concentrations may cause aggregation. I t has been assumed that large
aggregates (micelles) may be formed between a _single whitener molecule and
nonionic surfactants , whereas an anionic whitener/anionic surfactant aggre-
gate i s thought less l i k e l y t o occur ( r e f s . 2 6 , 2 7 ) .

Loo

Fig. 11. Influence o f surfactants on the fluorescence spectra o f BM i n zeol t e

A-containing powders. (1) alkylbenzene sulfonate; ( 2 ) t a l l o w f a t t y alcohol,
ethoxylated (5EO); ( 3 l i n o l e y l / l i n o l e n y l alcohol, ethoxylated ( 1 0 E O ) .
(enlargement X 1 0 ) .

Whitener aggregates or microcrystals should have new and d i f f e r e n t o p t i c a l

properties. Fig. 12 shows t h a t the emission spectra o f BM i n s o l u t i o n s w i t h
high STP or Na2S04 concentration show bathochromic s h i f t s , i.e. the f l u o r -
esence emission o f the aggregates takes place a t longer wavelengths than t h a t
o f the s i n g l e molecules. I t may be assumed t h a t the formation o f aggregates i n
the detergent s l u r r y i s responsible f o r the d e t e r i o r a t i o n i n the appearance of
the spray-dried powder. Z e o l i t e A as a water-insoluble b u i l d e r does n o t lead
t o aggregate formation and thus improves the o p t i c a l p r o p e r t i e s o f the deter-
gent.
 689

F i g . 1 2 . I n f l u e n c e o f b u i l d e r s on t h e fluorescence s p e c t r a o f BM i n aqueous
s o l u t i o n , pH 10. ( 1 ) water, ( 2 ) z e o l i t e A, ( 3 ) STP, ( 4 ) NapSO4.

s.:-co?Jcc!SreM
Z e o l i t e A/polycarboxylate b u i l d e r combinations a r e v e r y e f f i c i e n t i n reduc-
i n g calcium-containing t e x t i l e i n c r u s t a t i o n s on f i b r e s . Under German heavy-
d u t y laundry c o n d i t i o n s , t h i s e f f e c t i s caused by t h e b i n d i n g o f c a l c i u m ions
by t h e polymer i n a water-soluble form. This i s o n l y p o s s i b l e i n the presence
o f z e o l i t e A; otherwise, the water i n s o l u b l e calcium s a l t o f t h e polymer w i l l
p r e c i p i t a t e o u t . According t o t h i s mechanism, polymers w i t h h i g h c a r b o x y l a t e
content and r e l a t i v e l y h i g h molecular weight should be used i n combination
w i t h z e o l i t e A. I n detergents based on soda o n l y t h i s mode o f a c t i o n i s n o t
e f f e c t i v e . The same holds f o r t h e t h r e s h o l d e f f e c t a t h i g h washing tempera-
tures.
The o p t i c a l appearance o f detergent powders w i t h t y p i c a l c o t t o n whiteners
i s s t r o n g l y i n f l u e n c e d by b u i l d e r s and s u r f a c t a n t s . I t i s shown t h a t t h e de-
gree o f whiteness c o r r e l a t e s w i t h t h e p o s i t i o n s o f t h e maximum i n t h e f l u o r e s -
cence emission spectrum. Water-soluble i o n i c species l i k e STP, Na2S04 and
a n i o n i c s u r f a c t a n t s lead t o a bathochromic s h i f t i n t h e spectrum o f the o p t i -
c a l b r i g h t e n e r , causing t h e powder t o a c q u i r e a y e l l o w i s h t i n g e . Z e o l i t e A and
nonionic s u r f a c t a n t s cause a hypsochromic s h i f t leading t o a b e t t e r powder
appearance. This behavior i s explained on t h e b a s i s of an aggregation-
deaggregation model o f the o p t i c a l b r i g h t e n e r .
690

Summarizing the o v e r a l l r e s u l t s obtained w i t h detergents containing z e o l i t e

A, i t can be postulated t h a t under normal washing conditions such detergents
are equivalent t o conventional products containing STP. Under c e r t a i n circum-
stances z e o l i t e A-based products are even safer than conventional ones, due t o
new, special, modes o f action.

1) M.J. Schwuger, H.G. Smolka, C o l l o i d Polymer Sc. 254 (1976) 1062-1069

2) H.G. Smolka, M.J. Schwuger, C o l l o i d Polymer Sc. 256 (1978) 270-277
3) M.J. Schwuger, H.G. Smolka, C o l l o i d Polymer Sc , 26 (1978) 1014-1020
4) M.J. Schwuger, H.G. Smolka, C.P. Kurzendorfer, Tenside Detergents 13
(1976) 305-312
5 ) C.P. Kurzendorfer, M.J. Schwuger, H.G. Smolka, Tenside Detergents 16
(1979) 123-129
6 ) H.G. Smolka, M.J. Schwuger, Tenside Detergents 4 (1977) 222-228
7 ) M.J. Schwuger, H.G. Smolka, Tenside Detergents 16 (1979) 233-239
8 ) H. NuRlein, K. Schumann, M.J. Schwuger, Ber.Bunsenges.Phys.Chem. 83 (1979)
1229-1238
9 ) C.P. Kurzendorfer, M.Liphard, W.von Rybinski, M.J. Schwuger, C o l l o i d Poly-
mer Sci. 265 (1987) 542-547
10) M.J. Schwuger, E.J.Smulders, i n W.G.Cutler, E.Kissa ( E d i t o r s ) , Detergency,
Theory and Technology, Marcel Dekker, New York 1987 pp.371-439
11) C.P.Kurzendorfer, M.Schlag, i n : Dechema Monographien 102, VCH Verlags-.
gesellschaft 1986,pp.561-574
12) K.R.Franklin, R.P.Townsend, JCS Faraday I 81 (1985) 1071-1086
13) H.Andree, P.Krings, H.Upadek, H.Verbeek, i n : A.R.Baldwin ( E d i t o r )
Proceedings of the Second World Conference on Detergents, Montreux 1986,
Amer.Oil.Chem.Soc. 1987 p p. 148-152
14) P.Berth, M.Berg, K.Hachmann, Tenside Detergents 20 (1983) 276-282
15) H.G.Opgenorth, Tenside Surfactants Detergents 24 (1987) 366-369
16) A.Hettche, W.Trieselt, P.Disse1, Tenside Detergents 23 (1986) 12-19
17) G.Jacobi, Angew.Makromol.Chem.l23/124 (1984), 119-145
18) P.Zini, SBFW 113 (1987) 45-48
19) F-Richter, E.W.Winkler, Tenside Surfactants Detergents 24 (1987) 213-216
20) J.Perner, H.W.Neumann, Tenside Surfactants Detergents 24 (1987) 334-340
21) J.A.McDonel1, A.Liu, JAOCS 64 (1987) 769-775
22) M.J.Nagarajan, JAOCS 62 (1985) 949-955
23) F.Oosawa, Polyelectrolytes, Marcel Dekker, New York 1971
24) G.S.Manning, Acc. Chem. Res. 12 (1979) 443-449
25) J.Wegmann, Melliand T e x t i l b e r . 48 (1967) 59-69 und 183-190
26) P.S. Stensby, i n : W.G.Cutler, R.C.Davis, Detergency Theory and Test
Methods, p a r t , 111 Marcel Dekker, New York 1981, pp.730-806
27) J.R. Aspland, S p e c i a l i t i e s , November (1966) 3-12
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

ZEOLITE A - A BUILDER FOR LIQUID DETERGENTS ?

W. LEONHARDT and B.-M. SAX

Degussa AG, ZN Wolfgang, AC-AT2, R o d e n b a c h e r Chaussee 4 , D-6450

Hanau/Main, F . R . G .

ABSTRACT
The stability behaviour of liquid detergents containing zeolite A as a buil-
der is described. The sedimentation behaviour of this insoluble builder is
examined using various parameters, such as variation of the particle diameter
of zeolite A in the 8.6 um - 1 pm range, and also changes in the viscosity of
the external phase. The storage stability of the samples was determined at room
temperature and at 4O0 C, the viscosity by calculating the thixotropic index
and measuring the flow times.

INTRODUCTION
Differences can be observed in the development of liquid detergents in
Europe and the U.S.A. caused by a variety of factors such as legal measures and
washing practices. Whilst there has been a noticeable upwards trend in the use
of liquid detergents in the U.S.A. since the middle of the 1 9 7 0 ' ~a~signifi-
cant change in growth was only evident in Europe from the beginning of the
1980's (refs. 1-2).
In principle, it is possible to differentiate between two types of liquid
system: the most widespread liquid systems are the so-called "unbuilt liquids".
These contain no builders in the normal sense of the word, but soften the wash
liquor using soap. Lime soap, which is difficult to dissolve, is formed,
trapped in micelles with the aid of surfactants and then dispersed. This pre-
vents the lime soap from penetrating or being deposited on the fibres of the
fabric .
The proportion of surfactants amounts to between 40 and 505, including
10-20Z of soap (ref. 3 ) . In comparison with commercial powder detergents,
liquid detergents contain 2 to 3 times the amount of surfactants, and hence
organic components. Initial calculations referring to the degradability led to
COD and TOC values three times higher than with powder detergents, which demon-
strates that the use of inorganic builders is advantageous from an ecological
aspect (ref. 4 ) .
These kinds of system make up the second category of liquid detergents and
are known as "built liquids". They contain coaplexing agents such as phosphates
and citrates, which are common in powder detergents (refs. 5-71. However,
692

liquid detergents of this nature are not widespread in Europe and are mainly
used in the U.S.A. The application of zeolite in liquid systems could also be
of interest to prevent the eutrophication of lakes and rivers caused by
phosphates.

ZEOLITE A IN LIQUID SYSTEMS

Zeolite A differs from all other builders particularly as a result of its
insolubility in alkaline media. When zeolite A is incorporated into a liquid, a
suspension is formed which is not thermodynamically stable under normal condi-
tions (ref. 8 ) . As a result of the differing specific density of the solid and
the liquid, the zeolite settles to the bottom of the liquid as sediment,
causing the suspension to break up.
The stability of this kind of system is influenced by a diversity of fac-
tors. STOKE'S Law (eqn. 1) describes in idealized form the sinking behaviour of
a ball in a liquid medium under the influence of gravity and interprets the
connections between the individual factors.

v = 2 r2 . AQ . g I 90 (1)
v = sinking velocity of particle
r = radius of particle
g = gravitational constant
Ap= difference in density of phases
Q = viscosity of liquid phase

The particle size plays an important role in the sedimentation behaviour due
to the radius of the particle having a quadratic effect on the sedimentation
velocity. The viscosity of the liquid phase also affects the sedimentation
velocity, though this must not be so high as to hinder the pouring of the
liquid detergent. The liquid detergent must be easily flushed out of the deter-
gent dispenser into the drum of the washing machine. At the same time, however,
it must be ensured that the good detergency properties of a liquid detergent of
this nature be maintained when compared to previous systems.
The final parameter which should be mentioned is the variation of the pH
value. In order to prevent the zeolite from being decomposed, the pH value of
the liquid system should always be greater than 8.
The effect of zeolite A with different particle sizes on the stability and
on the viscosity of the liquid system is examined be1.0~.

EXPERIMENTAL SECTION
Zeollte
The zeolite grade NaA (formula: Na10 A1203 . 2Si02 . 4.5H20) was used
here. Zeolites with particle sizes of 3.2 pm and 8.6 p m were prepared synthe-
 693

tically to conform with the customary specifications (refs. 9-10]. Starting

with a 3 . 2 urn zeolite, a 1 . 8 p m zeolite was produced by grinding the initial
product in an air-jet mill; the 1 . 1 grade was wet-ground in a colloid mill,
dried and then ground in a pin mill. The particle size was measured using a
Cilas granulometer 715 E 627. The calcium and magnesium binding power (CaBP/
HgBP) were determined by complexometric titration of the remaining hardness of
Ca- and Hg-ions following contact times of 15 minutes.

TABLE 1
Calcium and magnesium binding power of the examined zeolites
as a function of the particle size.

Particle Size CaBP MgBP

[pml [ mgCaO/g 1 [ mgCaO/g 1

8.6 157 12

-
3.2 169 29
1.8 170 32
1.1 157 50

The following surfactants were used: sodium alkyl benzenesulphonate, HOLS;

C13-Cl5 oxoalcohol 7 EO, BASF; further ingredient: Defoaaer Wacker S132, WACKER
CHEMIE .

Viscositv He-
The viscosity was determined using a Brookfield viscometer RVT at 5 and 50
r.p.m. and spindle 4. For this purpose, the suspension was poured into a 100 ml
beaker into which the spindle was dipped up to the mark and read after 3
minutes. 3 minutes waiting time was allowed between measurements made on the
same system.

Test to Detemine the Flow Tipe

This is used to determine the length of tine required by 100 ml of liquid to
flow out of a flow cup with a nozzle of 6 mm in diameter without pressure (ref.
11).

%bruLT&
In order to be able to make a statement on the storage stability, samples of
100 ml were stored in closed glass bottles for 1 week and 1 month respectively
at 22 and 40 OC. The filling height was 50 m. The phase behaviour was judged
visually.
-
694

The raw materials are weighed into a 250 ml flask with stop cock, with
zeolite being added as the last component. The mixture is dispersed using a
dissolver (Ultra Turrax, 9 m/sec) under water jet vacuum for 15 minutes.

RESULTS AND DISCUSSION

Simple systems consisting of surfactant, zeolite A and water were used to
test the influence of surfactants and surfactant mixtures on the viscosity
behaviour and on the stability. Zeolite contents of 15, 25 and 35% were used
together with 20% of surfactant. Tests were carried out on pure surfactants and
on mixtures in a ratio of 1 : 2 , 1 : l and 2 : l .
Pure anionic surfactants and surfactant mixtures with a high anionic content
lead to a high degree of viscosity, which is particularly noticeable with
zeolite contents of 25 and 35% (see Fig. 1 ) . Although the high viscosities lead
to an improvement in the storage stability, applicational characteristics such
as pouring and flushing properties are negatively influenced as a result. The
flow times give a good indication of the two properties mentioned last (see
Fig. 2). Good flow times together with acceptable viscosities were attained
with mixtures of LAS (Lincar Alkylbenzene Sulfonate) and oxoalcohol in a ratio
of 2 : l and 1 : l .

12000
+ 15 X. 5 rpm

-+-.25 X. 5 rpm

- -.c. 25 X . 50 rpm
+
-V-
35 X . 5 rpm
3 5 X . 50 rpm

%
Y
8000
I \
-\ \ \

40
I
I
\

6/20 5/15 l0)lO 1g/5 2d/o

Nonlonic/Anlonlc [XI

Fig. 1. Viscosity at 5 and 50 r.p.n. as a function of the zeolite content and

surfactant mixture, particle size 3 . 2 vm.
 695

* + 15 x
\ - c . 25 X
\ -m- 35 x
200 ;

--
\
\
n \
150 \
\
E \
F \
\
s 100 h

Fig. 2. Flow times of the suspensions examined in Fig. 1.

3
-c 15 X
.
-& - 25 X
--c 35 71

0/20 5/20 10/10 15/5 20/0

7: Nonlonlc/Anlonic

Fig. 3. Thixotropic index TI of the suspensions shown in Fig. 1;

TI = rl ( 5 r.p.a) (50 r.p.n).
696

The term thixotropic index (TI) is used to define the quotient of two visco-
sities measured at different shear rates (rotational speed ratio 10:1); this
value indicates the structural viscosity of the systems. The higher the TI is,
the more structured the system and the more favourable the stability behaviour .
Taking into consideration the viscosity and flow times, the system containing
13% LAS and 7% oxoalcohol 7 ED was found to be the most effective (see Fig. 3).
The system containing 13% LAS and 7% oxoalcohol EO was used to examine the
stability and flow behaviour of zeolite A as a function of the particle size.
Particularly the zeolite with an average particle size of 1.1 vm demons-
trates well-defined thickening effects in its viscosity behaviour (Fig. 4 ) .
Systems containing 25\ and especially those with a zeolite content of 35% lead
to paste-like suspensions. The other zeolites result in more liquid suspen-
sions, whereby the zeolite with an average particle size of 1.8 vm shows the
least thickening effects with increasing zeolite content and is therefore said
to demonstrate relatively "neutral' behaviour. The low viscosity is an advan-
tage for the applicational properties, because these suspensions can be poured
easily. This is also apparent from the flow times which are virtually constant
at around 45 seconds for suspensions containing 25 and 35% zeolite (1.8 p a ) ,
(see Fig. 5).This independence is reflected in the thixotropic index (Fig. 6).
Values from 1.2 to 1.3 are attained with the 1.8 VI zeolite; all of the other
zeolites - with the exception of the zeolite with an average particle size of
1.1 m, which resulted in values between 3 and 4 - lie in the range from 1.3 to
2.0.

Fig. 4. Viscosity of the suspensions as a function of the particle size and

zeolite content; left: at 5 r.p.m.; right: at 50 r.p.m.
 697

--c 1.1 urn

.-c-1.8 prn
1
--
-+-
3.2
8.6 urn
pm
-

15 25 35
Zeolite [%I

Fig. 5. Flow times of the suspensions examined in Fig. 4

I
15 25 35
Zeolite [ X I

Fig. 6. Thixotropic index TI of the suspensions shown in Fig. 4.

698

Storage tests permit an assessment of the role played both by the viscosity
and the particle size (see Tab. 2 ) . The particle size has the greatest influ-
ence on the stability. The most favourable values, from a point of view of
viscosity ( ~ and
5 TI), are achieved with the zeolite with a particle size of
3 . 2 urn, yet the stability is greatly inferior to that of the 1 . 8 pm zeolite -
particularly when the values of the suspensions containing 25% zeolite are
coapared. As already mentioned above, the 1 . 1 vm zeolite leads to a well-
defined thickening effect, which is an advantage for the stability of the
system but not acceptable from an applicational aspect. An almost complete
phase separation becomes apparent within a few days with the 8 . 6 pm zeolite,
resulting in a breaking up of the suspension.

TABLE 2

Storage test carried out on suspensions containing zeolite (13% LAS, 7% C13/C15
oxoalcohol 7 EO, 15-25-35,. zeolite 4 A , 0.1% defoamer, remainder H 2 0 ) . The
degree of separation was determined as the amount of clear phase related to the
filling height and expressed as a percentage.

Particle Size Zeolite Content Separation

[ pml [%I [%I a
RT 4 0 OC

1.1 15 0 0
1.1 25 b - -
1.1 35 b

1.8 15 22 1 -
1.8 25 10 1 -
1.8 35 1 1 2

3.2 15 50 1 - 55 1 -
3.2 25 50 I - 50 1 -
3.2 35 3 1 6 3 1 8

8.6 15 60 1 - 68 1 -
8.6 25 30 1 - 40 1 -
8.6 35 12 1 - 20 1 -
a 1st number I 2nd number = separation following 7 days I following 28 days. If
the separation was more than 10% after 7 days, the value for 28 days was not
determined.
b Storage test was not carried out here, as these were pastes and not liquid
suspensions.
 699

CONCLUSION
The experiments described above have shown how the particle size of the
zeolite being examined influences the stability and flow behaviour of liquid
detergents. Particle sizes in the 2 Ma range were found to be favourable; this
value is far below the one which is currently considered to be optimum for
detergent zeolites - approx. 4 um.

REFERENCES
1 Chemical Marketing Reporter, 25 (1988) 30,39.
2 W. Budek, Seifen, Ole, Fette, Wachse, 113 (1987) 359-363.
3 DE-OS 3516091 ( 1 9 8 6 ) .
4 L. Huber, Seifen, Ole, Fette, Wachse, 113 (1987) 393-397.
5 EP 0203660 ( 1 9 8 6 ) .
6 EP 0200264 ( 1 9 8 6 ) .
7 DE 2916656 ( 1 9 8 0 ) .
8 Th. Tadros, Advances in Colloid and Interface Science, 12 (1980) 141-261.
9 DE 2517218 ( 1 9 8 6 ) .
10 DE 2660726 ( 1 9 8 6 ) .
11 DIN 53 211 ( 4 / 1 9 7 4 ) .
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent BuiMers
0 1989 Elsevier Science Publishers B.V., Amsterdam- Printed in The Netherlands

DEVELOPMENT AND PERFORMANCE OF ZEOLITE-A-BUILT NON-PHOSPHATE DETERGENTS

H. UPADEK and P. K R I N G S
Henkel KGaA, P.O. Box 1100, H e n k e l s t r a s s e 67, D-4000 D u s s e l d o r f (West-Germany)

ABSTRACT
Today's non-phosphate brand powder d e t e r g e n t s c o n t a i n z e o l i t e A as t h e main
b u i l d e r component. I n a d d i t i o n , p o l y c a r b o x y l a t e s and sodium c a r b o n a t e s u p p o r t
t h e a c t i o n o f z e o l i t e . Reduction o r replacement o f z e o l i t e i n non-phosphate
p r o d u c t s r e s u l t s i n unacceptable t e x t i l e i n c r u s t a t i o n s . From dosage e x p e r i m e n t s
i t i s concluded t h a t non-phosphate d e t e r g e n t s based on z e o l i t e a r e s a f e r t h a n
p h o s p h a t e - c o n t a i n i n g p r o d u c t s , as r e g a r d s t h e i n h i b i t i o n o f d e p o s i t s on
t e x t i l e s and on washing machines.

INTRODUCTION
E s s e n t i a l p r e r e q u i s i t e s f o r a good wash r e s u l t o f a d e t e r g e n t a r e t h e
q u a l i t y and q u a n t i t y o f t h e b u i l d e r s . They e x h i b i t n o t o n l y s p e c i f i c e f f e c t s
b u t a l s o e x e r t a d e c i s i v e i n f l u e n c e on t h e a c t i o n o f t h e o t h e r d e t e r g e n t
components.
U n t i l t h e e a r l y s e v e n t i e s , t h e t e r m " b u i l d e r " was synonymous w i t h sodium
t r i p h o s p h a t e (STP). I t s c o n t r i b u t i o n t o t h e wash r e s u l t i s l a r g e l y based on
t h r e e key f u n c t i o n s :
- e l i m i n a t i o n o f c a l c i u m and magnesium i o n s by s e q u e s t r a t i o n ;
- s p e c i f i c detergency performance;
- d i s p e r s i n g power.
When d e t e r g e n t s c o n t a i n i n g phosphates came under c r i t i c i s m , t h e search f o r
a l t e r n a t i v e s l e d t o z e o l i t e A ( r e f s . 1 - 3 ) . Comparison o f t h e c h a r a c t e r i s t i c s o f
STP and z e o l i t e A shows t h a t , s u r p r i s i n g l y , t h e y possess many i d e n t i c a l
p r o p e r t i e s , s o t h a t sodium aluminium s i l i c a t e can be used t o p a r t i a l l y o r
w h o l l y e l i m i n a t e t h e phosphate c o n t e n t i n d e t e r g e n t s ( r e f s . 4-5).
Since 1976, t h e r e f o r e , combinations o f z e o l i t e A and STP have been
i n c r e a s i n g l y i n c o r p o r a t e d i n European d e t e r g e n t s . As a r e s u l t , p r o d u c t i o n
c a p a c i t y o f z e o l i t e A was r a p i d l y expanded, and i s c u r r e n t l y above 400 000 t o n s
p e r y e a r worldwide .
102

PHOSPHATE SUBSTITUTION BY ZEOLITE/CO-BUILDER SYSTEMS

The improvement i n d e t e r g e n t f o r m u l a t i o n s b r o u g h t about by t h e use o f
z e o l i t e A f i n a l l y l e d t o t h e p r o d u c t i o n o f non-phosphate powder d e t e r g e n t s ,
which were f i r s t b r o u g h t o n t o t h e European m a r k e t i n 1983 ( r e f . 6 ) . T h i s new
p r o d u c t c a t e g o r y was made p o s s i b l e by t h e use o f s p e c i a l c o - b u i l d e r s , which
i d e a l l y complemented t h e b u i l d e r p r o p e r t i e s o f z e o l i t e A ( r e f s . 7-8).
N i t r i l o t r i a c e t i c a c i d (NTA) was, and i n S w i t z e r l a n d and The N e t h e r l a n d s s t i l l
i s , used as such. As a s o l u b l e o r g a n i c complexing agent, NTA has p r o p e r t i e s
s i m i l a r t o STP, and i n c o m b i n a t i o n w i t h z e o l i t e i t a c t s as a c a r r i e r f o r
t r a n s f e r r i n g c a l c i u m i o n s from t h e d e p o s i t o r s o i l t o t h e i o n exchanger
z e o l i t e A. However, t h e e c o l o g i c a l d e b a t e on NTA i n some European c o u n t r i e s l e d
t o t h e use o f a n o t h e r b u i l d e r c o m b i n a t i o n ,
T h i s c o n s i s t s o f t h e t e r n a r y b u i l d e r system z e o l i t e A, p o l y c a r b o x y l a t e and
sodium carbonate. While sodium c a r b o n a t e m a i n l y a c t s as an a l k a l i z i n g ,
d e t e r g e n c y - s u p p o r t i n g component, t h e p o l y c a r b o x y l a t e s p e r f o r m a number o f
f u n c t i o n s which c o n t r i b u t e t o t h e wash r e s u l t ( r e f s . 9-11). These sodium s a l t s
o f homopolymers o r copolymers o f a c r y l i c a c i d have m o l e c u l a r w e i g h t s between
2 000 and 120 000. One t y p e c u r r e n t l y w i d e l y used i n Europe i s a copolymer o f
a c r y l i c a c i d w i t h m a l e i c anhydride.
The mechanism by which t h i s new c l a s s o f d e t e r g e n t i n g r e d i e n t s i n h i b i t s
i n c r u s t a t i o n v a r i e s , depending on t h e t y p e o f polymer, c o m p o s i t i o n o f t h e
b u i l d e r system, t e m p e r a t u r e and w a t e r hardness. The p o l y c a r b o x y l a t e s can e i t h e r
produce a t h r e s h o l d e f f e c t , i. e . t h e y can i n h i b i t , i n small under-
s t o i c h i o m e t r i c amounts, c a l c i u m s a l t s f r o m p r e c i p i t a t i n g ; o r , by b i n d i n g
c a l c i u m , t h e y can p r e v e n t t h e f o r m a t i o n o f d e p o s i t s . They a l s o enhance t h e
detergency performance and due t o t h e i r d i s p e r s i n g power p r e v e n t redeposi t i o n
o f s o i l p a r t i c l e s on t h e f i b r e s .

BUILDER VARIATION I N NON-PHOSPHATE DETERGENTS

The z e o l i t e - A - b a s e d b u i l d e r system d e s c r i b e d h e r e i s now a p a r t o f t h e most
i m p o r t a n t non-phosphate heavy-duty powder d e t e r g e n t s i n Europe. The average
amounts o f z e o l i t e A (22.0 %), sodium c a r b o n a t e (9.7 %) and p o l y c a r b o x y l a t e
(3.5 %) c o n t a i n e d i n 27 analysed d e t e r g e n t s r o u g h l y correspond t o t h e o p t i m a l
p r o p o r t i o n s o f t h e s e b u i l d e r components needed t o o b t a i n good p r i m a r y and
secondary wash r e s u l t s ( F i g . 1). I f t h e p r o p o r t i o n s a r e v a r i e d , e . g. i f
z e o l i t e i s p a r t i a l l y o r c o m p l e t e l y r e p l a c e d by sodium c a r b o n a t e , as i s t h e c a s e
i n some non-phosphate p r o d u c t s on t h e American market, t h i s r e s u l t s i n p o o r e r
performance under European wash c o n d i t i o n s . T e x t i l e i n c r u s t a t i o n i s
p a r t i c u l a r l y a f f e c t e d . T h i s has been demonstrated i n washing machine t e s t s w i t h
a number o f f o r m u l a t i o n v a r i a t i o n s .
 103

'I
F i g . 1. Average percentages o f z e o l i t e A, sodium carbonate and p o l y c a r b o x y l a t e s
i n non-phosphate powder d e t e r g e n t s .

To make t h e r e s u l t s c l e a r e r , washing was i n t e n t i o n a l l y performed under

c r i t i c a l t e s t c o n d i t i o n s , i. e. r e l a t i v e l y h i g h water hardness and l o w dosage
(see Table 1).

TABLE 1

Builder variation - Test c o n d i t i o n s

T e s t i n g equi pment European drum t y p e washing machine

Washing p r o g r a m 90 'C ( w i t h o u t prewash)
Wash l o a d 3.5 kg o f l a u n d r y b a l l a s t ,
2 c o t t o n f a b r i c s , a r t i f i c i a l l y s o i l e d swatches
Water hardness 450 ppm (Ca:Mg = 5 : l )
Dosage 160 g o f d e t e r g e n t i n 20 1 o f w a t e r
Detergent base Non-phosphate heavy-duty d e t e r g e n t
(12.5 % s u r f a c t a n t s , 22.5 % p e r b o r a t e t e t r a h y d r a t e )
Number o f wash c y c l e s 25
Incrustation D e t e r m i n a t i o n by e x t r a c t i o n o f t h e c o t t o n
f a b r i c s w i t h ethylenediamine t e t r a a c e t i c a c i d

Under t h e s e c o n d i t i o n s , a 40 % r e d u c t i o n o f t h e z e o l i t e c o n t e n t ( D e t e r g e n t
B, see F i g . 2 ) l e d t o a moderate i n c r e a s e i n t e x t i l e i n c r u s t a t i o n a f t e r 25 wash
c y c l e s ; when no z e o l i t e was p r e s e n t ( D e t e r g e n t C) t h e r e was a d r a m a t i c i n c r e a s e
i n d e p o s i t s . The s u b s t i t u t i o n o f sodium carbonate f o r z e o l i t e ( D e t e r g e n t D )
a l s o l e d t o a c l e a r i n c r e a s e i n i n c r u s t a t i o n . It i s o b v i o u s t h a t , under t h e
104

chosen c o n d i t i o n s , t h e p o l y c a r b o x y l a t e cannot p r e v e n t t h e p r e c i p i t a t i o n and

d e p o s i t i o n o f c a l c i u m c a r b o n a t e w i t h o u t t h e s u p p o r t of o t h e r b u i l d e r s . A
c o n t r o l wash t e s t under almost t h e same c o n d i t i o n s showed t h a t , even when t h e
polymer c o n t e n t was doubled t o 8 %, f o r m u l a t i o n D was u n a b l e t o match t h e
i n c r u s t a t i o n - i n h i b i t i n g e f f e c t o f d e t e r g e n t A. On t h e o t h e r hand, comparison o f
f o r m u l a t i o n s A and E (see F i g . 2) s u b s t a n t i a t e s t h e e f f e c t i v e n e s s o f t h e
polymers when s u f f i c i e n t z e o l i t e i s p r e s e n t .

Incrustation
1%1

7
6
5
4
3
2
1

25 15 0 0 25 [% Zeolite A
4 4 4 4 0 [YO]Polycarboxylate
5 5 5 30 5 [%] Sodiumcarbonate
Detergent

F i g . 2. I n f l u e n c e o f b u i l d e r v a r i a t i o n on f a b r i c i n c r u s t a t i o n ( Z e o l i t e A =
Sasil @ , calcium exchange c a p a c i t y : 160 mg CaO/g) .
The o p t i m i z a t i o n o f t h e non-phosphate b u i l d e r system i s a p r e r e q u i s i t e f o r
t h e f i n e t u n i n g o f t h e o t h e r d e t e r g e n t components. By u t i l i z i n g s p e c i a l
s u r f a c t a n t combinations and a d a p t i n g t h e b l e a c h system, i n p a r t i c u l a r by
i n c o r p o r a t i n g b l e a c h a c t i v a t o r s , non-phosphate heavy-duty d e t e r g e n t s c a n .
a c h i e v e t h e same l e v e l o f performance o v e r t h e e n t i r e t e m p e r a t u r e range as t h e
t o p phosphate-containing products.

INFLUENCE OF DOSAGE ON THE PERFORMANCE OF NON-PHOSPHATE DETERGENTS

Under b o r d e r l i n e c o n d i t i o n s , however, t h e new non-phosphate d e t e r g e n t s show
c h a r a c t e r i s t i c s which c l e a r l y d i f f e r e n t i a t e them from p h o s p h a t e - c o n t a i n i n g
p r o d u c t s . T h i s i s e s p e c i a l l y t r u e i f the. dosage i s t o o low. As an example, a
non-phosphate d e t e r g e n t X and a p h o s p h a t e - c o n t a i n i n g heavy-duty d e t e r g e n t Y
were t e s t e d with r e g a r d t o t h e i r p r i m a r y d e t e r g e n c y performance and t o
secondary e f f e c t s a f t e r s e v e r a l washes. D e t e r g e n t X c o n t a i n e d t h e non-phosphate
b u i l d e r system w i t h 25 % z e o l i t e ; d e t e r g e n t Y c o n t a i n e d 2 1 % STP i n a n
S T P / z e o l i t e c o m b i n a t i o n ( T a b l e 2).
 705

TABLE 2
B u i l d e r composition o f two powder d e t e r g e n t s

Non-phosphate [ X ] a Phosphate-containing [ Y ]a

25.0 % Z e o l i t e Ab 21.0 % STP

4.0 % P o l y c a r b o x y l a t e C 14.0 % Z e o l i t e Ab
7.5 % Sodium carbonate 1.2 % Polycarboxyl ateC

aBoth d e t e r g e n t s c o n t a i n r o u g h l y t h e same amounts o f s u r f a c t a n t s , p e r b o r a t e

and b l e a c h a c t i v a t o r .
b S a s i l @c,a l c i u m exchange c a p a c i t y : 160 mg CaO/g.
C M a l e i c / a c r y l i c a c i d copolymer.

TABLE 3
Dosage v a r i a t i o n Test c o n d i t i o n s

T e s t i n g equi pment European drum-type washing machine

Washing programm 90 'C ( w i t h o u t prewash)
Wash l o a d 3.5 kg o f s o i l e d l a u n d r y , a r t i f i c i a l l y
s o i l e d swatches
Soi 1s Sebum, d u s t , l i p s t i c k , r e d wine, t e a , c o f f e e ,
c u r r a n t (on c o t t o n and c o t t o n / p o l y e s t e r b l e n d )
Water hardness 290 ppm (Ca:Mg = 5:l)
Dosage 100, 160 and 220 g o f d e t e r g e n t i n 20 1 o f w a t e r
Number o f wash c y c l e s 1 / 25

The t e s t s were c a r r i e d o u t under n e a r - p r a c t i c e c o n d i t i o n s w i t h 3 dosages,

whereby 220 g correspond t o t h e recommended h a r d water dosage, 160 g t o a
moderately low, and 100 g t o a v e r y low dosage ( T a b l e 3 ) .
When t h e recommended dosage was used, b o t h d e t e r g e n t s gave t h e same p r i m a r y
detergency r e s u l t s ( s e e F i g . 3 ) . T h i s was t r u e n o t o n l y f o r t h e 90 'C t e s t
shown here, b u t a l s o f o r analogous t e s t s a t 40 and 60 'C. As t h e dosage was
reduced, t h e detergency performance decreased, as expected, whereby t h e d r o p i n
t h e performance o f t h e non-phosphate p r o d u c t , e s p e c i a l l y a t v e r y l o w dosages,
was s l i g h t l y g r e a t e r t h a n t h a t o f t h e phosphate c o n t a i n i n g product.
The d i f f e r e n c e between t h e two b u i l d e r systems shows up more c l e a r l y when
t h e f a b r i c i n c r u s t a t i o n i s examined a f t e r 25 washes ( s e e F i g . 4 ) . W i t h t h e
non-phosphate z e o l i t e - c o n t a i n i n g d e t e r g e n t , s i m i l a r i n c r u s t a t i o n was produced
a t a l l t h r e e dosages under t h e chosen wash c o n d i t i o n s , whereas w i t h t h e
phosphate c o n t a i n i n g p r o d u c t t h e r e was a c l e a r i n c r e a s e i n d e p o s i t i o n as t h e
dosage was reduced. Analyses o f t h e f a b r i c showed t h a t i n case o f t h e
p h o s p h a t e - c o n t a i n i n g d e t e r g e n t s p a r i n g l y s o l u b l e c a l c i u m phosphate i s a l m o s t
s o l e l y r e s p o n s i b l e f o r t h e heavy i n c r u s t a t i o n s .
706

Rellectance (Mean values from all soils)

"1
60' I

100
1
160
I
220
Dosage
[gl

F i g . 3. I n f l u e n c e o f dosage on o v e r a l l detergency performance o f non-phosphate

and p h o s p h a t e - c o n t a i n i n g d e t e r g e n t .

lncrustalion (Cotton)
1%1

7- ---.--. Phosphalecantaining
6- -.-.-.
5- -.-.-- -_
4- --- -- ---<
3-
2-
. Nan-phosphate

'
01 100 160 220 Dosage
Is1

F i g . 4. I n f l u e n c e o f dosage on f a b r i c i n c r u s t a t i o n a f t e r 2 5 wash c y c l e s w i t h
non-phosphate and p h o s p h a t e - c o n t a i n i n g d e t e r g e n t .

I n a f u r t h e r t e s t , 50 wash c y c l e s were c a r r i e d o u t a t 90 'C w i t h t h e same

d e t e r g e n t s , t o i n v e s t i g a t e v a r i o u s f a c t o r s i n f l u e n c i n g d e p o s i t i o n on machine
p a r t s , i n p a r t i c u l a r on h e a t i n g elements.
The r e s u l t s o b t a i n e d were s i m i l a r t o t h o s e o b t a i n e d i n t h e f a b r i c
i n c r u s t a t i o n t e s t s , i. e. s t r o n g l y i n c r e a s e d d e p o s i t i o n w i t h l o w dosages o f t h e
p h o s p h a t e - c o n t a i n i n g d e t e r g e n t (see F i g . 5 ) .
 707

,
Deposits
Is1 50 Wash-cycles,

4i

Non-phosphate

F i g . 5. I n f l u e n c e o f dosage on d e p o s i t s on h e a t i n g c o i l s a f t e r 50 wash
c y c l e s w i t h non-phosphate and p h o s p h a t e - c o n t a i n i n g d e t e r g e n t .

G e n e r a l l y , w i t h a l l p h o s p h a t e - c o n t a i n i n g d e t e r g e n t s t h e r e i s a danger t h a t ,
a t l o w dosages, s p a r i n g l y s o l u b l e c a l c i u m phosphate w i l l be formed. The
consequences a r e premature wear and t e a r o f t h e wash l o a d and t h e machine, and
impairment o f t h e d e s i r e d a p p l i c a t i o n c h a r a c t e r i s t i c s ( r e f . 1 2 ) . T h i s i s
e s p e c i a l l y i m p o r t a n t i n view o f t h e i n c r e a s i n g general t r e n d towards low
dosages, brought about by economic and e c o l o g i c a l c o n s i d e r a t i o n s .
The dosage experiments show t h a t , on t h e whole, non-phosphate d e t e r g e n t s
based on z e o l i t e a r e s a f e r than p h o s p h a t e - c o n t a i n i n g p r o d u c t s , w i t h r e s p e c t t o
t h e i r e f f e c t s on t e x t i l e s and washing machines.

ECOLOGICAL ASPECTS AND MARKET TRENDS

I n v e s t i g a t i o n s i n t h e Federal R e p u b l i c o f Germany have shown t h a t consumers
want d e t e r g e n t s t o have good environmental c o m p a t i b i l i t y as w e l l as good wash
performance. The non-phosphate d e t e r g e n t s b u i l t up o f z e o l i t e A ,
p o l y c a r b o x y l a t e and sodium carbonate f u l f i l l t h e s e r e q u i r e m e n t s ( r e f s . 13-15).
T h e i r good e n v i ronmental compati b i 1 it y , t h e i r good d e t e r g e n t p r o p e r t i e s , and
t h e i r p r i c e , which i s comparable t o t h a t o f p h o s p h a t e - c o n t a i n i n g p r o d u c t s , a l l
h e l p e d them t o break through o n t o t h e market.
As a consequence t h e r e has been a d r a s t i c s h i f t i n t h e s h a r e o f t h e v a r i o u s
b u i l d e r components i n heavy-duty d e t e r g e n t s . T h i s i s i l l u s t r a t e d by a
r e p r e s e n t a t i o n o f t h e changes i n volume o f d e t e r g e n t b u i l d e r s i n t h e Federal
R e p u b l i c o f Germany ( r e f . 16, F i g . 6 ) . It can be seen t h a t , f o r example, t h e
phosphate c o n t e n t of heavy-duty powder d e t e r g e n t s has f a l l e n by 70 % s i n c e
1975. A t t h e same t i m e , t h e c a l c u l a t e d amount o f phosphate i n t h e s u r f a c e
waters o f West Germany f e l l f r o m 42 % t o 17 %, as f a r as t h e c o n t r i b u t i o n f r o m
d e t e r g e n t s and c l e a n s e r s i s concerned ( r e f . 16).

F i g . 6. Change i n volume o f d e t e r g e n t b u i l d e r s from 1975 t o 1987 i n t h e FRG.

0 Heavy-Duty Powder Detergents (End of 1987)

F i g . 7. R e l a t i v e market shares o f non-phosphate and p h o s p h a t e - c o n t a i n i n g

heavy-duty powder d e t e r g e n t s i n d i f f e r e n t European c o u n t r i e s
(A = A u s t r i a , CH = S w i t z e r l a n d , 0 = F e d e r a l R e p u b l i c o f Germany,
NL = The N e t h e r l a n d s ) .
 709

The use o f non-phosphate d e t e r g e n t s i s on t h e i n c r e a s e i n s e v e r a l European

c o u n t r i e s ( F i g . 7 ) . While i n t h e Federal R e p u b l i c o f Germany non-phosphate
heavy-duty powder d e t e r g e n t s had a market share o f 63 % by t h e end o f 1987, i n
S w i t z e r l a n d , f o r i n s t a n c e , a l l d e t e r g e n t s a r e r e q u i r e d by l a w t o b e f r e e o f
phosphates. I n t h e meantime, t h e s e p r o d u c t s have a l s o won a c o n s i d e r a b l e share
o f t h e market i n such c o u n t r i e s as A u s t r i a and The Netherlands.

The success o f z e o l i t e - c o n t a i n i n g d e t e r g e n t s t h r o u g h o u t Europe proves,

d e s p i t e a l l i n i t i a l s c e p t i c i s m , t h a t z e o l i t e A c o u l d be a s u b s t i t u t e f o r
phosphate: t h i s raw m a t e r i a l can be s a i d t o have proved i t s e l f i n t h e 15 y e a r s
s i n c e i t s d i s c o v e r y . I n view o f t h e growing need f o r e n v i r o n m e n t a l p r o t e c t i o n ,
i t s f u t u r e would seem t o be assured.

REFERENCES

1 DE 24 12 837 82, Henkel, 1974.

2 DE 24 12 838 82, Henkel, 1974.
3 P. B e r t h , G. J a k o b i , E. Schmadel, M.J. Schwuger and C.H. Krauch, Angew.
Chem. 87 (1975) 115.
4 P. B e r t h , J. Amer. O i l Chem. SOC. 55 (1978) 52.
5 M.J. Schwuger and E.J. Smulders, i n W.G. C u t l e r and E. K i s s a (Eds.),
Detergency Theory and Technology, Marcel Dekker, New York, 1987, Ch. 6, pp.
37 1-439.
6 P. B e r t h , P. K r i n g s and H. Verbeek, Tenside Deterg. 22 (1985) 169.
7 C.P. K u r z e n d o r f e r , M. L i p h a r d , W. von R y b i n s k i and M.J. Schwuger, C o l l o i d &
.
Polymer Sci 265 (1987) 542.
8 H. Andree, P. K r i n g s , H. Upadek and H. Verbeek, i n A.R. Baldwin (Ed.),
Proc. 2nd World Conference on Detergents, Montreux, 1986, p. 148.
9 W. W i r t h , I b i d . , p. 138.
10 M.K. Nagarajan, J. Amer. O i l Chem. SOC. 62 (1985) 949.
11 P. Z i n i , S e i f e n l l l e F e t t e Wachse 113 (1987) 45.
12 A. Lohr and K. Pracher, Tenside Deterg. 25 (1988) 36.
13 Umweltbundesamt, M a t e r i a l i e n 4/79, D i e Prufung des Umweltverhaltens von
Natrium-Aluminium-Silikat Z e o l i t h 4A a l s P h o s p h a t e r s a t z s t o f f i n Wasch- und
R e i n i g u n g s m i t t e l , E r i c h Schmidt (Ed.), B e r l i n , 1979.
14 L. Huber, S e i f e n U l e F e t t e Wachse 113 (1987) 393.
15 H.J. Opgenorth, Tenside Deterg. 24 (1987) 366.
16 P. B e r t h and P. K r i n g s , i n G e s e l l s c h a f t Deutscher Chemiker (Eds.),
Kompendi um Auswi rkungen d e r Phosphathochstmengenverordnung f u r Waschmi t t e l
a u f K l a r a n l a g e n und i n Gewassern, Sankt Augustin, 1988, i n press.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

S I M U L T A N E O U S S E P A R A T I O N OF S U S P E N D E D S O L I D S , A M M O N I U M A N D
P H O S P H A T E IONS FROM WASTE WATER B Y M O D I F I E D C L I N O P T I L O L I T E

J. O L A H Y 1 J. PAPP,2 A.MESZAROS-KIS,’ G Y . MUCSI’ and D. KALL02

‘ R e s e a r c h C e n t r e f o r W a t e r R e s o u r c e s D e v e l o p m e n t , 1453 B u d a p e s t ,
P.O.Box 2 7 ( H u n g a r y )
n
L
Central Research I n s t i t u t e f o r C h e m i s t r y , H u n g a r i a n A c a d e m y o f
S c i e n c e , H - 1 5 2 5 Budapest, P.O.Box 17 ( H u n g a r y )

ABSTRACT
A municipal s e w a g e t r e a t m e n t t e c h n o l o g y has been d e v e l o p e d
based o n t h e r e c o g n i t i o n t h a t ( i ) z e o l i t e - c o n t a i n i n g p o w d e r
(i.e. c r u s h e d z e o l i t i c r o c k ) o f a p p r o p r i a t e g r a i n s i z e a d d e d t o
w a s t e w a t e r i n c r e a s e s the biological a c t i v i t y o f the s l u d g e , ( i i )
removal o f s u s p e n d e d s o l i d s is i n c r e a s e d a n d ( i i i ) t h e p h o s p h a t e
removal e f f i c i e n c y o f t r i v a l e n t c a t i o n s ( F e 3 + , A l J + ) is h i g h e r
in the presence o f zeolite. A f t e r biological t r e a t m e n t t h e r e -
m a i n i n g a m m o n i u m and dissolved or c o l l o i d o r g a n i c s u b s t a n c e s c a n
be removed in a c o l u m n f i l l e d w i t h z e o l i t e (e.g. c l i n o p t i l o l i t e )
s e l e c t i v e f o r a m m o n i u m ions,

INTRODUCTION
A f t e r biological t r e a t m e n t w i t h a c t i v a t e d s l u d g e t h e o u t l e t
sewage mostly c o n t a i n s c o n t a m i n a n t s in u n a c c e p t a b l e a m o u n t s . In
o r d e r t o r e m o v e t h e r e m a i n i n g i m p u r i t i e s chemical m e t h o d s a r e
usually a p p l i e d , e.g. s u s p e n d e d s o l i d s can be c o a g u l a t e d by adding
a l u m i n i u m s u l f a t e or a s y n t h e t i c p o l y e l e c t r o l y t e s ; p h o s p h o r u s a s
p h o s p h a t e s a r e precipitated w i t h a l u m i n i u m o r i r o n s a l t s o r w i t h
l i m e ; a m m o n i u m removal proceeds via i o n - e x c h a n g e o r t h r o u g h
n i t r i f i c a t i o n f o l l o w e d by d e n i t r i f i c a t i o n (ref. 1).
C o n s i d e r i n g t h e p u b l i c a t i o n s o f p r o c e s s e s a p p l i e d it s e e m s
t h a t the i m p r o v e m e n t o f s e w a g e t r e a t m e n t t e c h n o l o g i e s is still
o f c u r r e n t interest.
As a r e s u l t s o f t h e a b o v e t r e a t m e n t s with e x p e n s i v e c h e m i c a l s ,
w a s t e s a r e f o r m e d wich c o n t a m i n a t e t h e e n v i r o n m e n t . T h e u s e o f
natural m a t e r i a l s 1 ike z e o l i t e s a s i o n - e x c h a n g e r s a n d / o r adsorbents
s e e m s r a t h e r promising, s i n c e they a r e much c h e a p e r and t h e i m p u -
r i t i e s a r e r e m o v e d in l e s s h a z a r d o u s forms.
712

Among n a t u r a l z e o l i t e s , c l i n o p t i l o l i t e o c c u r s m o s t frequently,
e.g. i n U.S.A., Japan, t h e S o v i e t U n i o n and Hungary ( r e f . 2 ) .
Ames was t h e f i r s t o b s e r v t h e s e l e c t i v e ammonium i o n - e x c h a n g e
f o r c l i n o p t i l o l i t e (ref. 3); thereafter the a p p l i c a b i l i t y o f
c l i n o p t i l o l i t e f o r ammonium r e m o v a l f r o m r a w a n d w a s t e w a t e r s was
extensively investigated. Koon a n d Kaufmann s t u d i e d i n d e t a i l
t h e ammonium r e m o v a l w i t h c l i n o p t i l o l i t e i n a f i x e d - b e d c o l u m n
and d e t e r m i n e d t h e r e g e n e r a t i o n c o n d i t i o n s ( r e f . 4 ) . Italian
experts found t h a t p h i l l i p s i t e i s applicable, too, f o r removal
o f ammonium f r o m w a t e r b y i o n - e x c h a n g e ( r e f . 5). Union Carbide
p r o d u c e d a z e o l i t e s p e c i a l l y s e l e c t i v e f o r ammonium i o n s ( r e f . 6 ) .
Similarly, i n f i x e d - b e d o p e r a t i o n L i b e r t i and c o - w o r k e r s (ref.
7,8) u t i l i z e d c l i n o p t i l o l i t e f o r ammonium r e m o v a l a n d an a n i o n -
- e x c h a n g e r e s i n f o r p h o s p h a t e r e m o v a l i n sewage t r e a t m e n t p i l o t
p l a n t s o f 10 a n d 240 m 3 / d c a p a c i t i e s .
When z e o l i t e A , came i n t o u s e as a d e t e r g e n t b u i l d e r i t s r o l e
i n sewage t r e a t m e n t was i n v e s t i g a t e d . N e i t h e r C a r r o n d o e t a l .
( r e f . 91, n o r Holman a n d H o p p i n g ( r e f . 10, 1 1 ) f o u n d any u n f a -
vourable e f f e c t o f z e o l i t e A during the treatment o f laundry
effluents.
I s h i i and K a j i p u b l i s h e d ( r e f . 1 2 1 , t h e e q u a t i o n s o f
a d s o r p t i o n i s o t h e r m s o f ammonium a n d p h o s p h a t e i o n s on s u s p e n d e d
c l i n o p t i l o l i t e doped w i t h a l u m i n i u m s u l f a t e .
The authors have succeeded i n i n c r e a s i n g t h e r e m o v a l o f s u s p e n d e d
solids, p h o s p h a t e a n d t o some e x t e n t ammonium i o n s f r o m m u n i c i p a l
sewage b y t h e u s e o f c l i n o p t i l o l i t e s u s p e n d e d i n c o n c e n t r a t e d
aqueous s o l u t i o n o f a F e 3 + s a l t . The r e m a i n i n g o f t h e ammonium
c a n t h e r e a f t e r be removed b y i o n - e x c h a n g e i n a f i x e d - b e d c o l u m n
f i l l e d w i t h c l i n o p t i l o l i t e . The a i m o f o u r f u r t h e r i n v e s t i g a t i o n s
was t o c o n f i r m t h e e a r l i e r r e s u l t s t h r o u g h l a r g e - s c a l e experiments
a n d f u r t h e r m o r e t o c l a r i f y up t h e i n f l u e n c e o f a c l i n o p t i l o l i t e
s u s p e n s i o n on t h e a c t i v i t y a n d p r o p e r t i e s o f a c t i v a t e d s l u d g e .

EXPERIMENT
Materials
A 6 3 - 1 8 0 I.cm f r a c t i o n o f a r h y o l i t e t u f f c o n t a i n i n g a b o u t 5 0 %
c l i n o p t i l o l i t e ( f r o m R a t k a , T o k a j H i l l s , H u n g a r y ) was s u s p e n d e d
i n d i f f e r e n t a m o u n t s o f aqueous i r o n c h l o r o - s u l f a t e s o l u t i o n
c o n t a i n i n g 200 g F e 3 + / l . S u s p e n s i o n s w i t h d i f f e r e n t c l i n o p t i l o l i t e /
/Fe3+ r a t i o s were used.
 713

The o p t i m a l g r a i n s i z e o f t h e t u f f was e x p e r i m e n t a l l y
determined:
( i ) t h e s m a l l e s t p a r t i c l e s must n o t escape t h e s e t t l i n g t a n k ,
( i i ) the e f f i c i e n c y o f t h e l a r g e s t p a r t i c l e s should n o t essen-
t i a l l y decrease because o f t h e s h o r t e r s e t t l i n g t i m e and t h e
slower d i f f u s i o n - c o n t r o l l e d processes,
To e n s u r e f a v o u r a b l e o p e r a t i n g c o n d i t i o n s , 0 . 5 - 2 . 0 mm g r a i n
s i z e f r a c t i o n o f t h e a b o v e t u f f was u s e d i n t h e i o n - e x c h a n g e
column.
The c l i n o p t i l o l i t e - c o n t a i n i n g t u f f i s c h a r a c t e r i z e d as
f o l l ows.
C l i n o p t i l o l i t e c r y s t a l s o f s i z e 1 - 1 0 ,urn a r e i r r e g u l a r l y
embedded i n t h e r o c k , w h i c h c o n t a i n s q u a r t z , crystobalite,
montmorillonite, f e l s p a r a n d some 1 0 % v o l c a n i c g l a s s . The
minerals form a texture w i t h a convenient pore-size d i s t r i b u t i o n .
No s w e l l i n g i s o b s e r v a b l e i n w a t e r , i . e . t h e s i z e o f p a r t i c l e s
does n o t change. The m a i n p h y s i c a l - c h e m i c a l d a t a o f t h e u s e d t u f f
a r e summarized i n T a b l e 1.

TABLE 1
The p r o p e r t i e s o f t h e c l i n o p t i l o l i t e - c o n t a i n i n g r o c k
Chemical Composition i n w t . % :
Si02 2'3 Fe203 Na20 K20 MgO CaO loss ign.
69.50 11.65 1.06 0.44 4.44 0.59 1.83 10.53

Pore-size d i s t r i b u t i o n - Volume o f p o r e s i n f u n c t i o n o f p o r e s i z e s

r d1.6 nm 0.1 c m 3 / g
1.6 -= r PP .= 1 0 nm 0.1 cm3/g
10 < r ~ 7 5 0 0nm 0.5 c m 3 / g
P
P o r o s i t y : 40-50 % ( t h e r a t i o o f t h e t o t a l p o r e volume and t h e
volume o f t h e p o r o u s m a t e r i a l )
S u r f a c e a r e a f r o m benzene a d s o r p t i o n : 20-30 mz/g
S u r f a c e a r e a f r o m n i t r o g e n a d s o r p t i o n : 400-500 mz/g
I o n - e x c h a n g e c a p a c i t y : 1.1 meq/g
The c h a r a c t e r i s t i c s o f sewages a r e l i s t e d i n T a b l e 2 t o g e t h e r
w i t h t h e mean v a l u e s o f e x p e r i m c n t a l d a t a , s i n c e d i f f e r e n t sewages
w e r e f e d i n d i f f e r e n t p l a n t s . The a m o u n t o f s u s p e n d e d s o l i d s , COD
( C h e m i c a l O x y g e n Demand) t o t a l p h o s p h o r u s a n d o r t h o - p h o s p h a t e ,
ammonium a n d n i t r a t e c o n t e n t s w e r e d e t e r m i n e d , M o h l m a n n i n d e x
( a datum f o r c h a r a c t e r i z i n g t h e s e d i m e n t a t i o n p r o p e r t i e s o f t h e
suspended s o l i d s ) and b i o l o g i c a l a c t i v i t y o f t h e s l u d g e were
m e a s u r e d , a s we1 1 .
714

TABLE 2
The m a i n p a r a m e t e r s o f sewage t r e a t m e n t s i n d i f f e r e n t p l a n t s

Location, Year Amount o f Biological Age o f sludge Character

(Type 1 sewage 1oadi ng o f sewage
m3 /d kg BOD
k g - l d-’ d

D u n a k e s z i , 1985 48 0.25 2.3 municipal

50%+canning
( p i l o t plant) f a c t o r y 50%

Zalaegerszeg, 1987 municipal 60%

1850 0.08 15.5 food i n d u s t r y 40%
(large scale)

Bal atonbereny , 1987

(large scale)
, 0.04 25 m u n i c ip a l

Equipment and Methods

C o n t i n u o u s e x p e r i m e n t s were c a r r i e d o u t i n a p i l o t p l a n t and
i n l a r g e - s c a l e p l a n t s . T y p i c a l t e c h n i c a l d a t a o f sewage treatment
a r e g i v e n i n Table 3.
The a r r a n g e m e n t o f t h e t e c h n o l o g i c a l u n i t s ( s c r e e n , g r i t
chamber, a e r a t o r , s e c o n d a r y s e t t l i n g t a n k ) w e r e t h e same f o r a l l
i n s t a l l a t i o n s . The z e o l i t e s u s p e n s i o n was a d d e d t o t h e sewage i n
t h e c h a n n e l j u s t b e f o r e t h e a e r a t o r , w h e r e a p e r f e c t m i x i n g was
achieved. The t e c h n o l o g i c a l p a r a m e t e r s ( e . g . residence time,
loading, etc.) and t h e s i z e o f equipment were i d e n t i c a l f o r b o t h
t h e e x p e r i m e n t a l a n d c o n t r o l l i n e s . The p i l o t p l a n t ( i n D u n a k e s z i )
operated w i t h high loading, t h e o t h e r s i n a t o t a l o x i d a t i o n mode.

RESULTS A N D D I S C U S S I O N
A v e r a g e s o f a g r e a t amount o f e x p e r i m e n t a l d a t a d e t e r m i n e d
b o t h i n p i l o t p l a n t and i n l a r g e - s c a l e p l a n t s a r e summarized i n
T a b l e 3 . The l a t t e r p l a n t s a r e l o c a t e d i n t h e w e l l p r o t e c t e d a r e a
o f Lake-Balaton.
 715
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716

Removal o f P h o s p h o r u s
D e p e n d i n g on t h e amount o f c o n t a m i n a n t s 15-30 mg F e 3 + a n d
30-100 mg p o w d e r e d c l i n o p t i l o l i t e c o n t a i n i n g r o c k i s a d d e d t o
one l i t r e o f sewage. The r e m o v a l o f p h o s p h o r u s i n t h e p i l o t p l a n t
( i n D u n a k e s z i ) as a f u n c t i o n o f t i m e on f l o w i s i l l u s t r a t e d i n
Fig. 1. I n most p r o t e c t e d d i s t r i c t s o f Hungary (around t h e g r e a t
l a k e s ) t h e p e r m i t t e d l i m i t o f p h o s p h o r u s c o n t e n t i n emmissions i s
1.8 mg P/1 (5,5 mg P O i - / l ) , w h i c h c a n r e l i a b l y be a t t a i n e d w i t h
t h i s treatment.

5 10 15 20 25 30 50 55 60
time, day

F i g . 1. O r t h o - p h o s p h a t e c o n c e n t r a t i o n as a f u n c t i o n o f t i m e on
f l o w i n t h e s e t t l e d sewage i n l e t (l), i n t h e c o n t r o l sewage o u t l e t
( w i t h o u t additives, 2 ) , w i t h a d d i t i o n o f a suspension c o n t a i n i n g
18.3 mg F e 3 + / l + 65 mg z e o l i t e / l ( 3 )
On a d d i n g 1.16-1.95 i r o n i o n s t o g e t h e r , w i t h the suspension o f
z e o l i t i c r o c k t o 1 atom phosphorus, a d e p h o s p h o r i z a t i o n t o 1.8 mg
P/1 c a n be g u a r a n t e e d . W i t h o u t z e o l i t e a d d i t i v e 1.7-2.5 i r o n ions
a r e needed f o r c o m p a r a b l e p u r i f i c a t i o n . Our o b s e r v a t i o n s , sup-
p o r t e d by t h e f i n d i n g o f I s h i i and K a j i ( r e f . 12), a r e s i m i l a r
f o r A12(S04)3 a d d i t o n w i t h and w i t h o u t z e o l i t e s . Consequently,
t h e e f f i c i e n c y o f phosphate removal w i t h t r i v a l e n t c a t i o n s
increases i n the presence o f z e o l i t e ; 1 g o f z e o l i t i c rock i t s e l f
removes 6 . 4 mg p h o s p h o r u s o w i n g t o t h e m o b i l e Ca a n d Mg ( F e ) i o n s
i n t h e z e o l i t e phase which f o r m phosphate p r e c i p i t a t e
 717

a f t e r e x c h a n g e f o r ammonium i o n s f r o m t h e sewage. The o b s e r v e d

e f f e c t o f c l i n o p t i l o l i t e i s 3-6 times g r e a t e r t h a n t h e v a l u e o f
6.4 mg/g. A f t e r an o p e r a t i o n p e r i o d f o r some weeks t h e p h o s p h a t e
removal e f f i c i e n c y i s preserved i n the z e o l i t e containing aerator,
when t h e dosage i s s t o p p e d e v e n f o r o n e d a y .
The r e a s o n f o r t h i s e f f e c t i s t h e r e t e n t i o n o f i r o n i n t h e
z e o l i t i c r o c k i n t h e a e r a t o r . The r e s i d e n c e t i m e o f z e o l i t i c r o c k
w i t h i r o n s a l t occluded i n the pores o f d i f f e r e n t s i z e i s l o n g e r
t h a n t h a t o f n o n - f i x e d i r o n s o l u t i o n . The r e t a r d e d d e s o r p t i o n o f
i r o n during a longer residence time r e s u l t s i n a b e t t e r utilization
o f t h e Fe3+ introduced. This i s i n q u a n t i t a t i v e c o r r e l a t i o n w i t h
the experimental findings.
Removal o f Suspended S o l i d s
I n each case t h e c o n t e n t o f suspended s o l i d s i n t h e e f f l u e n t
i s l e s s when t h e b i o l o g i c a l t r e a t m e n t o f t h e sewage i s c a r r i e d
out with z e o l i t e / i r o n - s a l t addition than without i t (c.f.
" e x p e r i m e n t a l " a n d " c o n t r o l " d a t a i n T a b l e 3 ) : e.g. i n a large
s c a l e p l a n t ( Z a l a e g e r s z e g ) t h e e f f l u e n t c o n t a i n e d 35 m g / l
s u s p e n d e d s o l i d s w h i c h d e c r e a s e d t o 18 m g / l b y z e o l i t e / i r o n - s a l t
addition. The z e o l i t e p a r t i c l e s p r e f e r a b l y a d s o r b c o l l o i d s , and
c o a g u l a t i o n s e e d s a r e t h u s f o r m e d . The h y d r o x i d e s o f m e t a l s
f o r m e d f r o m t h e i n t r o d u c e d s a l t s e x e r t an a d d i t i o n a l c o a g u l a t i o n
effect .
As a r e s u l t o f z e o l i t e t r e a t m e n t ( i ) t h e d e n s i t y o f a c t i v -
a t e d s l u d g e i n c r e a s e s f r o m 1 5 g / l t o 30 g / 1 i n t h e s e c o n d a r y
s e t t l i n g tank, ( i i ) the d e w a t e r a b i l i t y improves, i . e . the
c a p i l l a r y s u c t i o n t i m e decreases f r o m 30 s t o 10-15 s , and ( i i i )
t h e Mohlmann i n d e x d i m i n i s h e s s i g n i f i c a n t l y .
The E f f e c t o f Z e o l i t e on t h e B i o l o g i c a l A c t i v i t y o f t h e S l u d g e
An i n c r e a s e d b i o l o g i c a l a c t i v i t y i s r e f l e c t e d b y t h e C O D
v a l u e s o f t h e f i l t e r e d e f f l u e n t s ( T a b l e 3 ) s i n c e w i t h t h e same
residence times, they are r e g u l a r l y lower a f t e r z e o l i t e treatment
than i n the c o n t r o l l i n e .
The d i g e s t i o n a c t i v i t y o f t h e s l u d g e c a n be b e t t e r e x p r e s s e d
i n terms o f COD g - l h - l . Pilot p l a n t experiments (Dunakeszi, 1986)
showed an a c t i v i t y o f 52 C O D 9 - l h - l i n t h e c o n t r o l l i n e and 65 COD
g-'h-' i n t h e case o f z e o l i t e i n t r o d u c t i o n . The c o r r e s p o n d i n g
v a l u e s i n an o p e r a t i n g p l a n t ( B a l a t o n b e r e n y , 1 9 8 7 ) w e r e 35 a n d
44 C O D g - l h - ' , respectively. These e x a m p l e s ( a n d a s e r i e s o f
o t h e r d a t a ) p o i n t t o an i n c r e a s e o f t h e b i o l o g i c a l a c t i v y b y
a b o u t 2 5 % due t o z e o l i t e i n t r o d u c t i o n .
 Upon z e o l i t e a d d i t i o n a s i g n i f i c a n t i n c r e a s e o f n i t r i f i c a t i o n
has b e e n o b s e r v e d a s w e l l . For instance, i n Zanka ( 1 9 8 6 ) i t was
a b o u t 60%, i . e . 53 m g / l a n d 85 m g / l n i t r a t e c o n t e n t s w e r e f o u n d
i n the effluents o f c o n t r o l and e x p e r i m e n t a l l i n e s r e s p e c t i v e l y .
The c o r r e s p o n d i n g v a l u e s i n B a l a t o n b e r e n y ( 1 9 8 7 ) w e r e 24 m g / l
a n d 57 m g / l , respectively.
The i n c r e a s e o f b i o l o g i c a l a c t i v i t y e f f e c t e d t r o u g h z e o l i t i c
a d d i t i v e c a n be e x p l a i n e d as f o l l o w s :
( i ) Z e o l i t e p a r t i c l e s a r e seeds f o r b a c t e r i a f l o c k s .
F l o c k s a r e t h u s f o r m e d i n g r e a t e r number a n d o f s m a l l e r s i z e t h a n
i n t h e absence o f z e o l i t i c g r a i n s . With z e o l i t e s the f l o c k s are
s m a l l e r t h a n 0.3 mm; w i t h o u t z e o l i t e s t h e i r s i z e i s b e t w e e n 0.4
a n d 2 mm. The t r a n s p o r t o f o x y g e n a n d n u t r i e n t s i s f a s t e r i n t h e
s m a l l e r f l o c k s t h a n i n l a r g e r ones.
( i i ) Z e o l i t e p a r t i c l e s s o r b ammonia w h i c h i s a c c e s s i b l e f o r
n i t r i f i c a t i o n b a c t e r i a c o n c e n t r a t e d on z e o l i t e c r y s t a l s , thus the
n i t r i f i c a t i o n accelerates.
( i i i ) The b i o l o g i c a l c o m p o s i t i o n o f a c t i v a t e d s l u d g e c h a n g e s
f a v o u r a b l y i n t h e p r e s e n c e o f z e o l i t e . The " p r e d a t o r c i l i a t e s "
(Litonotus, Loxophillum, Vorticella, Convallaria, Opercularia,
C o a r e t a t a ) m u l t i p l y . Nematodes a l s o a p p e a r i n t h e s l u d g e . These
a n i m a l s f e e d on t h e f r e e - s w i m m i n g b a c t e r i a i n l i q u i d phase.
( i v ) The b i o l o g i c a l s t a b i l i t y o f t h e s e p a r a t e d a n d z e o l i t e
containing sludge i s greater than without z e o l i t e : observable
a n a e r o b i c d i g e s t i o n proceeds w i t h i n f i v e days i n t h e absence o f
z e o l i t e w h e r e a s t h e s l u d g e r e m a i n s u n c h a n g e d e v e n f o r t h r e e weeks
u n d e r t h e same c o n d i t i o n s , i f i t c o n t a i n s z e o l i t e . The phenomenon
i s being investigated i n d e t a i l .
( v ) Contrary t o usual sludges, the desiccated sludge
c o n t a i n i n g z e o l i t e i s o f h i g h v a l u e because a f t e r composting i t
c a n be u s e d a s a f e r t i l i z e r o f s u f f i c i e n t n u t r i e n t v a l u e s . When
i n s t e a d o f i r o n s a l t an a l u m i n i u m s a l t i s u s e d f o r t h e treatment,
h o w e v e r , t h e s l u d g e c a n h a r d l y be u t i l i z e d i n a g r i c u l t u r e .
F i n a l Treatment
A f t e r b i o l o g i c a l treatment o f increased a c t i v i t y the r e s t o f
t h e ammonium c a n be r e m o v e d c o n v e n t i o n a l l y b y i o n - e x c h a n g e w i t h
zeolite, p r e f e r a b l y w i t h c l i n o p t i l o l i t e because o f i t s h i g h
s e l e c t i v i t y f o r ammonium. The ammonium c o n t e n t i n t h e o u t l e t c a n be
kept below 4 mg/l. The o p e r a t i o n p a r a m e t e r s f o r o u r p i l o t p l a n t w e r e
o p t i m i z e d . The f i l l i n g c a n be r e p e a t e d l y r e g e n e r a t e d w i t h a 2 w t . %
 719

KCl/NaCl s o l u t i o n o f pH =- 1 0 . The ammonia was r e m o v e d e i t h e r b y

s t r i p p i n g w i t h a i r and a b s o r b i n g , e.g. i n a phosphoric a c i d
solution, o r b y p r e c i p i t a t i o n i n t h e f o r m o f MgNH4P04. We
observed t h a t t h e f i r s t s e c t i o n o f ion-exchanger works as a
filter, where d i s s o l v e d o r c o l l o i d ( m a i n l y o r g a n i c ) c o n t a m i n a n t s
n o t a l r e a d y removed a r e bound. A f t e r t h e c o u n t e r c u r r e n t r e g e n e r -
a t i o n they can be s e t t l e d from t h e r e g e n e r a t i n g s o l u t i o n .

REFERENCES

1 Water T r e a t m e n t Handbook, V . E d i t i o n , Degremont 1979, pp.

57-74, 141-144.
2 Y . M u r a k a m i , A . I i j i m a a n d J.W. Ward ( E d i t o r s ) : New Development
i n Z e o l i t e Science and Technology. E l s e v i e r S c i e n t i f i c P u b l .
Co. A m s t e r d a m , 1 9 8 6 .
3 L . L . Ames: Amer. M i n e r a l o g i s t 4 5 ( 1 9 6 0 ) 6 8 9 - 7 0 0 .
4 J.H. Koon a n d W.J. K a u f m a n : O p t i m a t i o n o f Ammonia Removal b y
I o n E x c h a n g e U s i n g C l i n o p t i l o l i t e . U S R e p o r t f o r t h e EPA, 1 9 7 1 .
5 P. C i a m b e l l i , P . C o r b o , C . P o r c e l l i a n d A . R i m o l i : Z e o l i t e s 5
( 1 9 8 5 ) 184-187.
6 US P a t e n t 3 723 3 0 8
7 L. L i b e r t i , G. B o a r i a n d R. P a s s i n o : Wat. S u p p l y 1 ( 1 9 8 3 ) ,
169-176.
8 L . L i b e r t i , N. L i m o n i , A . L o p e z , R . P a s s i n o a n d G . B o a r i :
Water Research 20 ( 1 9 8 6 ) 735-739.
9 M.J.T. C a r r o n d o , R . P e r r y a n d J.N. L e s t e r : J. Wat. P o l l u t .
C o n t r o l Fed. 52 ( 1 9 8 0 ) 2 7 9 6 - 2 8 0 6 .
1 0 W.F. H o l m a n a n d W.D. H o.p.p i n q- : J. W a t . P o l l u t . C o n t r o l F e d . 52
(1980) 2887-2905.
1 1 J.E. K i n g , D.W. H o p p i n g a n d F.W. H o l m a n : I . J . Wat. P o l l u t .
C o n t r o l Fed. 52 ( 1 9 8 0 1 2 8 7 5 - 2 8 8 6 .
1 2 M . I s h i i a n d K. K a j i : . G y p s u m a t L i m e 186 ( 1 9 8 3 ) 8 - 1 6 .
This Page Intentionally Left Blank
IV . M0DIFICATI0N AND CHARACT ER IZ AT I0N
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

FRAMEWORK AND NON-FRAMEWORK A1 SPECIES IN DEALUMINATED ZEOLITE Y

P.J. Grobet, H. Geerts, M. Tielen, J.A. Martens and P.A. Jacobs

Laboratorium voor Oppervlaktechemie, Kathol ieke Universitei t Leuven,
Kardinaal Mercierlaan 92, B-3030 Leuven, Belgium

ABSTRACT
The hydrothermal dealumination of zeolite Y was followed by "Si and 27Al
MAS NMR. From deconvoluted MAS NMR spectra the amount of the different silicon
and aluminium s cies, formed during steaming, could be determined. Next to
well documented signals at 60 ppm of tetrahedral framework A1 and at 0 ppm
of octahedral Al, lines at 50 ppm, 30 ppm and in the region of 4-0 ppm are
observed, the chemical nature of which is discussed. Zeolite Y with framework
Si/Al ratio from 3.5 to 17 contains non-negligible amounts of extra-framework
silicon and aluminium species, which complicate the determination of the
framework Si/Al and non-framework:framework A1 r ios. A considerable amount of
extra-framework aluminium is missing in the "A1 MAS spectra. This 'NMR-
invisible' aluminium, assigned to oligomeric alumina species, can be made 'NMR-
visible' by complexation with acetylacetone under specific conditions.

INTRODUCTION
"Si and 27Al MAS NMR is a powerful technique to provide direct information
pertaining the local environment of these nuclei in zeolite structures (ref.
1). Knowledge of the coordination and quantification of the different A1
species is essential in understanding the catalytic activity (ref. 2). In
principle, from "Si MAS NMR spectra the si1icon:aluminium ratio of the
framework (SiF/AIF) can be determined and from 27Al spectra the non-
framework:total A1 ratio (AINF/A1).
With hydrothermally dealuminated faujasites incorrect AINF/A1 are obtained
(refs. 3-6) due to the presence of so-called 'NMR-invisible' aluminium which
resides in non-framework environments of low symmetry subjected to large
electric field gradients; the corresponding large quadrupole effect on the 27Al
nucleus results in a broadening of the NMR signal beyond the detection limit.
In a previous paper (ref. 7) we reported on a technique to visualize all NMR-
invisible Al. The method consists of converting non-framework aluminium with
acetylacetone (acac) into A l ( a ~ a c ) ~complexes, the 27Al MAS NMR signals of
which can be re1 iably used for quantitative interpretation.
In this report we show that our method is applicable to weakly as well as
strongly dealuminated faujasites. The application of our acac impregnation
method is discussed and compared to former efforts (refs. 8-10). In steamed
faujasites different non-framework aluminium and silicon species are observed.
Their chemical nature and quantification will also be elucidated.
122

EXPERIMENTAL
M a t e r i a l s . NaY from Ventron w i t h Si/Al=2.46 was exchanged 90% w i t h NH4' and
steamed i n various ways. Samole 1 was obtained by self-steaming hydrated NH4-Y
i n deep-bed geometry (height x diameter=3x3 cm) a t 873 K f o r 4 h. SamDle 2
r e s u l t e d from t h e same treatment a t 823 K f o r 24 h, followed by NH4-exchange, a
second c a l c i n a t i o n a t 973 K, and a f i n a l NH4-exchange. SamDles 3. 4 and 5 were
obtained from Sample 2 by a treatment under 0.1 MPa o f steam a t 823 K f o r 1 h,
a t 973 K f o r 3 h and a t 973 K f o r 7 h, r e s p e c t i v e l y . Hydrated samples were
obtained by immersing t h e z e o l i t e s i n water and d r y i n g a t room temperature.
S i l ica-alumina w i t h Si/A1=7.7 was prepared by h y d r o l y s i n g t e t r a e t h y l o r t h o -
s i l i c a t e and aluminium isopropoxide. A1 ( a c a c l j comolex was purchased from
Janssens Chimica.
Acac treatment. A 1 g q u a n t i t y o f hydrated z e o l i t e was soaked i n 2 m l 38
v01.-% acac i n ethanol a t 293 K. A f t e r 1 h t h e ethanol and t h e excess acac was
evaporated a t 293 K under a f l o w o f dry a i r . MAS NMR spectra were recorded 24 h
a f t e r t h e impregnation.
NMR measurements. The NMR measurements were performed using a Bruker 400
MSL spectrometer w i t h a magnetic f i e l d o f 9.4 T. The "Si MAS NMR experiments
were r u n a t 79.5 MHz, w i t h a pulse l e n g t h o f 4 p s , a pulse i n t e r v a l o f 5 s, a
spinning r a t e o f 3 kHz and 10,000 scans. 27Al MAS NMR was performed a t 104.2
MHz, w i t h a pulse l e n g t h o f 0.6 ps, a radiofrequency f i e l d s t r e n g t h o f 5 mT, a
pulse i n t e r v a l o f 1 s, u s u a l l y a spinning frequency o f 5 kHz and 3,000 scans.
The r a t h e r strong and very s h o r t pulse i s necessary t o s a t i s f y t h e c r i t e r i a o f
uniform, quadrupole-interaction-independent e x c i t a t i o n o f t h e c e n t r a l 27Al
t r a n s i t i o n ( r e f . 11). The d i f f e r e n t l i n e s i n the "Si and 2 7 A l spectra were
deconvoluted using the Bruker GLINFIT program ( r e f . 12). The best f i t s o f the
29Si and 2 7 A l spectra were obtained w i t h Gaussian and Lorentz l i n e form,
respectively .
RESULTS
29Si and 27Al MAS NMR spectra and t h e i r deconvolution are shown i n Figs.1-5
f o r t h e hydrated and acac-treated Samples 1-5. The 29Si spectra encompass
S i ( O A l ) , S i ( l A l ) , Si(ZA1) and Si(3A1) l i n e s and a l i n e a t -110 ppm, denoted
w i t h ' a ' . The Si(OA1) and Si(lA1) l i n e are o f t e n asymmetric and were f i t t e d
w i t h a double l i n e s t r u c t u r e . The 2 9 S i spectra o f t h e acac-treated samples and
o f the hydrated samples are very s i m i l a r .
The 27Al spectra i n Figs. 1-5 o f Jwdrated Samples 1-5 e x h i b i t a l i n e T a t
60 ppm. I n t h e 4-0 ppm region a second l i n e , 0', i s observed. An a d d i t i o n a l
l i n e , p o s i t i o n e d between -5- -15 ppm i s present i n t h e spectra o f Samples 2-5
and i s denoted a l s o w i t h 0'. A weak, sharp l i n e , 0, i s superimposed on the
broad l i n e s 0' a t 0 ppm i n t h e 27Al spectrum o f Sample 4 (Fig. 4). Besides the
0' and T l i n e s , i n t h e 27Al MAS NMR spectrum o f Samples 1 and 2 a l i n e i s
observed a t 50 ppm, denoted w i t h T' (Figs. 1 and 2). Samples 3 and 4 e x h i b i t an
a d d i t i o n a l l i n e T" a t 30 ppm (Figs. 3 and 4). Sample 5 shows o n l y a T" l i n e ,
w h i l e T' i s absent (Fig. 5).
 123

29si NMR
"Yd Acac
3fl 2fd 1Al
n

I . . d . 1 . * . . 1 . . . , 1 . . . .
-90 -100 -110 -90 -100 -110
PPH PPH

NMR
Acac

T T' ?' T T'

Fig. 1. Experimental (A) and deconvoluted (B) "Si and *'A1 MAS NMR spectra o f
hydrated (Hyd) and acac-treated (Acac) Sample 1. Side bands o f l i n e T
are i n d i c a t e d w i t h '*'.
724

~ Q SNMR
I
Acac
3AI 2AI 1Al OAl a 3AI 2AI 1Al OAl a
I I I I

2 7 NMR
~ ~
HYd Acac
T T' 0' T T' 0' 0"
I I
h I I

1 , , , , 1 , , , , 1 , . . . l , . ,
100 50 0 -50
PPH

Fig. 2. Experimental (A) and deconvoluted (B) 29Si and 27Al MAS NMR spectra o f
hydrated (Hyd) and acac-treated (Acac) Sample 2. Side bands o f line T
and 0" are indicated with '*' and 'm', respectively.
 725

29Si NMR
Acac
3f1 2f1 if1 0
4 a
I
3AI
I
2AI
I
1Al OAl
i n
7

2 7 NMR
~ ~
Acac
T T'
I l
T"
l
0'
h
T T' T"
I 1 1
?'$"

100 58 8 -50 100 50 8 -50

PPM PPH

Fig. 3. Experimental (A) and deconvoluted (B) 2 9 S i and 27Al MAS NMR spectra o f
hydrated (Hyd) and acac-treated (Acac) Sample 3. Side bands o f l i n e T
and 0" are i n d i c a t e d w i t h '*' and 'm', r e s p e c t i v e l y .
726

2 9 NMR
~ ~
Acac
3Al 2T1 1A1 OAla 3AI 2AI 1Al OAl a
I I nl I I I ni

2 7 NMR
~ ~
HYd Acac
T T' T" 0'0 T T' T"
I l l I 1 I

Fig. 4 . Experimental (A) and deconvoluted [S) 29Si and 2 7 A l MAS NMR spectra o f
hydrated (Hyd) and acac-treated (Acac) Sample 4 . Side bands of l i n e T
and 0" are indicated with '*' and 'm', respectively.
 121

2% NMR
HYd Acac
2fl 1Al OAl a 2AI ltl ( l a
I I l l I I

I
0

-90 -100
PPH
G
-110

2 7 NMR
~ ~
Acac
T
I
1" 0 0"
I r n

Fig. 5. Experimental (A) and deconvoluted (B) *'Si and 27Al MAS NMR spectra o f
hydrated (Hyd) and acac-treated (Acac) Sample 5. Side bands o f line T
and 0" are indicated with and 'a', respectively.
I*'
128

The 27Al spectra of the acac-treated samples show T signals for Samples 1 -
5, T' lines for Samples 1-4, T" lines for Samples 3-5, a signal 0' in the 4-0
ppm region for Samples 2-5, and for all samples three additional lines at -2, -
7 and -12 ppm, denoted with 0" (Figs. 1-5). The 27Al MAS NMR spectra of Sample
1 and 2 did not change after a second treatment with acac. For Samples 4 and 5
the relative intensity of the 0" lines with respect to the other signals
increased after a second acac treatment. Further acac treatments did not change
the spectra.

2 7 NMR
~ ~
T
I
0
I
' T do
I I I

Fig. 6. 27Al MAS NMR spectra of Sample 4 with (A) and without (8) NHq-exchange.

2 g NMR
~ ~ 2 7 NMR
~ ~
T' T" 0'
h

1 . 1 . I . ' " ' l . . . . . . . . . I . . . . . . . . . I . . . . . . . . . l . .

-100 -120 200 180 0 -100
PPM PPti

Fig. 7. Experimental "Si and experimental (A) and deconvoluted (B) 27Al MAS
NMR spectra of silica-alumina. The side bands of line T'are indicated
with '*' and I * * ' .
 729

2%1 NMR

, 1 1 1 1 I , I # 6 I I I I 1 1 1 l I L 1 , I * , I I I , , , , I ,
10 5 0 -5 -10 -15 -20
PPM

Fig. 8. 27Al MAS NMR spectrum of Al(acac)j.

The 27Al spectra of Sample 4 with and without NH4-exchange are compared in
Fig.6. These NMR spectra were obtained using a long delay time in order to
enhance the resolution of the broad 0' signals and the sharp line 0. Line 0
disappears after NH4-exchange.
Silica-alumina exhibits 27Al signals at 50, 30, 0 and -15 ppm and a very
broad 29Si line with maximum intensity at -108 ppm shown in Fig. 7. The 27Al
spectrum of A l ( a ~ a c ) shown
~ in Fig. 8 is a spectrum with three maxima at - 2 , -7
and -12 ppm.

DISCUSSION
NMR-visible extra-framework aluminium soecies in hydrated fau.iasites
The assignments of the 27Al line at 60 ppm to aluminium, tetrahedrally
coordinated in the zeolite Y framework, and at 0 pprn to octahedral non-
framework aluminium is generally accepted (ref. 1). In hydrothermally
dealuminated faujasites additional 27Al lines in the range of 50-30 ppm have
been observed by several authors. Gilson et al. found next to lines at 61 and 0
ppm a resonance at 34 ppm in zeolite Y with SiF/AlF=23, obtained by steaming at
1033 K in 100% steam (ref. 13). Samoson et al. observed 60, 50, 30 and 0 ppm
lines in the 27Al spectrum of zeolite Y, dealuminated under 0.1 MPa of steam
successively at 873 and 1123 K and with SiF/AlF=20 (ref. 11). Freude et al.
(ref. 4,5) reported 60, 50 and 0 ppm 27Al signals in zeolite Y with SiF/AlF=26,
obtained by hydrothermal dealumination at 1043 K. From these data it seems that
50 and/or 30 ppm 27Al lines are typical for highly dealuminated faujasites, but
it is not clear which factors govern their appearence.
The data of Figs. 1-5 shed more light on the conditions under which the
species that give rise to 30 and 50 ppm signals are formed. Samples 1 and 2
exhibit a 50 ppm signal and no 30 ppm signal (Figs. 1-2). These zeolites are
self-steamed and are weakly dealuminated. For Samples 3, 4 and 5, which were
steamed under 0.1 MPa of steam, the intensity of the 50 ppm signal decreases
while that of the 30 ppm signal increases with increasing steaming severity
730

(Figs. 3-5). The species which g i v e r i s e t o t h e 50 ppm s i g n a l seem t o be

unstable under t h e steaming c o n d i t i o n s applied, w h i l e t h e ones responsible f o r
the 30 ppm seem t o be formed under such conditions. Thus t h e 30 ppm l i n e has t o
be assigned t o non-framework aluminium.
Signals a t 50, 30 and 0 ppm were observed w i t h s i l i c a - a l u m i n a ( r e f . 13).
Before steaming s i l i c a - a l u m i n a shows one s i n g l e signal a t about 50 ppm,
assigned t o aluminium, t e t r a h e d r a l l y coordinated i n an amorphous s i l i c a m a t r i x ,
w h i l e a f t e r steaming a d d i t i o n a l s i g n a l s appear a t 0 and 30 ppm ( r e f . 13). I n
the spectrum o f s i l i c a - a l u m i n a shown i n Fig. 7 t h e main s i g n a l s are a t 50 and 0
ppm and weaker l i n e s are positioned a t 30 and -15 ppm. Corma e t a l . ( r e f . 14)
suggested t h a t upon dealumination o f z e o l i t e Y amorphous s i l i c a - a l u m i n a w i t h
strong B r ~ n s t e da c i d i t y i s formed. It i s found now t h a t 2 7 A l s i g n a l s a t 50, 30,
0 and -15 ppm, observed w i t h s i l i c a - a l u m i n a (Fig. 7), appear i n t h e spectra o f
steamed z e o l i t e Y (Figs. 1-5). I n view o f t h i s evidence, we are tempted t o
associate the 50 ppm signal t o aluminium, t e t r a h e d r a l l y coordinated in
amorphous s i l i c a - a l u m i n a . The 50 ppm l i n e i s denoted as T' i n order to
d i s t i n g u i s h i t from the framework T l i n e . Freude e t a l . a s c r i b e t h e 50 ppm l i n e
t o t e t r a h e d r a l non-framework aluminium however, i n a d i f f e r e n t environment,
v i z . AlOOH associated w i t h two framework oxygens ( r e f s . 4,5).
Samoson e t a l . using LD-spectroscopy found t h a t t h e apparent l i n e p o s i t i o n
o f t e t r a h e d r a l l y coordinated aluminium can vary between 70 and 30 ppm, due t o
second-order quadrupole e f f e c t s ( r e f . 11). I n t h a t work 27Al l i n e s a t 30 and 50
ppm i n spectra o f dealuminated f a u j a s i t e were both assigned t o T'. Gilson e t
a l . a t t r i b u t e d the 30 ppm l i n e t o penta-coordinated non-framework aluminium
(ref. 13), based on t h e l i n e p o s i t i o n o f penta-coordinated aluminium in
andalusite. Our work provides evidence t h a t t h e species responsible f o r the 30
ppm signal are chemically d i f f e r e n t from those o f t h e T' l i n e as t h e i r r e l a t i v e
i n t e n s i t y v a r i e s w i t h t h e s e v e r i t y o f t h e steaming. Although t h e n a t u r e of i t s
coordination i s n o t c l e a r , t h e 30 ppm l i n e w i l l be considered f u r t h e r as
t e t r a h e d r a l and denoted w i t h T" i n Figs. 1-5.
Mobile octahedral A ~ ( H z O ) ~ ~complexes
+ l o c a t e d i n t h e z e o l i t e pores on
c a t i o n i c s i t e s g i v e r i s e t o 0 ppm s i g n a l s ( r e f . 3). A narrow 0 ppm l i n e i s
observed i n hydrated Sample 4, next t o broader l i n e s w i t h s l i g h t l y p o s i t i v e
chemical s h i f t a t 4-0 ppm and s l i g h t l y negative s h i f t a t -15 ppm (Fig. 4). The
0 ppm l i n e disappears a f t e r NH4-exchange (Fig.6), w h i l e t h e broad l i n e s are n o t
influenced. Therefore, t h e narrow l i n e a t 0 ppm i s caused by exchangeable
aluminium c a t i o n s and t h e broader l i n e s by unexchangeable species. Due t o t h e i r
d i f f e r e n t nature the 0 ppm l i n e w i l l be f u r t h e r denoted by 0, and t h e 4-0 and
- 5 - -15 ppm l i n e s by 0', r e s p e c t i v e l y . I n Samples 1-3 and 5 l i n e 0 i s n o t
observed. An assignment o f l i n e s 0' t o s p e c i f i c non-exchangeable species i s
d i f f i c u l t . Several s t r u c t u r e s w i t h 6-coordinated A1 show 27Al NMR l i n e s i n t h e
 731

15 t o -15 ppm range ( r e f . 15). Perhaps the broad l i n e s 0' are due t o polymeric
aluminium species left i n the pores a f t e r dealumination of the zeolite
framework by steaming. Support t o this assignment is provided by X-ray
d i f f r a c t i o n measurements o f Shannon e t a l . (ref. 16); i n steamed Y they
observed octahedral A1 i n a boehmite topology.

SiF/AIF r a t i o from 2 9 S i MAS NMR sDectra

The S i F / A I F r a t i o o f a f a u j a s i t e can be c a l c u l a t e d from t h e 29Si spectrum
using the i n t e n s i t y o f the i n d i v i d u a l Si(nA1) l i n e s ( r e f . 1). For dealuminated
faujasites a c o r r e c t determination o f t h e Si(nA1) l i n e i n t e n s i t i e s can be
complicated due t o the presence o f signals o f non-framework s i l i c o n ( S i N F ) . I n
t h e "Si spectra o f Sample 1-5 a signal appears a t -110 ppm (Figs. 1-5). This
p o s i t i o n i s t y p i c a l f o r a Si(OA1) amorphous environment ( r e f . 17). As discussed
i n previous section, amorphous s i l i c a - a l u m i n a i s a l s o present i n the
dealuminated samples. The corresponding 29Si signals, which are expected t o be
broad (Fig. 7), could not be resolved (Figs. 1-5). The amount o f amorphous
s i l i c a i n t h e samples ( S i N F / S i ) and t h e S i F / A I F r a t i o c a l c u l a t e d from the
deconvoluted "Si spectra o f Figs. 1-5 are given i n Table 1. The S i F / A I F and
the SiNF/Si r a t i o s o f the d i f f e r e n t hydrated and acac-impregnated samples are,
w i t h i n experimental error, the same (Table l), i n d i c a t i n g t h a t t h e acac-
treatment does not modify the z e o l i t e s .

TABLE 1
SiF/AIF, S i N F / S i and AINF/Al r a t i o o f hydrated and acac-treated Sample 1-5

Sample 29si NMR 2 7 ~ 1NMR

No. S i F / A I F S i N F / S i AINF/Al(a) AINF/Al(b) ~i

NF/AI A1 F/Al
(%I (%I (%I T' TI1 0' 0 oll(e,f) T(f)
(%) (%) (%) (%) (%) (%) (%))

1 3.49 8 29 35 1 4 7 - 7 - - 86
1 A(d) 3.47 6 28 33 26 6 - 20 74
2 H 4.8 6 48 51 34 9 - 2 5 - - 66
2A 5.1 7 49 54 56 8 - 48 44
3 H 6.3 17 61 67 42 5 4 3 3 - - 58
3A 6.0 16 58 65 60 4 3 53 40
4H 7.4 20 66 72 52 8 16 27 1 - 48
4A 7.7 19 68 73 68 6 13 49 38
5H 13 10 81 83 47 - 19 28 - - 53
5A 17 7 85 86 81 - 13 68 19
a, from eqn. 1; b, from eqn. 3; c, hydrated; d, acac-treated; e, i n c l u d i n g 0';
f, i n c l u d i n g associated side bands; t h e average accuracy on t h e i n t e n s i t y o f
the l i n e s i s about 10%.
13 2

AINFIAI ratio from 29si MAS NMR sDectra

From the deconvoluted 29Si NMR spectra and the ratio of silicon to
aluminium of the sample (Si/Al), AINF/Al (X) can be calculated from the
following equation (ref. 7,ll):

For steamed faujasites for reasons explained above Si/AIF is different from
SiF/AIF, derived from the 29Si spectrum. Indeed, Si=SiFtSiNF. Therefore, eqn. 1
can be written as:

or else:

The Si/A1 ratio of the starting material can be used to calculate AINF/A1
from eqn. 1 if no aluminium or silicon was leaving the sample during steaming
and NH4-exchange. The data of Fig. 6 indicate that during the latter treatment
exchangeable aluminium species, responsible for 27Al line 0, can be lost.
Nevertheless, the intensity o f line 0 in Sample 4 is low and non-existing in
Sample 1-3 and 5. A loss of silicon is highly improbable. For the calculation
of AINF/Al of Sample 1-5, a Si/Al value of 2.49 was used, determined for NaY
with "Si NMR and in excellent agreement with the value of 2.46 from chemical
analysis. SiNF/SiF was the ratio o f the intensities of line a (-110 ppm) to
that of the Si(nA1) lines. In Table 1, AINF/Al was calculated from eqn. 1 using
SiF/AIF, and according to eqn. 3. It can be seen from Table 1 that the
correction for non-framework silicon is significant.
Visualization of NMR-invisible extra-framework aluminium soecies
For hydrated Samples 1-5, AINF/A1 calculated as the 27Al (T'tT"tOtO')/
(TtT'tT"tOt0') line intensity ratio is given in Table 1. The values of AINF/A1
thus obtained are systematically lower than those obtained from the 29Si
spectra (Table 1). This is the well-known problem of invisible aluminium in the
27Al spectra of dealuminated zeolites explained in the introduction and which
cannot be solved even when optimized instrumental conditions (short, strong
excitation pulse, high spinning and resonance frequency) are used (ref. 1).
To detect the NMR-invisible aluminium and to quantify the total amount of
octahedral extra-framework A1 in Samples 1-5 the acac method (ref. 7) was
applied. The acac-treated Samples 1-5 exhibit 27Al signals at -2, -7 and -12
ppm. These three lines are also found in the spectrum of solid Al(acac)j under
 733

MAS c o n d i t i o n (Fig. 8). The s p l i t t i n g o f t h e 0" s i g n a l i s caused by the

presence o f the quadrupolar 27Al nucleus i n an e l e c t r i c f i e l d g r a d i e n t w i t h
a x i a l symmetry ( r e f . 18), corresponding t o t h e symmetry o f Al(acac)3. From t h e
p o s i t i o n o f t h e maxima i n the 27Al NMR spectrum o f Al(acac)g a value o f 3 MHz
was obtained f o r t h e quadrupole coupling constant, Cp.
For acac-treated Samples 1-5, AINF/A1 c a l c u l a t e d as t h e 27Al (T'+T"tO'tO")/
(TtT'+T''tO'tO") l i n e i n t e n s i t y i s given i n Table 1. The AINF/A1 r a t i o thus
obtained f o r Samples 1-5 i s i n r e l a t i v e l y good agreement w i t h t h e values
measured by "Si NMR (Table 1). The (T'tT")/T r a t i o w i l l g i v e an i n d i c a t i o n o f
the r e a c t i v i t y o f t h e T' and T" s i t e s towards acac. From Table 1 one can d e r i v e
that for every sample hydrated and acac-treated this ratio is similar.
Therefore, t h e a d d i t i o n o f acac does n o t a f f e c t t h e population o f T' and T"
s i t e s and consequently complexes o n l y formerly NMR-invisible aluminium.
One can speculate on the possible s t a t u s o f t h e NMR-invisible aluminium
species, which should reside on s i t e s w i t h very strong quadrupole i n t e r a c t i o n
(Cq>>3 MHz). I n t h e 27Al spectra o f the acac-treated samples l i n e 0' i s present
(Figs. 1-5), i n d i c a t i n g t h a t a t l e a s t p a r t o f t h e alumina polymers are not
converted i n t o A1 ( a ~ a c ) ~ As
. a l l NMR-invisible aluminium i s complexed w i t h
acac, i t probably i s l e s s polymerised. The NMR-invisible aluminium can be
assigned t o oligomeric alumina species i n the z e o l i t e pores.
Complexation o f extra-framework aluminium w i t h acac proves t o be a r e l i a b l e
and general method f o r the s e l e c t i v e q u a n t i f i c a t i o n o f NMR-invisible e x t r a -
framework aluminium. Statements t h a t q u a n t i f i c a t i o n o f non-framework
aluminium on hydrated samples i s possible, as proposed e.g. i n r e f . 11 and 19,
should be considered w i t h great caution.
The procedure t o perform t h e complexation w i t h acac i s very c r i t i c a l . The
impregnation should be performed a t 293 K. Acetylacetone can e x t r a c t aluminium
from t h e z e o l i t e Y l a t t i c e ( r e f . Z O ) , c e r t a i n l y a t h i g h temperature. We
experienced w i t h Sample 1 t h a t a t 333 K dealumination does indeed occur.
Prolonged contact o f the sample w i t h acac s o l u t i o n can be another cause of
dealumination ( r e f . 8). Ray e t a l . ( r e f . 10) proceeded by adding t h r e e drops of
acac t o the sample i n the MAS r o t o r . According t o t h a t procedure f o r a USY
z e o l i t e w i t h Si/A1=4.8 the f u l l i n t e n s i t y o f the 0" l i n e i s obtained o n l y a f t e r
f i v e days. According t o our method, 24 h i s s u f f i c i e n t . Bosacek e t a l . ( r e f . 8)
and Freude e t a l . ( r e f . 9) performed s t a t i c 27Al NMR experiments on z e o l i t e Y,
soaked w i t h 38 v o l - % acac i n ethanol i n a sealed-off sample holder. A narrow
27Al signal from A l ( a ~ a c ) dissolved
~ i n ethanol was observed next t o signals
from s o l i d s t a t e aluminium species. I n t h a t procedure more acac than necessary
t o complex the i n v i s i b l e aluminium i s l e f t on the sample, leading probably t o a
slow a d d i t i o n a l dealumination o f the z e o l i t e framework ( r e f . 7).
734

ACKNOWLEDGMENT
We acknowledge t h e support o f t h e Belgian National Fund f o r S c i e n t i f i c
Research f o r a Research D i r e c t o r s h i p t o P.A.J., a Senior Research Associateship
t o P.J.G. and a Research Associateship t o J.A.M. T h i s work has been sponsored
by t h e Belgian Government i n the frame o f a concerted a c t i o n on c a t a l y s i s . We
are very much indebted t o J.B. Uytterhoeven f o r h i s a c t i v e c o n t r i b u t i o n i n
o b t a i n i n g funds f o r t h e NMR f a c i l i t y (IIKW p r o j e c t no 4.0002.84) and t o
Synfina-Oleofina f o r f i n a n c i a l support.

REFERENCES
1 G. Engelhardt and D. Michel, High-Resolution S o l i d - s t a t e NMR o f S i l i c a t e s
and Z e o l i t e s , John Wiley 8 Sons, Chichester, 1987.
2 W.O. Haag, R.M. Lago and P.B. Weisz, Nature (London) 309 (1984) 589.
3 J. Klinowski, C.A. Fyfe and G.C. Gobbi, J. Chem. SOC., Faraday Trans. 1,
81 (1985) 3003.
4 D. Freude, M. Hunger and H. P f e i f e r , Z. Phys. Chem. NF 152 (1987) 171.
5 D. Freude, E. Brunner, H. P f e i f e r , D. Prager, H.-G. Jerschkewitz, U. Lohse
and 6. Oehlmann, Chem. Phys. L e t t . 139 (1987) 325.
6 E. Brunner, H. Ernst, D. Freude, M. Hunger and H. P f e i f e r , Stud. S u r f .
Sci. Catal. 37 (1988) 155.
7 P.J. Grobet, H. Geerts, J.A. Martens and P.A. Jacobs, J. Chem. SOC., Chem.
Commun. (1987) 1688.
8 V. Bosacek, 0. Freude, T. Frohlich, H. P f e i f e r and H. Schmiedel, J.
C o l l o i d I n t e r f a c e Sci. 85 (1982) 502.
9 D. Freude, T. Frohlich, H. P f e i f e r and 6. Scheler, Z e o l i t e s 3 (1983) 171.
10 G.J. Ray, B.L. Meyers and C.L. Marshall, Z e o l i t e s 7 (1987) 307.
11 A. Samoson, E. Lippmaa, G. Engelhardt, U. Lohse and H.-G. Jerschkewitz,
Chem. Phys. L e t t . 134 (1987) 589.
12 Bruker ABACUS Catalog n o ABA078.
13 J.-P. Gilson, G.C. Edwards, A.W. Peters, K. Rajagopalan, R.F. Wormsbecher,
T.G. Roberie and M.P. Shatlock, J. Chem. SOC., Chem. Commun. (1987) 91.
14 A. Corma, V. Fornes, A. Martinez, F. Melo and 0. P a l l o t a , Stud. S u r f . Sci.
Catal . 37 (1988) 495.
15 D. Muller, W. Gessner, H.-J. Behrens and G. Scheler, Chem. Phys. L e t t . 79
(1981) 59.
16 R.D. Shannon, K.H. Gardner, R.H. Staley, 6. Bergeret, P. G a l l e z o t and A.
Auroux, J. Phys. Chem. 89 (1985) 4778.
i7 R. Dupree, D. Holland and D.S. Williams, P h i l o s . Mag. 850 (1984) L13.
18 A. Kentgens, K. Scholle and W. Veeman, J. Phys. Chem. 87 (1983) 4357.
19 C. Fernandez, F. Lefebvre, J . B.Nagy and E.G. Derouane, Stud. Surf. Sci.
Catal . 37 (1988) 223.
.
20 R. Beaumont and D. Barthomeuf, J. Catal 27 (1972) 45.
H.G.Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V.,Amsterdam - Printed in T h e Netherlands

CHARACTERIZATION OF CALCINED FAPO-5

S. Schubert', H.M. Ziethen', A.X. Trautweini, F. Schmidt*, Auong-Xin Li3, J.A.

Martens3 and P.A. Jacobs3
'Inst. f. Physik, Med. Universitllt, Ratzeburger Allee 160, D-2400 Labeck (FRG)
2SOd-Chemie AG, Katalyse-Labor, Waldheimer Strape 13, D-8206 BruckmUhl-Heufeld
(FRG)
3Laboratorium voor Oppervlaktechemie, K.U. Leuven, 92, Kardinaal Mercierlaan,
8-3030 Leuven (Belgium)

ABSTRACT
FAPO-5 samples were synthesized according to a patent method and character-
ized by chemical analysis, differential thermal analysis, scanning and trans-
mission electron microscopy, electron spin resonance, X-ray diffraction, MBss-
bauer spectroscopy and magnetic susceptibility measurements. The as-synthesized
material contains about 70% of Fe(II1) and about 30% of Fe(I1) with structures
similar to those of the Fe(II1)- and Fe(I1)-phosphates. Ki impurities are en-
riched in cracked sphere-shaped particles, whilst the Ki -free particles exhibit
a hexagonal leaf-type morphology. Calcination at 973 K of the as-synthesized
molecular sieve finally yields three different iron phases as identified by
Mossbauer spectroscopy, 1.e. a-Fe2Or (25%), Fe(II1)-phosphate clusters (40%)
which are probably occluded within the calcined FAPO-5, and Fe(II1) (35%) in a
site with tetracoordination and high structural symmetry. According to X-ray
diffraction studies the latter phase corresponds to AlPO4-tridymite, with
Al(II1) being partially substituted by Fe(II1).

INTRODUCTION
The aluminophosphates are an important new class of molecular sieves (ref .1).
The crystallization from the gel is affected between 373 K (100OC) and 523 K
(25OOC) in the presence of an organic template under hydrothermal conditions.
For applications as catalysts or adsorbent materials, the resulting solid must
be calcined to remove both template and water.
The crystal structure of one member of this family, designated AlPO-5, was
reported some years ago (ref.2). Four-coordinated aluminum and phosphorous oxide
was found with occasional secondary coordination of some of the aluminum with
non-framework species such as HzO or OH- occluded in the cavities.
Iron-containing molecular-sieve FAPO-5 belongs to a class of metal-alumino-
phosphates denoted by the acronym MeAPO (ref.3). They can crystallize as a large-
pore variant with AlPO-5 structure, as an intermediate-pore system with AlPO-11
structure and as a small-pore sieve with AlPO-34 structure (ref.1).
FAPO-5 was synthesized according to Messina et al. (ref.4). We already repor-
ted on the synthesis and characterization of a FAPO-5 sample (ref.5). Fe(I1)
salt was used as a source for iron and TEAOH as a template. The synthesis gel
736

was doped by K'. Under the synthesis conditions approx. 66 wt.% of the iron is
oxidized and substituted in the framework, and 34 wt.% remains in the divalent
state. Whether Fe(1I) is partly or totally incorporated in the framework is not
completely clear. Two types of morphologies were found: hexagonal leaf- and
ball-shape particles. The latter crystals are ten times smaller by volume. TEA'
is the main charge-compensating cation in the leaf-type morphology and K* in the
small balls. The aim of this work was to study the thermal stability of FAPO-5
and to elucidate the behaviour of the iron-containing phases during calcination
in air.

EXPERIMENT
Materials
A FAPO-5 synthesis gel was prepared using the procedure described in example
3 of ref.4. Fe(I1) chloride tetrahydrate was from Janssen Chim., pseudo-boehmite
from Vista, tetraethylammonium hydroxide (TEAOH) 40% in water (containing
1.25 wt% of K20 as impurity) and 85% phosphoric acid from Fluka. The gel with
molar composition
(TEAOH) : (FenO3)O.l : (Al203)O.g : (PzOs) : (Hz0)40 (1)
was crystallized at 423 K for 24 hours. A reference AlPO-5 material was synthe-
sized in the same way in the absence of iron.
Some of the material was adjusted for constant humidity and then used for
measurements (FAPO-5/0). The remaining part was calcined at 673 (400), 773
(5001, 873 (600) and 973 K (700OC) over 24 h in air and then again adjusted to
constant humidity. The latter samples are denoted as FAPO-51400, FAPO-5/500,
FAPO-5/600 and FAPO-5/700, respectively. In order to characterize the structure
of FAPO-510 and its calcined forms several spectroscopic techniques were
applied.

Methods
The FAPO-5 material was characterized using differential thermal analysis
(DTA) in an inert atmosphere (ref.61, electron spin resonance (ESR) (ref.71,
X-ray diffraction (XRD) (ref.81, scanning and transmission electron microscopy
(SBM, T E N , Mbssbauer spectroscopy (ref.9,10) and magnetic susceptibility mea-
surements (ref.11).
The chemical analysis of the FAPO-5 samples, after their dissolution in RC1,
was made with a PE ICP 5,500 instrument. The unit cell dimensions of the samples

-
were determined in the hexagonal system with
4/3 (h2+hk+ka)/a2 + 12/c2 4 sins 8/22 (2)
by a least-squares fit of hk1 reflections (ref -12). 8 is the diffraction angle
and 3 the wavelength of the incident X-rays.
 131

u . ~ ~~~

273 773
T I K l
Fig. 1. DTA of FAPO-5 in air.

RESULTS AND DISCUSSION

Differential thermal analysis
Differential thermal gravimetry (DTG) in He has been reported and discussed
in a previous paper (ref.5). In contrast to DTG in He and DTA of AlPO-5 (ref.13)
the DTA measurements in air (Fig. 1) show an additional strong exothermic peak
in the range between 673 K and 1043 K. The exothermic peak is related to a phase
transition from the AlPO-5 structure to the AlPO4-tridymite structure.

X-ray diffraction
XRD measurements (Table 1) have been performed with FAPO-510, calcined at
increasing temperatures. The pattern of FAPO-5/0 is comparable to that of FAPO-5
(ref .4). The pattern of FAPO-51400 exhibits only slight changes compared to that
of FAPO-5/0. The changes of FAPO-5/500, FAPO-5/600 and FAPO-51700 are consider-
able. FAPO-51600 and FAPO-51700 are identical and represent the tridymite
structure of bulk aluminophosphate.

Electron microscopy
SEW: measurements have been performed with FAPO-510, FAPO-5/400 and
FAPO-5/700. The images of FAPO-5/0 show two morphological types, one hexagonal
leaf-shape (which is similar to that of AlPO-5 (ref.14)) and one ball-shape with
large pores (which is 3 times smaller in diameter than the hexagonal crystals
(ref.5)). It is interesting to note that the crystal structure of both morpho-
logies is the same, as evidenced from XRD. During calcination the two types of
crystal shape remain. Fig. 2 shows images of FAPO-51700. However, as mentioned
above, the XRD pattern, i.e. the crystal structure, changes on going from 673 K
to 973 K.
738

TABLE 1
dbkl [nm] versus I/I.OX of FAPO-5/0,..,/700 and AlPO4-tridymite (ref.15).
Reflexes are counted only when I/Imax ) 10%.

FAPO-5/600 I FAPO-5/700 I Tridymite I

dbkl I/Imax drri :/Imar dbkl I/hx :/Imax dbkl I / I m a x
[nml [nml [nml [nml
-
1.173 80b 1.179 86b 1.179 lOOb 0.438 lOOC 0.435 lOOC 0.431 lOOc
0.676 llb 0.685 27b 0.681 26b 0.413 76c 0.413 6gC 0.413 lOOc
0.587 29b 0.448 38’ 0.448 35b 0.387 64C 0.385 65c 0.386 85c
0.444 76b 0.421 45b 0.435 22c 0.300 21c 0.300 22c 0.328 30C
0.419 61b 0.395 100b 0.421 50b 0.252 24c 0.252 24c 0.320 10c
0.393 lOOb 0.343 3gb 0.413 18c 0.233 11c 0.233 1lC 0.300 3OC
0.339 35b 0.307 26b 0.395 85b 0.211 10c 0.211 loc 0.255 50c
0.305 23b 0.296 25b 0.385 13C 0.233 50c
0.295 29b 0.266 llb 0.341 40b 0.211 5OC
0.264 llb 0.259 26b 0.307 21b
0.258 25b 0.238 llb 0.296 31b
0.239 15b 0.266 10b
0.259 24b
0.252 1Oc
0.239 llb
a Unit cell dimensions were calculated by a least-squares fit of the hkl re-
flections using eq.(2), which yields a=1.367 nm and c=0.845 nm.
AlPO-5 phase.
AlPOa-tridymite phase.

Fig. 2. SEN images of FAPO-5/700 with hexagonal leaf-shape crystals (a) and
ball-shape crystals (b).

TEM was applied to selected samples. Fig. 3 shows a TEN image of FAPO-5/0
showing the (100) lattice planes. The distance between these lattice planes
amounts to 1.18 nm. The corresponding diffraction image of this area of the
sample shows lattice spacings of 0.23 nm, 0.403 nm and 0.43 nm, respectively.
These values are in agreement with the XRD data.
 739

Fig. 3. TEH image of FAPO-5/0 showing the (100) lattice planes.

Mossbauer and ESR spectroscopy of FAPO-5 samples calcined at increasing

temperatures
Hossbauer spectra have been recorded between 4.2 K and room temperature (RT)
for FAPO-5/0 calcined at different temperatures. The spectra have been analyzed
with a least-squares procedure using Lorentzian lines. The resulting Mdssbauer
parameters are summarized in Table 2.
_ _ The as-sunthezised sample.
(1) In the case of FAPO-5/0, Fe(II1) species
contribute about 70% and Fe(I1) species about 30% to the measured Hossbauer
spectral area (Table 2 ) . The characterization of these species is unambiguous
from the measured isomer shifts. Part of Fe(II1) in FAPO-5/0 is identified as
framework iron with coordination similar to that of bulk Fe(1II)POd but with
Fe(II1) ions being magnetically diluted and forming a single-phase solid solu-
tion of (Al,Fe)P04. For completeness, ESR spectra of this sample at RT and at
2.2 K are presented in Fig. 4a and 4b. The resonance at g=4.3 is due to tetra-
coordinated Fe(III)-ions in framework positions while that at g=2 is due to
Fe(II1)-oxy or -hydroxy products occluded in the cavities.
(11) Calcination at 673 K (400OC). After calcination in air of FAPO-5/0, the
Fe(1I) species are no longer detectable in the Ndssbauer spectrum at RT and
4.2 K (Fig. 5a and 5b). The RT spectrum does not exhibit magnetic broadening.
The 4.2 K spectrum of FAPO-5/400 exhibits a broad and unresolved magnetic fea-
ture of about 35% of the total absorption area. It is interesting to note that
about the same amount of iron was originally present as Fe(I1) in FAPO-5/0.
The remaining 6511 of the absorption area corresponds to paramagnetic Fe(II1)
ions, the same amount which was already present in FAPO-5/0. Thus from compari-
son of the Hossbauer spectra of the FAPO-5/0 and FAPO-5/400 samples, it is clear
740

that calcination at 673 K converts Fe(I1) into Fe(II1) species. This tentative
picture is supported by ESR and XRD data:
a) At 2.2 K and at RT the ESR spectra of FAPO-5/400 show additional Fe(II1)
species compared to FAPO-5/0, and
b) the RT XRD pattern of FAPO-5/400 exhibits essentially the same lines as
FAPO- 510.
(iii) Calcination at 773 K (500oC). The analysis of the Mdssbauer spectrum at
4.2 K (Fig. 6a and 6b) of FAPO-5/500 yields about 55% of the absorption area
corresponding to paramagnetic Fe(II1) ions. The decreasing amount of paramag-
netic Fe(II1) ions from 65% for FAPO-5/400 to 55% for FAPO-5/500 indicates that
part of the FAPO-5 structure has collapsed to a new phase in FAPO-5/500 with
iron ions being closer together and hence exhibiting cooperative magnetic pro-
perties at low temperature.
The ESR spectra (Fig. 7a and 7b) recorded at RT and at 2.2 K, respectively,
show that the g=4.3 signal which corresponds to framework Fe(II1) ions has
decreased in intensity compared to the situation of FAPO-5/400. In addition, the
XRD pattern shows that part of the FAPO-5 structure has been destroyed.
(iv) Calcination at 873 K (600oC). The Mdssbauer spectrum of FAPO-5/600 at
4.2 K (Fig. 8a and 8b) exhibits a magnetic pattern with total absorption area of
about 60% consisting of two subspectra. One is due to small a-Fe~O3 particles
and the other to magnetically inhomogeneous Fe(II1) species whose hyperfine
parameters are close to Fe(II1)-phosphate.
Comparing the amount of the paramagnetic Fe (111) species of FAPO-5/400 (65%),
FAPO-515OO (55%) and FAPO-51600 (40%),it is tempting to assume that FAPO-5
undergoes a structural phase transition with increasing calcination temperature.
From the XRD pattern it is obvious that the original FAPO-5 structure was trans-
formed into a tridymite-type structure when calcined at 873 K. The remaining 40%
of the absorption area is due to a broad and a sharp single line, which will be
explained below.
(v) Calcination at 973 K (700oC). The RT and 4.2 K Mdssbauer spectra of
FAPO-5/700 (Fig. 9a-9d) show that about 25% of the absorption area is due to
a-Fe~03, characterized by a Morin transition (compare the quadrupole splittings
of sub-spectra I11 in Fig. 9a-d).
About 75% of the absorption area at RT corresponds to Fe(II1) species, which
are further characterized as follows. Their microscopic iron-ligand structure
is to a considerable extent homogeneous, as exemplified by the sharp quadrupole
doublet at RT; however, this doublet is superimposed by a single line which
becomes visible only below 77 K. The spectrum at 77 K (not shown) has a complex
structure, as part of the Fe(II1) species exhibit hyperfine field distribution
at this temperature.
 741

g-values
3.0 2.0 1.0

%
/--- I
L , ,
I
v ,.
, l
v , , , , , l , , , l , , , ~
0 500 1000
H [mTl
Fig. 4 . ESR spectra lor FAPO-5/0 recorded at RT ( a ) and 2.2 K (b).

1 .ooo

c
.-0
.-4 .995

.ooo

.995

.990

.985
-10 0 10
Velocity [mm/sI
Fig. 5. Hdssbauer spectra for pAPO-5/400 recorded at RT ( a ) and 4.2 K (b).
742

Q,
.-2 1 . 0 0 0
t
a
d
a,
a .995

.905
*ggO* -'I u 0
. 10

Velocity [mm/s]

Fig. 6. Mdssbauer spectra for FAPO-5/500 recorded at RT (a) and 4.2 K (b),

g-values
3.0 2.0 1.0

500 1000
H [mT]
Fig. 7. ESR spectra for FAPO-5/500 recorded at RT (a) and 2.2 K (b).
 743

~1.000
I-
Q,
.->
.995
d

a,
LT

.990

-10 10
Velocity [mm/s]

Fig. 8. Mdssbauer spectra for FAPO-5/600 recorded at RT (a) and 4.2 K (b).

The spectrum at 4.2 K (Fig. 9b) consists of two resolved, magnetically split
subspectra (111) and (IV), a single line (11) and an unresolved broad absorption
line (I). Undoubtedly subspectrum (111) can be attributed to a-FezOa (see
above). Subspectrum (IV), because of its hyperfine parameters, is attributed to
"bulk" FePO4 (ref.16). lost likely this Fe(II1)-phosphate is not a separate
macroscopic crystalline phase but is occluded as FePO4 clusters within the
calcined FAPO-5. This picture is supported by the SEH images of FAPO-5/700
(Fig. 2 ) , which do not show macroscopic crystalline phases except for those
already present in FAPO-5/0. Both a-FezOt and the FePO4 clusters reveal canted
antiferromagnetism (ref .16,17). Therefore they exhibit a specific ratio of peak
intensities of their magnetic hyperfine pattern when exposed to an external
magnetic field, parallel and perpendicular to the gamma-beam. These ratios are
3:4:1 and 3:2:1, respectively (Fig. 9c,d and Table 2). The remaining 35% of the
absorption area at 4.2 K (Fig. 9b) due to subspectra I and I1 yield a broad and
a sharp single line with identical isomer shifts (0.3 mm/s). We attribute these
two subspectra to a paramagnetic Fe(II1) species, which exhibits intermediate
magnetic relaxation at this low temperature. From magnetic susceptibility mea-
surements between 7 K and 170 K using a Faraday balance it is obvious that this
paramagnetic iron is in the ferric high-spin state (p=6.05 t0.35 Bohr magnetons)
(ref.11). Under the applied field, parallel and perpendicular to the gamma-beam,
744

this species yields a six-line pattern with sharp lines and zero magnetic aniso-
tropy. The latter follows from the specific ratio of peak intensities of 3:O:l
and 3:4:1, respectively, in parallel and perpendicular field geometry (see sub-
spectra I and I1 in Fig. 9c,d). This behaviour, together with the moderate
internal field of 54 T, the relatively small isomer shift of 0.3 mm/s and the
zero quadrupole splitting, suggests that Fe(II1) of this species occupies a site
with high structural symmetry and tetracoordination by oxygen ligands. Therefore
it most likely corresponds to framework iron of FAPO-5/700. This framework
mainly represents the tridymite structure of Alp04 (ref.15). It is therefore
reasonable to conclude that Fe(III1, corresponding to subspectra I and 11,
substitutes Al(II1) in a formed phase of AlPO4-tridymite. The individual phases
identified by N6ssbauer spectroscopy remain undetectable by XRD, because of the
small iron content.

CONCLUSIONS
The PAPO-5 sample, synthezised in the presence of ferrous iron according to
procedures in the literature, is thermally unstable. One should note that the
organic template was contaminated by small amounts of K+. The role of the potas-
sium is still not clear.
The as-synthesized sample contains 70% Fe(II1) and 30% Fe(I1). While the
theoretical degree of rubstitution of the iron in the AlPO-5 framework is 101,
it can clearly be seen from H6ssbauer spectroscopy that only part of the Fe(II1)
is present as framework iron. The remaining part is occluded as Fe(II1)- oxy- or
hydroxy-species in the pores.
At increasing calcination temperatures the Fe(I1) species are rapidly oxi-
dized to Fe(II1). At the calcination temperature of 773 K the micropore-struc-
t w e starts to collapse to an AlPOa-tridymite form. At 973 K the phase transi-
tion is completed.
During the calcination process, the extra-framework iron sinters to small
a-FenO:, particles not detectable by XRD. Part of the FAPO-5 framework iron goes
through the phase transition and finally occupies an AlPOa-tridymite framework
site. The remaining part is identified as small FePO4 clusters occluded within
the calcined material.
 745

1.00

.98
c
0
.-
ln
.-v)
E
vl
c
a
4 .
1.000
W
.->
+ .995
d
d
W
fx .990

.985

-10 0 10
Velocity [mm/sl

Fig. 9a,b. Hdssbauer spectra for FAPO-5/700 recorded at RT (a) and 4.2 K (b).

I 1 1
1 1 1 1 1
4
1~ 1 1

-10 0 10
Velocity [m/sl

Fig. 9c,d. Hbssbauer spectra for FAPO-5/700 recorded at 4.2 K and U.~t=6.21 T
I X-beam (c) and 4.2 K and 8.~;=6.21 l’d-beam (d).
TABLE 2
Isomer shift (I.S.), quadrupole splitting (Q.S.), line width (L.W.), internal
magnetic field ( H i n t ) and relative absorption area (A) at various temperatures
for FAPO-5/0 samples. Isomer shifts are given relative to a-Fe at RT. The num-
bering of the subspectra is the same as in the figures. Standard deviations are
of the order of 5%.
-
I.S. Q.S. L.W. Ratio of peak
Fig. Subsp. [mm/sl [mm/sl Cmm/sl intensity (d)
APO-5/0 (a) RT 0.4 0.73 0.55 - 74.3
0.98 2.14 0.3 - 12.6
1.2 2.97 0.3 - 13.1

APO-51400
I"
IRT 5a I
0.5
1.23
0.5

0.37
0.87
2.76
-0.25

1.00
0.49
0.47
0.52

0.88
-
5i.2 1 54.4
33.8
11.9

--
4.2 5b I 0.41 0.97 0.97
I1 0.38 0.39 0.58
I11 0.39 0.07 1.16 43.0 13.0
IV 0.39 -0.11 1.16 50.8 22.1
-
APO-5/500 6a
RT I 0.34 1.05 0.74
-
4.2 6b I 0.41 0.97 0.97 - 42.6
I1 0.38 0.39 0.58 - 11.6
I11 0.39 0.07 1.16 43.0 24.6
IV 0.39 -0.11 1.16 50.8 21.2
'APO-51600
-
RT 8a I
I11
0.36
0.39
0.74
0.99
0.49
4.51
-
- I 65.1
34.9
4.2 8b I 0.38 0.0 5.3 - 24.5
I1 0.38 0.0 0.7 - 18.6
I11 0.46 0.08 , 0.51 52.7 16.8
IV 0.49 0.12 0.65 49.0 40.2
'APO-51700 RT 9a I 0.37 0.76 0.38 - 75.4
I11 0.36 -0.22 0.3 51.6 24.6
-
4.2 9b I 0.31 0.0 5.31 - 26.4
I1 0.33 0.0 0.52 - 10.2
I11 0.46 0.04 0.45 53.1 23.1
IV 0.47 0.26 0.45 49.0 40.3
-
(b) 4.2 9c I+II 0.37 -0.03 0.38 54.4 34.9 3:0:1

(C) i;; 9d
I11
IV
I+II
I11
IV
0.5
0.5
0.35
0.43
0.53
-0.04
0.27
-0.04
0.00
0.29
~

~
0.42
0.7
0.33
0.43
0.92
53.6
47.8
54.1
53.6
47.4
25.2
39.9
34.6
25.4
40.1
3:4:1
3:4:1
3:4:1
3:2:1
3:2:1
~~

(a) Taken from (ref.5).

(b) External magnetic field 6.21 T, parallel to gamma-beam.
(c) External magnetic field 6.21 T, perpendicular to gamma-beam.
(d) Counted from outer to inner lines. Line intensity ratio for least-squares
fit of experimental spectrum.
 747
ACKNOWLEDGEMENTS
HXL acknowledges the KU Leuven for a Ph.D. grant. JAM and PAJ are grateful
to NFWO-FNRS for a Senior Research Associate Fellowship and a position as
Research Director, respectively. PAJ also acknowledges the Belgian Government
for financial support in the frame of a concerted action. AXT and SS appreciate
financial support from the Deutsche Forschungsgemeinschaft. We are grateful to
Kontron GmbH, Munich, and to Philips, Eindhoven, for carrying out some of the
SEM and TEM measurements.

REFERENCES
1 E.M.Flanigen, B.M.T.K.Lok, R.L.Patton and S.T.Wilson, Pure and Appl. Chem.
58 (1986) 1351.
2 J.M. Bennett, J.P. Cohen, E.H. Flanigen, J.J. Pluth and J.V. Smith, ACS
Symp. Ser. 218 (1983) 109.
3 E.M. Flanigen, B.M.T.K. Lok, R.L. Patton and S.T. Wilson, Stud. Surf. Sci.
Catal. 28 (1986) 103.
4 C.A. Messina, B.M.T.K. Lok and E.M. Flanigen, EPA 131, 946 (19841, assigned
to Union Carbide Corp.
5 Hong-Xin Li, J.A.Martens, P.A.Jacobs, S.Schubert, F.Schmidt, H.M.Ziethen and
A.X.Trautwein, Stud. Surf.Sci.Catal.37 (1988) 75.
6 J. Perez-Pariente, J.A. Martens and P.A.Jacobs, Appl. Catal. 31 (1987) 35.
7 L.R.M. Martens, P.J. Grobet, W.J.M. Vermeiren and P.A. Jacobs, Stud. Surf.
Sci. Catal. 28 (1986) 935.
8 J.A. Martens, M. Mertens, P.J. Grobet and P.A. Jacobs, Stud.Surf. Sci. Ca-
tal. 37 (1988) 97.
9 N.N. Greenwood and T.C. Gibb, "MBssbauer Spectroscopy", Chapman & Hall,
London 116 (1971) 134.
10 G.J. Long, J.G. Stevens, "Industrial Application of the Mdssbauer Effect",
Plenum Press, New York (1986).
11 S. Schubert, Diplom-Arbeit, Universit(Lt Hamburg (1987).
12 W.J. Mortier, unpublished results.
13 X. Qinhua, D. Jialu, Y. Aizhen and J. Changtaiin "Proceedings of the Int.
Symp. on Zeolite Catal.", Siofok, Hungary (1985) 99.
14 S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan, E.M. Flanigen, Intrazeo.
Chem., ACS Symp.Ser. 218 (1983) 79.
15 Inorganic Index to the Powder Diffration Pile, ASTM (1972).
16 V.Beckmann, Y. Bruckner, W. Fuchs, G. Ritter, H. Yegener, Phys. Stat. Sol.
29 (1968) 781.
17 R.L. Nininger, D. Schroer, J. Phys. Chem. Solids, 39 (1978) 137.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors ), Zeolites as Catal.ysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Y. F. chul, C. F. Keweshanl and E. F. Vansant2

lEngeuard Corporation, Menlo Park CN-28, Edison, N.J. 08818, USA
2university of ~ntwerp(UIA) , Deparbnent of hemi is try,
Universiteitsplein 1, B-2610 Wilrijk, Belgium

AEnRACT
A simple methcd to control the inlet pore dimter of H-zeolite (HZ) by
chemical vapor deposition (CVD) is described. ?he technique involves batch
contacting of 'IMOS with Hz through a manifold system with sanple weight change
gravimetrically monitored. The degree of pore reduction is controlled
by repeated deposition and calcining cycles;
to reduce unwantd polymerization ard irwxease the efficiency of 1M)6 depos-
ition. High acidity and law deposition temperature favor 1M)6 deposition, but
at l m tenprature physical adsorption of 1M)6 occuzs which could lead to
polymerization. For ZSM-5, both tennhal silanol gmups (with IR f near
3740 m-l) and aluminum-related framework hydrcocyl g m q s (at 3 6 l O X o n
the zeolite external surface play i m p r t a n t mles in the IM3s deposition. Mild
Steaming of silicalite generates mre terminal silanol groups at 3740 an-l and
contributes to TMOS deposition. HF treatment generates mre internal hydroxyl
grcprps which are inaccessible for 1M3s reaction.

rtmammIcN
control of the pore-opening size of zeolites can be an important capability
in performing shap-selective catalytic reactions. prnper reduction of the
Opening size of the zeolite pore channels auld increase the shape selectivity
of catalysts without adversely affecting inherent activity. Wre size reduction
auld be accamplished by coating the zeolite with mdifyh-c~ agents, such as
P
IDS (refs. 1-2) and methyl-chlorosilanes (ref. 3) which are wlecules larger
than the zeolite pore-opning size, so that only the zeolite externdl surface
reacts. "he reactions are believed to h l v e ard the zeolite external
silanol groups (ref. 2):

In addition, polymerization reactions of the organosilanes on the zeolite

surface could also take place (ref. 4). Calcining h air at 538% m e s the
750

organics resulting i n a thin layer of Si% and regenerates silanol grcups for
further readion. Modifying agents containiq S i are nonwdly used since the
silica formed is relatively inert u d e r most m c t i o n conditions. %modified
catalyst could be used for mny reactions that requke shape selectivity ard
high activity. Examples have been given of the selective production of p
dialkylbmzene (i.e. xylene ard diethylbenzene) and the selective cracking of
paraffins, etc. over both modified mordenite ard ZSM-5 (refs. 1,5).
lb CVD technique is normally used to uniformly coat silica since monolayers
of can be added stepwise. ?he method involves a m e n t i o n a l adsorption
system which incorporates a quartz-spring balance to monitor the in-situ weight
gain. small Samples of 1 Fpn or less are usually contacted ard vacum of about
0.13 to 0.67 Pa is used for sample degassing. 'Ihe pqmse of this paper is t o
describe a s*le technique which allows effective preparation of a larger
sample, to be used for both catalyst characterization anl catalytic studies. It
u t i l i z e s an inexpasive amunexcially available Airless-ware manifold system for
both CVD ard probe molecule uptake to detennhe the extent of pore s i z e
reduction. Moreover, since 'IM3s deposition is affected by temperature of
deposition ard zeolite acidity, experimmts were also undertaken to study their
roles and ways t o increase D ' m deposition rate.

DcPEmmm
?he apparatus used for this study cansists of a ccrranercially available
Airless-ware manifold obtained fran Kontes, for the contact of "IMX w i t h 5-10

-F.:'
gm of z e o l i t e in stand2ud 100 m l flasks (see Fig. 1).

Drier

Bubbler

Fig.1 Shawing the setup for CVD of "IMX on zeolite sanples us- a swle
manifold system.

In contrast t o the in-situ quartz-sprhq balance system used i n the cawen-

tional adsorption systern to d t o r the sanple weight m e , the flasks in the
present system r~.ereeasily remDved frap Me d f o l d f o r weighing on an analyt-
i d balance. me use of t h i s sinple systen enabled u s to deterrmne
' ,inavery
short t i m e , the pmper conditions mquimd for rpauCing the zeolite pore-
 751

opening sizes.
Abut 5-10 qm of the acid form of a zeolite was introduoed i n t o a t a r e d d r y
flask which was then placed in a heat- mantle. &atwas applied while the
flask was open to the atmqhere to drive off most of the water. when evidence
of Steaming had ceased, the flask was closed with the teflon valve assembly and
installed on the manifold. Degassing was carried cut for 1-2 hr a t 320% and
12-13.3 pa. The flask was then oooled, anl dry Nwe
n was achnitted after
which the dry sample weirplt was cbtained. ?he flask assanbly was re-conneded
w i t h the manifold and re-evamated a t 320%. ?he system was then isolated f m
the pmp, and the previously evacuated flask containing the was apened t o
the manifold. The i n i t i a l pressure in the manifold, 2 . w 0 . 2 7 kpa, rose to abwt
3 . e 0 . 2 7 kpa over a 20 to 40 minute period. Since the reactions cited above
generate methanol which can further react to form methyl ether, water and
hydrocarbons, the pressure rise is expe&ed. ?he sample was then evacuated,
cooled and reweighed. Following this, intermittent a i r calchation of the
sample a t 538OC was n o m l l y carried cut before another deposition. This
cycling contact procedure was repeated until the desired weight gain w a s
dstained.
After CVD, the zeolite n o m l l y changed frun an o f f a t e to a b m color
(due to carkon deposition) as the TMX was deposited. Haever, after a i r
calcination, it returned t o its original a m . 'Ihe resulting S ~ H Zwas
then subjected t o probe-moleculeadsorption analysis us* toluene, n-hexane
and water. The same experimental technique as the CVD was used for the probe
adsorption study. Hawever, the pressure over the SiHZ a t roan temperature was
kept below the pmbe vapor pressure, usually 2.420.27 kF5. After the probe
analysis, the S% samples w e r e evacuated and subjected to a second CVD of 'IMOS
and then calcined and prabe analyzed. Further poreapening reduction occurred
as monitored by probe molecule adsorption. Table 1 lists the dimensions of the
chemical species involved in the study.
TABLE 1
kpa
Species Critical Dimension (mi) Vapor Press.@ 25%
H-Mordenite 0.67 x 0.70 -
H-234-5 0.54 x 0.56 -
'IMOS 0.89 ca 1.07
H20 0.32 3.20
n-Hexane 0.49 17.7
Toluene 0.67 3.60

m e zeolites used i n this study included mordenite and zm-5. camercial

mrdenite samples with silica/alumina mlar ratio of -20 we.re obtained f m the
me
gel
h a
rd Corporation and used for developnent of the new methcd since
752

mrdenite has higher activity for IM)6 deposition than ZSM-5. H-ZSM-5
(silica/almina mlar ratio -70) was Kepared according to Ref. 6 and
prekeate-3 according to pblished pmcedwes (ref. 7). H-silicalite (i.e. ZSM-
5 with a silica/alumina ratio of abart 440) was cbtained f m Union m i d e .
'IMS deposition on these samples was carried cut in a conventional adsorption
unit since only mall samples were available for sbxly. "he infrared (IR)
spectra of various samples were cbtained via F"IR-PE (Fhoto Accustic
SpectroscoW) or DFUFT (Diffuse Reflectance I n f h Fcurier Transform)
techniques. Note that all IR Spectra of the sanples with IM)6 deposition were
obtained after the samples were evacuated at xxxn tenperature to remwe
Fhysically adsorbed m. -re, htqxetation of the difference spectra
cbtained for silicalite must be carefully considered since the siqnals are
relatively weak and could be misls&irq.

RIisJLm
Effectiveness of the atmaratus
The inlet size of the mrdenite porediameter is controlled by the m t of
Si% deposited on the surface. Tb detennine if the zeolite pore q e n h g d d
be modified by just coating the right amcunt of Si% on the zeolite surface
without intennittent air calchtion, two graups of sanples (i.e. A & B vs. C )
w e r e prepared and studied. Sample A (4.0 gm) and sample B (10.1 gm) were
allawed to accumulate SiO2 weight by cycling betwen TbC6 deposition and evacu-
ation without frequent calcinations, but sample C (5.8 gm) was calcined mre
frequently between depositions. ?he d a t i v e TbC6 deposition t h used were
120 rnir~utesfor A (i.e. 6x20 min) and 266 m i n u t e s for B (i.e. 1lx20-40 &),
but the contact time for c was limited to two 10 m i n u t e periods.
Fig. 2 shows the deposition rate by percent wight gain of 'IMS versus time
for these three samples. It is cbserved that the initial rate of deposition for
the A & B samples is identical (2.9 %-), in spite of the fact that sample B
is 2.5 tinis larger. ?he significantly higher rate of C (9.9 %/hour) canpared
to A & B indicates that the deposition of TMX on the surface of HM was very
fast initially and that additiondl contact time pmhbly only mtribute-3to
polymerization, as will be discussed further below. After a c h i n g , sample A
was left with 3.6% added Si% and sample B with 8.1%. Both sanples were then
subjected to a further CVD, ea& with a total deposition time of 130 minutes.
The deposition rate for the second (ND on both samples was markedly 1- and
the respective rates differed significantly f m n each other: the rate of A' was
1.29 %/hour while that of B' was 0.40 %/hcur. Calcining of these samples
resulted in a total of 5.3% added Si% on A' and 8.6% on B'. Calcinirq C
resulted in 2.0% SiO2 added to the surface. C was subjected to two additional
depositions (at deposition rates of 6.9 %/hour for C' and 9.7 %/hourfor C"
 753

respectively) of 10 minutes duration with each aeposition follawed by

calcining. It was abserveed that the CVD rates f o r C'(2.7% acWd Si%) and C"
(3.7% added S i q ) do not d i f f e r significantly f m that f o r C. ?his is in
sharp Contrast to the differmce in rates cbserved between A-A' and B-B',
indicating again that a different mecharu'm (i.e. polywrization) had prcbably
ooavred d u r k the longer contact: pericds of A & B.

A. SJU SILICA
I C*C.C"
A'

8'. 8.8s SILICA

C
A 0

CONT*CI nYE UN. coWT*cI TIME. YlN

Fig. 2 showing that TMOS deposition rates are Fig. 3 a w i n g the effect of silica coating on
affected by intermediate calcination rtepa. Bilicamodified mordenite samples. Sample A'
Samples C-C" have the highest rate. k, better coated than sample 9.

The s i z e of the inlet diameter of the pore is monitored by the sample's

a b i l i t y to exclude p r o b m o l d e s of a specific critical dimension. S i m e the
s i z e of the toluene molecule is near the s i z e of the mrdenite pore, it wnuld
be the most sensitive of the probes used to indicate initial pore reduction.
Fig. 3 i l l u s t r a t e s the effect of pore restriction thruqh the exclusion of
toluene for A - A'& B - B' SiHM samples. It is evident that the twu depo-
sitions of A' (i.e. 5.3% S i q ) are more effective than the single deposition
sample of B (i.e. 8.1% Si02). As discussed above, it is possible that polymer-
ization occurred t o a greater eXterrt during the CVD of B in whi& case the
sample w a s exposed for a longer mntact time thereby prcduciq more non-
selective deposition. ?his is further evidenced by the data for the C sample
sham in Table 2, where the shorter deposition time was u t i l i z e d in conjunction
w i t h more frequent calcining. RLis resulted i n a much more efficient S i q
coating than either A o r B samples. ?herefore, repeated depositions of IM)6
w i t h short contact times and frequent intermittent calcination between each
depasition is fllggested for controllhg the inlet pore diameter efficiently.
To determine i f the adsorption capacity is mintained after the deposition,
H20 is selected as a probe. By examhhg a l l of the prcbes applied to a sample,
one can infer the approximate s i z e of the pore s i z e apenirrgs. Table 2 surmua-
754

H-M~dedte
3.6%SiHM (A)
O/ 0
1/ 120
9.2
8.1 -
6.4 13.6
- 0.67
-0.65
5.3%Sm (A') 2/ 130 3.0 3.0 10.4 0.5-0.6

8.1%SW (B) 1/ 266 5.2 5.7 - 0.5-0.6

8.6%SiHM (B') 2/ 130 0.5 1.1 10.8 C0.5

2.0%SiHM ( C ) 1/ 20 6.1 d 13.4 0.5-0.6

2.7%SiI-lM (C') 2/ 10 3.0 4.1 12.0 0.5-0.6
3.7%SiHM (C") 3/ 10 0.7 0.8 10.0 C0.5

rizes the key observations. Note that while the adsorption of toluene and n-
hewne is significantly reduced for a l l sarrples, the adsorption of H S is not
greatly affected. It is concluded that even though the inlet pore s i z e of the
m o d m i t e was reduced to <0.5m a t least 80% of the internal capacity
maintained.

Ihe nature of 'IMX dewsition

Ixlring the c(xuse of the study, it was observed t h a t the rate of depo-
sition semd to be deperdent on zeolite acidity. nJ0 -1- of ZSM-5 w i t h
different silica/alunina molar ratios (i.e. 70 vs. 440) werx, therefore,
studied a t r w m temperature and 105%. The acidity of the sanple was rnoniton&
by the intensity of the I R signals of the Brcplsted sites of -5 near 3610
a-1(ref. 8). The lawer silica/alumh ZSM-5 has higher acidity, as indicated
by the strunger IR signal i n that region. Ikwwer, both sarrples seem to have
similar Concentrations of teminal silanol grrups the IR 3740 m-l fnquency
region (see Fig. 4), even thcugh the nystal s i z e of silicalite is abmt 4
t i m e s that of the ZSM-5 sanple (i.e. 2 vs. 0.5 um). N o t e also that prior to
deposition, a l l the samples were deh-td wemight a t 450%. The w t
s
show that both lm temperature and higher acidity favor the TICS uptake rates
(see Fig. 5). Morearer, silicalite (i.e. low acidity -5) has a very small
TIC6 adsorption capacity a t 105%.
f i l . Effect of termerature. Temperature plays an important role in TICS
deposition. The higher 'IMas adsorption of -5 a t man tenperature relative t o
that a t 105% could be attrilmtd to @ysical adsorptim, s h abaxt 70% of
the adsorbed species could be removed by 1 hr evacuation a t the me tenper-
ature. In contrast, the lK6 chanisorbed a t 105% cuild mt be removed s a -
 755

w
0
z
a
m
a
0
v)
n
4
x:,
'jcm-;lc 3740 c m
AFTER TMOS
DEPOSITION

PARENT

DIFFERENCE

1
I

W
0 4c
z
a
m
a
53P
a

AFTER TMOS
DEPOSITION
3 7 4 0 cm -' PARENT

p' 3610 cm - 1

DIFFERENCE

3700 3600 3700 3000

HUVENUMBERS. cm -'
Fig. 4 s h & q
(a) 70/1 Sioz/A1203 ZSM-5 at 25%. (b) -
the FTIR-PAS spectra for the effect of 'MB & p c s i t h l Q1
as (a) ht at 105%. (c) 440/1
Sio2/A1203 294-5 at 25%. (a) same as (c) ht at 105%.
156

40 I

I- 70 Z S M - I . 2 6 %

% 30 [ -*- 70 Z S M - I , 106.C
G 25 ~ -s- M O z ~ r - 5 . IOS'C
A ' Y SAFTEREVAC.
I
N 2ok 0 +AFTEREVAC.

, 15 1 0 S AFTER EVAC.
x 0 AFTER EVAC.

0 5
S
0 2 4 6 8 10 12
JWZ,MINO.?
Fig. 5 &wing the effects of tenperatme and zeolite acidity on lMls
adsorption on 234-5 at 25 and 105%.

larly. m e fraction of m which was adsorbed at roan temperature and remained

after evacuation is still higher than that obtained by depostion at 105% (see
Fig. 5 campare X and * points). The extra 'IM3s seem to be a result of lK6
adsorption at the 3610 an-l framemrk hydroxyl groups. The adsorption is
slightly stronger than physical adsorption h t is relatively weak and the
a d s o m species d d be removed by heating up to 105*. ?his can be seen by
amparing Figs. 4a and 4b which shw that for the adsorption at rocm
temperature the intensity of the 3610 an-l signal was reduced but that for the
105% sample was not affeded. For silicalite the effect is less pronaunced
due to its l w acidity.
jii). Effect of zeolite acidity. 'Ihe higher adsorption of TPSX on higher-
acidity ZSM-5 is -; for if only k m h a l silanol groups (i.e. 3740
m-l) are important for lK6 deposition then both ZSM-5 and silicalite samples,
which seem to have similar amxlTlt of the 3740 m - l groups, shculd have the same
nc6 activity. A close examination of the FTIR-PAS difference spectra of the
parent an3 the samples after deposition (see for exanple, Figs. 4b and 4d)
reveals that there is a greater reduction of the 3740 c W 1 sigml of the higher
acidity ZSM-5, inaicatimg that it has mre terminal silanol ~lmupsnxcted
during the TPDS deposition. !the nedmusn
' is not clearly understood, h t it is
possible that the framework hydruxyl gmups (i.e. 3610 m-l, even thcqh few in
number on the external surface) play an important mle in the readions of
with the terminal silanol grarps. Thenfore, the cbervation here only
partially agrees with the observation of Niwa and m r e T s (refs. 1-2) that
external silanol groups existing on the zeolite surface are primarily responsi-
ble for the TPDS deposition.
 157

Activation of hydmxy1srouDs for 'DES deDosition

Since it is determind that zeolite external 1-
h grarps are responsible
for the lMX deposition on mrdenite and ZSM-5, it is desirable to explore ways
to activate these groups and their effects on !lMX deposition. Mild Steaming
has been known to be effective for incxeasing the acidity of ZSM-5 (ref. 9).
The 2234-5 sample, with a Sioz/A1203 ratio of 440, was mildly steamed at 260%
for 2 hours and studied using a DRIFT technique. An examination of the IR
Spectrum shm only a slight increase in the intensity of the signal at 3740
can-l (see Fig. '3);and a small hmxse !lMX uptake rate was observed. In
addition, a fresh ZSM-5(440) sanple was also mildly treated with dilute HF
solutions to generate additional hydruxyl grarps. Interestingly, instead of the
signal at 3740cm-l, the signal of silicalite at 3720 an-l was enhanced, and
that signal seems to increase with increased severity of HF treatment (see Fig.
6b). Unfortunately, there was also no enhancement in 'DES uptake rate,
confirming the assumption that the 3720 an-l 1 -
h signal belongs to an
internal hydroxyl grcep, which &ts in high-silica ZSM-5 and is inaozessible
for lMX reaction. The assignment of this hydrmcyl signal is the subject of a
separate paper.

MILDLY STEAMED DILUTE HF TREATED

Fig. 6 &awing the GRIFT spedra

for the effects of mild s t e a n h g
and dilute HF treatment an the
generation of 1- gmups on
silicalite ( m - 5 , Sio2/A120+40)

3100 3600 3700 3600

WAVE N u M B E R S, c rn- '

DIS<USSION AND CoNcLIlSIapJ
This work has demonstrated the scaleup of a s w l e CVD technique for con-
trolling inlet pore diameter of zeolites. It has sham that the pore size
openings of HM can be reduced to beccane sizeselective by miltiple SiO, dep-
sition and calchtion. Our result is consistent with that obsemed by Niwa and
mrkers (ref. 1) using a conventional adsorption system. For example, to
reduce the pore dieter to <O.5nmI Niwa's work shaws that about 2.8% Si%
dewition is required ccanpared to our 3.7%. 'Ihe small difference might be
caused by (1) different quality of vacuum applied to prepre the surface for
deposition, i.e. cur 13.3 Pa versus Niwa's 0.13 Pa: (2) dqme of
polymerization; (3) sample size: or (4) Sio2/A1203 ratio (i.e. cur 20 versus
Niwa's approxhtely 12). Concernhg the observed reduction in H20 capacity in
this work, it is uncertain whether the reduction is related to pore blockage
due to polymerization or merely reduction of the pore cpening approaching that
of water molecules. 'Ihe nature of W deposition on ZSM-5 is also examined
using different FTIR techniques. It is found that the T W X deposition rate is a
function of temperature and zeolite acidity. The higher the zeolite acidity the
higher is the deposition rate. ILWWtemperature also favors TIE6 adsorption
but about 70% of the species are physically adsorbd and cauld be rennred by a
shple law-temperature evacuation or hiqh-hperature heat-. ?he effect of
the non-selectively physisorkd TIE6 species on pore size reduction has not
been thoroughly studied, but the detrimental effect of excessive TMX, which
could lead to polymerization, has been shm.
Terminal silanol grwps play an important mle in the TIE6 reaction as well
as a m l l fraction of framework hydroxyl qmup (i.e. EQmnstcd acid sites)
which are exposed on the external surface of zeolite. Mild Steaming could
enhance the signal of the 3740 cm-l silanol g r u q s ard the zate of TIE6 depo-
sition. Hmever, HF treatment of silicalite resulted in an hcreaze of internal
silanol groups which are ins-ible for reaction.

R e f e m
1. M. Niwa and Y. Murakarm', Mat. Chem. fiys. 17 (1987) 73-85.
2. M. Niwa, S. &to, T. Hattori and Y. Mwakanu ', J. them. Soc. Faraday Trans.
1 (1984) 80, 3135-3145.
3. E.F. vansant, Innovation in zeolite Materids science, Elsevier, Amsterdam,
1988, pp.143-154.
4 . R.M. Barrer, R.G. Jenkins and G. F % x & e r ~ ,Molecular Sieves 11, Am. Chem.
Soc., Washington D.C., 1977, vol. 40, 258-265.
5. I. Wang and C.L. Ay, m-oceeding of the 8* International Oxqress on mtal-
ysis, Calgary, canada, 1988, Vol 1, 324-331.
6. R.J. Aryaur and G.R. Landolt, US P am 3,702,886 (1972).
7. D.H. Olson, W.O. Haag and R.M. lago, J. Qtdl. 61 (1980) 390-396.
8. J.C. vedrine, A. ~uroux,v. Bolis, P. Dejaifve, C . Naccache, P.
Wierzchmki, E.G. Derouane, J.B. Naqy, J-P. Gilson, J.H.C. Van Hooff, J.P.
van den E e q and J. Wolthuizen, J. Cam . 59 (1979) 248-262.
9. Y.F. Chu and A.W. olester, U.S. Patent 429,176.
H.G.Karge, J. Weitkamp (Editors), Zeolites us Catalysts, Sorbents and Detergent BuiMers
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

A NEW STRUCTURAL-MODIFICATION T E C H N I Q U E F O R ZEOLITES:

CHEM I S O R P T I O N OF S i t HI

Yongan Yan,J.Verbiest,J.Philippaerts,E.F.Vansant and P.De Hulsters

University of Antwerp tU.1.A. ), Department of Chemistry,

Laboratory of Inorganic Chemistry, 8-2610 wilrijk, Belgium.

Chemisorption of disilane o n H-mordenite small port

causes two types of structural modification: 1)
homogeneous intracrystalline Implantation of additional
groups and/or 2 ) preferential pore entrance and external
surface modification. T h e obtained t y p e depends on the
applied reaction conditions. The second modification
process causes a n efficient pore s i z e reduction without
loss of sorption capacity or acidity. The obtained
substrates show a high resistance to a steaming
treatment. The properties of t h e s e modified z e o l i t e s h a v e
been evaluated b y c h e m i s o r p t i o n kinetics, gas a d s o r p t i o n
experiments and F T I R - P A S spectroscopy.

INTRODUCTION

The methods by which additional g r o u p s a r e chemisorbed into

the zeolitic framework a r e well established techniques for fine
tuning of gas separators, gas encapsulators and shape-selective
catalysts I 1 31. T h e s e modification techniques are based o n an
internal i m p antat ion of electrophilic groups which causes a
stable narrow ng of the pore dimensions and a distinct c h a n g e in
elect.rical f eld grad ent within the zeolite channel system.
During chemical modif cations of micro-porous substrates the
reaction rate can be controlled or limited either by low
reactivity or b y slow diffusion of the modifying agent through
the channe I s. Therefore b y choosing suitable modifying a g e n t s of
different molecular sizes and reactivities, or by controlling t h e
modification conditions, the desired modified s u b s t r a t e s c a n be
obtained. T h i s can result in external s u r f a c e or intracrystalline
modification.

In this work we have studied t h e mechanisms of disilane

chemisorption on small port H-mordenite. T h e resulting porosity
is investigated by a d s o r p t i o n experiments using various gases
with different molecular s i z e s and shapes. T h e modified z e o l i t e s
are characterised by Fourier T r a n s f o r m Infrared Photoacoustic
Spectroscopy (FTIR-PAS). We have demonstrated that d i s i l a n e is a
suitable modifying agent for H-mordenite. the chemisorption can
be controlled by either the reactivity or a d i f f u s i o n process,
and the final products, a s anticipated, show different structural
properties.

EXPERIMENT

The synthetic Na-mordenite SP, supplied by La SociCtC

Chemique de la G r a n d e P a r o i s s e ( F r a n c e ) , w a s converted into t h e
NH.-form by a conventional ion-exchange procedure. The ammonium
content of the zeolite was 2.36 mmole/g. A thermal treatment of
NH,-mordenite at 7 3 3 K in vacuum resulted in t h e f o r m a t i o n of the
H-form zeolite (deam.). T h e void volume of this substrate is
0.221 c m s / g , a s measured by n i t r o g e n s o r p t i o n at 7 7 K . Disilane,
obtained from UCAR (Belgium), w a s purified by destillatlon.

T h e structural modification of the z e o l i t e was c a r r i e d out in

a dynamic gas adsorption a p p a r a t u s [ 1 , 2 1 , in which a fixed-bed
reactor with a porous f r i t was used. This permitted continuous
circulation of the gas phase t h r o u g h the sorbent during the
react ion. The react ion progress was fo I lowed b y measuring the
amounts of H n evolved and S i l H I chemisorbed at different times.
Adsorption kinetics of Ar, Kr. Xe. N, and O 2 were used to
evaluate the sorption c h a r a c t e r i s t i c s after each modification
step. Infrared spectra were recorded o n a Nicolet SDXB-FTIR
spectrometer equipped with an M T E C - 1 0 0 photoacoustic cell.
 761

RESULTS AND DISCUSSION

S t r u c t u r a b M o d i f i c a t i o n Process

The structural modification was studied by following the

kinetics of disilane chemisorption o n H-mordenite. Figure 1 shows
the evolution of the reaction during chemisorption at ambient
temperature (Region I ) , the secondary reaction at 3 7 3 K (Region
11) and the hydrolysis reaction at 423K (Region 111). For a
period of 100 hr a dose of disilane, with initial pressure of 128
Torr was contacted with 1.7 grams of zeolite at ambient
temperature. The reaction was monitored by trapping the gaseous
and physically sorbed disilane at 77K and measuring the amount of
HZ produced during the reaction. Within the first hour, the

7 , I I

4 4
B

i 3

0
0 2 4 6 8 1 0 2 4 2 4 6 8
/'t hr'

Fig.1. Chemisorption of SiaH. on H-mordenitr SP and

further reactions. mmole S i z H . chemisorbed; 0 mmole
H a evolved. 0 R the ratio of H a / S i a H . . The steps
are: I. 18;';hr chemisorption at 2 9 8 K . 11. After
evacuation of disilane 25 hr secondary reactions at
373K. I l l . After introducing excess H z O 49 hr
hydrolysis at 4 2 3 K .
largest amount of disilane is adsorbed, and after 16 hours an
equilibrium is reached. However, the R value, the ratio of HI
evolved to the SilHI chemisorbed, is much lower than 1 (=0.42),
indicating a strong physisorption of disilane in the initial
stages. As the reaction progresses, the R value increases and
becomes 1 after about 100 hours. This suggests that each chemi-
sorbed disilane molecule forms one covalent bond with the zeolite
framework. Under these reaction conditions the modification
process is controlled by the relatively low reactivity. Disilane
is allowed to diffuse within the intracrystalline channels and
uniformly distribute itself along the entire pore system before
chemisorption occurs. A t the end of the reaction, 0.85 mmol/g
disilane was chemisorbed.

The uniformity of the modification was further demonstrated

when the disilanated zeolite was heated at 3731(, after evacuation
of the remaining gaseous and physically sorbed S i 2 H L . Another
dose of HZ was liberated, as can be seen in region I I of figure
1. During this treatment the chemisorbed hydrides i n the zeolite
react with the available structural OH-groups, rather than
dehydrogenating between each other C 5 1 . About 1.72 mmole/g of O H -
groups reacted w i t h disilane. Therefore, the chrmisorption of
disilane at ambient temperature is associated with an implan-
tation p ocess throughout the entire volume of the channels.

A s milar procedure was followed to carry out reactions at

higher temperatures. The dehydrated zeolite samples were
initially heated to 373K, 423K, 4731.;and 52.3k:, and allowed to
stabilize for 30 minutes before contact with identical amounts of
disilane. This treatment results in a dramatic decrease of the
amount of chemisorbed disilane, when compared to the reaction at
ambient temperature, as shown in f i g . 2. At higher temperature
equilibrium is reached within 30 minutes, and no m o r e disilane is
chemisorbed after a longer period of time. The number of
structural hydroxyl groups which react with disilane also
decreases as a function of the reaction temperature. in spite of
the increasing R-values.
 763

1.0 1 t 2.0
n

-1.6 d
- 1.2 !I
- 0.8 1
1

- 0.4

0.0 0.0
213 313 113 573

M c m m a t u r e tK1

Fig.?. Intluence of the reaction temperature o n the

chemisorption process. disi lane chemisorbed; 0 the
amount of reacted OH-groub)s in H-mordeni te.

The observed phenomena can be explained in terms of a n in-

creased reactivity at higher temperatures. Under these
conditions, the entering disilane molecules immediately react
with OH-groups on the external surface and at the pore entrances.
These chemisorbed molecules prevent the other disilane molecules
from diffusing into the internal pore system. Because of the
lower accessibility of the internal volume, a preferential
reaction w i l l occur at the channel entrances and o n the external
surface. Furthermore, the chemisorption at temperatures between
373 and 523K gives rise to the formation of 2 t o 3 covalent bonds
per disilane molecule with the zeolitic structure. It can be
concluded that, when these results are compared to the charac-
teristics of the implantation process, the reaction conditions a s
described here w i l l lead to a n external (surface) modification.

After hydrolysis of the disilyl groups at 423K-523K with

HnO-vapour, R values between 6 and 7 a r e obtained, which in-
dicates that at least a portion of the incorporated Si-Si bonds
of disilane molecules a r e broken during this treatment. After
764

dehydration at 733K. the modified z e o l i t e s show no further

reaction with disilane. T h i s behaviour is d u e to 1) complete
blocking of the z e o l i t e c h a n n e l s b y t h e modifying groups and, 2 )
the inert character or the modified s u r f a c e of the zeolite.

Characterization of the Disilanated Z e o l i t e s

In order to confirm the r e l a t i o n s h i p between the chemi-

sorption temperature and the different m o d i f i c a t i o n mechanisms,
and to allow an e s t i m a t i o n of the c h a n g e s in pore size during
these treatments, a d s o r p t i o n e x p e r i m e n t s have been carried out
using various test gases with different kinetic diameters. Figure
3 shows the a d s o r p t i o n rate of X e a t 273K o n m o r d e n i t e samples,
modified with different a m o u n t s of S i n H I at a m b i e n t temperature.
A f t e r chemisorption of more than 0.5 m m o l e / g of disilane. the Xe

0 2 4 6 8 1 0 1 2
t+/.in4

Fig.3. Adsor tion kinetics

modified H - m o r d e n parent
0h
c . 5e 2
symbols,
A o n the zeolites. ,
m i s o r b e d O.67;'&:*0.78;
res ectively
v
correspond to t h e a d s o r p t i o n of X e
before and afrer hydrolysis-dehydration. Qe=1.96 mmole- g - ' .
 765

5,
U
u

0.4

0.2

0.0 0.2 0.4 0.6 0.8 1.0

The amounta of chemiaorbed Sip6 / m m l

Fig.4. The va iation of relative adsorption amounts

of
with’:%dferent’
A
Ar* 6
K r ; o n modified zeolites chemisorbed
amounts of disilane. Qe(02 )=0.160;
Qe(Ar)=0.174; Qe(Kr)=0.796 m m o l e . g - * .

adsorption becomes controlled by a diffusion process. A further

increase in the amount of chemisorbed disilane causes an even
lower sorption rate of Xe. Hydrolysis of t h e residual Si.H,
groups, followed by dehydration, results in a further reduction
of the pore sine so that more pronounced diffusion processes of
Xe and K r were observed. Moreover, the incorporated obstructions
cause a significant decrease in the adsorption capacity for small
molecules such a s O n and A r , a s c a n be seen in figure 4. These
results are in agreement with the hypothesis of a uniform
disilane implantation throughout the zeolite channel system.

Figure 5 shows the kinetic plots of Xe o n two H-mordenite

samples, containing the same amount (0.675 mmolelg) of disilane
but chemisorbed at different reaction temperatures. The sample
treated at 353K exhibits a much lower adsorption rate compared t o
a substrate modified at ambient temperature. On the other hand,
the sorption capacity after 1 7 hours contact time is larger after
a high temperature modification. This effect is even more pro-
nounced after hydrolysis of the residual Si-H bonds and
dehydration. Considering the kinetic diameter of Xe (3.96A).
these experiments show that the effective pore size, originally
6.2A [El, was reduced to about 4 A .
766

I
1.0

0.8
If--
a"
\
0.6

~ ~ ~ 0 . 4

0.2

0.0
:/
0 2 4 6 8 1 0 1 2 3 2

,.
t%.ink

Fig.5 Xe adsorption at 273K o n ,o

parent sam le
after chemisorption of 0.67 m m o l e l g disilane 0 at %Sb
and at 3 7 3 K ; after hydrolysis of t h e two respective
samples .

-1
4
z
Q
H
ul
I

f
n

I
I
V

3800.0 P700.0 P800.0 PSOO.0

WAVMUWERS (CM-1)

F i g . 6 FTIR-PAS spectra of modified H-Mordenite SP

after deuterium exchange: a ) parent sample; b ) 0.67
mmole/ disilane chemieorbed at 353K; c ) 0 . 5 2 ; d ) 0 . 6 7 ;
e) 0.8g mmole/g disilane chemisorbed at 298K.
 These results c a n be correlated with observations from infra-
red spectroscopy. The acidic hydroxyl groups which absorb a t 3605
cm-I (at 2664 cm-' after deuterium-exchange) in mordenite are
the reactive centra for chemisorption reactions 15-71. The inten-
sity of this vibration band decreases a s a function of the amount
of chemisorbed disilane at ambient temperature. On the other
hand, at higher reaction temperatures only a small decrease is
observed, which indicates that most of the OH-groups inside the
channels a r e not affected (figure 6). T h e adsorption experiments,
as well a s the infrared data, confirm that chemisorption at
higher temperatures causes a preferential reaction of disilane at
the channel entrances, thus enhancing the pore-blocking effect
without great loss in adsorption capacity and acidity of the
zeol i te.

CONCLUSION

Chemisorption of disilane on H-mordenite SP at ambient

temperatures causes a homogeneous modification of the substrate
resulting in a pore-narrowing effect and capacity loss for the
used test gases. A t more elevated temperatures the chemisorption
occurs preferentially on the pore entrances, causing a more
profound pore narrowing but only a small decrease in adsorption
capacity and acidity. These results indicate that disilane has a
great potential in zeolite modifications f o r gas separation and
shape-selective catalysis.

REFERENCES

1. R. M. Barrer, E. F. Vansant and G. Peeters, J. Chem. SOC.,

Faraday I , 74, (1978), 1871.
2. A . Thijs, G T e e t e r s , E. F. Vansant, 1 . Verhaert and
P. De Bihvre, J. Chem. Sac., Faraday I , 7 9 , (1983). 2821.
3. E. F. Vansant, "Studies in Surface Science and Catalysis",
Elsevier (Amsterdami. 37. (1987), 143.
4. Y. A. Yan, J , Verbiest and E. F. Vansant tin reparation).
5. J.Phi 1 ippaerts, E.F.Vansant, G.Peeters,?and E.Fanderheyden.
Analytlca Chimica Acta. 195, ( l Y 8 7 ) , -37.
6. J. Philippaerts and E.F.ansant, "Silanes Surface and
Interface, Vol. Z " , D. E. Leyden Ed., (1987).(in press)
7. J. Phili paerts. E. Vansant and Y.A.Yan. Proc. Int. m osium
on Zeorite Catalysts. Sorbents and Detergent 'iuflders.
WIirzbur FRG, Sept. 4-@, (19HEIJ. tsubmi:ted for ubl ication)
%. D. i;eck. "Zeolite Molecular Sieves , W i ley Pnterscience.
This Page Intentionally Left Blank
H.G. Karge,J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science PublishersB.V., Amsterdam - Printed in The Netherlands

DEALUMINATION OF THE ZEOLITES OFFRETITE AND ERIONITE STUDIED BY

SOLID-STATE zgSi- AND Z7A1-MAS NMR SPECTROSCOPY

Karl Petter Lillerudl and Michael Stockerz,

'Department of Chemistry, University of Oslo, P.O.Box 1033
Blindern, N-0315 Oslo 3, Norway.
ZDepartment of Hydrocarbon Process Chemistry, Center for
Industrial Research, P.O.Box 124 Blindern, N-0314 Oslo 3 , Norway.

ABSTRACT
The ZeSi- and 27A1-MAS NMR spectra of the zeolites offretite,
offretite/(lO%)erionite, offretite/(30%)erionite and erionite were
recorded including their dealuminated samples. The interpretation
of the NMR spectra was made by computer simulation assuming a
binomial distribution of the aluminium atoms, and a graphic
comparison of the calculated and measured spectra. It is shown
that aluminium was mainly removed from the Ti sites of the
offretite lattice during the dealumination process.

INTRODUCTION
Zeolites have been applied as heterogeneous catalysts during
the last few decades. Their unique channel dimensions (pore
diameter less than 1 0 A ) and the existence of exchangeable cations,
which permits introduction of cations with various catalytic
properties (ref. l), makes them particularly useful to the oil and
petrochemical industry. Much effort has been spent to
elucidate the zeolite structure and its relation to activity and
selectivity in chemical reactions. Shape selectivity and acid
strength of zeolites are important aspects of their catalytic
activity. Offretite and erionite are zeolites of increasing
interest, e.g. as catalysts in t.he methanol conversion to light
olefins. Industrial application of zeolites requires usually a
hiqh catalyst lifetime, a problem which miqht be solved by
dealumination of the zeolites, i.e., partial removal of aluminium
atoms from their lattice positions. Solid-state 29Si- and 27A1-MAS
NMR spectroscopy should be a powerful tool to follow possible
structure modifications due to dealumination effects.
770

Since it was shown by Lippmaa et al. (ref. 2 ) that ZgSi-MAS

NMR-spectra were sensitive to the nature and chemical environment
of the atoms, considerable knowledge has been gained during the
last years about the structures of zeolites from the study of
their 2gSi- and 2”A1-MAS NMR spectra (ref. 3 ) .
The Z9Si-MAS NMR spectra of zeolites with one crystallographic
T site exhibit up to five lines which correspond to the five
possibilities for the linkage of an SiOa-tetrahedron through
oxygen bridges to n AlOa-tetrahedra (n = 0 - 4 ) : Si (n Al)
(ref. 4 ) . In zeolites with multiple T site positions up
to five resonance lines per T site could be observed. Since
chemical shift dispersion due to crystallographic inequivalent
sites often is of the same order of magnitude as the shift due to
the above-mentioned different number of aluminium atoms in the
first coordination sphere (ref. 51, severe resonance line overlap
may result. In addition, we are dealing with solid-state NMR which
means lower resolution compared with high-resolution NMR. The
assignment of signals may, therefore, be more complex
(ref. 6 ) . Furthermore, if Lowenstein’s rule is obeyed, the
A1 atoms always have four Si atoms in the first coordination
sphere, and the 27A1-MAS NMR spectra show, therefore, only one
resonance line per crystallographic position.
ZrA1-MASNMR chemical shifts allow discrimination between the
different framework positions (TI and Tz, tetrahedrally
coordinated) and non-framework (octahedrally coordinated)
aluminium (ref. 7 ) . 27A1-MAS NMR spectra of zeolites exhibit only
one central line per T site corresponding to the transition
between the energy levels. However, this line is broadened by
quadrupolar interactions. The chemical shifts of framework
aluminium in zeolites cover only a narrow range between 53 and 62
ppm (ref. 7 ) , whereas octahedrally coordinated A1 is observed
around 0 ppm. The Z7A1-NMR linewidth (AH), measured at half height
of the NMR resonance line, is the best parameter to investigate
the chemical environment. The quadrupolar nuclei are very
sensitive to the coordination number. the nature of ligands and
the symmetry of substitution (ref.7).
In the present study. we report the 29Si- and (partly) 27A1-MAS
 771

NMR spectra, together with the computer-simulated spectra, for the

following zeolites (dealuminated to various extent):
Off retite
Offretite/(<lOt) erionite
Offretite/(30%) erionite
Erionite
The purpose of this investigation was to follow possible
structure modifications due to dealumination effects.

EXPERIMENTAL
Synthesis
The synthesis of the zeolites is described in ref. 8 , except
for erionite, which is a naturale sample from Pine Valley (USA).
The dealumination was carried out by hydrothermal treatment
according to the procedure described by Fyfe et al. (ref. 6): The
zeolites were cation-exchanged with 2 M NHqC1, calcined and then
exposed to water vapour for 12 h at 700 OC in a quartz tube
furnace. Finally the samples were washed, ion-exchanged and
calcined. The Si/A1 ratios of the samples were determined by EDX
analysis in a microprobe and by X-ray fluorescence spectroscopy.

S-olid-state MAS NMR spectra

The solid-state MAS NMR spectra were recorded at 4 . 7 Tesla,
using a Bruker CXP-200 pulse Fourier transform NMR spectrometer,
operating at 3 9 . 7 MHz (Z9Si) and 52.1 MHz (2'Al). The spectrometer
was fitted with a magicangle spinning probe (rotor speed between
3.1 and 3 . 6 kHz). A pulse width of 6 usec was used with repetition
times of 3 sec (29Si) and 0.1 sec (Z7Al). 4 K data points were
recorded over spectral width ranges of 2 . 5 - 3 kHz (29Si) and 26 -
6 5 kHz (27Al). The chemical shifts were referenced towards
external Si (CHI) 4 and A 1 (HZ0 )6 , respectively.

Computer-simulated spectra
The computer-simulation procedure is described in ref.5 and 9 .
Mikovsky (ref. 10) has calculated the relative resonance
intensities of 29Si-NMR spectra of zeolites with only one type of
tetrahedral site. This calculation may also be applied to each of
the two subspectra of the offretite spectrum, since the Si atoms
112

are occupying two different types of tetrahedral sites (TI and T2)
in this zeolite. Each type of tetrahedral site gives rise to a
maximum of five resonance lines, separated by 5 - 6 ppm, which may
be correlated with the number of A 1 atoms surrounding a given Si
atom (Si(n Al), with n = 0 - 4 ) . Since in the offretite structure
there are twice as many TI-atom sites as Tz-atom sites, the total
intensity of the TI spectrum should be twice that of the T2
spectrum. The spectra are superimposed in such a way that a
Si(n Al) atom occupying a TI tetrahedral site has a chemical shift
very close to a Si ((n + 1) All occupying a T2 tetrahedral site
(ref.9). The A1 atoms are assumed to be randomly distributed among
the TI or TZ tetrahedral sites in such a way that LBwenstein's
rule is obeyed, i.e. no A1-0-A1 linkages are present, whereas A1
distribution between TI and TZ sites may not be random. The
intensity of an individual resonance may be calculated according
to (ref. 9)

IsiT (n All: Intensity of the resonance resulting from silicon

atoms occupying Si TI type or Tz type tetrahedral
sites and having n A1 atoms as nearest neighbours
(n = 0 - 4).
Itot : Total intensity.
P : Probability that the n-th neighbour is a Si atom.
q : 1-p

The compuker-generated spectra are calculated according to

equations (1) and ( 2 ) and compared with the experimental spectra
The single resonance lines are represented as Gaussian curves.

RESULTS AND DISCUSSION

The tetrahedral framework of offretite is composed of
interconnected double and single six-membered rings. Each unit
cell contains 12 tetrahedral atoms (TI atoms) located in double
six-membered rings and 6 tetrahedral atoms (Tz atoms) located in
single six-membered rings, resulting in an overall ratio of two
 773

TI atoms for each Tz atom in offretite (ref. 9 ) . In erionite, each

second Tz site is turned around 60° compared to the first TZ site
(see Figure 1). In the case of offretite a number of different
assignments of the resonance lines in the observed aqSi-MAS NMR
spectra have been made to bring the Si/A1 ratios from chemical
analysis into agreement with those calculated from the NMR spectra
(refs. 6 and 9 and references cited therein). The assignment of
the lines in an observed spectrum to their respective crystallo-
graphic sites and number of aluminium atoms in the first
coordination sphere is well understood. This allows us a detailed
interpretation of the Si and A1 distribution in the framework
structure of zeolites by solid-state NMR spectroscopy.

Fig.1. Structure of offretite (upper figure) and

erionite (lower figure).
 114

-:iS:2 MAS- NMR spectLa

The ZqSi-MAS NMR chemical shifts for the different Si (n All
atoms range from about - 8 5 ppm to about -112 ppm.
As shown in Figures 2 - 4 , the 29Si-MAS NMR spectra can be
deconvoluted in terms of ten overlapping Gaussian curves (dashed
lines: simulated patterns). The parameters adjusted to obtain the
best agreement in the simulations were the total Si/A1 ratio
(values from the chemical analysis are used as total Si/A1
ratios), the relative distribution of A1 between the Ti and T2
sites and the line width. The Si/A1 ratios resulting in the best
fits are reported in the Figures 2 - 4 , shown for the zeolites
offretite (Fig. 2 1 , erionite (Fig. 3 ) and offretite/(30%) erionite
(Fig. 4 ) . A general trend was observed for the offretite
zeolites: during the dealumination process aluminium is mainly
removed from the TI sites of the zeolite lattice. This is valid
for offretite and the two offretite-erionite intergrowths (see
also Figs. 2 and 4 , no figure for offretite/(<lO%)erionite).
Concerning erionite, the best agreement was obtained by
simultaneous removal of A1 from both TI and Tz sites.
Dealumination of specific crystallographic sites in the erionite
structure is obviously not preferred. This difference in
dealumination properties may be due to the lack of the open
12-membered ring channels in erionite. In all cases, the
calculated spectra correspond very well to the measured spectra.
Furthermore, an increase in line width by increasing the number
of dealumination steps is in agreement with the observed decrease
in crystallinity (determined by X-ray diffraction) due to several
dealumination steps.

ZlAl-MAS NMR spectra

So far only one group has reported z7A1-MAS NMR parameters for
offretite and erionite zeolites (ref. 7 ) . As shown in Fig. 5 , the
Z'Al-MAS NMR spectra can be deconvoluted in terms of two
overlapping Gaussian curves, representing two signals due to
tetrahedral aluminium from the T-site inequivalence (Ti and T2
sites, dashed lines: simulated patterns). Assuming random A1
distribution for the T sites an ideal ratio of 2 : 1 for Tt : TZ
should be expected, resulting in an asymmetric peak at the
high-field site of the resonance signal. Removing aluminium from
 115

TI sites results in a decrease of T t intensity followed by a

relative increase of the intensity of the T2 line. This is well
demonstrated by the formation of a clear shoulder in the spectrum
of the most dealuminated sample (see Fig.5). The experimental
findings are confirmed by our simulated spectra.
The difference in chemical shift for the TI and Tz sites used
in our simulations is larger than expected for offretite ( = 13
ppm) compared to that observed by Fyfe et al. (ref. 6 ) for the
zeolite omega ( = 6-7 ppm). On the other hand, our 27A1-MAS NMR
line widths (AH) are smaller (between 940 and 1820 Hz) than those
measured by Nagy et al. (ref. 7) for offretite (2800 Hz), erionite
(3500 Hz) and T-zeolite (2200 Hz).

Sl/Al r e t l o :
- T o t a l = 2.1

Dsalumlnated onc 0.
Sl/Al r a t l o : S V A 1 ratlo:
-Total- 5 . 2

,' t \

--f
I
---,I
', \

IT 'A'
Dsalumlnated f o u r t,.l%tbs.
\
S ioItAa l - r 0e .t 0l o :
' I
Sl/Al r a t l o :
Total- 10.0

. T, - 1 0 . 0

80 90 100 110 120 80 ao

, -.-- . .,--a
100 110
I

120
-ppm -ppn

Fig. 2. Si-MAS NMR spectra Fig. 3 . Si-MAS NMR spectra

of offretite. of erionite.
776

Not daalumlnDte
Si/A1 ratlo: A1 -nnr

D a ~ l u n l n ~ t a onca.
d Daalunlnatad onca.
S i / A 1 ratio: Al-nnr
Total. 4.e . T,: e a ~i
T,: 372 A1

__-I _--'
,
', '\. \

eo ao 100 110 120

-Pm

Fig. 4. Si-MAS NMR spectra of Fig. 5. A1-MAS NMR spectra of

offretite/(30%)erionite. erionite/(30%)erionite.

The Z'Al-MAS NMR chemical shifts range from 51 to 58.6 ppm for
tetrahedrally coordinated Al. Only small amounts of octahedrally
coordinated A1 were found in the dealuminated samples (see Fig.6).

CONCLUSION
From the examination of our results we conclude that 2SSi- and
Z'Al-MAS NMR spectroscopy can be used to monitor the removal of A1
from a specific lattice site during dealumination of zeolites.
It was shown that aluminium is mainly removed from the TI sites of
the offretite lattice. The same conclusion could be drawn from the
Z'Al-MAS NMR measurements. In addition, high-field Z'Al-MAS NMR
investigation could yield better-resolved TI and Tz resonance
lines for detailed interpretation of P7A1-NMR spectra.

150 100 K) 0 -50pprn

Fig. 6. 27Al-MAS NMR spectrum of erionite (dealuminated once).

ACKNOWLEDGEMENT
The authors are indebted to the Royal Norwegian Council for
Scientific and Industrial Research for financial support of this
investigation and to Prof. J.B. Nagy (University of Namur) for
recording the NMR spectra.

REFERENCES
1 S.M. Csicsery, Zeolites, 4 (1984) 202.
2 E. Lippmaa, M. Magi, A. Samoson, M. Tarmak and G. Engelhardt,
J. Am. Chem. S O C . , 103 (1981) 4992.
3 C.A. Fyfe, J.M. Thomas, J. Klinowski and G.C. Gobbi,
Angew. Chem., 9 5 (1983) 257.
4 J.B. Nagy, 2. Gabelica, G. Debras, P. Bodart, E.G. Derouane
and P . A . Jacobs, J. Mol. Catal., 20 (1983) 327.
5 K.P. Lillerud, Zeolites, 7 (1987) 14.
6 C.A. Fyfe, G . C . Gobbi, G.J. Kennedy, J.D. Graham, R.S. Ozubko,
W.J. Murphy, A. Bothner-By, J. Dadok and A.S. Cheenick,
Zeolites, 5 (1985) 179.
7 J.B. Nagy, Z. Gabelica, G. Debras, E.G. Derouane, J.-P. Gilson
and P.A. Jacobs, Zeolites, 4 (1984) 133.
8 K.P. Lillerud and J.H. RiEder, Zeolites, 6 (1986) 474.
9 J.H. Rader, Zeolites, 4 (1984) 311.
10 R.J. Mikovsky, Zeolites, 3 (1983) 90.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V.,Amsterdam - Printed in The Netherlands

Galliation and '*O-exchange Reactivities of ZSM-5 and ZSM-11

A. Endoh, K. Nishimiya, K. Tsutsumi' and T. Takaishi

Toyohashi University of Technology, Toyohashi 440, Japan

ABSTRACT
The "0-exchange between COa and ZSM-5 and ZSM-11 was measured,
along with their galliation. There was a strong correlation between the
reactivities €or these two processes, and they markedly depended upon the
sources of starting materials. The reactivities stem from defects the concen-
tration of which may depend upon the know-how of synthesis of the suppliers.
About 6 €ramework oxygen atoms became reactive for exchange per Ga
atom inserted, which suggests that Ga occupies a corner o€ the 4-membered
oxygen ring.
The initial heats of adsorption of NHB, calorimetrically determined, were
ca. 160 kJ.mol-' in H-Ga-ZSM-5 and ZSM-11. The catalytic activity on
galliated zeolites is due to the fact that one acid site is produced by each
Ga atom in the framework.

INTRODUCTION
The isomorphous substitution of T-site atoms ( T = Si or A1 ) of the
zeolitic framework by Ga attracts wide attention in connection with its cat-
alytic activity. Usually, zeolite containing Ga is directly synthesized by the ad-
dition o€ a gallium source into the reactant mixture. Recently, a new method
for the substitution was discovered, that is, galliation of highly siliceous zeo-
lites could be achieved by dipping them in sodium galliate solution (ref. 1). To
understand their catalytic properties of Ga-zeolites, further knowledge is re-
quired about the nature and location o€ acid sites produced in the framework.
In the present paper, we investigated the reactivity for galliation of ZSM-5 and
Z S M - 1 1 supplied €rom several source, because such a reactivity may depend
upon the concentration of de€ectu contained. Furthermore, the '*O-exchange
reactivities between COz and these zeolites were measured to estimate the
concentration of defects in the starting zeolites, and to search the location of
Ga in the framework.
780

EXPERIMENT

ZSM-5 and ZSM-11 zeolites, in highly siliceous or galliated forms, were

supplied from several sources. Their compositions are listed in Table 1.

TABLE 1
Compositions of ZSM-5 and ZSM-11, and abbreviated notations
for various samples studied.

Sample Si/Al( Ga ) ratio Abbreviation*

Na-ZSM-11 1066 N a- 11-C

Na- Ga- ZSM- 11 9.8 ( by c.a. )** Na- Ga- 11- C
15.4 ( by n.m.r. )
H- G a-Z S M- 11
Na- Z S M- 11
Na- Z SM-5
-
9.8 ( by c.a. )
A1 trace
685
H- Ga- 11-C
Na-11-M
Na-5-M
Na- Ga-Z SM- 5 10.7 ( by c.a. ) Na-Ga-5- M
H-Ga-ZSM-5 10.7 ( by c.a. ) H-Ga-5-M
H-ZSM-5 0S9 H-5-M

* C and M denote sample suppliers, Cambridge school and Mobil groups,

res pee tivel y.
* * c.a., chemical analysis; n.m.r., 29Si m.a.s. n.m.r. spectroscopic analysis
( These values were determined by the supplier ). For details concerning
the samples refer to the supplier's paper (ref. 1).

The standard procedure for galliation was used as follows. One gram of
zeolite was added to SO ml of the aqueous solution of Gas03/ NaOH ( 0.0278
rnol4-l Gaz03, 0.10 mo1.l-l NaOH). The mixture was heated to 575 K under
stirring and kept at this temperature for 24 hr. The product was filtered,
washed with distilled water and dried in air a t 555 K. The amount of Gaa03/
NaOH solution used. for 1 g of zeolite, was varied in some cases from 5.5 to
120 ml, and the treating time was also changed from 24 to 48 hr. The degree
of galliation was checked by i.r. and "Si m.a.9. n.m.r. NH4+ exchange of the
samples was carried out by the usual procedure.
 781

High - Temperature Adsorption Calorimetry

Differential molar heats of adsorption of NH3 on the zeolites were measured
at 47s K using a twin-conduction-type micro-calorimeter after the sample waa
evacuated at 773K. The apparatus and the procedure of measurement were
described in a previous paper (ref. 2).

Exchange of Oxygen Isotopes between CO1 and the Zeolites

The apparatus used for the reaction was the same as that described in a
previous paper (ref. 3). The zeolite, ca. 40 mg, was completely dehydrated
at 775 K for 2 0 h r under a vacuum of lo-' Pa before exchange reaction.
The reactions were carried out at a pressure ca. 1850 Pa of C O z and a t
temperatures between 073 and 775 K.

RESULTS AND ANALYSIS

Figure 1 shows 29Si m.a.s. n.m.r. spectra of H-5-M as-received and its
products treated with G a z 0 3 / NaOH solution. The products gave almost the
same chemical shifts and peak-intensities as the starting zeolite. 1.r. spectra,
in the region of the framework vibration, did not change by the treatments.
This tendency prevailed even if the treating time was prolonged to 4 8 h r and
the amount of solution was increased to 120 ml. It is concluded that under
the present conditions H-5-M was not galliated at all. The same w a s the case
with Na-11-M.
Na-5-M, on the other hand, was galliated. Figure 2 shows i.r. spectra of
the product ( abbreviated hereafter as Na-Ga-5-M ) and the starting zeolite.
In this case, the peaks referred to the vibration of the framework were shifted
to the low-wavenumber side after the treatment. This means that a change
has occurred in the force constant of the T-0 bond by the insertion of Ga
into the framework (ref. 1). Figure 5 shows m.a.9. n.m.r. spectra of the
samples. Slight changes were observed in the shapes and chemical shifts in
these spectra. However, the change was too small to calculate the Si/Ga ratio.
Chemical analysis of Na-Ga-5-M, on the other hand, showed that the sample
contained 7.7 Ga atoms and 0.5 A1 atoms per unit cell, that is, a large amount
of gallium oxide impurity existed in the channels.
Figure 4 shows the differential molar heats of adsorption of NH3, q d , f f , on
the samples. The initial heats on Na-11-C and Na-5-M were ca. 50 kJ.mol-',
and amounts of ammonia adsorbed were very small. By galliation, the initial
782

heats increased to ca. 90 kJ.mo1-I in Na-Ga-11-C and Na-Ga-5-M. A fur-

ther drastic increase to ca. 180 kJ.mol-' was achieved by protonating of the
galliated zeolite t o H-Ga-11-C and H-Ga-5-M, and amount of

I\
1 1 1 1 1 1 1 1 1
Aaym. 8ym. atretch 0-rlng 1-0
2.0111. l*,

L I 1 I I
-105 -110 -115 -120 -125
1400 1200 1000 800 600 400
ppm from TMS Wavenumber 1 cm-'

Fig.1 29Sim.a.s. n.m.r. spec- Fig.2 1.r. spectra of Na-5-M and

tra of H-5-M and prod- galliated zeolite ( Na-Ga-5-PuI
ucts treated with GazO3/ ) in the region of the frame-
NaOH solution. work vibration. Spectra were
recorded by a conventional
KBr disc technique in air at
room temperature.

Na-Ga-6-M

-
-10s -110 -11s -120 -12s

ppm from TMS

H-Ga-1 1-C

F i g 3 29Sim.a.s. n.m.r. 0 1000

I I
2poo
I I
00
spectra of Na- NH3 Adsorbed j II mo1.g-

5- M and Na- Fig.4 Differential molar heats of adsorption of NH3

Ga-5-M. on the zeolites at 475 K.
 NH3-adsorption markedly increased.
The high initial heats, ca. 160 kJ.mol-',
clearly correspond to the acid-base in-
teraction of the acidic site with NH3.
Tsutsumi et al (ref. 4 ) suggested that
the adsorption with a small q d r t f . , less
than 80 kJ.mol-', is referred to the in-
teraction between the framework and
0 10 20 30
NH3, and the adsorption with a greater
Reaction Time / hr
heat to the interaction with an acid
site, either Bronsted or Lewis acid.
Since no A1 was detected in H-Ga-11- \
C
C (ref. l ) , the acid sites must result P)
0
%
from the presence of Ga atoms in the
25
framework. The adsorbed amount with -0
0)
higher q d , f f . was ca. 800 pmo1.g-l in P
Q
H-Ga-11-C; namely, there are flve acid 0 r
X
sites per unit cell, which is well related w
0 10 20 30
to the number of Ga atoms, 6.7, de-
Reaction Time / hr
duced from 29Si m.a.9. n.m.r.. The
difference amounting to ca. 1.7 is non-
negligible and may be attributed to
amorphous impurities coating the acid
sites. The initial high heats of adsorp-
tion observed in H-Ga-ZSM-5 may be
due to a small amount of Ga atoms as
well as A1 atoms in the fkamework.
Figure 5(a) shows the degree of
10 20 30
exchange of oxygen between ZSM-11
Reaction Time / hr
samples and COz at 775 K. Na-11-C
had a much higher exchange reactivity Fig.5 180-exchange reactivities be-
than Na-11-M. Furthermore, Na-11-C tween CO2 and the zeolites.
was galliated rather easily, while Na- (a) ZSM-11 series (b) ZSM-
11-M was not. Na-11-C and Na-11-M 6 series ( c ) Temperature de-
could not be distinguished macroscop- pendences of the reactivities
ically, and the above difference in their in Na-Ga-5-11.
784

reactivities may be attributed to the content of defects.

When Na-11-C was galliated to Na-Ga-ll-C, the '*O-exchange reactivity
was drastically increased. The same was the case with a pair of ZSM-5 zeolites
( Na-5-M and Na-Ga-5-M )( Fig.S(b)).
Fig.5( c) shows the temperature dependence of the reactivity in Na-Ga-11-
C.

DISCUSSION
The reactivities in galliation and '*O-exchange had a good correlation with
each other. For example, Na-11-C is easily galliated up to 6.7 Ga atoms per
unit cell, and showed high reactivity in isotopic exchange. Na-11-M exhibited
no reactivity for either galliation o r isotopic exchange. Hence, we propose the
following model for defects to explain the present results. If one Si on a T-site of
the framework is removed, then four silanol groups are formed. Oxygen atoms
in these silanol groups may have a much higher reactivity for isotopic exchange
than the normal framework oxygen atom. When the sample is treated with
sodium galliate solution, Ga is easily inserted into this position. Thus, the
galliation is controlled by the concentration of defects in the framework.

S,i Ti Si
0 0 0

I
-Si-O- Si- O-Si- -%OH
H
HO-Si-
I
-Si- 0-Ga- 0-Si-

0
I H
I
0 0
I
s'i $i ii

Now, we adopt the following approximation to analyze kinetics data of Na-

Ga-11-C, and search for the location of G a i n the framework. The oxygen atoms
in the crystal are classifled into three kinds, that is, reactive and less-reactive
framework-oxygen atoms ( specifled by the subscripts 2 and S, respectively ),
and oxygen atoms in amorphous oxide or silanol groups ( specifled by the
subscript 1 ), and they should have very different rate constants,

where k is the rate conetant.

 185

In a later stage of the reaction, the first and second kinds of oxygen atoms
are in equilibrium with the gas phase, and the rate of exchange is determined
by the third kind of oxygen atoms. Then, according to eqn.(O) in the preceding
paper (ref. S ) . we have

-
where n g and n, ( i = 1 S ) denote the number of moles of the oxygen atoms
in the gas phase and those of the i-th kinds, respectively, y, the fraction of l a 0
in C 0 2 and yJ0 its initial value at t = 0 . Plots of

against t becomes linear apart from the initial portion near t = 0 , as shown in
+ +
Fig.B(a). From the slope of the linear part the value for lc3(n1+ n2 n3 n g )
is obtained. The total amount of oxygen, (n1 + n 2 + n 3 ) , is known, and hence
the value for k3 is obtained. The intersect of the linear part with the ordinate
gives the value for

n3n&
(nl + n2 + n g ) ( n l+ n2 + n3 + n g )
and hence the values for n3 and ( n l + n 2 ) are determined.
Next, in the intermediate stage of the reaction, the flrst kind of oxygen
atoms is in equilibrium with the gas phase, and the third dose not participate in
the exchange because of its small rate constant, and hence the rate of exchange
is determined by the second kind of oxygen atoms. Then, eqn.(2) is replaced
by the following equation,
786

-
f
QO
01

+, -45

I
m
>. -1.0
Y

m
-
0
0 20 40 60
t/h

-
om
0 ,

Q-. I
C

-
O
x
m
-1.0

-
0

0 I 10

t/h

Fig.6 Plots of the degree of exchange us. time, based on eqns.(2) and
(3) a t 723 K. vgo = 0.90; amount of oxygen atoms in gas ( nJ),
0.251 mmol; in solid ( n, ), 1.168 mmol.

+
where the value of (nl 7x2) has already been obtained from Fig.B(a). Fig.B(b)
shows plots of eqn.(3), and unknown parameters n1, na and k3 are determined
by a method similar to the above. There were small variances in the values
for n l , n2 and n3 determined from data at four different temperatures. Their
average values are,
 787

+ n2 + n3 ) = 0.11
n1
0.01,
nl

(nl

( nl +
::zz
+ + n3)
+ n3)
= 0.20 f 0.01,

= 0.69 f 0.01.

Temperature dependences of kZ and k3 gave the activation energies of l.22eV

and 0.82eV, respectively.
If one Ga atom introduced produced u exchange-reactive framework- oxy-
gen atoms, then 8 . 7 oxygen
~ atoms per unit cell must easily be exchanged. On
the other hand, the number of easily exchangeable framework oxygen atoms,
+
n2, is 45 (= 192 x nZ/(n? 713)). Therefore we have

u = 4316.7 = 6 4 (4)

Since Ga atom has a larger radius ( 0.061 nm ) than Si ( 0.040 nit1 ), i t

distorts neighbouring oxygen atoms, which are then displaced in order to re-
lax the stress induced. The oxygen atoms displaced alqo push their bridging
Si and neighbouring oxygen atoms, which are also a little displaced. Thus,
the stress induced by Ga substitution propagates over a wide range, and it
decays with the increasing distance from Ga. Oxygen atoms directly neigh-
boured to Ga may be in an unstable state and highly reactive to the isotope
exchange. Next-neighboured oxygen atoms may become reactive to some ex-
tent. According to eqn.(4), four oxygen atoms directly neighboured to Ga
and two next-neighboured are easily exchanged. In the framework of ZSM-
11, the T-site has twelve next-neighbouring oxygen atoms. Thus, two out of
twelve oxygen atoms next-neighboured to a Ga atom have special properties
o r geometry. The T-site on a corner of the 4-membered oxygen ring has such
two special next-neighboured oxygen atoms. The stress in the framework may
decay with the increasing distance, and the second neighbour in the 5-ring
may experience only a small stress, but the stress may not be relaxed in the
closed 4-ring. Thus, we arrived at the conclusion that Ga atoms are selectively
inserted at the corner of the 4-ring. This result supports Kraushaar et al.'s
view on the silylation of ZSM-5 (ref. 5).
In conclusion, the "0-exchange and galliation reactivities are mainly re-
lated to defects, and strongly depend upon the quality of the crystal. There-
fore, one must carefully characterize such qualities. by using the present tech-
niques and the silylation method, to clarify catalytic properties of ZSM-5 and
11.

We thank Prof.J.M.Thomas, Dr.X.S.Liu, University of Cambridge,

Dr.A.W.Chester, Mobil Research and Develop., and Mobil Cat. Corp. of
Japan, for the supply of the samples.

REFERENCES

1 J.M.Thomas and X.S.Liu, J. Phys. Chem., 90 (1986) 4843-4851.

2 K.Tsutsumi, S.Hagiwara, Y.Mitani and H.Takahashi, Bull. Chem. SOC.
Japan, 5 5 (1982) 2572-2575.
3 T.Takaishi and A.Endoh, J. Chem. Soc., Faraday Trans. I, 83 (1987)
411-424.
4 K.Tsutsumi and K.Nishimiya, Thermochemica Acta, in press
5 B.Kraushaar, L.J.M.Van de Ven, J.W.de Haan and J.H.C.van Hoof",
International Symp. on Innovation Zeolite Materials Science, Belgium,
Sept. 1987, pp.167-174.
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THERMAL DECOMPOSITION OF IRONPENTACARBONYL I N ZEOLITES OF FAUJASITE TYPE. A

STUDY OF THE INFLUENCE OF ARGON, H2, H2/C0 GAS MIXTURE AND VARIOUS S i / A l RATIOS
USING MUSSBAUER, ESR AND MASS SPECTROSCOPY

H.M. Ziethen and A.X. Trautwein

I n s t . f . Physik, Med. U n i v e r s i t a t , Ratzeburger A l l e e 160, D-2400 Lubeck, FRG

ABSTRACT
The thermal decomposition o f Fe(C0)5 i n z e o l i t e o f t h e F a u j a s i t e t y p e de-
pends on h e a t treatment, on the a p p l i c a t i o n o f s t a t i c o r continuous vacuum, on
p a r t i a l pressure and composition o f gas m i x t u r e s i n t h e r e a c t o r , and on S i / A l
r a t i o . Decomposition products i n s i d e t h e z e o l i t e have been analyzed by tempera-
ture-dependent Mossbauer and ESR measurements. Desorption products were inves-
t i g a t e d by mass spectroscopy.

INTRODUCTION
Thermogravimetric measurements have shown t h a t the thermal decomposition of
Fe(C0)5 i n NaX z e o l i t e occurs i n two steps, w h i l e i n NaY i t i s a one-step pro-
cess / r e f . I/. I n b o t h z e o l i t e s the thernial decomposition under continuous va-
cuum (?.10-3Pa) y i e l d s c r y s t a l 1 i n e a-Fe p a r t i c l e s which a r e considerably l a r g e r
than t h e z e o l i t e c a v i t i e s and which are l o c a t e d o u t s i d e t h e z e o l i t e m a t r i x . Un-
der t h e s p e c i f i c c o n d i t i o n t h a t the decomposition o f ironpentacarbonyl i n NaX
takes place under s t a t i c vacuum, i . e . w i t h o u t removing t h e decomposition pro-
ducts from t h e r e a c t o r , a subcarbonyl i s formed above about350K. This subcarbo-
n y l , Fe(C0I3, o r i t s polymerized form, (Fe(C0)3)n, i s probably anchored t o t h e
z e o l i t e frame i n s i d e NaX, thus forming (Fe(C0)3)n...NaX. I t i s s t a b l e up t o ca.
600K, and i t stays i n s i d e the z e o l i t e c a v i t i e s even under continuous vacuum con-
ditions /ref. 2 / . The f o r m a t i o n o f t h i s subcarbonyl e x p l a i n s t h e stepwise decom-
p o s i t i o n o f ironpentacarbonyl i n NaX. F u r t h e r thermal decomposition o f (Fe(C0)3)n
... NaX under continuous vacuum up t o ca. 800K y i e l d s m e t a l l i c i r o n p a r t i c l e s
w i t h a r e l a t i v e l y broad d i s t r i b u t i o n o f magnetic h y p e r f i n e f i e l d s b u t w i t h a r e -
l a t i v e l y narrow s i z e d i s t r i b u t i o n . The superparamagnetic behavior o f these par-
t i c l e s i n d i c a t e s t h a t t h e i r diameter i s comparable t o t h a t o f t h e z e o l i t e c a v i -
t i e s / r e f . 2/. We have supplemented t h i s i n v e s t i g a t i o n
( i ) by s t u d y i n g t h e thermal decomposition o f ironpentacarbonyl i n NaX under
the presence o f A r o r H2 w i t h i n the i n s i t u c e l l ,
( i i ) by u s i n g z e o l i t e s w i t h d i f f e r e n t S i / A l r a t i o f o r t h e decomposition under
790

argon, and
( i i i ) by r e c o r d i n g Mossbauer s p e c t r a o f i r o n p a r t i c l e s which have been ex-
posed t o a H2/C0 gas m i x t u r e and by m o n i t o r i n g r e a c t i o n p r o d u c t s v i a mass spec-
troscopy.

MATERIAL AND METHODS

The a n a l y t i c a l c o m p o s i t i o n o f t h e e l e m e n t a r y u n i t o f t h e z e o l i t e s under s t u d y
i s g i v e n by a S i / A l - r a t i o o f
( i ) 1.18 (NaX) with Na74.5 (A'88.6 Si103.4 0384),
( i i ) 1.32 (NaX) w i t h Na(H)82.8 SilOgs2 0384), and
( i i i ) 2.48 (Nay) w i t h Na43.7 H,1.5
Si136.8 0384).
F o r t h e a d s o r p t i o n o f Fe(C0)5 i n t h e v a r i o u s z e o l i t e s and t h e subsequent
thermal decomposition, we have combined a gas-dosing system d e s c r i b e d by B e i n
/ r e f . 3/ and an i n - s i t u g l a s s c e l l / r e f . 2/. L o a d i n g o f t h e z e o l i t e s w i t h two
Fe(C0)5 molecules p e r supercage was achieved by l o w - t e m p e r a t u r e a d s o r p t i o n .
Thermal decomposition o f Fe(C0)5 under A r and H2 was c a r r i e d o u t under an i n i -
5
t i a l p r e s s u r e o f ca. 1 0 Pa. Maximum d e c o m p o s i t i o n t e m p e r a t u r e Tmax was reached
w i t h a h e a t r a t e o f 0.5Kmin-'. A f t e r h a v i n g a r r i v e d a t Tmax t h e m a t e r i a l was
c o o l e d down t o t h e Mossbauer measuring t e m p e r a t u r e w i t h i n a b o u t 10 min. The A r -
gas wasdeprived from O2 by a BTS c a t a l y s t ( f r o m BASF) and f r o m H20 by e i t h e r a
L i n d e 4A m o l e c u l a r s i e v e o r a c o l d t r a p . The r e m a i n i n g O2 c o n t e n t was <1 ppm.
Mossbauer and mass s p e c t r o s c o p i c measurements and t h e i r analyses c o r r e s p o n d t o
those d e s c r i b e d e a r l i e r / r e f s . 1, 2, 4/.

RESULTS AND DISCUSSION

Thermal decomposition under argon
A f t e r thermal decomposition o f Fe(C0)5 i n NaX up t o Tmax=433K, 503K, and
673K, Mossbauer s p e c t r a were r e c o r d e d i n t h e t e m p e r a t u r e range between 4.2K and
room temperature (RT). Here we show t h e 4.2K s p e c t r a ( F i g . 1 ) and t h e c o r r e s -
ponding Mossbauer parameters ( T a b l e 1 ) which were d e r i v e d f r o m l e a s t - s q u a r e
f i t s of experimental s p e c t r a u s i n g L o r e n t z i a n 1 i n e s .
C o n t r a r y t o t h e s i t u a t i o n where Fe(C0)5 i s c o m p l e t e l y decomposed a t 433K un-
d e r vacuum, we f i n d i n t h e p r e s e n t s t u d y , under argon, s t i l l ca. 27% o f i n t a c t
i r o n p e n t a c a r b o n y l ( S 5 , F i g . l a and T a b l e 1 ) . As decomposition p r o d u c t s we i d e n t i
f y ca. 58% ( S 1 ) i r o n s u b c a r b o n y l s , (Fe(C0)3)n, and ca. 15% (S2-S4) Fe2+ s p e c i e s
a c c o r d i n g t o t h e i r Irlossbauer parameters ( T a b l e 1 ) as d e s c r i b e d e a r l i e r / r e f . 2/.
By mass spectroscopy we have observed d u r i n g t h e thermal decomposition o f
Fe(C0)5 i n NaX under A r a r e l a t i v e l y h i g h amount o f H2 gas ( p r o b a b l y f r o m r e s i d -
u a l h y d r o x y l groups o f NaX), w h i c h g i v e s r i s e t o t h e o x i d a t i o n o f z e r o - v a l e n t
i r o n t o Fe2+ / r e f . 5, 6/.
A f t e r r e a c h i n g decomposition temperature Tmax=503K, Fe(C0)5 i s c o m p l e t e l y
 791

g- values

M 2 1.

b
0
-
d x'
dB
-5

B lmTl

Velocity Irnrn/sl

F i g . 1 ( l e f t ) . Experimental Mossbauer s p e c t r a o f t h e thermal decomposition p r o -

d u c t s o f Fe(CO)S i n NaX under a r g o n w i t h maximum decomposition t e m p e r a t u r e of
a ) 433K, b ) 503K and c ) 673K. The Mossbauer measurements were performed a t
4.2K. F i t parameters o f c a l c u l a t e d s p e c t r a ( s o l i d l i n e s ) a r e summarized i n
Table 1.

F i g . 2 ( r i g h t ) . ESR s p e c t r a measured a t a ) RT and b ) 2K o f thermal d e c o m p o s i t i o n

p r o d u c t s o f Fe(COIs i n NaX under argon w i t h Tmax=673K.

decomposed ( F i g . I b ) , and a t h i g h e r temperature (Tmax>673K) t h e i r o n s u b c a r b o n y l

(Fe(CO)3)n f u r t h e r decomposes under f o r m a t i o n o f a magnetic species ( b r o a d sub-
spectrum S6 i n Fig. I c ) . Isomer s h i f t 6*0.lmms-l a t 4.2K as w e l l as f e r r o m a g n e t -
i c resonance b e h a v i o r a t RT and 2K ( F i g . 2 ) i n d i c a t e t h a t we a r e concerned h e r e
w i t h magnetic i r o n p a r t i c l e s . The Fe3+ c o n t r i b u t i o n s , v i s i b l e i n t h e ESR s i g n a l
a t 9=4.3, a r e m i n o r and a r e t h e r e f o r e n o t d e t e c t a b l e i n t h e Mossbauer spectrum.
Thermal decomposition up t o 733K y i e l d s decomposition p r o d u c t s t h e Mossbauer
s p e c t r a o f which a r e shown i n F i g . 3. C h a r a c t e r i s t i c o f t h e s e s p e c t r a i s t h a t
t h e magnetic s p e c i e s e x h i b i t more s t r u c t u r a l i n f o r m a t i o n t h a n t h e b r o a d sub-
spectrum S 6 i n F i g . l c . The 4.2K spectrum ( F i g . 3 c ) c o n s i s t s o f 20% o f Fe
2+
s p e c i e s (6>0.7mms-') and 10% o f a-Fe p a r t i c l e s (6~0.1mms-1 and Bint=34 Tesla).
The r e m a i n i n g 70% o f i r o n correspond t o t h e " s t r i p p e d " spectrum i n F i g . 4a,
792

TABLE 1
Isomer s h i f t s 6 ( i n mm/s), quadrupole s p l i t t i n g s AE ( i n mm/s), l i n e w i d t h s r
Q
( i n mm/s), and r e l a t i v e abundances A o f subspectra ( i n %) f o r v a r i o u s thermal
decomposition products o f Fe(C0)5 i n NaX under argon. Measurements were per-
formed a t 4.2K.

Figure subspectrum AE
Q r A

0.02 0.47 0.43 58.3

s1
s2 0.90 0.65 0.46 7.6
1 .oo 2.10 0.40 3.3
la s3
1.19 2.60 0.40 4.3
s4
s5 -0.06 2.47 0.28 26.5

0.00 0.60 0.49 73.0

s1
s2 0.97 0.65 0.30 6.8
1b
s3 0.94 2.10 0.40 9.3
1.34 2.60 0.40 10.9
s4

S1
0.02 0.56 0.37 18.5
0.97 0.65 0.48 3.8
lc s2
s3 1.30 2.55 0.75 11.9
0.09 0 9.65 65.7
s6

( a ) 6 g i v e n r e l a t i v e t o a-Fe a t RT.

which was c a l c u l a t e d w i t h t h e h y p e r f i n e f i e l d d i s t r i b u t i o n p a t t e r n drawn i n F i g .

4b. The d e v i a t i o n of t h i s p a t t e r n from t h e b u l k - v a l u e o f a-Fe o f Bint=34 Tesla
and i t s broad d i s t r i b u t i o n around 30 Tesla i n d i c a t e s t h e inhomogeneous composi-
t i o n o f t h i s species. A p a r t from n o n c r y s t a l l i n e i r o n f o r m a t i o n and s u r f a c e l a y -
e r s of c r y s t a l l i n e i r o n p a r t i c l e s , which have been t h e main sources f o r t h e Bint
d i s t r i b u t i o n discussed i n r e f . 2, p o s s i b l e c o n t r i b u t i o n s t o Bint may a l s o a r i s e
from i r o n - c a r b i d e s and surface-chemisorption o f CO by i r o n p a r t i c l e s . The s o l i d
l i n e of Fig. 3c represents a successful f i t w i t h Fez+ species (20%), a-Fe p a r -
t i c l e s (10%) and magnetic species w i t h inhomogeneous composition (70%). The s i n -
u l a t i o n s a t 77K and RT (Fig. 3a, b ) , i n a d d i t i o n , t a k e care o f t h e superparamag-
n e t i c r e l a x a t i o n of the magnetic species / r e f . 7/. The r e s u l t i n g superparaiag-
n e t i c blocking-temperature TB o f 230K i s used t o e s t i m a t e t h e average p a r t i c l e
volume V o f t h e magnetic species by comparing magnetic a n i s o t r o p y energy w i t h
thermal energy, KVskTB, w i t h t h e a n i s o t r o p y c o n s t a n t K b e i n g 7.10 5Jmq3 f o r small
iron particles /ref. 8/. The e s t i m a t e f o r V y i e l d s as average p a r t i c l e diameter
t h e value 201, which o b v i o u s l y i s l a r g e r than t h e diameter o f t h e z e o l i t e super-
 793

-10 -6 i 4 10
Velocity Imm/sl

.005
c
404
5$ ,003
0
U
,002
.->
z ,001
.992L’ ’ ’ 1 .
. -.
! ’ . ’ ’
&

OI

-10 -8 -6 - C - 2 0 2 C 6 0 10 10 20 30 w) $I 60 70
Velocity Imm/sl Hyprfinefield B [Teslnl

F i g . 3 ( l e f t ) . Experimental Mossbauer s p e c t r a o f t h e thermal decomposition p r o -

d u c t s o f Fe(CO)s i n NaX under argon w i t h maximum decomposition t e m e r a t u r e o f
733K. The Mossbauer measurements were performed a t a ) RT, b ) 77K, and c ) 4.2K.
The sol i d 1i n e s r e p r e s e n t t h e o r e t i c a l s p e c t r a i n c l u d i n g
k e 2 + s e c i e s i.e. 5% w i t h 6=0.82mm~-~, A E -2.18mm~-~, 5% w i t h 6 = U . 7 4 m m ~ - ~ ,
A’,
&, and 10% w i t h 6=1.27mm~-~, A&=2.81mms-’,
i.e. 10% w i t h 6=0,1mms-1, A E 0, B i n t = 3 4 Tesla, and
magnetic species, i.e. 70% w i t h 6=8f25ms-’, AEQ=O, and t h e B i n t d i s t r i b u t i o n as
shown i n F i g . 4b.
The c a l c u l a t e d s p e c t r a i n c l u d e , i n a d d i t i o n , t h e superparamagnetic r e l a x a t i o n be-
h a v i o r o f a-Fe and o f t h e magnetic species w i t h inhomogeneous c o m p o s i t i o n , i . e .
t h e 4.2K spectrum i s i n t h e s l o w and t h e RT spectrum i s i n t h e f a s t r e l a x a t i o n
1 i m i t.

F i g . 4 ( r i g h t ) . a ) Mossbauer spectrum o f F i g . 3c which has been s t r i p p e d f r o m

Fez+ and a-Fe c o n t r i b u t i o n s . The s o l i d l i n e r e p r e s e n t s a c a l c u l a t e d spectrum
w i t h 6=0.25mms-’, AEQ=O, and t h e Bint d i s t r i b u t i o n as shown i n b ) .

cages (13A). Since d u r i n g thermal decomposit.ion n e i t h e r was a m e t a l - m i r r o r ob-

served i n t h e i n - s i t u g l a s s c e l l n o r a desorbed i r o n d e t e c t e d i n t h e mass spec-.
trum, we conclude t h a t t h e i r o n p a r t i c l e s remained i n s i d e t h e z e o l i t e m a t r i x . I t
i s very l i k e l y t h a t t h e anisotropy constant i n our estimate i s t o o small; sur-
f a c e a n i s o t r o p i e s o f i r o n p a r t i c l e s , due t o c h e m i s o r p t i o n o f CO f o r example,may
y i e l d an i n c r e a s e o f t h e a n i s o t r o p y c o n s t a n t by 30% / r e f . 9/. I t n i g h t a l s o
be p o s s i b l e , as suggested i n c o n n e c t i o n w i t h t h e f o r m a t i o n o f P t p a r t i c l e s i n
NaX / r e f . l o / , t h a t t h e i r o n p a r t i c l e s a r e i n d e e d l a r g e r i n s i z e t h a n 1 3 1 due t o
794

pressure [Pa)

0 10 20 30 50 50 60

CO
- ---- ------/------10+
6-
8: .yo
CH4

90 -
L l * I I
t
! . . a .
C

I
2
4: F I :
7 : :
-10 -8 -6 -4 -2 0 2 4 6’ 8 10
Velocity Imdsl mass

Fig. 5 ( l e f t ) . Experimental Mossbauer s p e c t r a o f t h e thermal decomposition p r o -

ducts o f Fe(COI5 i n NaX under H, w i t h maximum decomposition temperature o f a)
433K and b ) ,c) 573K. The Mossbauer measurements were performed a t a ) ,c) 4.2K
and b ) RT. S o l i d l i n e s correspond t o c a l c u l a t e d s p e c t r a u s i n g t h e parameters
summarized i n Table 2.

F i g . 6 ( r i g h t ) . Mass s p e c t r a o f desorbed gases a r i s i n g from thermal decomposition

o f Fe(CO)S i n NaX under H, w i t h maximum decomposition temperature a) 433K and
b ) 573K.

s t r u c t u r a l rearrangement o f t h e z e o l i t e m a t r i x d u r i n g h e a t treatment. Transmis-

s i o n e l e c t r o n microscopy s t u d i e s a r e i n progress t o e l u c i d a t e t h i s behavior.

Thermal decomposition under H2

Complementary t o t h e s i t u a t i o n under i n e r t gas ( A r ) , described i n t h e pre-
vious s e c t i o n , we have a l s o s t u d i e d t h e thermal decomposition o f Fe(C0)5 i n
NaX under H2. The Mossbauer s p e c t r a o f decomposition products, o b t a i n e d a f t e r
heating up t o TmaX=433K and 573K a r e shown i n F i g . 5. Comparing t h e decomposi-

Fe(COI5 has completely vanished a t Tma,=433K

-
t i o n under A r (Fig. l a ) and under H2 ( F i g . 5a, Table 2 ) i t i s obvious t h a t
under H2, c o n t r a r y t o t h e s i t u a t i o n
 795

under A r . The c o r r e s p o n d i n g mass spectrum ( F i g . 6 a ) i n d i c a t e s t h a t CO i s de-

sorbed from t h e z e o l i t e . Flossbauer s p e c t r a o f decomposition p r o d u c t s correspond-
i n g t o Tmax=573K ( F i g . 5b,c, Table 2) r e v e a l t h a t t h e i r o n s u b c a r b o n y l has been
decomposed c o m p l e t e l y : a c o n s i d e r a b l e amount o f i r o n (ca. 30%) has been o x i d i z e d
t o Fez+ (S4, F i g . 5 c ) , and a s i g n i f i c a n t p o r t i o n o f i r o n (ca. 70%) has formed
magnetic components (S5, F i g . 5c). The l a t t e r e x h i b i k a broad magnetic p a t t e r n
even a t RT ( F i g . 5b); t h i s o b s e r v a t i o n i s a s s o c i a t e d w i t h i r o n p a r t i c l e s w i t h
c o n s i d e r a b l e magnetic a n i s o t r o p y , which p r o b a b l y a r i s e s because o f c h e m i s o r p t i o n
of CO and H2 a t t h e i r s u r f a c e o r because o f t h e i r i n t e r a c t i o n s w i t h t h e z e o l i t e
frame. Due t o t h e l a c k o f Fe peaks i n t h e mass spectrum o f t h e desorbed gases
of t h i s probe ( F i g . 6b) we s t i l l b e l i e v e t h a t t h e s e i r o n p a r t i c l e s a r e enclosed
i n t h e c a v i t i e s o f t h e m o l e c u l a r s i e v e . The mass spectrum o f F i g . 6b i n a d d i t i o n
r e v e a l s t h a t , besides t h e c o n t r i b u t i o n s a l r e a d y i n h e r e n t i n F i g . 6a, methane
was formed. Methane i s i d e n t i f i e d by i t s c h a r a c t e r i s t i c fragments / r e f . 11/ a t
masses 1 4 ( 1 . 6 ~ 1 0 - ~ P a ) ,15(2.7*10-6Pa) and 16(3.3.10-6Pa). I t i s tempting t o
assume t h a t a t e l e v a t e d temperature t h e f o r m a t i o n o f CH4 and Fez+ has o c c u r r e d
v i a t h e r e a c t i o n s 3H2+C0 -+ CH4+H20 and Feo+H20 + FeO+H2.

TABLE 2
Isomer s h i f t s 6 ( i n mm/s), quadrupole s p l i t t i n g AE ( i n mm/s), l i n e widths r
Q
( i n mm/s), and r e l a t i v e abundances A ( i n % ) o f s u b s p e c t r a f o r thermal decompo-
s i t i o n p r o d u c t s o f Fe(CO)5 i n NaX under H2. Measurements were performed a t
4.2K.

Figure su bspec t r u m &(a) r A

AEQ

0.01 0.43 0.46 78.5

s2 0.95 0.65 0.31 7.3

5a
s3 0.78 2.10 0.42 4.1
s4 1.31 2.61 0.50 10.1

s4 1.27 2.69 0.50 30.0

5c
s5 0.1 0 7.0 70.0(b)

( a ) 6 g i v e n r e l a t i v e t o a-Fe a t RT.
( b ) The broad magnetic p a t t e r n has a l s o been s i m u l a t e d by u s i n g a Bint d i s t r i -
b u t i o n , T h i s d i s t r i b u t i o n i s s i m i l a r t o t h e p a t t e r n shown i n F i g . 4b; i t i s ,
however, c e n t e r e d h e r e around ca. 25 T e s l a compared t o ca. 30 T e s l a i n F i g . 4b.
796

Reaction products under H2/C0 atmosphere

Thermal decomposition products o b t a i n e d from Fe(C0I5 i n NaX under A r a t
Tmax=733K (corresponding t o t h e s p e c t r a shown i n F i g . 3 ) were exposed a t 523K
t o a gas m i x t u r e w i t h composition 3H2tC0 f o r 16h. The i n i t i a l pressure o f t h e
5
H2/C0 m i x t u r e i n t h e g l a s s - i n s i t u c e l l a t RT was ca. 10 Pa. The r e s u l t i n g reac-
t i o n products y i e l d Mossbauer and mass s p e c t r a as shown i n F i g . 7a,b and F i g . 8,
r e s p e c t i v e l y . From t h e quadrupole d o u b l e t w i t h 6.~1.3mm/s i t i s obvious t h a t
about 70% o f t h e i r o n (Table 3 ) appears as Fe2+ species (S1). Only about 30% o f
t h e i r o n (S2) c o n t r i b u t e s a t 4.2K w i t h a broad unresolved magnetic p a t t e r n ( F i g .
7b), which i s h a r d l y d e t e c t a b l e a t 77K (Fig. 7a), i n d i c a t i n g t h a t S2 r e p r e s e n t s
small magnetic p a r t i c l e s . A comparison o f t h i s s i t u a t i o n w i t h t h e p r e c u r s o r
( F i g . 3 ) o f the r e a c t i o n products r e v e a l s t h a t most o f t h e z e r o - v a l e n t i r o n has
been o x i d i z e d by t h e H2/C0 gas m i x t u r e a t 523K t o f e r r o u s i r o n . Because o f t h i s
f i n d i n g and due t o t h e appearance o f methane, ethane and C02 i n t h e mass spec-
trum ( F i g . 8 ) we suspect t h a t t h e d i s s o c i a t i v e a d s o r p t i o n o f CO a t t h e s u r f a c e
o f iron particles /ref. 12, 13/ i s f o l l o w e d by t h e f o r m a t i o n o f hydrocarbons
and by t h e o x i d a t i o n o f Fe" t o FeO and o f CO t o C02. To f u r t h e r c h a r a c t e r i z e
t h e magnetic p a r t i c l e s which a r e represented by t h e broad l i n e ( S 2 ) i n F i g . 7b,
we have s i n t e r e d the r e a c t i o n products a t 823K i n continuous vacuum (ca. 10-3Pa)
f o r I h r and subsequently recorded a Mossbauer spectrum a t 4.2K ( F i g . 7 c ) . T h i s
2t
spectrum c o n t a i n s ca. 70% o f c o n t r i b u t i o n s from Fe species (S1), w h i l e t h e
remaining ca. 30% ( S 2 ) o f t h e a b s o r p t i o n p a t t e r n undoubtedly r e p r e s e n t s a-Fe
p a r t i c l e s (Table 3 ) . T h i s r e s u l t p r o v i d e s f u r t h e r evidence t h a t t h e above
mentioned r e a c t i o n s i n c l u d e zero-val e n t i r o n p a r t i c l e s .
Thermal decomposition i n z e o l i t e s w i t h d i f f e r e n t Si/A1 r a t i o
A l t e r n a t i v e l y t o t h e thermal decomposition o f Fe(C0I5 i n NaY under c o n t i n u -
ous vacuum, which has y i e l d e d r e l a t i v e l y l a r g e c r y s t a l l i n e a-Fe p a r t i c l e s o u t -
s i d e t h e z e o l i t e m a t r i x /ref. I/,we have i n v e s t i g a t e d t h e f o r m a t i o n o f decom-
p o s i t i o n products under argon. F i g . 9 shows t h e corresponding CO d e s o r p t i o n from
300 t o 503K. From t h e f i n a l CO p a r t i a l pressure o f 2.87.103Pa a t 503K and t h e
o r i g i n a l amount o f carbonyls o f 9.44.10-4mol we e s t i m a t e t h a t 9424% o f t h e over-
a l l amount o f CO has been desorbed a t 503K. The r e s u l t i n g decomposition products
y i e l d Mossbauer spectra ( F i g . 10a,b) w i t h a d i s t r i b u t i o n o f i n t e r n a l f i e l d s
( F i g . 1Oc) which i s p r a c t i c a l l y i d e n t i c a l a t 4.2K and a t RT. T h i s o b s e r v a t i o n
i n d i c a t e s t h a t Fe(C0j5 has been completely desorbed from NaY and decomposed i n -
t o CO and r e l a t i v e l y l a r g e i r o n p a r t i c l e s o u t s i d e t h e z e o l i t e m a t r i x . Only about
10% o f t h e i r o n forms c r y s t a l l i n e a-Fe p a r t i c l e s w h i l e t h e remaining 90% o f t h e
i r o n forms amorphous i r o n , i r o n c a r b i d e s o r oxycarbides and t o a m i n o r e x t e n t
(<5%) i r o n oxides. Comparison o f t h e thermal decomposition o f Fe(C0)5 in
NaY under argon a t 503K ( F i g . l o b ) w i t h t h e s i t u a t i o n i n NaX under t h e same
 I91

1.00

.99

.90

1.00 pressure ( P o l
c
.-YI
',. .9s
w

ce
.98
.-+
>

-e
LT
01
10 - 5

1.00

.99
0 10 20 30
moss
40
- 50 60

-10 -5 0 5 10
Velocity Imm/sl

F i g . 7 ( l e f t ) . a,b) Experimental Mossbauer s p e c t r a o f r e a c t i o n p r o d u c t s o b t a i n -

ed by exposing t h e m a t e r i a l c o r r e s p o n d i n g t o F i g . 3 t o a gas m i x t u r e w i t h compo-
sition3H2+C0, p r e s s u r e ca. lO5Pa, and temperature Tmax=523K f o r 16h. The Moss-
bauer measurements have been performed a t a ) 77K and b ) 4.2K. c ) Experimental
Mossbauer spectrum a t 4.2K o f t h e m a t e r i a l c o r r e s p o n d i n g t o a,b) a f t e r s i n t e r i n g
a t 823K i n continuous vacuum ( ~ a l O - ~ P af )o r 5h. S o l i d l i n e s i n a ) - c ) r e p r e s e n t
c a l c u l a t e d s p e c t r a w i t h t h e parameters summarized i n Table 3.

F i g . 8 ( r i g h t ) . Mass spectrum o f desorbed gases o b t a i n e d b y exposing t h e m a t e r i -

a l corresponding t o F i g . 3 t o a gas m i x t u r e w i t h c o m p o s i t i o n 3H,+CO, p r e s s u r e
ca. lOSPa, and temperature Tmax=523K f o r 16h under s t a t i c c o n d i t i o n s .

conditions (Fig. l b ) again reveals t h a t ironcarbonylsare s t a b i l i z e d i n z e o l i t e s

w i t h small Si/A1 r a t i o (1.18 f o r NaX) compared t o t h o s e w i t h l a r g e Si/A1 r a t i o
(2.48 f o r Nay). T h i s r e s u l t may be a s s o c i a t e d (i)
w i t h t h e s u g g e s t i o n / r e f s . 14,
15/ t h a t t h e acid-base i n t e r a c t i o n between t h e Na+ c a t i o n s o f t h e z e o l i t e (Le-
w i s - a c i d ) and t h e oxygen atoms o f t h e c a r b o n y l s (Lewis-base) i s a s t a b i l i z i n g
f a c t o r , and ( i i ) w i t h t h e f a c t t h a t t h e number o f Na+ c a t i o n s i n NaX i s ca. two
times as l a r g e as t h a t i n Nay. I t i s i n t e r e s t i n g t o n o t e t h a t an a d d i t i o n a l mea-
surement u s i n g a z e o l i t e w i t h S i / A l r a t i o 1.32 s u p p o r t s t h i s r e a s o n i n g . The
Mossbauer spectrum a t 4.2K o f t h e thermal decomposition p r o d u c t s o f Fe(C0)5, ob-
798

300 350 LOO 450 500

1 decomposition temperature lK1
-10 -5 0 5 10
V e l o c i t y Imm/sl
I I

-10 -5 Q 5 10
Hyperfinefield B ITeslal Velocity I m d s l

F i g . 9 ( t o p r i g h t ) . CO-desorption c u r v e r e c o r d e d f r o m mass s p e c t r a of t h e t h e r -
mal decomposition o f Fe(C0)S i n NaY under a r g o n (ca. 105Pa).

F i g . 10 ( l e f t ) . a,b) E x p e r i m e n t a l Mossbauer s p e c t r a o f thermal decomposition

p r o d u c t s of Fe[CO), o b t a i n e d i n NaY under argon (ca. IO’Pa) a t Tmax=503K. The
Mossbauer measurements were performed a t a ) RT and b ) 4.2K. S o l i d l i n e i n b ) r e -
p r e s e n t s c a l c u l a t e d spectrum which c o n s i s t s o f 10% o f a-Fe and 90% o f t h e B i n t
d i s t r i b u t i o n shown i n c ) . The f i e l d o f 34 T (a-Fe) corresponds t o 6=O.lmm/s,
f i e l d s of <40 T correspond t o 6=0.25mm/s and >40 T t o 6=0.45mm/s.

F i g . 1 1 ( b o t t o m r i g h t ) . Experimental Mossbauer spectrum a t 4.2K o f t h e thermal

decomposition p r o d u c t of Fe(C0)’ o b t a i n e d i n a z e o l i t e w i t h S i / A l r a t i o 1.32 un-
d e r argon (ca. 105Pa) a t Tmax=433K. Subspectra Si-Ss c o r r e s p o n d t o t h e a s s i g n -
ment i n F i g . l a . The c o n t r i b u t i o n o f Fe(C0)5 amounts t o 12%.

t a i n e d i n t h i s z e o l i t e under argon a t Tmax=433K ( F i g . 111, r e v e a l s t h a t i r o n -

pentacarbonyl c o n t r i b u t e s o n l y 12% t o t h e o v e r a l l a b s o r p t i o n . I n NaX w i t h Si/A1
r a t i o 1.18 under t h e same c o n d i t i o n s t h i s c o n t r i b u t i o n i s 27% ( F i g . l a ) . Thus i t
i s obvious t h a t a l r e a d y a s m a l l v a r i a t i o n i n S i / A l r a t i o i s r e f l e c t e d by a s i g -
n i f i c a n t change o f z e o l i t e - F e ( C 0 ) 5 i n t e r a c t i o n .

CONCLUSIONS
Thermal decomposition o f Fe(C0)5 i n NaX under c o n t i n u o u s vacuum ( c a . 10-3Pa)
 799

TABLE 3
Isomer s h i f t s 6 ( i n mm/s),quadrupole s p l i t t i n g s AE ( i n trun/s), l i n e w i d t h s r,
Q
( i n mm/s), r e l a t i v e abundances A ( i n %), and i n t e r n a l magnetic f i e l d Bint (in
T e s l a ) o f subspectra c o r r e s p o n d i n g t o F i g . 7. Measurements were p e r f o r m e d a t
77K (7a) and 4.2K (7b,c), respectively.

Figure subspectrum ,(a) A 8int

r
A,EQ

7a 1.27 2.66 0.68 100

1.27 2.85 0.5 71.9

s1
7b
0.18 0 4.5 28.1
s2
1.32 2.80 0.71 66.3
s1
7c
0.14 0 0.43 33.7 34.3
s2

( a ) 6 g i v e n r e l a t i v e t o a-Fe a t RT.

y i e l d s i r o n p a r t i c l e s o u t s i d e t h e z e o l i t e . Under s t a t i c vacuum and under gas

atmosphere (argon, H2, H2/C0 m i x t u r e ) t h e i r o n c a r b o n y l remains i n s i d e t h e NaX
m a t r i x d u r i n g thermal decomposition. However, upon i n c r e a s i n g t h e S i / A l r a t i o
f r o m 1.18 (NaX), o v e r 1.32 t o 2.48 (Nay), t h e acid-base i n t e r a c t i o n between t h e
Na' c a t i o n s o f t h e z e o l i t e and t h e c a r b o n y l s o f Fe(C0I5 fades because t h e number
o f Na' c a t i o n s decreases. Thus, i r o n p e n t a c a r b o n y l i s s t a b i l i z e d i n z e o l i t e s w i t h
small Si/A1 r a t i o and i t i s e a s i l y desorbed f r o m z e o l i t e s w i t h enhanced Si/A1
ratio.
Formation o f i r o n s u b c a r b o n y l s , (Fe(C0)3)n, occurs i n NaX under s t a t i c vacuum
o r gas atmosphere a t moderate decomposition temperatures. They a r e s t a b l e up t o
%570K under vacuum, up t o Tmax670K under A r and up t o Tmax~500Kunder H2.
Tmax
These i r o n s u b c a r b o n y l s a r e anchored t o t h e NaX frame; hence, f u r t h e r decomposi-
t i o n a t h i g h e r temperatures i s p o s s i b l e even under c o n t i n u o u s vacuum (ca. l t ~ - ~ P a )
w i t h o u t d e s o r p t i o n o f i r o n from t h e NaX m a t r i x .
Thermal decomposition o f i r o n s u b c a r b o n y l s i n NaX under argon a t e l e v a t e d
temperature (Tmax%730K) y i e l d s r e l a t i v e l y l a r g e n o n c r y s t a l l i n e i r o n p a r t i c l e s ,
which a r e l o c a t e d undoubtedly i n s i d e t h e z e o l i t e m a t r i x . A t p r e s e n t i t i s n o t
c l e a r whether these p a r t i c l e s e x h i b i t l a r g e s u r f a c e a n i s o t r o p i e s due t o chemi-
s o r p t i o n o f CO o r shape a n i s o t r o p y o r a r e indeed l a r g e r i n s i z e t h a n t h e super-
cages (13A) due t o s t r u c t u r a l rearrangement o f t h e z e o l i t e m a t r i x d u r i n g h e a t
t r e a t m e n t . T h i s b e h a v i o r w i l l be f u r t h e r t e s t e d by e l e c t r o n t r a n s m i s s i o n m i c r o s -
copy s t u d i e s .
Thermal decomposition o f i r o n s u b c a r b o n y l s i n NaX under H2 and exposure o f
n o n c r y s t a l l i n e i r o n p a r t i c l e s t o H2/C0 gas m i x t u r e l e a d s t o t h e d i s s o c i a t i v e
 800

a d s o r p t i o n o f CO a t t h e s u r f a c e o f i r o n p a r t i c l e s w i t h t h e subsequent f o r m a t i o n
o f hydrocarbons and the o x i d a t i o n o f Fe" t o Fe2+ and o f CO t o C02.
Our f u r t h e r i n v e s t i g a t i o n o f t h e i r o n - z e o l i t e system i n c l u d e s s t u d i e s w i t h
Si/A1 r a t i o between 1.3 and 2.4, m u l t i p l e a d s o r p t i o n and decomposition steps,
and exposure t o v a r i o u s gas m i x t u r e s .

ACKNOWLEDGEMENT
This work was supported by t h e Deutsche Forschungsgemeinschaft. D i s t r i b u t i o n s
o f h y p e r f i n e f i e l d s were o b t a i n e d w i t h a procedure d e s c r i b e d by G. Le Caer and
J.M. Dubois, and spectra i n c l u d i n g superparamagnetic r e l a x a t i o n were c a l c u l a t e d
by u s i n g a r o u t i n e w r i t t e n by H. Winkler; t h e use o f these programs i s g r a t e -
f u l l y acknowledged.

REFERENCES

1 F. Seel, B. Wolf, U. Gonser, R. K l e i n , G. Doppler, E. B i l l and A.X. T r a u t -

wein, Z e i t s c h r i f t f u r anorganische und allgemeine Chemie 534 (1986) 159.
2 H.M. Ziethen, G. Doppler, A.X. Trautwein and F. Schmidt, C a t a l y s i s Today 3
(1988) 83.
3 T. Bein, F. Schmidt and P.A. Jacobs, Z e o l i t e s 5 (1985) 240.
4 G. Doppler, E. B i l l , U. Gonser, F. Seel and A.X. Trautwein, H y p e r f i n e I n t e r -
a c t i o n s 29 (1986) 1307.
5 D. Ballivet-Tkatchenko and G. Coudurier, I n o r g a n i c Chemistry 18 (1979) 558.
6 T. Bein, P.A. Jacobs and F. Schmidt, Studies i n Surface Science and C a t a l y s i s
12 (1982) 111.
7 H.M. Ziethen, D i s s e r t a t i o n , Lubeck (1988).
8 P.H. Christensen, S . MBrup and J.W. Niemantsverdriet, J. Phys. Chem. 89
(1985) 4898.
9 S. MBrup, B.S. Clausen and H. Topsbe, J. Physique Colloq. 41 (1981) C1 331.
10 A. K l e i n e , P.L. Ryder, N. Jaeger and G. S c h u l z - E k l o f f , J. Chem. SOC., Faraday
Trans. I,82 (1986) 206.
11 A. Cornu and R. Mussot, Compilation o f Mass S p e c t r a l Data, Heydon & Son Ltd.,
London (1975) p. 1 A .
12 J.W. Niemantsverdriet, C.F.J. F l i p s e , A.M. van der Kraan and J.J. van L o e f ,
A p p l i c a t i o n s o f Surface Science 10 (1982) 302.
13 F. Schmidt, I n d u s t r i a l A p p l i c a t i o n o f t h e Mossbauer E f f e c t , G.J. Long and
J.G. Stevens (eds.), Plenum Press, N.Y. (1986) p. 667.
14 D. Ballivet-Tkatchenko, G. Coudurier and H. Mozzanega, S t u d i e s i n Surface
Science and C a t a l y s i s 5 (1980) 309.
15 T. Bein, S.J. McLain, D.R. Corbin, R.D. F a r l e e , K. M o l l e r , G.D. Stucky, G.
Woolery and D. Sayers, J. Am. Chem. SOC. 110 (1988) 1801.
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Investigation of Ultra Stable Y by Differential Thermal Analysis after

Injection of Water Vapour

A.YCSHIDA and .K.INOUE

Government Industrial Research Institute, Kyushu; Shuku-machi, Tosu-shi, Saga-
ken 841 Japan

ABSTRACT
Differernt.ia1 thermal analysis(DTA) of ultra stable Y(USY) with pre-
injection of water vapour was performed with an improved DTA unit. The
exotherms with water vapour were compared with the results of the
traditional steaming test. The peak shap and temperature were affected by
the rate of rising temperature and amount of water pre-injected into a t h m l
chamber. However, the pre-injection temperature of water vapour did not
affect them rerrarkably. The collapse of the pore system was confirmed by XRD
and nitrogen gas adsorption. The correlations between the intersection
temperatures of maximum rising gradients of peaks relative to the base lines
and the results of the steaming test at 75OoC were comparatively good.

Introduction
Zeolite Y has been used as an active ingredient in fluid catalytic cracking
(Fcc) catalysts(ref.1). One of the most important properties of zeolite Y
used in FCC catalysts is its hydrotherml stability(ref.2-10). As sham by
McDaniel et al.(ref.2), zeolite Y can be ultrastabilized by a conventional ion
exchange and heat treatment. The dealumination of zeolite Y was also achieved
by treatment with HC1 solution(ref.3-4). The hydrothermal stability of USY
.
has been studied by means of the steaming test (ref.5-6) Bremer et al. (ref.7),
Skeels et al. (ref.8) and Li et al. (ref.9) carried out investigations using
convenient DTA method. Hmver, in DTA the sample is usually exposed to an
atmsphere of air or inert gas flow. The stability of zeolite Y under 100%
steam is different from that in an inert gas or in air. To solve this
problem, DTA with pre-injection of water vapour was conceived.

METHODS
Zeolite sodium Y samples were prepared from colloidal silica, silica sol
and sodium aluminate. LZ-Y52, LZ-Y82(U.C.C.) and 3 reference catalysts, JEC-Z-
Y4.8(Y4.8) , JK-Z-HY4.8(HY4.8) and JEC-Z-Y5.6(Y5.6) supplied from the
Catalysis Scciety of Japan were used too. NH4NaY samples were prepared by the
conventional cation-exchange procedure and heated in a capsule or with steam.
After the second cation exchange, HNH4Y samples(=USY) were prepared. Sane of
802

them were again heated in a capsule or with steam, and treated with 0.096N and
0.95N HC1 solutions.
The improved DTA unit is sham in Fig.1. Until the injection temperature
was reached, with a heating rate of 2OoC min-', 60 cm3 min-' of helium gas was
introduced through the water vapour effluent without the pin. Then, 1 to 10
cm3 of water were injected through the penetrating pipe at the bottom of the
furnace at the rate of 1 cm3 min-1, ax^ evaporated. The programed
temperature was held at the injection temperature for 15 min. From the
injection temperature up to 100O-143O0C, a small amount of water vapour
continued to evaporate. At an appropriate temperature, the furnace was removed
and quenched i n air. It was checked by XRD arid nitrogen gas adsorption to
determine to what extent the sample had retained its crystallinity and pore
system. The exotherms of DTA and the results of the steaming test (with 100%
steam, for 6 hours) were anpared.
Some of the zeolite samples were chemically analyzed by a wet process.

Fig.1 Apparatus for DTA with pre-injection of water vapour

l=vacuum compound, 2=penetrating injection pipe, 3=acrylic resin, I=silicon
ruber, 5=refractary,6=furnace, 7=alumjna, 8=sample, 9 = t h m l chanber, lO=pin
or tube, ll=water vapour effluent, 12=Mohr pipette, 13=micro-tube punp
 803

RESULTS AND DISCUSSION

As the amunt of water injected increased, the exotherm of HY4.8 shifted t o
3
laver temperature, and equilibrated(Fig.2). Five cm of water evaporated t o
3
about 24.4 dm a t 800°C, i.e. about 1000 times that of the thermal chandxr.
Hence, we supposed t h a t the atmosphere i n the themdl c h a h x reached 100 %
stem a f t e r injection of 5 cm3 of water.
The exotherms were affected by the heating rate a f t e r injection of water.
However, the injection temperature had no remarkable e f f e c t when enough water
was pre-injected(Fig.3). In the case of 2OC m i n . - l and l 0 C min.-', the peak
temperatures increased slightly, because the real heating rates were s l i g h t l y

n
u
W

0 ~ ~ 3 - b
1c m 3 - =
2!
W

1
I-
x 3
9 960
4
I
0
Q

U
C
W

800 900 1000 1100 700 800 900 1000

Temperature('C) Injection Temperature(OC)

Fig.2 The e f f e c t of the amount of Fig.3 The e f f e c t s of heating rate arad

water pre-injected on the exo- injection t e n p r a t u r e on the exother-
t h m s of HY4.8 a t heating rate ma1 peak temperature of HY4.8.
of 10°C min-l. Amount of H2C=7 rn
3
.
In] ection temperature=860'C lwithout 'injection, 2=200cmin.-l
-1 -1
3=1OoC min. , 4=5'C min.
6=2*C min.-', 6=loC min.-'
804

850 950 1050 1150 1250

Temperature(OC)

Fig.4 Differential therrrcgrams of zeolite Y under 100 % steam.

1,2:NH4NaY(LZ-Y52), 1=Na20=3.8%; 2=2.9%; 3:NH4NaY(3-3-103) Na20=2.9%;
4:HNaY(LZ-Y52), U.D.=2.449 nm, 5:HNHqY(HY4.8), U.D.=2.450 run;
6:HY(LZ-Y52; 2 cycles of ibn exchange and heat treatment), U.D.=2.428 nm;
7:HY(LZ-Y52) after treatment with 0.096N HC1 solution, U.D.=2.428 run;
8:HY(Y5.6) after treatment with 0.95N HC1 solution, U.D.=2.426 nm.
 805

higher than the programed one. The amount of zeolite sample did not change
the exothemal peak temperature remarkably. The shapesof exothenns of the
zeolite samples are shown in Fig.4. In the case of NH4NaY, the peak shape
and the exothermal peak temperature were affected by the Si02/A1203 molar
ratio of the original sodium Y. After the second ion exchage, the
hydrothermal stability was inproved remarkably, though the unit cell dimension
did not shrink, because of the decrease of Na' ions. Mter the second heat
treatment and subsequent treatment with 0.096N HC1, the unit cell dimension
shrunk to 2.428 nm, and the content of sodium oxide decreased to ca. 0.1%;
hawever, the exothermal peak temperature did not shift to higher temperature.
HY treated with 0.096N HC1 contains ca. 12% of A1203 while HY treated with
0.95N HC1 contains only ca. 1.5% of A1203. These results shaw that the
dealumination improved the hydrothermal stability of zeolite Yr as shown by
Patzelova et al. (ref.10). For NH4NaY(3-3-103)r HY4.8 and HY(LZ-Y52, two
cycles of ion exchange and heat treatment) after the treatment with 0.95N HCl

" 850 950 1050 900 lo00 1000 1100 1200 1300

Temperature ("C)

Fig.5 The changes of M!A curves, XRD intensities and specific surface areas
during the course of degradation of zeolite Y samples.
A;NH4NaY(3-3-103), B;HNH,Y(JK-Z-HY4.8) , C;HY(JRC-Z-Y5.6) after treatment with
0.95N HC1 solut.ion.
I=sum of peak heights of 6 strong lines in the range of 18-32.
I,=sum of peak heights of 6 strong lines of LZ-Y52(sodium form).
806

0 / 2
-4
948 950 952 9%
- 956 958
T ('C 1
Fig.6 Correlations betwen T and the retained crystallinity after the
.
steaming test.of USY (heating rate of DTA=lO°C min.-')
Blank marks=75OVCfor 6 hours, Solid marks=810°C for 6 hours,
0 a:LZ-Y82, 0 :USY(LZ-Y52), V :HY4.8, A A :USY(Y4.8)
0 .:prepared from silica sol, 0 + :prepared from colloidal silica
.
Iniection temp.=710°C, amount.of water=8 cm3 =I- before steaming test

1 . 0 1
m
3 0.8
.-?l
5 0.6
a,
c
m
& 0.4
c
w
b

-0
CI
\
0.2

-924 926 928 930 932

n
934 936
TP'C)

Fig.7 Correlations between T and the retained crystallinity after the

steaming test (heating rate of DTA=2'C min.-').
Symbols and experimental conditions are the same as Fig.6 except for the
heating rate of ETA.
 807

solution, the change of X-ray intensities and BFT surface aeas(SSA) of

mounted samples in the pt cell of the DTA unit are shm in Fig.5. In the
case of NH4NaY(3-3-103), XRD intensity and SSA decreased sharply before the
rising of the second peak c, so that the first broad peak(a) shaws the
destruction of crystalline structure and the disappearance of the pore system
in the zeolite. After the second peak(c), no crystalline phase was detected.
Hawever, in the case of NH4NaY(LZ-Y52, Na20=2.9%), the sample quenched at
1060 'C(d in Fig. 4) contained a small amount of crystalline phase, whose d-
spacings are 0.547, 0.345, 0.288, 0.270 and 0.254 m. In the cases of
NH4NaY(LZ-Y52, Na2G=2.9% and 3.8%), the second small peaks seems to overlap
with a large third peaks. Further investigations seem to be necessary to
clarify these pheIxxnena. In the case of HNH4Y(=UsY, B in Fig.5) and HY after
0.95N HC1 treatment(C in Fig.51, the decreases in intensities of XRD were
slightly faster than those of SSA. Here the second sharp peak(b) shows the
collapse of the pore system. The results &awn in Fig.5 indicate that about
40-50% of of the pore systems in U S and HY treated with HC1 solution were
destroyed before the emergence of second peaks. The correlations between the
intersection temperature of the maximun rising gradient of the peaks to the
base (T in Fig.4) and the results of the steaming test at 750 'C were

"70 750 790 830 870

Temperature(T 1

Fig.8 Correlations between the crystallinities after steaming test and the
steaming tenprature.
The symbols are the same as in Fig.6. lbtted lines shaw the crystallinities
before the steaming test.
808

comparatively good, but not as good as the results obtained at 810°C(Fig.6,7).

Fig.8 shaws the retained crystallinities after the steaming tests. These
results are similar to those in Fig.5, though the initial slopes of the
degradation have very slight gradients. The exotherms seem to corespond to
the change between A and B in Fig.8. The results at 75OoC are the data before
the final complete destruction, and T in Fig.4 means the begining of the final
destruction. Then, as for USY, these two values seem to correlate with each
other. However, the results at 810°C correlate with intermediate states or
final states of complete destruction. we examined the correlations between the
exothermal peak temperatures and the results at 810°C. They were, however,
not so good. Finally, we confirmed the relationships between the
crystallinities before DTA, the unit cell dimensions and T (Fig.9). The
results shaw that the decrease of crystallinity, which was led by the
formation of defect sites during the ultrastabilization, decreases T
remarkably. Furthermore, the samples with high crystallinities and with large
shrinkage of unit cell dimensions show the highest hydrothermal stabilities.
However, it seems that the effect of shrinkage of unit cell dimension is not
so great as the crystallinity of USY. The future aim of this work is to

I
U. D. ( n m )

Fig.9 Correlations between the crystallhities before DTA, the unit cell
dimensions and T of USY samples.
 809

predict the static degradation curve such as Fig.8 from the exothenns with
different heating rates. For this purpose, further investigations are
necessary.

References
1 C.J. Plank and E.J. Rosinski, U.S.P. 3,140,253 (1964)
2 C.V. &Daniel and P.K. Maher, "Molecular Sieves", Society of Chemical
Industry, London, 1968, pp. 186-195.
3 J. Scherzer, J. Catal., 54 (1978) 285-288.
4 V. Basacek, V. Patzelova, Z. Tvaruzkova, D. Freude, U. LOhse, W. Schirmer,
H. Stach and H. Thamn, J. Catal., 61 (1980), 435-442.
5 J.M. Ward, U.S.P. 3,929,672 (1975).
6 H. Nakamoto, T. Matsuda, T. Ida, K. Shirono, M. ogata, Y. Nishimura, "New
Developnents in Zeolite Science and Technology", Preprints of Poster Papers
The 7th International Zeolite Conference. Japan Association of Zeolite.
1986, pp. 77-78.
7 H. Bremer, W. Morke, R. Schodel and F. V c q t , ACS 121 (1973), pp. 249-257.
8 G.W. Skeels and D.W. Breck, "Proceedings of The Sixth International Zeolite
Conference", Butterworths, 1984, pp. 87-96.
9 Cai-Ying Li and L.V.C. Rees, Zeolites, 1986(6), 60-65.
10 V. Patzelova, U. Lohse, E. Engelhardt, E. Altsdorf and P. Koelsch, Ropa
Uhlie, 28 (1986), 343-350.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors ), Zeolites as Catalysts, Sorbents and Detergent Builders
01989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

PROPERTIES OF HYDROTHERMAL LOW-DAMAGEO 5A AND 1OX ZEOLITES

R. SCHOLLNER' and H. SIEGEL

IOepartment of Chemistry , Karl-Marx-University , Talstr . 35, L e i p z i g , GOR-7010
2VEB Chemieanlagenbaukombinat Leipzig-Grimma, Eahnhofstr . 3/5, Grimma, GRD-7240

ABSTRACT
Treatment o f A and X z e o l i t e s under hydrothermal c o n d i t i o n s leads t o frame-
work a l t e r a t i o n . New adsorption s i t e s with weaker Md+-adsorbate i n t e r a c t i o n s
a r i s e because o f t h e formation o f
(-) (-) (-) (-)
( 5 Si-0l3 A1-OH, (2Si-O)* A1.0, ( 2 9 - 0 ) Al(0)OH and A 1 O(OH)?
-
and other s i m i l a r species i n and o u t s i d e o f t h e z e o l i t e cages. This simulates a
d e f i c i e n c y o f e f f e c t i v e c a t i o n i c adsorption s i t e s .

INTRODUCTION
5A and 1OX z e o l i t e s are cormonly employed as adsorbents i n pressure-swing-
adsorption (PSA) processes f o r gas separation e s p e c i a l l y f o r p r o d u c t i o n o f hy-
drogen from a v a r i e t y o f feedstocks and oxygen or n i t r o g e n from a i r .
The values o f s t a t i c and dynamic adsorption c a p a c i t i e s as a f u n c t i o n o f par-
t i a l pressures and heats o f adsorption o f t h e i n t e r e s t i n g components are c r i -
t e r i a f o r the s e l e c t i o n o f u s e f u l adsorbents.
We have shown t h a t commercial 5A and 1OX z e o l i t e s are p a r t i a l l y damaged /l/.
The hydrothermal degradation process o f the z e o l i t i c framework takes p l a c e dur-
i n g t h e i o n exchange a t an unfavourable pH-value and a t thermal dehydration i n
t h e temperature range from 350 t o 820 K.
The hydrothermal degradation o f t h e z e o l i t i c framework, e s p e c i a l l y f o r zeo-
l i t e s o f type A, i s o f course a t t a i n a b l e when t h e z e o l i t e i s t r e a t e d with water
o r steam a t higher temperatures f o r a longer time /5/.

EXPERIMENT
(1) Measurements with the gases N2, CH4 and CO adsorbed on 5A and 10 X zeo-
l i t e s without a d d i t i o n a l hydrothermal damage were c a r r i e d o u t i n a microbalance
o f t h e Satorius-Verke AG/FRG. Samples o f about 100 mg were evacuated a t 0.1 Pa
f o r 1 h, then heated f o r 6 h a t 725 K with an i n i t i a l h e a t i n g r a t e o f 1 K/min.
(2) Oehydration c o n d i t i o n s ( f o r the r e s u l t s i n f i g u r e 2)
The z e o l i t e samples were d r i e d a t 323 K, than pressed, crushed t o a g r a i n s i z e
o f 0.2 t o 0.25 mm and f i l l e d i n t o a U-tube o f g l a s s with i n n e r diameter o f
4 mm.
812

Sample amount: 1 g z e o l i t e (dehydrated); f i l l i n g level 150 mn, g a s stream:

4 l / h (3000 v/vh)
a ) measurements without hydrothermal damage (see experiment (1))
b ) h e a t i n g of t h e samples f o r 2.5 h t o 575 K i n a i r , f u r t h e r h e a t i n g f o r 2 h
a t 575 K , then f o r 3 h t o 725 K i n dry i n e r t g a s
c ) h e a t i n g of t h e samples f o r 1 h t o 475 K i n a i r , f u r t h e r h e a t i n g f o r 2 h a t
475 K , then i n dry g a s stream f o r 1 h t o 725 K
d ) h e a t i n g of t h e samples f o r 2 h t o 725 K i n dry inert g a s
e) h e a t i n g of t h e samples f o r 1 h t o 475 K w i t h a i r , f u r t h e r h e a t i n g f o r 2 h a t
475 K , t h e n f o r 1 h t o 725 K without g a s s t r e a m
f ) h e a t i n g of t h e samples f o r 2 h t o 725 K without g a s stream.
(3) For thermal a n a l y t i c a l measurements a microthetnoanalyzer (Setaram, Lyon,
France) was used. This a p p a r a t u s a l l o w s combined TG-OTG-DTA i n v e s t i g a t i o n s .
Experiments were c a r r i e d o u t by h e a t i n g approximately 10 mg of loaded z e o l i t e
powder ( < 0.1 mm) i n an argon flow of 50 m l min-l a t a h e a t i n g r a t e of
10 K min-'. The g a s stream was d r i e d with z e o l i t e A.
P r i o r t o t h e i r measurement, t h e a c t i v a t e d z e o l i t e powders were s t o r e d f o r 10
days i n a d e s i c c a t o r over a l i q u i d of benzene o r n-butanol.
The following z e o l i t e s were i n v e s t i g a t e d :
Ca4, 4NaA I n d u s t r i a l l y prepared zeolite 5A (VEB Chemiekombinat B i t t e r f e l d -
Wolfen, G.D.R.).
Ca4.4NaA-DB Air-dried CaNaA thermally a c t i v a t e d a t 873 K i n a muffle f u r n a c e
under deep-bed c o n d i t i o n s (08).

RESULTS AND DISCUSSION

I n f i g u r e 1 a r e shown t h e measured s t a t i c a d s o r p t i o n c a p a c i t i e s o f N2 a s a
f u n c t i o n of t h e p a r t i a l p r e s s u r e a t 293 K of 5AZ powder a f t e r ion exchange, of
g r a n u l a t e d 5AZ and of a 5AZ commercial product (VEE Chemiekombinat B i t t e r f e l d -
Wolfen, G.D.R.) a f t e r dehydration and c a l c i n a t i o n . For comparison N2 v a l u e s
f o r commercial 5A z e o l i t e s a r e given i n t a b l e 1.

TABLE 1
N2 amount adsorbed a t 293 K and 0.1 MPa on commercial 5A z e o l i t e s

Zeolite N2 amount (mg/g>

5A UCC 11.2
5A B a v l i t h K 254 11.5
5A Grace 5285 11.2
5A CKB 10.0
5AZ CKB 11.2
 813

The d i f f e r e n c e between an undamaged and a s t r o n g l y h y d r o l y t i c a l l y t r e a t e d

1OX z e o l i t e , c h a r a c t e r i z e d by values o f s t a t i c adsorption c a p a c i t i e s o f N2, i s
enormous ( f i g u r e 2).
I n our measurements we have used a method o f thermal a c t i v a t i o n (dehydration
and c a l c i n a t i o n ) c o n s i s t i n g of t h e a d d i t i o n o f s m a l l amounts o f ammonia i n t o
t h e gas stream of e i t h e r a f l u i d - b e d r e a c t o r o r a fixed-bed r e a c t o r a t h i g h
r a t e s o f streaming d r y i n e r t gas or a i r a t temperatures up t o 820 K / 3 , 4/.
The s t a t i c and dynamic adsorption c a p a c i t i e s o f N2, CH4 and CO o f t h e new
5AZ(KMU) and lOX(KMU) z e o l i t e s were measured up t o 1.0 MPa. They a r e s i g n i f i -
c a n t l y higher than t h e c a p a c i t i e s o f t h e c o n e r c i a l l y a v a i l a b l e 5A and 1OX zeo-
l i t e s (see t a b l e 2). The presence o f ammonia under t h e c o n d i t i o n s o f dehydra-
t i o n and c a l c i n a t i o n changes t h e pH-values i n t h e c a v i t i e s and t h e e q u i l i b r i u m
o f t h e s a l t h y d r o l y s i s . The formed protons a r e n e u t r a l i z e d by amnonia i n t h e
presence o f water, and NH; i o n s are produced. These NH; i o n s a r e s t a b l e up t o
a temperature o f 560 K. A t higher temperature t h e d i s s o c i a t i o n o f NH; i n t o NH3
and protons takes p l a c e and the h y d r o l y t i c degradation process can proceed
again.
I n the 1OX z e o l i t e s most o f t h e water i s removed up t o 560 K, hence i t i s
p o s s i b l e t o prepare undamaged 1OX(KMU) z e o l i t e s . I n t h e case o f 5A z e o l i t e s
a s m a l l amount of water i s s t i l l adsorbed between 560 and 700 K, and t h e formed
protons can a t t a c k Si-0-A1 bondings. Therefore o n l y s m a l l damaged 5AZ(KMU) zeo-
l i t e s can be produced.
Such hydrothermal low-damaged z e o l i t e s are u s e f u l f o r PSA processes.

TABLE 2
Values o f s t a t i c adsorption c a p a c i t i e s

zeolite pellets N2 (mg/g) CH4 (mg/g)

with 25 % binder 0.1 MPa 1.0 MPa 0.1 MPa 1.0 MPa
~~~~ ~~ ~ ~~~

5AZ CKB 11.2 44.0 10.5 41.0

5AZ KMU 17.0 58.0 15.0 48.0
1OX CKB 10.8 37.0 8.5 32.0
1OX KMU 20.5 52.0 14.5 40.0

In t h e presence o f water i n 4A, 5A, 13X and 1OX z e o l i t e s h y d r o l y s i s proces-

ses a r e s t a r t e d and protons on t h e framework and NaOH, Ca(OH)+ or Ca(OH)2 i n
d i f f e r e n t amounts i n t h e water phase a r e formed. This f i r s t s t e p of h y d r o l y s i s ,
t h e so-called s a l t - h y d r o l y s i s , i s dependent on t h e type of framework and t h e
k i n d o f cations.
I n A z e o l i t e s t h e framework c o n s i s t s o f an a l t e r n a t i o n o f A104 and Si04
tetrahedrons. The p r o t o n form of t h i s z e o l i t e i s n o t s t a b l e . 4A z e o l i t e s repre-
814

Figure 1 Figure 2
I mg'g

35

30 -
- i'" 35 N a C a ( 8 9 ) X /5?-
\30 deln v d r a t e d h n d e r different.
I -
conditions/ -
h

25 - -25 C

20 -

15 -
pellets u n a c t i v a t e d
10

I I I
5AZ-CKB
commercial prod.
I
100 200 300 400 500 600 700
I 1
:;*
-

100 200 300 400 500 600 700

N2-Isotherms at 293 K N2-Isotherms at 293 K

Figure 3 Mechanism of hydrolysis during thermal dehydration

2 S i- O,(-) Me' H
Met
3Si-0 3si-0,
SSi-0-Al-0-SifL > S i - O p A\l - O - S i $ 3Si-OpAI-OHtHO-Si T
/
0
SSi-0 3Si-0 SSi-0
+Me OH

M
=: N i , Ca(0H): I/z Cat'

-
Salt hydrolysis

-
-Si-O,(-) Met , SSi-OH HO-Si f >Si-O-Sig

-= -
Me+
S S i - 0 - Al- 0 H+HO-Si
0
qA - - At I-)
3 Si-0
*' =Si-OJA,),OH
SSi-0' + (3)
37 S i - 00'L A l -0 Md+)
components 1,and are
(1)
produced d u r i n g dehydration At
process depending on temper-
ature Si-OH Me' HO-Si SSi,o HO-Si s
(as a f u n c t i o n of temperature: S i - O H (-1 O H At SSi'
/ (-),OH (+)
one component 1 per c a v i t y = si-0 - A\ -OH ssi - 0 -A1
1 d i s i l i c i c a c i d per c a v i t y =
83 % m o n o s i l i c i c a c i d
1 'OH
- i
N O
Me

At H20 (4) (2)

one component 5 per c a v i t y =
2 d i s i l i c i c a c i d per c a v i t y =
67 % m o n o s i l i c i c a c i d Si-OH HO-Si f 2 3Si-0-Si
S i - O H t A L (OH),,Me tL\t
- H20 (-1
At O , ( O H ) ~ - Z ~ Me
(t)

Si-OH
(4) 1s)
 815

sent a s a l t between a weak polybasic a c i d and a s t r o n g base. 5A z e o l i t e s are

s a l t s o f a weak polybasic a c i d and a weak base. Oepending on t h e S i / A l r a t i o ,
1OX z e o l i t e s are conceivable as a s a l t o f a stronger p o l y b a s i c a c i d r a t h e r than
i n t h e 5A form and a weak base. For t h e X z e o l i t e s i t i s known t h a t t h e a c i d
s t r e n g t h increases with t h e % / A 1 r a t i o . I n t h e presence of water, a r e v e r s i b l e
e q u i l i b r i u m e x i s t s between b o t h forms of a c i d s i t e s o f t h e framework (see f i g u r e
3).
I n t h e case o f 5A z e o l i t e s t h e number o f a c i d s i t e s i s h i g h e r than i n t h e
4A z e o l i t e s and t h e r e f o r e t h e h y d r o l y t i c s t a b i l i t y o f 5A z e o l i t e s i s smaller.
Depending on t h e amount o f a c i d s i t e s i n t h e presence o f water and a t tempera-
t u r e s higher than 370 K, f u r t h e r h y d r o l y s i s products a r e formed by decomposition
o f Si-0-A1 bondings a t t h e a c i d s i t e s o f s a l t h y d r o l y s i s . Such a h y d r o l y s i s pro-
cess can only be explained when t h e a t t a c k o f water i n t h e presence o f protons
takes p l a c e a t Si-0-A1 bondings i n t h e neighbourhood o f a c i d s i t e s i n a s t a t i s -
t i c a l manner. I n such a case A l - s i t e s are damaged step-by-step a t t h e s u r f a c e
and a l s o i n t h e b u l k .
The f i r s t evidence o f t h i s h y d r o l y s i s process i s the f o r m a t i o n o f e x t r a frame-
work aluminate species. We were able t o show t h i s by X-ray s t r u c t u r a l i n v e s t i g a -
t i o n s on deep-bed-activated and rehydrated 5A z e o l i t e s . I n t h e hydrated form o f
hydrothermally t r e a t e d z e o l i t e s Al(0H)i species were found /2/. Freude e t a1 . / 6 /
discuss a l s o t h e formation o f Al(0H)i anions a f t e r deep-bed a c t i v a t i o n and f o l -
l o w i n g r e h y d r a t i o n by means o f t h e 27Al-MASNMR method. Besides A l ( 0 H ) i anions,
on t h e other hand, other s i t e s with p a r t i a l l y hydrolysed Al(OH)-containing sites
are generated by t h e a t t a c k o f water (see f i g u r e 3, compounds 3 and 4). During
the c a l c i n a t i o n process t h e OH groups a t t h e A 1 atoms and t h e Si-OH groups are
changed by desorption o f water, and Si-0-Si bondings are formed. A f t e r t h i s
h e a l i n g process t h e a l t e r a t i o n o f the A 1 s i t e s i s i r r e v e r s i b l e .
The existence o f A l ( 0 H ) i anions, i n c l u d i n g the other p a r t i a l l y hydrolysed A 1
s i t e s , and the statement t h a t two Si-OH groups depending on geometric f a c t o r s
can c r e a t e no more than one S i - 0 - 5 group form t h e b a s i s f o r t h e q u a n t i t a t i v e
explanation f o r t h e r e s u l t s o f t h e molybdate method.
The molybdate method used t h e formation o f the yellow-coloured D-dodeca-
molybdo s i l i c i c a c i d complex on r e a c t i o n between o r t h o s i l i c i c a c i d and molybdic
a c i d / 9 , 10/. A f t e r the a c i d i c d i s s o l u t i o n o f 4A z e o l i t e s ( w i t h o u t any process
o f thermal dehydration) o n l y m o n o s i l i c i c a c i d s a r e detectable. I n t h e case of
pure r n o n o s i l i c i c a c i d the formation o f the y e l l o w complex i s completed a f t e r
2 . 1 min a t 298 K and with pure d i s i l i c i c a c i d under the same c o n d i t i o n s o n l y
a f t e r 5 min. The measured k i n e t i c curves p e r m i t an i n t e r p r e t a t i o n o f t h e r e s u l t s .
The formation o f t h r e e - s i l i c i c or other o l i g o m e r i c s i l i c i c acids i s p o s s i b l e
when two A 1 s i t e s i n the neighbourhood are hydrolysed. The molybdate method i s
816

a proof f o r t h e degradation process. With d e c r e a s i n g c o n t e n t of m o n o s i l i c i c

a c i d an e n l a r g e d h y d r o l y s i s of Si-0-A1 bondings and a h i g h e r number of damaged
A 1 s i t e s is i n d i c a t e d . The p a r t i a l l y damaged A 1 s i t e s have an i n f l u e n c e on t h e
a d s o r p t i o n p r o p e r t i e s of 5A and 1OX z e o l i t e s .
I n a l l c a s e s t h e s t a t i c a d s o r p t i o n c a p a c i t i e s of such molecules a s N
2' O2'
CO, CH4, A t and o t h e r nonpolar s p e c i e s a r e diminished, depending on t h e k i n d s
of i n t e r a c t i o n f o r c e s between adsorbed molecules and t h e changed z e o l i t e frame-
work. The s t a t i c a d s o r p t i o n c a p a c i t i e s of p o l a r molecules, l i k e H20 and C02,
a r e a l s o dependent on t h e degree of d e g r a d a t i o n . Water has a dipolemoment and
is a molecule with an e l e c t r o n - d o n a t i n g s i t e . It i n t e r a c t s with d i p o l e s of t h e
z e o l i t e s u r f a c e and e s p e c i a l l y with e l e c t r o n d e f i c i e n c y sites, t h e c a t i o n s i n
t h e A and X z e o l i t e s . The formation of d i f f e r e n t Ca-alurninate and Ca-alumino-
s i l i c a t e s p e c i e s a f t e r dehydration of t h e hydrolysed A 1 sites (see f i g u r e 3 )
modifies t h e i n t e r a c t i o n p r o p e t t i e s of t h e Ca i o n s . I n t h e o t h e r surroundings
t h e s t r e n g t h of i o n i c bonding of t h e Ca ion w i t h t h e new anion s p e c i e s is less.
With i n c r e a s e d damage t h e i n t e r a c t i o n f o r c e s , and t h e r e f o r e t h e amount of ad-
sorbed water, d e c r e a s e s .
Nitrogen is a very s e n s i t i v e molecule f o r t h e i n t e r a c t i o n of t h i s h y d r o l y s i s
process. The i n t e r a c t i o n f o r c e s between t h e quadrupole moment of N2 and t h e
f i e l d g r a d i e n t of Ca i o n s a r e r e s p o n s i b l e f o r t h e number of molecules adsorbed
a t room temperature. By means of t h e NMR method i t is p o s s i b l e t o compare t h e
v a l u e s of i n t e r a c t i o n f o r c e s between t h e c a t i o n s ( l i k e Na' and Ca2+) and ad-
sorbed N2 molecules / l / .
Ca i o n s have a more i n t e n s i v e i n t e r a c t i o n with N2 t h a n Na i o n s because of
t h e higher i o n i c s t r e n g t h a t n e a r l y t h e same ion diameter. With t h e formation
of Ca-aluminate o r Ca-aluminosilicate s p e c i e s t h e i o n i c p a r t of bonding is
s m a l l e r than t h e Ca-framework bonding i n z e o l i t e , and t h e r e f o r e t h e f i e l d g r a d i -
e n t is s i g n i f i c a n t l y s m a l l e r . Consequently t h e amount of adsorbed N2 a t 293 K
and 0 . 1 MPa d e c r e a s e s s t r o n g l y with t h e p r o g r e s s i v e d e g r a d a t i o n p r o c e s s .
I n t a b l e 3 t h e amount of adsorbed water and n i t r o g e n and t h e amount of mono-
s i l i c i c a c i d determined by t h e nolybdate method a r e l i s t e d f o r a NaL,Mg4A zeo-
l i t e hydrothermally t r e a t e d under t h e same c o n d i t i o n s . The results of t h e meth-
ods used show t h e same tendency. The p r o g r e s s i v e degree of d e g r a d a t i o n of t h e
A 1 sites i n t h e framework l e a d s t o s m a l l e r s t a t i c a d s o r p t i o n c a p a c i t i e s of wa-
ter and n i t r o g e n and s m a l l e r amounts of m o n o s i l i c i c a c i d . The measured amount
of adsorbed N2 is a u s e f u l v a l u e f o r t h e c h a r a c t e r i z a t i o n of t h e degree of
framework degradation i n t h e f i r s t s t a g e when t h e framework of A or X z e o l i t e
is damaged but undestroyed, i . e . , no amorphous m a t e r i a l was formed. The de-
c r e a s e of N2 adsorbed and t h e d e c r e a s e of m o n o s i l i c i c a c i d i n d i c a t e t h e same
process.
 817

TABLE 3
Behaviour of a Na4Mg4A z e o l i t e a f t e r d i f f e r e n t hydrothermal treatments

thermal treatment monosilicic N capacity

H2°
capacity acid 263 K , 0.1 MPa
time (%) (%) (ng/g)

untreated 21.5 100 35.8

(3 c y c l e s ) 26.5 90 30.1
dry nitrogen ( 6 cycles) 26.0 85 29.4
( 9 cycles) 25.3 80 27.3
(3 c y c l e s ) 25.2 80 27.0
air ( 6 cycles) 24.5 80 26.8
( 9 cycles) 24.3 75 23.1
Conditions: 1 g z e o l i t e powder were a c t i v a t e d a t 670 K f o r 2 h i n a r o t a t i n g
quartz tube with d r y n i t r o g e n o r a i r i n counter-current (1.2 l / h ) . A f t e r rehy-
d r a t i o n a new a c t i v a t i o n process was s t a r t e d .

With i n c r e a s i n g content o f Ca c a t i o n s i n t h e 4A z e o l i t e t h e amount o f adsorb-

ed N2 i s increased (see f i g u r e 4). Depending on t h e degree o f Ca2+-ion exchange
t h e amounts o f adsorbed A t , CH4 and CO increased t o o ( f i g u r e 5).
The h i g h e r t h e i n t e r a c t i o n f o r c e s a f t e r t h e exchange o f one Ca2+ i o n t o two Na+
ions, t h e stronger the ascent of adsorbed molecules, depending on number o f
Ca2+ ions per l a r g e c a v i t y i n t h e A z e o l i t e ( A r has o n l y d i s p e r s i o n i n t e r a c t i o n
f o r c e s , CH4 a d d i t i o n a l p o l a r i s a t i o n i n t e r a c t i o n forces, N2 a d d i t i o n a l quadrupol-
f i e l d g r a d i e n t i n t e r a c t i o n forces, and CO a d d i t i o n a l d i p o l e - d i p o l e i n t e r a c t i o n
forces).
A comparison o f t h e heat o f adsorption as a f u n c t i o n o f t h e l o a d i n g between
two NaMgA z e o l i t e s with d i f f e r e n t degrees o f hydrothermal degradation shows t h a t
d u r i n g the thermal h y d r o l y t i c process t h e primary Me2+ z e o l i t i c p o s i t i o n s are
changed, probably by formation o f other chemical compounds.
This simulates a d e f i c i e n c y o f Me2+ ions. I n t h e case of g r a d u a l l y damaged
NaMgA z e o l i t e by deep-bed a c t i v a t i o n t h e decrease o f a d s o r p t i o n heat i s r a p i d ;
only a small number of unchanged A 1 s i t e s are present and t h e r e f o r e o n l y a s m a l l
number o f Mef+ c a t i o n s e x i s t s i n t h e i r o r i g i n a l p o s i t i o n s . On t h a t account t h e
adsorption heat, dependent on Nli loading, decreases r a p i d l y (see f i g u r e 6 ) .
2+
T.t i s concluded t h a t d u r i n g t h e hydrothermal damage o f A z e o l i t e s new Ca
bondings are formed with weaker i o n i c i t y , as w e l l as a h m i n o s i l i c a t e anions with
p r o p e r t i e s other than t h a t o f t h e o r i g i n a l framework and e x t r a l a t t i c e Al-spe-
c i e s o u t s i d e t h e framework. This a l t e r a t i o n can be s t u d i e d by desorption o f
molecules with s p e c i f i c i n t e r a c t i o n f o r c e s t o these new s i t e s . We s e l e c t e d water,
methanol, ethanol, n-propanol, n-butanol, tetrachlorrnethane, dioxan and benzene
f o r these measurements.
818

Figure 4 Figure 5
a (mglg)

Gases adsorbed on
X-78
No &,A-Zeolites
Zeolite No C a l X ) A /

10

5
Torr

100 200 300 400 500 600 700

z 1 2 3 4 5 6

N2-Isotherms at 293 K Number of Ca-ions per

Large cavity

Figure 6 Figure 7

t K J l m o 'NO M g (80)A dehydrated

without damage

\
It -C a N a A
\\ NaMg(80lA I - -- Ca No A - D B
\ deep-bed
'\ dehydrated

-1
\
22 \

20
\
N a A dehydrated
without damage
mglg
~

I
5 10 15

lsostere adsorption heat DTG -curves

 819

The best r e s u l t s were obtained w i t h n-propanol, n-butanol and benzene because

the possible i n t e r a c t i o n s o f t h e OH-groups o r o f the aromatic system t o the Ca
(- (-
ions o f the o r i g i n a l framework and o f the new ( 3Si-O), A]-OH, ( 2 Si-O)2 AI=O,
(- (-
( 3 Si-0) A?(O)OH, AI(0)(OH)2 anions and o t h e r s i m i l a r species i n our o u t s i d e
the framework are d i f f e r e n t .
I n a l l cases t h e s p e c i f i c i n t e r a c t i o n forces between t h e e l e c t r o n d e f i c i e n c y
s i t e s , the o r i g i n a l Ca2+-ions i n the z e o l i t i c framework and t h e electron-dona-
t i n g s i t e s (OH groups of the a l c o h o l molecules o r the aromatic benzene c y c l e s )
are the h i g h e s t .
A l l other i n t e r a c t i o n forces i n t h e hydrothermally damaged 5A z e o l i t e s , espe-
c i a l l y t h e i n t e r a c t i o n forces with t h e new Ca species, are weaker. The f a c t t h a t
more than 4 molecules o f n-butanol a r e adsorbed per l a r g e c a v i t y f a c i l i t a t e s
t h i s i n t e r p r e t a t i o n . I n t h e case o f Ca4.4NaA z e o l i t e each Ca i o n i n t e r a c t s with
one OH group o f a n-butanol molecule ( f i g u r e 7).
After hydrothermal treatment o f t h i s z e o l i t e t h e desorption behaviour o f
n-butanol i s markedly changed ( f i g u r e 7).

REFERENCES
1 R. Schollner, Sitzungsber. der Adll der DDR, 10 N (1985) 38.
2 H. Siegel, R. Schollner, 8. Staude, J. J . van Dun, W. J . M o r t i e r , Z e o l i t e s
7 (1987) 372.
3 R. Schollner, C. Bode, H. Siegel, R. Broddack, E. Petzold, I. F o r s t e r ,
6. Kulbe, H. Herden, R. Kunze, M. Jusek, OD 239533, 26. 7. 1985.
4 R. Schollner, C. Bode, H. Siegel, R. Broddack, M. Jusek, 8. Kulbe, H. Her-
den, R. Kunze, DO 239534, 2 6 . 7. 1985.
5 W. Lutz, 8. Fahlke, K. Lohse, R. Seidel, Chem. Techn. 35 (1983) 35.
6 0. Freude, J. Karger, H. P f e i f e r , Proc. I n t . Symp. Z e o l i t e C a t a l y s i s ,
Siofok, Hungary, 1985, p. 89.
7 W. Oehme, W. M e i l e r , J . R. Lochmann, H. Siegel, Z. Chem. 27 (1987) 431.
8 H. Siegel, Thesis 8, Karl-Marx-University L e i p z i g , 1986.
9 E. T h i l o , W. Wieker, H. Stade, Z. anorg. a l l g . Chem. 340 (1965) 261.
10 H. Stade, Z. anorg. a l l g . Chem. 441 (1978) 29, 446 (1978) 5.
This Page Intentionally Left Blank
H.G. Karge, J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

PHASE TRANSFORMATIONS AND CIlANGES IN LATHCE PARAMETERS OF ZSM-5 AS A

FUNCTION OF Al CONTENT AND TEMPERATURE

G.T. KOKOTAILO*, L. RIEKERT and A. TISSLER

Institut fur Chemische Verfahrenstechnik, UniversitEt Karlsruhe, D-7500 Karlsruhe
* present address: 98 North American Street, Woodbury, NJ 08096, USA

ABSTRACT
Very high quality Z S M J with Si/Al ratios from 35 to 12000 were synthesized and converted
to the H-form. Their lattice parameters were determined from high resolution X-ray data as a
function of temperature up to 585°C. The nionoclinic phase with p angle reduced from 90.6" for
ZSM-5 with a Si/AI ratio of 12000 to 90.090 is evident in ZSM-5 with a SVAI ratio of 35 at room
temperature (25°C). The monoclinic-onhorhombic phase transition is dependent on Si/AI and
temperature. For highly silicious ZSM-5 the temperature range for this phase transition was found
to be greater than that determined by MASNMR. Lowering the temperature of the monoclinic phase
tends to increase the p angle.

INTRODUCTION
ZSM-5, a high-silica zeolite with a unique framework and pore system, was synthesized by
Argauer and Landolt (ref. 1). The framework topology of ZSM-5 was detemiined (ref. 2) and
found to contain an unique bui!ding block consisting of eight 5 membered rings. The uncalcined
ZSM-5 is orthorhombic, space group Pnma and lattice parameters a=19.92, b=20.07, c=l3.42A
(refs. 3-5). It has been reponed (ref. 6) that high silica ZSM-5 on calcination undergoes a phase
transformation from orthorhombic Pnma to monoclinic, &i/n. The angle p is a function of occluded
material but attains a maximum of 90.6" for highly dealuminated ZSM-5. Nakamoto and Takahashi
(ref. 7) reported that the ease of transfomiation of the orthorhombic to the monoclinic phase is a
function of Si/AI increasing with decreasing Al content and does not appear for SVAI less than 80.
Fyfe (ref. 8) has shown that the MASNMR spectrum of as synthesized high silica ZSM-5
exhibits 12 resonances characteristic of the orthorhombic form. On calcination and removal of the
organic material in the pore system the NMR spectrum exhibits 24 resonances characteristic of the
monoclinic phase. Sorption of organic molecules induces a change from the monoclinic to the
orthorhombic phase (ref. 9). This phase transformation is also temperature-sensitive and occurs at
80 - W C as indicated by MASNMR (ref. 8). Hay and Jaeger (ref. 10) observed the same effect
with X-ray diffraction but at a lower temperature, 44 - 5 2 C .
The effect of SVAI ratio and temperature on the symmetry and lattice parameters of ZSM-5
are discussed in this report.

EXPERIMENTAL
Very high quality ZSM-5 with SVAI ratios of 35, 100, 800 and 12OOO were synthesized by
the method of Argauer and Landolt (ref. l), as very good crystalline samples are required in order to
obtain high resolution X-ray diffraction patterns. The samples were calcined 4 hours at 500°C in a
muffle furnace and ion exchanged twice for 1 hour at 100°C in 1 molar W C I solutions, filtered,
washed and dried, and calcined at 5OOOC for 4 hours to obtain the hydrogen form. X-ray diffraction
patterns were obtained with a Philips diffractometer and a Huber 4-circle Guinier camera (631) with
CuKa radiation, a Johannsen monochromator, a Si internal standard and temperature controller.
The samples for the Guinier camera were packed in 0.5 mm silica glass capillaries to avoid preferred
orientation. A series of X-ray film patterns were obtained by advancing the film 0.5 cm and
increasing the temperature from 25°C to 725°C in 100°C intervals for Si/AI = 35.50" intervals for
a22

WAl = 100.75" intervals for Si/AI = 800 and 12000. The films were read with a Nonius
comparator with a resolution of 0.05 mm or 0.015" 20 and lattice parameters were determined to f
.oOO6nm. The d spacings were extrapolated from the (1 1l), (200) and (31 1) lines of Si and the
parameters a, b. c and p were obtained using computer programs GIVER,REFINE and THEOWIE
courtesy of the Instifit fur Anorganische Chemie, Universitlit Karlsruhe. The films were
microphotometered, courtesy of the Astrophysics Dept.. Princeton University.
RESULTS AND CONCLUSIONS
The plot of the change in angle p or the degree of separation of the 313 and 313 lines for H-
ZSMJ at room temperature (25°C) is given in fig. 1.

90.6 -
39)
m, -
-a 90.4
K
.-0C
-00
.-
90.2 -
c
3
90.0 , I I I I

Figure 1: Monoclinic angle in H-ZSM-5

samples with different Si/AI ratios at room temperature

The angle decreases with Si/AI ratio but does not reach 900 for the lowest Si/AI ratio measured. The
a and b parameters drop to a minimum at Si/AI = 100 and then gradually increase with increasing
Si/AI while the c parameter increases with Si/AI up to 100 and then tends to level off, fig. 2. This is
unexpected as with increasing Si/Al ratio the average T-0 distance would decrease and the lattice
parameters would follow suit. The increase in silanol groups and or the change in the ratio of ionic
and covalent bonding may with increased Si in the structure have an affect on the lattice parameters
and the unit-cell volume.

The plot of angle p as a function of temperature T and Si/AI as shown in figure 3 indicates a decrease
in p with temperature. This effect becomes more pronounced with increasing Si/AI ratio; there is a
marked increase for Si/AI = 12OOO. The lattice parameters as a function of temperature and Si/AI
ratio are given in Table 1. There is very little variation in a, b and c with only p varying at low
temperatures. The angle p approaches 9W with decreasing Si/AI ratio and increasing temperature. It
would be expected that a highly siliceous ZSM-5 would be orthorhombic at high temperatures. It
has been shown by von Ballmoos and Meier (1 1) that the Al distribution i n ZSM-5crystiils is non
uniform. with a high alumina outershell. Nitrogen adsorption isotherms in ZSM-5exhibit hysterisis
loops low at temperature and pressures (3,12,13). Mfiller and Unger (12) have shown variations in
A1 distribution with Si/AI ratios. The shape of the nitrogen adsorption isotherms is affected by the
Si/Al ratio and the variation in A1 distribution in the crystals (12,13). The quality of the crystals. the
Al distribution in the crystals, the presence of faults and errors in the determination of the lattice
parameters may be the contributing factors in the p angle not reaching 900 at high temperatures with
 823

2.02 r
-
E
- 2.00
c
!!
aJ
c.
f 1.99
E
a
aJ
2.01

1.98

1.33
I0 I
p

2 3 4 5
Log(SVAI)

Figure 2: Lattice parameters in H-ZSM-5 samples of different Si/AI ratio a; o h;O'c

90.6

4
n
90.0 I I I I I n
0 100 200 300 600 500 600
Temperaturr[oC)
Figure 3: Change of the monoclinic angle in H-ZSM-5 samples of different Si/AI ratio by heating,
0 SVAI = 35; ISi/AI = 100, Si/AI = 800; o Si/AI = 12000
024

w L
I 1 I I
10 9 0 7
20

Figure 4: Microphotometer trace of ZSM-5 (Si/AI = 35) spectrum 7 -10' 28 *

the exception of the Si/AI = 100 sample. The phase transition monoclinic to orthorhombic occurs
over a small temperature range below 100°C (14) and is dependent on the Si/AI ratio decreasing with
A1 content. High resolution X-ray diffraction and good crystals are required to determine whether
313 and 313 reflections are doublets or whether the angle p is 9P, a single sharp line indicating
orthorhombic symmetry. The crystallinity of the low SUAI = 35 ZSM-5 sample and the resolution
of the Guinier camera are clearly shown by the resolution of the 200 and the 020 doublet in fig. 4.
The X-ray diffraction pattern of this sample at mom temperature (25°C) indicates the 31 3,313 and
the 501,501 doublets in a microphotometer trace of that section of the Guinier film pattern, fig.
5(a). The shoulders disappear and the peaks sharpen up at 125"C, fig. 5b, indicating that ZSM-5
with Si/AI = 35 at 25°C has monoclinic symmetry.
 825

4
v\
0

a b
-I+
0 0
v\v\

I
25
I I I 1 1 -
24 20 23 25 24 20 23

Fig. 5: Microphotometer traces of ZSM-5 spectra, 21 - 25'28, (a) at 25°C (b) at 125°C

TABLE 1
Lattice Parameters as a Functionof Si/AlRatioand Temperature

SVAI T("C) a(m) Mnm) c(m) P

35 25 1.992 2.01 1 1.336 90.09
35 447 I .993 2.008 1.338 90.07
100 25 I .986 2.004 1.340 90.13
100 575 1.99 1 2.004 1.342 90.00
800 25 1.987 2.008 1.338 90.18
800 287 I .986 2.007 1.336 90.12
800 587 1.986 2.003 1.335 90.09
12000 25 1.989 2.010 1.340 90.52
12000 90 1.991 2.010 1.340 90.23
12000 250 1.990 2.007 1.336 90.07
12000 450 1.991 2.008 1.338 90.05
12000 575 1.990 2.007 1.338 90.05
826

The Guinier X-ray film pattern of €1-ZSM-5 with a Si/Al ratio of 100 indicates the
monoclinic phase with the 313 - 313doublet evident. At -173°C the separation of this doublet has
increased, indicating a litrger p angle. This demonstrates that lowering the temperature of the
monoclinic form of ZSM-5 results in the increase of the p angle. Thus, the Si/AI ratio of ZSM-5
determines the magnitude of the p angle in the monoclinic phase which persists for a SVAI ratio of:
at 25°C. The displacive phase transformation, monoclinic-orthorhonibicand orthorhombic-
monoclinic, is temperature-dependent. The presence of sorbate or extraneous material also affects
the phase transformation.

ACKNOWLEDGEMENTS
We wish to thank Prof. E. Althaus and G.Ott of the Institute of Mineralogy, Dr. H. Henke
of the Institut flir Chemische Verfahrenstechnik, Universi6t Karlsruhe and S. Honenbach of
Astrophysics Dept. Princeton University, for their help. G.T. Kokotailo acknowledges the
Alexander von Humboldt Senior US Scientist Award.

LITERATURE

1. US Patent 3,702,886, 1972

2. G.T. Kokotailo, S.L. Lawton, D.H. Olson and W.M. Meier, Nature, 272, 56, 52, 437,
1978
3. D.H. Olson, G.T. Kokotailo, S.L. Lawton, W.M. Meier, J. Phys. Chem. 8.r. 2238. 1981
4. H. Lermer, J. Steffen, M. Draeger and K.K. Unger, Zeolites 1, 57, 1985
5. K.T. Chao, J.Ch. Lin, Y.Wang, G.H. Lee, Zeolites 6,35, 1986
6. E.L. Wu, S.L. Liiwton, D.H. Olson, A.C. Rohrman Jr. and G.T. Kokotailo, J. Pliys.
Chem. a, 2777, 1979
7. H. Nakamoto iind 11. Takithitshi, Chemical Society of Japan, Chem. Letters 10 13, 19x1
8. C.A. Fyfe, G.J. Kennedy, G.T.Kokotailo, J.R. Lyerla and W.W. Fleming, J. Chem. So
Chem. Conim. 740, 1985
9. C.A. Fyfe, G.J. Kennedy, C.T. De Schutter and G.T.Kokotailo, J. Chem. Soc. Chem.
Comm. 541, 1984
10. D.G. Hay and H. Jaeger, J. Chem. Soc. Chem. Comm. 1433, 1984
11. R.Von Ballmoos, W.M. Meier, Nature 289,78, 1981
12. K. Muller, K.K. Unger, Characterization of Porous Solids, Elsevier Science Publ.,
B.V. Amsterdam 1988 p. 101
13. K. Beschmann, G.T. Kokotailo, L. Riekert, ibid 1988, p. 355.
14. C.A. Fyfe, H. Strobl, G.T. Kokotailo, G.J. Kennedy and G.E. Barlow, JACS, 110,
3373, 1988
H.G.Karge,J. Weitkamp (Editors),Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V.,Amsterdam - Printed in The Netherlands

The Effect of Sorbates and Elevated Temperatures on the

Structures of Some Zeolite Catalysts

C.A. Fyfe. G.T. Kokotailo, H. Strobl, H. Gies, G.J. Kennedy,

C.T. Pasztor, and G.E. Barlow

Department of Chemistry, University of British Columbia,

Vancouver, British Columbia, Canada V6T 1Y6

The catalytic properties of zeolite catalysts are

dependent on their unique structural features, such as
pore geometry, distribution and concentration of
T-atoms and adsorbed species, presence of defects, and
temperature. Solid state NMR is highly sensitive to
changes in the local environments of T-atoms, and when
used in conjunction with X-ray diffraction provides a
more complete description of zeolite framework struc-
tures.
This combined use of XRD and MAS NMR to determine
the changes in the framework of zeolite catalysts due
to temperature and organic molecule adsorption will be
discussed in detail.

The importance of zeolites as catalysts, catalyst supports, adsor-

bents, and ion exchangers is well established. The properties of a
particular zeolite are dependent on the topology of its framework,
the size of its free channels, the location of charges, the size of
the cations within the framework, the presence of faults and
occulded material, and the ordering of the T-atoms. Therefore,
structural information is necessary in order to understand the
sorptive and catalytic properties of zeolites ( E l .
The unavailability of large crystals suitable for single
crystal studies has necessitated the use of powder diffraction
techniques to resolve the structures with the more recent use of
synchrotron radiation (6-8) and the Rietveld x-ray powder profile
method for refining structures (9). A number of other techniques
have been used to characterize zeolite catalysts. X-ray photon
spectroscopy has been used to determine the composition of surfaces
(10) and the use of neutron scattering has made it possible to
identify OH groups (11). Electron diffraction (121, contrast line
transmission electron microscopy (13) and lattice imaging have been
used to determine the presence of faults in zeolites.
Since Si and A1 have essentially the same scattering factors
the Si and A1 sites may be distinguished by the T-0 bond lengths
828

-
(Si-0 1.62 A and A1-0 = 1.73 A) if there is long range Si and A1
ordering throughout the crystal, although this is seldom the case.
ZSM-5 crystals tend to grow with a high A1 content outer shell (14)
and it is not known whether A1 occupies certain sites
preferentially (15) and whether some of it is not in the
framework.
Recently, powder X-ray diffraction has acquired a
complimentary technique in high-resolution MAS NMR spectroscopy
(14-19) and their combined use has made it possible to obtain a
more complete elucidation of zeolite structures, and how they are
affected by sorption of organic species, temperature and the
presence of defects. In these studies, X-ray diffraction is used
to determine long range order while MAS NMR is sensitive to changes
in local environments and short range order.

Solid State NMR

The direct dipole-dipole interaction between nuclei dominate
the NMR spectra of abundant nuclei in solids, yielding spectra with
broad lines and negligible resolution. The interactions are orders
of magnitude larger than the chemical shifts and spin-spin
couplings which are related to the chemical and molecular structure
as observed for species in solution where the dipolar interactions
average out to exactly zero.
The situation is simplified by "diluting" the nuclei in the
sample by observing nuclei with low natural isotopic abundance or
by physical dilution in the system as homonuclear dipolar
interactions drop off very rapidly with internuclear distance.
Heteronuclear interactions may be removed by dipolar decoupling and
the remaining interaction, the chemical shift anisotropy, can be
averaged by "magic angle" spinning (19) about an axis inclined at
54'44' to the magnetic field and is reduced to the isotropic
component of the anisotropic tensor, just as for random molecular
motion in solution. Cross polarization may also in general be used
to enhance the dilute nucleus magnetization from that of protons in
the system (20). In zeolites, protons are not covalently bonded
into the solid matrix so that a9Si and "A1 spectra may be obtained
using magic angle- spinning alone. These experiments are best
performed at the highest possible field strength and a conventional
high-resolution spectrometer may be used.
Since the initial work of Lippmaa and Engelhardt (16) a number
of investigations of a9Si and "A1 spectra of low Si/A1 ratio have
been reported and for structures with a single independent T atom
there is a maximum of 5 resonances for a Si/A1 > 1, indicating that
the spectrum is sensitive to the local Si environment or the
composition and distribution of Si and A1 in the first coordination
sphere. The resonances are broad due to a distribution of local
environments. A typical "Si spectrum of analcite and the chemical
shift ranges of the 5 possible local silicon environments are shown
in figures 1 and 2.
It has been shown that the main contributing factor to line
broadening in agSi MAS NMR spectra of a zeolite with a random
distribution of A1 in the framework is the distribution of local Si
environments due to the non-ordered neighbouring Si and A1 sites.
Zeolite A which has a completely ordered Si (4A1) framework gives a
sharp spectrum consisting of one line due to Si (4A1) as seen in
 829

Fig. 3a. A high Si A (ZK-4 with Si/A1=3) yields a characteristic

5 resonance spectrum, Fig. 3b, with the Si(4A1) line very weak due
to the high Si/Al racio. The lines are broad due to a distribution
of local envircnments. The ZK-4 sample (Fig. 3b) was highly
dealuminated by passing water vapor over the hydrogen form at
atmospheric pressure and 973*K for 48 hrs. (21). Its a*SI MAS NMR
spectrum consists of a single sharp line (Fig. 3) which can be
assigned to Si(OA1) indicating the complete removal of A1 from the
framework with the integrity of the structure preserved as shown by
the XRD patterns in Fig. 3. The upfield shift of the Si(OA1) lines
is evident and is consistent with the reduction in chemical shift
distribution arising from the disordering of Si,Al in the local
environment ( 2 2 ) .

-8 0 - -90 -100 - ppm from T M S

-
Fig. 1. SOSi HAS spectrum of the zeolite analcite showing the
resolution of the different silicon environments indicated (ref..17)

Si( 1Al)

w
m3 -s(-si)
=uSi(4Al)
I I I I I 1 I 1
-80 -90 -100 -110

Fig. 2. The five possible local environments of a silicon atom

together with their characteristic chemical shift ranges. The
dashed lines show the shift values of zeolite ZK-4 as indicated.
The inner boxes represent the shift ranges suggested in the earlier
literature (ref. 16) while the outer ones reflect more recent data
(ref. 1 7 ) .
830

Thus, the removal of lattice aluminum yields very narrow 19Si

resonances all of which are due to Si(OA1, 4Si) and which
correspond to crystallographically independent Si atoms in the
structure (23). The number, relatlve intensities and shifts of the
resonances yield direct informatioi as to the structure of a
zeolite catalyst and are very sensitive to subtle and small changes
in the lattice due to defects or distortion. It should be
emphasized again that the XRD and MAS NMR techniques are
complimentary, the former determining long range order while the
latter is sensitive to local, short range order.

2 9 ~ 1 mas n m r X rd.

& , I 0 1 , , . I . L
-80 -100 -120
p.pm from Hr'Si

Fig. 3. "Si (79.6 MHz) HAS NMR spectra of (A) zeolite A, (B)
zeolite ZK-4, (C) completely siliceous zeolite A, and (D-F) the
corresponding powder XRD patterns (ref.21) .
 831

ZSM-5
ZSM-5 (24) is of particular intsrest because of its high
catalytic activity and its unique shape selective and sorptive
properties which enable 4.t to convert methanol to hydrocarbons,
(25) in the gasoline range to selectively produce p-xylene ( 2 6 )
and hydrodewax (27).
ZSM-5 is the end member of the pentasil family of zeolites
the other being ZSM-11 (28b). The structure of the low Si/A1 ratio
ZSM-5 is orthorhombic with space group Pnma, (28d) while that of
the high Si/A1 phase is monoclinic with space group P2,/n (29).
The orthorhombic phase has 12 independent T atoms and the
monoclinic 24. This was confirmed by SSSi MAS NMR (30, 31).
Template-loaded ZSM-5 regardless of Si/A1 ratio is orthorhombic
with Pnma space group.
Recently, extremely pure samples of a very highly crystalline
ZSM-5 were synthesized and completely dealuminated. Combined with
careful optimization of all NMR experimental variables this enabled
us to obtain ultra high resolution a@Si MAS NMR spectra of ZSM-5
(Fig. 4) in which 21 of the 24 possible resonances are clearly
resolved (32, 3 3 ) . The line widths are approximately 5Hz (x 0.06
ppm) which is an improvement of an order of magnitude over original
spectra (obtained in 1982). The deconvolution of the spectrum is
straightforward. The spectrum obtained at 295K has no resolution
enhancement. Powder XRD patterns using a Rigaku X-ray
diffractometer confirmed the highly crystallhe nature of the
sample which was subsequently used to determine the effect of
temperature and/or sorbate. The x-ray diffraction samples were
covered with an amorphous collodion film to prevent any change in

I I 1 I I 1 I I I I I
- 108 PPM FROM TMS - 118

Fig. 4. SOSi MAS NMR spectrum of highly crystalline ZSM-5.

832

sorbate content. The experimental PAS NMR variables were optimized

as previously desxibed (32,331 and it was found that the high
degree of resolution is essentially maintained at both elevated
temperatures and in the presence of sorbed species (33).
Temperature and sorbed specips induce a phase transformation
of the monoclinic to the orthorhombic with a decrease in the
independent atoms from 24 to 12 (30, 31).
The effect of p-xylene adsorption at ambient temperature on
the 29Si MAS NMR spectrum of highly siliceous ZSM-5 as a function
of concentration is shown in Fig. 5. At low loading (0.4 molecules
/unit cell) the effect on the spectrum is minimal, with small
shifts in individual peaks which increase with increased loading.
At 1.6 molecules/unit cell the change in the spectrum is complete
and it now shows only 12 resonances indicating a phase transition
to the orthorhombic (30) in agreement with XRD data.

10
I 2.0

8 4 1.6
n .
I
t

G .7 1 .4

1.2

Fig. 5 . Effect of p-xylene on ZSM-5 at ambient temperature (ref. 33)

 833

The NMR spectra indicate both orthorhombic (12 T atoms) and

monoclinic (24 T atoms) phases are present in the intermediate
loadings in different proportions. The change in relative
intensity of some of the better resolved resonances indicates the
midpoint of the transition a t 1 molecule/ unit cell with a complete
transition at 2 moleculedunit cell.
As in the case of sorbed species, the effect of raising
temperature is to induce a phase transformation from monoclinic to
orthorhombic. Detailed spectra at 10" intervals fig. 6 show
gradual shifts of individual resonances up to 353'K with a rapid
change between 353 and 363°K. This is confirmed by synchrotron
X-ray diffraction analysis of the phase transformation as a
function of temperature ( 3 4 ) . which also shows that above the
transition temperature only a single phase (the orthorhombic)
persists. The temperature and range over which the phase
transition takes place is a function of framework A1 content
decreasing with increasing Al.
A I 6 I
TEMP (K)

393

Fig. 6 . Effect Of temperatureon ZSM-5 (ref. 33).

834

The combined effect of temperature and rorbate shown in Fig. 7

is to lower the phase transition temperature and increase its
range. In the phase transition temperature range, both phases now
coexist with the material being crystalline. Above the
transition temperature, there are only minor changes reflecting
lattice expansion due to temperature within the orthorhombic (12 T
atom) phase ( 3 3 ) .

tamp

363 K

353 K

343 K

333 K

323 K
*
dk
0
h

t
363

553

343

333

323

313 K 313

303 K 303

105 K 205

Pig. 7. Combined effect6 of temperature and p-xylene on the

"Si Pus NHR 6peCttum of 2811-5 at the conditions indicated
(ref. 33).
 835

ZSM-1 1
ZSM-11, the other end member of the pentasil family of
zeolites was synthesized by Chu (35). ZSM-11 crystallizes in the
tetragonal system with space group I4m2 (36). It is very difficult
to synthesize pure ZSM-11 without intergrowths with ZSM-5 or
stacking faults, so that for hkl reflections, h + k + 1 = 2n and
the doublets merge into singlets. '9Si MAS NMR spectra of a highly
dealuminated and phase- pure ZSM-11 sample (37) have been obtained
as a function of temperature. As in the case of ZSM-5 where
elevated temperatures promote a transition to a phase of higher
symmetry, it was found that at a temperature of 373"K, Fig. 8 , the
spectrum is resolved into six sharp Lorentzian peaks with relative
intensities 1:(2+2):2:1:2:2 which is consistent with the proposed
structure, tetragonal with space group I4m2. with the six
resonances due to the 7 independent atoms in the ideal framework
structure [16(T,,T,,T,,T,,T,)8(T, ,T6)]. At room-temperature, the
symmetry is lower and the limiting structure is reached only at
253°K.

I I l l l ,
105 -420

20°

1 1 1 ( , 1 , , 1

-
1 1 1 1
-105
120

Fig. 8 . 2BSi MAS NMR spectra from ZSM-11 (a)293OK (b) 373%. At
373°K the expected seven resonances are observed, but at 293°K the
spectrum shows additional resonances, indicative of a lowering of
the local symmetry.
836

Synchrotron X-ray powder diffraction data were obtained using

beam-line X13 A at the Brookhaven National Synchrotron Light Source
( 3 8 ) . Rietveld refinement (39) shows that the high-temperature
structure is exactly that previously proposed and is currently
being applied to deterrine the structure of the low temperature
from (41). Initial results indicate the much greater sensitivity
of MAS NMR to detecting phase transitions in this system and
additional synchrotron X-ray data collected at 253OK may be needed
to resolve this problem.

I I 1 1 1 1 1 1 1 1
410 -114 -118

Fig. 9. a's1 MAS NMR spectra obtained at 79.5 MHz.

A. highly siliceous zeolite ZSM-11, and this material
after sorption of,
B. 25 p1 quinoline,
C. 25 p1 acetylacetone, and
D. 20 p1 n-octane.
(In all cases, 250 mg of zeolite was used.)
 837

The effect of sorbed species on the "Si MAS NMR spectra of

ZSM-5 has been clearly shown (32.33). The syrmoetry of ZSM-11 being
higher than that of ZSM-5, smaller changes in local environment are
to be expected due to the presence of sorbed species. As in the
case of ZSM-5, the effect of sorbed molecu-es on the ZgSi MAS NMR
spectra is thought to be a modification of the framework structure
which alters the local T-atom environment. This is confirmed by
the small but significant changes observed in the XRD patterns.
which are reversible on desorption. The spectra in Fig. 9 show
the effect of 25 p1 of quinoline, acetyl acetone and 20 p1 of
n-octane on 250 mg of highly dealuminated ZSM-11 (42). Unlike the
case of ZSM-5, the changes induced do not appear to lead to a
clearly defined highly crystalline state and may involve a degree
of disruption of local geometry. It is interesting to note that
the room temperature spectrum due to the sorption of 20 p1 of
n-octane is modified to be very similar to that of ZSM-11 at 273°K
which indicates the n-octane sorption increases the symmetry of
the ambient temperature phase of ZSM-11.

ZSM-39
The highly siliceous zeolite ZSM-39 (431, is the silicate
analog of the 17A cubic gas hydrate. Crystals of ZSM-39 tend to
have octahedral habit. Its structure was determined by Schlenker
et a1 (44a) and refined from single crystal data in space group Fd3
by Gies et al. (44b). X-ray powder patterns of the room
temperature form however show a few very weak extra reflections
indicating a space group synnnetry lower than face centered cubic

Fig. 10. Framework structure of ZSM-39.

synnnetry. There are 3 independent atoms in the ideal cubic face

centered structure of ZSM-39, 8(T,), 32(T,) and 96(T,). The "Si
MAS NMR spectra of four different ZSM-39 samples (Fig. 11) (a-d)
show varying degrees of line broadening which cannot be due to A1
distribution as the Si/Al ratios of 3 of the samples (11. a-c) are
very high and the fourth was synthesized with aminopropane as
template (sample courtesy of D.M. Bibby) (45). In the spectra b
and c the lines narrow and extra resonances are resolved. In
apectrum 2d the T, resonance is split into 3 resonances of equal
intensity making the relative spectral intensities 1:4:4:4:4. This
splitting is probably due to the removal of the 3-fold symmetry
838

w i s . The same distortion appears in the other spectra (a b and c)

to varying degrees due to a distribution of local environments and
consequent line broadening. The a9Si MAS NMR spectra of the ZSM-39
(aminopropane base) seen at ambient temperature in Fig. 11 d, vyere
obtained over a temperature range 373-383'K. Fig. 12. As the
temperature is raised, all the resonances remain sharp but there is
a clear change over a 10' temperature range to a new spectrum of
three resonances with relative intensities 1:4:12 clearly
indicating cubic face centered symmetry at least on a local basis
on the NMR time scale. The changes are completely reversible and
also apply to the samples with less well resolved spectra.
The nature of these high temperature phases is somewhat
ambiguous. The spectra may well be reflecting much more flexible
frameworks for zeolites in general than hitherto anticipated or may
indicate changes to new but relatively higher symmetry lattices.
However, investigations of the phase transition temperature of
silicon ZSM-39 (dodecasil 3C) synthesized in the presence of
different quest molecules (45) showed that it varies. This
demonstrates the influence of nonframework constituents on the
symmetry of the silicon framework even for more dense structures as
ZSM-39.

Fig. 11. a9Si MAS NMR spectra of zeolite ZSM-39 with differing
Si/Al ratios; (a) Si/A1 = 285, (b) Si/Al = 2400, (c) Si/A1 = 310,
and (d) from aminopropane base synthesis.
 839

I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
-100 -125
PPM FROM TMS

Fig. 12. "Si MAS NMR spectra of ZSM-39 recorded at the

temperatures indicated.

(1) Bragg; W.L.; Claringbull, C.F., The Crystal Structure of

Minerals, Bill and Sons, London, 1965.
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(3) Breck, D.W., Zeolite Molecular Sieves, Wiley Interscience.
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(4) Smith, J . V . , Zeolite Chemistry and Catalysis, Ed. Rabo, J.A.,

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(8) Toby, B.H; Eddy, M.M.; Fyfe, C.A.; Kokotailo, G.T.; Strobl,
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 H.G. Karge, J. Weitkamp (Editors ), Zeolites as Catalysts, Sorbents and Detergent Builders
0 1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THE EFFECT OF TEMPERATURE AND SORPTION OF p-XYLENE AND BENZENE ON

THE STRUCTURE OF ZSM-5
G.T. KOKOTAILO, L. dIEKERT and A. TISSLER
Institut filr Chemische Verfahrenstechnik, Universitft Karlsruhe, D-7500Karlsruhe

ABSTRACT
The effect of p-xylene and benzene adsorption on the structure of ZSM-5 with varying
SUAI ratios, temperature and pressure has been determined. High quality ZSM-5 with SQA1
ratios of 35, 100 and 800 were synthesized and converted to the hydrogen form. The lattice
parameters were accurately determined from data obtained with a Guinier 4 circle camera.
Room temperature sorption of p-xylene and benzene promoted the monoclinic-to-onhorhombic
phase transition with some changes in the a. b and c parameters especially in the case of
benzene sorption; where the a and b parameters become equal on full loading.
Low pressure p-xylene and benzene flow over ZSM-5 samples maintained at various
temperatures caused the monoclinic to orthorhombic phase transition with changes mainly in
the a and b parameters and unit cell volume as a function of temperature.
INTRODUCTION
ZSM-5 and ZSM-11are high silica zeolites which have been of particular interest in
recent years because of their high catalytic activity, adsorptive properties and unique pore
geomery. Their selective accessibility to sorbates and reactant molecules is an unique feature
of these zeolites. It was only recently that the interaction between sorbed species and the
zeolite framework was demonStrated (1,2) by high resolution MASNMR for sorbed species in
highly siliceous ZSM-5.The 2% MASNMR spectra of high Si ZSM-5and ZSM-I 1 are
modified by the sorption of organic molecules with related changes in corresponding x-ray
diffraction patterns. The spectra arc characteristic for the sorbed molecule. As the
concentration of the sorbed molecule is increased the character of the NMR spectrum is altered
until a limiting spectrum is obtained which with further increases in concentration does not
change except for a loss in resolution. This indicates that structural changes arc occurring
which are characteristicDf the'sarbate while the integrity of the framework is maintained.
These changes are completely reversible. Temperatun has an effect on the rate at which these
changes take place. The effect of p-xylene and acetylacetone on the structure of highly
siliceous ZSM-5 as determined by NMR has been described (3). In this report the effect of p-
xylene and benzene sorption on the structure of ZSM-5has been extended to ZSM-5 with
lower SVAI ratios, and the effect of subjecting the samples to reactor conditions of flow at
various temperatures and pressure will be discussed.
EXPERIhENTAL
ZSM-5with SVAI ratios of 35,100 and 800 were synthesized by the method of
Argauer and Landolt (4) and reduced to the H-form by calcining 4 hours at 5oO.C. ion
exchanging with 1 molar W C I for 1 hour at 1oO.C.washing twice, filtering. drying and
calcining for 4 hours at 5WC.
The x-ray dihction patterns were obtained at room ternpaatwe with a Philips
diffractometer and CuKa radiation, Samples with sorbed species wcrc c o d with a
collodion film to prcvent evaporation. Samples were also packed in silica glass capillaries to
avoid prefemd orientation and sealed to prevent evaporation. X-ray patterns for these samples
844

were obtained with a lluber 4 circle Guinier camera (631) with CuKa radiation. ii Jo1l;lnnscn
monochromator and a silicon internal standard.
A capillary microreactor was designed using 0.6 mm silica glass tubes with 0.05 nini
wall thickness in which the zeolite samples werc packed and a flow of p-xylene and benzene a t
1-2 mlhr and prcssurcs of 12700 and 1270 Pa resp. with nitrogen as a carrier gas were
maintained. X-ray diffractionfilm patterns we^ obtained at various temperatures up to 525°C
using a Guinier 4 circle camera (5). The films ~ r exposed
c for 5 hours at each temperature
with a total exposure of up to 80 hours. The temperatures were determined from the (1 1 I )
reflection of a silver internal standard. The films were read and the d spacings and lattice
parameters determined as previously described (5).
RESULTS AND CONCLUSIONS
Room temperature sorption of p-xylene on ZSM-5with SVAI ratios of 35, 100 and 800
has very little effect on the a, b and c parameters after an initial increase on adsorption of 0.7
rnoVuc but the p angle decreases to 90”with sorption of nbout 3 molecules per unit cell, Table
1. This indicates that sorption of 3 molecules per unit cell causes nionoclinic-to-onhorhombic
phase transition.
In the case of benzene the b pmmeter tends to increase with sorption and a phase
transition occurs with a sorption of about 4 molecules/uc as indicated by the change in 0 angle
to 90”.Table 2. The anomaly is the sample with a Si/AI ratio of 800 where the final transition
is to the pseudo-tetragonal phase with a=b. The effect of sorption on the lattice parameters is
given in fig. I .

n
2.01
E
2.00
ff
Y
A
v
$ 1.99
m
Q 1
.98
b
8 1.35
‘J

4 C
n
v
0
1.34

0 2 4 6 8
MdAJ.C.
Figurc 1: Lattice Parameters of H-ZSM-5 with Si/A1=800 as a Function of Benzene
Concentration
 845

Table 1
Effect of p-Xylene on Lattice Pmmeters of Z S M J
with Si/AI Ratio 35,100 and 800 at Room Temperatures

% wt. MoVuc SVAl a b C P VOl. uc

0 0 35 1.992 nrn 2.01 I nm 1.336 nm 90.09O 5.349(nm)3

1.35 .7 " 1.997 2.015 1.342 90.08 5.400
2.69 1.4 " 2.002 2.014 1.347 90.09 5.430
5.38 2.8 " 2.000 2.014 1.351 90.01 5.442
6.85 3.6 " 2.000 2.015 1.349 90.00 5.437
10.76 5.7 " 1.995 2.016 1.348 90.00 5.422
15.00 8 1.993 2.018 1.346 90.00 5.406
0 0 100 1.986 2.004 1.340 90.13 5.332
3.86 2 " 1.994 2.008 1.342 90.09 5.372
5.38 2.8 " 1.997 2.008 1.343 90.02 5.381
10.76 5.7 " 2.000 2.010 1.349 90.00 5.410
15.00 8 I ' 1.995 2.007 1.346 90.0 5.388
0 0 800 1.987 2.008 1.338 90.18 5.340
2.69 1.4 " 1.991 2.010 1.337 90.02 5.350
5.38 2.8 " 1.999 2.007 1.342 90.05 5.382
7.46 4 I ' 1.993 2.008 1.340 90.00 5.361
10.76 5.7 " 1.997 2.008 1.341 90.00 5.375
15.00 8 I ' 1.984 2.012 1.343 90.00 5.358

Tiihlc 2
Effect of J3cn7snc on Iiiitice 1';irnincters of ZSM-5 with
SVAI k i h s 35, 100 and XO() ;it Room Tempcr;iture
lo wt Mol/uc SVAI n b C P Vol. tic

0 0 35 1.992 nm 2.01 1 nm 1.336 nni 90.09 5.349 (11m)-1

2.80 2.3 'I 1.998 2.014 1.342 90.00 5.400
5.60 4.6 " 1.998 2.018 1.341 90.1 1 5.430
8.00 6.6 I' 1.999 2.019 1.349 90.00 5.444
1 1.00 9.0 " 2.000 2.014 1.347 90.00 5.423
0 100 1.986 2.004 1.340 90.13 5.332
3.20 2.7 " 1.997 2.0 15 1.345 90.02 5.4 10
5.10 4.2 I' 1.996 2.013 1.344 90.00 5.402
8.106.7 2.001 2.017 1.348 90.00 5.440
I 1 .oo
9.0 'I 1.999 2.0 13 1.350 90.00 5.433
0 0 8()0 1.987 2.008 1.338 90.18 5.330
2.001.64 'I 1.995 2.016 1.341 90.09 5.392
3.262.7 1.999 2.109 1.346 Y0.07
4.00
4.26
3.3
3.5
:
'I

1.998
1.995
2.015
2.015
1.344
1.343
90.05
90.03
5.3OX
5.412
5.399
7.606.3
11.00 9.0
: 1.998
1.995
2.001
1.995
1.343
1.345
90.00
90.00
5.364
5.353
846

The effect of p-xylenc, flowing tinder pressure over ZSM-5. on the I;ittice pirratiieicrs i \
shown in fig. 2. The a and b parirmetcrs drop off wiih temperature while the decrease is les\
for c. The change in the unit cell volume for ZSM-5with SVAI ratios of 35 and I(X) is shown
in fipn 3; it also decreases with tempenturc.
The lattice parameters and unit cell volume at ambient-tempenture are higher than for
the unloaded sample. This is true for flow as well as static sorption. The interaction of the
sorbate with the framework and cations is evident from the changes in the MASNMR spectr;!
and the x-ray diffraction patterns.

i
0
g 2.00
C
Y

0
a,

cm T

I I

100
OI
I

200
0

300
P
400
'p
500
T(C)
Figure 2: Lattice Parameters of 11-ISM-5 Samples with p-Xylene Flaw as a Function of
Temperature for a Si/A1=35 and o Si/AI=100.

0 100 200 300 400 500

T (C)
Figure 3: The Volume of the Unit Cell of H-ZSM-5 Samples with p-xylene Flow RS n function
of temperature for 0 Si/AI=3S and o Si/AI=IOo.
 The effect of flowing benxne on the structure of ZSM-5at elevated temperatures is
shown in figure 4. The samples with SVAI ratios 35, 100 and 800 were run up to temperatures
200,425 and 525°C resp. The b arameter decreases at a greater rate than the a to 425°C for
d
the sample wilh SVAI ratio of 8 and the c parameter remains essentially constant. For the 35
and 100 SVAI ratio samples the a and b parameters decnase with temperature while the c
parameter remains relatively constant. The initial effect of benzene flow through ZSM-5 with
varying SVAI ratios causes an increase in the lattice parameters but not as large as for p-xylene.
The change in lattice pmmeters is significant as film distance are measured with a
resolution off 0.05 m m or 0.015"20 and lattice parameters determined to & .006mm.

0
2.01 -.
+
* *0 0
0

-+
I~
I+
0 100 200 300 400 500
T(C)

Figure 4: Lattice Parameters of fi-ZSM-5 with Benzene Flow Through as a Function of

Temperature for * Si/AI = 35,o SVAI = 100, + Si/AI = 800
The temperature at which the phase transition, monoclinic to onhorhombic, takes place
is lowered with gas flow and increasing temperature.
Benzene and p-xylene flowing over ZSM-5 at 12700 and 1270 Pa pnssures, resp. and
elevated temperature cause the phase transition, monoclinic to onhorhombic. Elevated
temperatures tend to decrease the lattice parameter and the unit cell volumes are reduced.
Whether this reduction is due to coking which was observed remains to be determined. It is
evident that ZSM-5with varying alumina content is in the onhorhombic phase under these
siniuhted catalytic conditions. Whether the lattice pmmeters ;ue related to catalytic activity is
not i I S yet known.

The effect of sorption and tcmpcriitun: as determined by x-ray diffraction confirms

MASNMR studies (3) of highly siliceous zeolites and extrapolates these results to lower SdAl
848

ratios which are in the catalytic range. As in the NMR studies, the effect of adsorption and
temperaturr on the ZSM-5 structure is characteristicof the sorbed molecule and also the A1
content of the zeolite. This work is proceeding with other sorbants and reactor conditions.
ACKNOWLEDGEMENT
We wish to thank Prof. E. Althaus and Dr. G.011, of the Institute of Mineralogy. for
the use of their x-ray diffraction equipment and valuable discussions.
G.T.Kokotailo wishes to acknowledge the Alexander von Humboldt U.S. Sr.
Scientist Award.
REFERENCES

(I) C.A. Fyfe. G.J.Kennedy, C.T. DeSchutter and G.T. Kokotailo. J. Chem. SOC.
Chem. Comni.. 541, 1984.
(7) G.W. West, Aust. J. Chem.. 37, 455. 1984.
(3) C.A. Fyfe, H. Strohl. G.T.Kokotailo, G.T. Kennedy and G.E. Barlow. J. Am.
Chem. Soc. in press.
(4) U.S. Patent, 3,702,886, 1972.
(5) A. Tissler, L. Riekert, G.T. Kokotailo. this volume.
H.G. Karge, J. Weitkamp (Editors), Zeolites as Catalysts, Sorbents and Detergent Builders
1989 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

ThE CYARACTERIZATION OF MODIFIED ZSM-5 CATALYSTS PREPARED V I A A

SOLID STATE REACTION FOR PROPANE AROMATIZFITION

YANG Yashu, GUO Xiexiari, DENG Maicun, WANG Limin and FU Zaihui
Dalian Institute of Chemical Physics, Chinese FIcademy o f Sciences
P.O. SOX 100, Dalian, P.3.CHINA

I.iESTRAZT
This paper dsscribes a simple method o f solid state reaction for preparation
o f Zn-, V o - , a;>d Cr-ZSM-5 catalysts instead o f ion exchange. NH,-TPD, I R , TPR,
ESR and UPS techniques x e r e used to characterize the interaction o f HZSM-5 with
Znn, %C1:.I and CrC.. ahich leads to introduction o f cations into the channels o f
zeo1i:cs. Zn-ZSM-5 is more active f o r propane conversion and gives the better
BTX selectivity. Over Mo-ZSM-5, propane mainly undergoes cracking into methane
a:id ethane, J X ~ the loading o f CrT’ o f ZSM-5 enhances the propar@ dehydrogena-
tion t o propsne.

iXTPODUCT1ON
The aromatiiation o f liqht hydrocarbons h a s been investigated since the
eal-ly ;;eventies ’. 1 - i ’ ) . Interest in studies of modified ZSM-5 catalysts for
propane aromatizatian was greatly stimulated by the Cylar Process jointly
developed by UC)P 3nd RP. in yeneral, the modified high-silica zeolites a r e
prepared via the introduction o f metal cations by meaiis o f an ion exchange.
This DrrJccss requires a lor,g period of refluwing in the ion-exchange solution,
:ghiih is iI!convenient in industry. Thus the introduction of metal ions into
higti-iilica . : e o I i t e s .via a s o l i d state reaction deserves attmtion from both
the.7retiral a n d zractical p o i r t s of view. Thjs paper dESCi-ihS the characteri-
z a t i o n of Zn, ?‘u and C r ior% introduced by a solid state reaction Ohto EdtiiJniC
t:a;is in 2 3 - 5 z ~ o iltes.
C~si Chemical and physical nethods such as T P D - W ~ ,
TPR, !a, ESR and XPS ;,Ere used. 4s the test reaction, propane aromatization was
c a r r i e d o u t in a fired--Sedpulse reactor.

EXPERIYFNT
M a T a 1a t 5
Catdly3ts of Z11(2.0wt%l-, Ma(3.5wtXI- and Cr(l.3vct%;-ZSM-5 wore prepared by
mixing and grinding the powder o f HZSM-5 (obtained f r o m Nan Gai University, SiOc/
A1.Ua=34) wjth ZnO, MoCl- and CrO-. respectively. CIfter pelleting, they were
crus’led t o 40-60 mesh aiid calcined 3% shown in Tab:e 1 .
850

TABLE 1 CATOLYSTS
Ka t e r i a l s Preparation Conditions
ZnO H e a t i n g a f Zn a c e t a t e a t 540C i n a i r f o r 6 h r
CrO:: H e a t i n g o f Cr(NOsr:., a t 550°C i n a i r f o r 4 h r
roc1:. Y9.99%
Zn/ZS#-5 Calcination of d m i x t u r e o f ZnOtHZSM-5 i n He a t 980nC f o r 1 h r
Zn/ZS?l-S(i) I o n e x c h a n g e o f 29 o f NH,,ZS?I-5 w i t h 2 0 0 ml o f 0.1M O F Zn(NO:,):..
s o l u t i o n f o r 16 h r a t 8O'.,C, t h o r o u g h w a s h i n g w i t h w a t e r t o f r e e
NO:,, d r i e d o v e r n i g h t a t l 2 O r ' C , c a l c i n e d i n a i r a t 540DC f o r 3 h r
Mo/ZSM-5 C a l c i n a t i o n o f a m i x t u r e o f MoCI:;+HZSM-J ii? Ar a t 450'X f o r 4 h r
Cr /ZSM-5 Calcination o f d m i x t u r e o f CI-C:,*ICSM-~i n s i r a t 54cS'T f o r 4 h r

F r o p a n e h a s 99.0% p u r e a n d f r e e d f r s m t r a c e s o f 0:: arid w a t e r p r i o r t o use.

CATFLYST C;H~RAC:TERIZATION
NH-.:-TPD NH-?-TPD s p e c t r a were measured w i t h a c c n v e n b i o n a l TP3 a p p a r a t u s .
About 0.29 o f s d s p l e m a t e r i a l w i s p l a c e d i n a q u a i t z r e s c t o i - a n d a d s o r p t i o n -
s a t u r a t e d by ptjlses o f dry ammonia a t lEO<'C. TPD *as c a r r i e d o u t f r o m 120°C
t o 5OO.C w i t h 3 h e a t i n g r a t e o f @ - 3 2 T / m i n arid w i t h H e ( 3 0 nrl/min) as t h e
c a r r i e r gas. . W e t o t a l NH., u p t a b e was d e t e r m i n e d b y a t h e r m a l c o n d u c t i v i t y
d e t e c t o r , c o l n p 3 r i n g tbe i r ? t e g r a t e d a r e a b e l o w t h e c u r v s w i t h t h a t o f a known
v o l m e o f NH3.
19 SPECTROSCCPY T h e s a m p l e s were p r e s s e d i n t o s e l f - s u p p o r t i n g wafers and
placed i n a quartz i n - s i t u I R c e l l . The s a m p l e s here p r e t r e a t e d a t 580'C i n He
(30 m l / a i n ) f a r 1 h r , evacu.ited a t 50rJr'C t o 10"" T o r r f o r 4 lir, c o o l e d t o 230r'C
and e x p o s e d t o d s a t u r a t e d v a p o r p r e s s u r e o f p y r i d i w o f 2rJ,C, a f t e r 1 h o f dd-
s o r o t i o n . t h e e x c e 5 s a c d w e a k l y a d s o r b e d p y r i d i n e was 1-evoked by e v a c u a t i o n a t
:he sime t e m p e r a t u r e f o r 30 min t~ S e l o w 10-" T o r r t a Ie3've only chmisorbed
pyi-idioe on the s u r f a c e . 1R s p e c t r a luere r e c o r d e d o n a Per t i ri-E 1rner 580
s;>ecCrometer .at r o o m t e m p e r a t u r e .
X-RAY PHOTOELECTRON SPECTROSCOPY XPS s p e c t r a * e r e r e c a r d e d o n a PHI 550
;pectrometcr u s i n g Al-K6 X-rays, b i r d i n g e n e r g i e s (EE) wer E! i o r r x t e d by
r e f e r e n c i n g t o t h e BE o f C,,, (?86.4 EV). Pie s u r f a c e a t o m i c r a t i o s o f S i , A I ,
a n d 21-1 were c a l c u l a t e d f r o m t h e i n t e G r a t e d XPS s i g n a l i n t e n s i t y c o r r e c t e d f o r
atomic s e n s i t i v i t y f a c t o r s " + ) . F o r t h e XPS s t u d i e s ? s e l f - s ~ ; p p o r t e dwafers were
l o a d e d i n t o a s t a i n l e s s steel h o l d e r and e v a c u a t e d t o lo-" Torr a t 25-500'-'C
f o r 1 hr.
TPR The TPR e x p x i m n t a l p r o c e d u r e u s e d :*as e s s e n t i a l l y s i m i l a r t o t h a t d e s -
c r i b e d by McNicol'r.". An i n - s i t u a d e o r b e n t t r a p h o u s e d a h e a d o f ttie r e a c t o r
was u s e d t o remove the l a s t traces o f H,JJ and O:.. From che c a r r i e r q a s .
 861

a b o u t 0.29 o f c a t a l y s t was p l a c e d i n a q u a r t z r e a c t o r , p r e t r e a t e d a t 590°C i n

d r y He (30 m l l m i n ) f o r 1 h r and c o o l e d i n He t o room t e r p e r a t u r e . The gas
s t r e a m was t h e n s w i t c h c d t o a mixture of 6% Ii,: i n Or b e f o r e r u n n i n g t h e TFR.
The f l o w r a t e of t h e r e d t i c i n 5 gas was 30 ml/cnin and t h e h e a t i n g r a t e was i6"C/
min.The t o t a l !ir:u p t a k e bas !neiisured b y i n t e g r a t i n g t h e a r e a below t h e c u r v e
and c a l i b r a t i n g w i t h a known volume o f He.
ESR SPECTROSCOPY T h e c a t a l y s t s a m p l e s (40-hO mesh) were l o a d e d i n t o a n ESR
t u b e , h e a t e d i n Ye o r a i r (30ml/min) a t 5O0-55OFC f o r 1 h r and t h e n e v a c u a t e d
a t the stlme t e m p e r a t u r e t o lo-.'' Tori- f o r 4h p r i o r t o ESR measurements. The ESR
s p e c t r a Hiere r u n on a JES-FEZSG s p e c t r o m e t e r a t 20-C. The g f a c t o r s f o r t h e ESR
s i g n a l were d e t e r m i n e d I - e l a t i v e t o DPPH w i t h g-2.0036.
CFITNYTIC KTIVITY y l s c m i c r o r e a c t o r was used w i t h 0.29 o f c a t a l y s t . Thi?
p u l s e volume o f 0.4Bml o f p r o p a n e was c a r r i e d through t h e c a t a l y s t bed by cle a t
a f l o w r a t e o f 35 ml/min. The c a t a l y s t was p r e t r e a t e d in He a t 580 C f o r 30 min
and 5OOrsC f o r 1 h r . R e a c t i o n p r o d u c t s u e r e a n a l y z e d o n l i n e u5iiv.l a gas chromato-
g r a p h w i t h a ttrermal c o n d u c t i v i t y d e t e c t o r . A porapak I) column programmed from
20 t o 200'>C N J S used , The e l u t i o : ) t i m e was a b o u t 60 min f o r Cv a r o m a t i c s .

RES!JL'TS FIN3 D I SCtJSS I Chi

I ) In/ZStI-J
NHv-TPD and IR s p e c t r o s c o p y ai-e t h e nost p o t e n t methods f a r i n v e s t i g a t i n g t h e
3 c i d p r o p e r t i e s o f ZSM-5 t y p e z e o l i t e s . T y p i c a l TPD p a t t e r n s o n HZSM-5 and Zn/
E M - 5 a r e shown i n F i q . 1 . T h e r e 31-8 two p e a k s o f t h e 1 ( o r @aboLt 220°C) and h
( o r l a b o u t 430eC) s t a t e s , i n acjreement w i t h Topsfie e t a l . ( * ' . The amounts o f NH,:
d e s o r b e d froin t h e s e c a t a l y s t s arid t h e rlraxima t e m p e r a t u r e s a r e summarized i n
T a b l e 2.

TASLE 2 NH.!-TPD RESULTS

Cat a 1 y s t H2SM-5 Zn/Z5M-5

Max imum load ii-q (mmo 1/g 1 0.92 0.90
FIctual loadingOnmol/g) 1.37 1.10
Peak maxima (T,."C)
1 215 229
h 439 lt30
% a r e a under t h e peak
1 53 63
h 47 37
852

100 200 300 400 500 600

TEMPERATURE ["C]

-- Figure 1 TPD spectra of NH3 desorbing from HZSM-5 and ZnnSM-5;

B = 8'Umin.
1 1 1 1 1 I 7

w
x
4
k
3
n
I

1900 3500 1600

--
I
I \
I,/
I
, 1 1 1
--
1 1

400 600 800

WAVENUMBER [crn"] TEMPERATURE ["C]

Figure 2 IR spectra, obtained at 2O"C, Figure 3 TPR spectra of ZnO and

of HZSM-5 and ZnRSM-5 ZnRSM-5
(a) evacuated at 500°C, 0 = 16"Umin; sample
followed by pyridine ad- weight: 0.2 g;
flow rate of H Ar
sorption at 2OO"C, then gas mixture: &rnl/rnin.
evacuated at (b) 200"C,
(c) 450°C.
 853

The NHS TPD r e s u 1 t s . m t h e a b o v e c a t a l y s t s show t h a t ( 1 ) t h e t o t a l NH3 u p t a k e

&a5 lowered by 20% on Zn/ZSM-5 w i t h t h e h p e a k b e i n g p r e f e r e n t i a l l y d e c r e a s e d
rathec- t h a n t h e 1 peak. ( 2 ) t h e Tm o f t h e 1 peak i n c r e a s e d and t h a t o f t h e h
peak d e c r e a s e d by 5 c C o n Zn/ZSM-5. I R s p e c t r a on Zn/ZSM-5 and HZSM-5 are shown
i n Fig.2a.. The i n t e n s i t i e s o f t h e b a n d s a t 3600 cm-' and 3740cm'-l a r e l o w e r on
Zn/ZSM-5. When p y r i d i n e was a d s o r b e d and e v a c u a t e d a t 20OC8C, t h e 3600cm-1 band
d i s a p p e a r e d more q u i c k l y t h a n t h e band a t 3740cm-' , and new b a n d s a t 1 5 4 3 ~ m - - ~
( B r k n s t e d a c i d s i t e s ) , a t 1455cm-'(Lewis acid sites ) rnd a t 1 4 8 8 c r n - ' ( t o t a l acid
s i t z s ) appeared a s shown i n F i g 2b. The r e s u l t s o f p y r i d i n e a d s o r p t i o n a r e sum-
m a r i z e d i n T a b l e 3. T h i s shows t h a t t h e i n t e n s i t y c f I , at: 1543 cm-'' was
lowered f r o m 6.21 on HZSM-5 t o 3.30 on Zn/ZSM-5, avd I l . a t 1455cm.' was i n -
c r e a s e d c o r r e s p o n d i n g l y f r o m 1 . 3 6 t o 3.85 w i t h l i t t l e l o s s o f t o t a l a c i d s i t e s
a t 1WBcm-l.

TABLE 3 IR INTENSITIES OF PVRIDINE ADSOSPTION

Cata l y s t HZSM-5 7n:ZSM-5

Evacaat ion t e m p e r a t u r e 230 450 ?00 450

1, 1.36 3.39 3.05 1.21

1l./:* 4.57 6.46 0.86 1.CG

NH.,-TPD and I R s t u d i e s o f t h e a c i d i c p r o p e r t i e s o f Z5M-5 z e o l i t e s h a d e b e e n

d e s c r i b e d i n v a r i o u s ~ a p e r s ( ' ~ - ~ 'I .t is w ? l l known t h a t the a c t i v e a c i d s i t e s
a r e c h a r a c t e r i z e d by ~n IR bar:d a t 3600 c m ' ' arid d d e s o r p t i o n peak o f t t : e h o r r
s t a t o a r o u n d 670-770k. Weaker a c i d s i t e s a r e c h a r a c t e r i z e d by a 3724-3740rm.'
band w h i c h i s c o r r e l a t e 9 w i t h d e s o r p t i o n o f YlW, a t a h o u t X O I : f o r t h e 1 01' 0
state. The Si-OH-Rl g r o u p s a t 3hDOcm-* arid thF? hvdro.cy1 group:; a t 3 7 2 0 c 1 n - ~i r e
shown t o b e B r t n s t e d a c i d s i t e s . T ~ EI R and NH..-TPD e:!perini;+ntal results des-
c r i b e d a b o v e a g r e e i n i n d i c a t i n g t h a t the Br.#risted a c i d s i t e s on HZSII-5 r e a c t
w i t h Zinc ions, i.e, t h e Zne' ions s e l e c t i v e l y r e d u c e t h e number o f s t r o n g a c l d
s i t e s , and c h a n g e t h e a c i d d i s t r i b u t i o n , l , - / I , . , and T,, as w e l l .
TPR and XPS d e s c r i b e t h e 280 d i s t r i b b t i o n i n t h e channels o f ZSM-5 z e o l i t e s .
The a f f e c t o f Z n z e o l i t e i n t e r a c t i o n on t h e TPD p r o f i l e o f n o n - s u p p o r t e d ZnO
and s u p o r t e d 2-10 i r e shown in F i g . 3 , and the t o t a l Ii!>u p t a k e i s s u n r n a r i z e d i n
T a b l e 4. The t o t a l HI* u p t a k e d u r i n g TPR is much h i g h e r o n Zn/iSM-5 t h a n c n ZnO
f o r which t h e r e l a t i v e r e d u c i b i l i t y is 5.4%. T h s H:; t i p t a k ~ so n t h e 2nIZSM-5
c a t a l v s t s a r e n e a r l y c o n s t a n t f o r d i f f e r e n t Zn l o a d i n g s f;-on 0.4 t o 2.0% a r d f o r
catalv5t5 prepared hv ion exchange. This implies that ZnO is widely dispersed in
the channels o f the zeolites. Measurements of H, consumption indicate that the
TABLE 4 TPR" DATA F3R ZnO AND Zn/ZSM-J

Sample Zn(wt%) pretreatment peak temp. He uptake re1 at i ve

1.7I T" ,I mmol/q-Zn reducibility X
ihO 80.3 S40r,C,Air,6 hr 386 675 0.14 5.4
Zii/ZSM-S 2.3 58OC'C!He, 1 hr 347 623 2.55 100
ZnIZSM-5 0.4 580"C,He, 1 hr 515 700 2.26 88.6
L'n/XM-SD 3.L 540°C. a i r 420 680 2.37 09.R
( a ) sample weight 0.29
( t ) prepared b y ion exchange method

extant o f reductioii o f Zn". to Zn is abaut I & % , i.e. it is lot4 charge density

of Zn+-' ions and n o t Zn metdl that are formed during 7PR . The TPR profile of
MI exhibits trio peaks: low temperature peak T m j o f 386% attributes to
easily reduced senall particles, and h i g h temperature peak T,,+: of 675 C rslates
60 large particles mors difficult to reduce. The low teniperature peak. rapidly
decrca?;es f o r ZilO supoorted on ZSM-5 zeolites, when the 211 loading is reduced
fr.om 2.0 to O.G%, the tiiqh temperature peak splits into two and the low terrpera-
t L r e pc;k disappears. The change in the TPR profile is due ta an interaction
between Zn iors and the zeolites on ZnIZSM-5 which gives rise to the high
reducing temperature around !r20-70O0C.
%PS XPS data are listed in Table 5. These show that the surface Si/Al ratio
of H X M - 5 is higher than the n m i n a l hulk composition o f S i / A l =17, and that
this surface Si/P1 ratio increases from 25.0 to 30.3 Khen the evacuation tem-
p e r a t u r e is increased from 25°C t a 500'.C. This suggests that thare is a loss
nf 5urface A i atoms from tiZSM-5 under v d c w m even at 25lSC, end this 105s is
increased at elevated temperatures. En Zn/ZSM-S, the surface Si/Al r a t i o shows
only a modest increase t o 19.2 after eracuation at 2S"C and to 2G.4 dfter L'VI-

c t l J t i o n at 500°C. The higher eracuation temperature causes increases in t h e

Zn/51 and Zn/Al ratios from 4.BxlO-e to 6 . 7 ~ 1 0 -.md
~ 0.92 to 1.37 respectively.
The Zn/Si and Zn/A1 data from Zn/ZSM-5 is further evidence that the solid state
reaction of HZSM-5 w i t h ZnO causes the migration of Zn ions from the outer stir-
face into the chanriels of the zeolites even at room temperature, with more
extensive migration at the hipher temperature. Zn ions located near R 1 atoms
protect the A1 atom; f r a m escaping from the surface.
CATALYTIC K T I V I T Y The catalytic activity for propane conversion is Shown in
Tabje 6. This shows a higher activity and selectivity for propane aromatilation
on Zn/ZSM-5 prepared either by sol id calcination or liouid ion-exchange, than
 855

200 400 600

TEMPERATURE ["C]

Figure 4 TPD spectra of NH3 desorbing from HZSM-5 and MoESM-5;

fl = 32'Umin.

gl'= 1.99

100G
H-
H

Figure 5 ESR spectra of M o (V)at 20°C; Figure 6 ESR spectra of Cr (V);

mixture of H-ZSM-5and MoC15 CrESM-5 calcined in He at
calcined in He at 450°C. (a) 500°C. (b) 550°C
856

on HZSM-5. Zn ions enhance the rate of dehydrogenatioi of propane and t.he

transformation of intermediates into aromatics. With regard t o Zn state and
Zn*'-ZSM-5 bifunctional action on Zn/ZSM-5 catalysts will be discussed elss-
where (:C).
TC\BCE 5 XPS CATA

~ ~~ ~~ ~ ~~
~~

Ca tal yst H-2SM-5 ;7n/ZSM-S

E v a c . Temp.( C ) 25 500 25 500
El. ( O v : , e v ) 532.8 532.1 532.0 532.0
En (4lry. , e v ) 74.c 74.4 74.3 74.4
Es (Sir:,. ,av) 103.6 103.2 103.0 iC3.1
Et. ftnTw , e v ) 1021.5 1021.3
E,,,, :Zn,ev) 503.3 502.9
Surface atomic ratio
O/Si 1.91 1.84 2.13 I .91
Si/FI1 25.0 30.3 13.2 20.4
Z d S i ( x lo+) 4.8 6.7
Zn//S: 0.92 1.37

Catalyst H-2SM-5 Zn/ZSM-5 Mo/ZSM-S C r IZSM-J

?I (at % ) 2.0 1.5 1 * 5 4 < i , 3.5 1.3
Coiiversion(C%) 17.4 96.4 79.9 81.4 70.4 16.5
BTX se1ec.X 27.1 50.7 42.0 37.1 a.6 3.6
Producu t d i 5 tr ihu t ion(C% )
methane 16.8 14.4 17.0 i7.0 33.7 .
I 9

e thy1 ene 24.5 1.1 1.7 1 .D 3.b 13.9

ethane 11.3 27.5 36.0 42.0 54.3 1.9
propyl ene .-.. 2.0 1.5 1.2 -..- ?O.?
bu tene 2.6 --.. 1.0 --.- - - _ I
0.b
butane 15.8 _....I 0.4 0.9 1.2 4.2
C!,.. 1 .b 3.3 ---- 0.4 3.1 - ---
benzene 8.7 39. I 30.6 28.3 h.7 1.8

toluene 13.1 10.E 11.0 8.2 1.3 1 .r7

xylmes 5.3 0.8 0.4 0.6 0.6 0.6

a. 0.29 catalyst calcined at 580C for 0.5 hr in He prior- to r e a c t i o n :

Reaction Temp. 500C, flow rate o f He 35ml/rnin. (except f o r Znc,, )
 867

2 ) Mo/ZSM-5 and Cr/ZSM-5

ESR s p e c t r a h a v e b e e n a p p l i e d t o s t u d y t h e s o l i d s t a t e r e a c t i o n o f h i g h -
si1:ca z e o l i t e s w i t h t h e compounds o f MoCl?. a n d CrOo"l'. Calcination of a
m i x t u r e o f MoCI,; and H%SM-J(in He), CrOn and HZSM-5 ( i n a i r , f o l l o w e d b y
e v a c u a t i o n ) r e s u l t s i n t h e a p p e a r a n c e o f i n t s n s e e.5.r. s i g n a l s of M o ( v )
( g =1.93, g =1.89) and C r ( v ) fg=1.967) shown i n F i g . 4 a n d F i g . 5 r e s p e c t i v e l y .
NH,,-TPD s p e c t r a shown i n F i g . 6 i n d i c a t s s t h a t t h e h i g h t e m p e r a t u r e p e a k is
very weak o n M o C S M - 5 . I t is b e l i e v e d t h a t t h e r e a c t i o n b e t w e e n HZSM-5
and M C C I , ~ , Cr03 i n t h e s o l i d s t a t e l e a d s t o t h e i n t r o d u c t i o n o f M o ( v ) , C r ( v )
ions onto c a t i o n i c p o s i t i o n s o f the high-silica zeolites. The h i g h t e m p e r a t u r e
treatment of Ci-/ZSM-S shows t h a t t h e b i n d i n y o f C r ( v ) t o c a t i o n p o s i t i c n s o n the
z e o i i t e framework is s t r o n g e r t h a n t h a t o n t h e s u r f a c e o f s i l i c a - a l u m i n a because
c a l c i n a t i o n o f :he a i x t u r e (HZSM-S+CrO.,) a t 550-C i n a i r l e a d s t o a c o n s i d e r a b l e
d e c r e a s e i n t h e i n t e n s i t y o f t h e e.5.r. s i g n a l o f c r ( v ) i o n s and t h e a p p e a r a n c e
of hyperfine s p ! i t t i n q (h.f.s.) a s shown i n F i q . 5 . In h i g h - s i l i c a zeolites the
A t atoms a r e h i p h l y d i l u t e d j n t h e z e o l i : e framework, and t h e d i s t a n c e b e t w e e n
+ +
A 1 atonis is l a r p e . T h e r e f o r e , i t is s u a g e s t e d t h a t i t is CrOn, M o C l , a n d n o t
j s o l a t e c ! i o r . 5 ( C I - ~ + , Mo5:,') t h a t are coordirated t o t h e z e o l i t e c a t i o n i c posi-
tions. t is t h e c o o r d i n a t e d C r ( v ) , V o ( v ) large molecc;lcs t h a t s h i e l d s acid
s i t e s r:eecled f o r o l i g o m e r i z j t i o n and c : ~ c l l z a t i o n , a n d l e a d s t o a low s e l e c t i v i t y
f o r DrGpane a r o m a t i z a t i o n and a 9 i g h a c t i v i t y f o r p r o p a n e c r a c k i n g o n Mo/ZSt?-lj
and p r o p a n e d e h ~ ~ d r o g e n a t i oonn Cr/XM-5, as shown i n TPblc- 6.
Evidently, t h e Dossibilty o f c a t i o n introduction i n t o high-silica zeolites
by a s o l i d s t a t e r e a c t i o n is d e t e r m i n e d by p h v s i c a l p r o p e r t i e s o f metal o x i d e s ,
s u c h as m e l t i n g p o i n t , s u b l i m a t i o n p o i n t , e t c . and t h e p r u s e n c e of a c i d c i t e s On

z e o l i t e s kchirh may b e c o n r i d e r e d 9 s p o w e r f u l t r a p s f o r t h e m i g r a t i n g CatiJii5.

S i n c e PioCI,, : 2 t B * ' C ) and C r O n ( 1 6 7 ° C ) a r e low-me1 tii-q-point-compounds, ion-

z r c h a n p takes p l a c e s m m t t i l y iii the c o n d i t i o n s of c a l c i i m t i o n of t h e ini*tur€
1-1;5;1-5 + mctal-ccmpounds s t a b o v e 500 C. The m e l t i n g poin! o f 3 0 is h i g h
(1978"'C). P ~ o t h e rf a c t o r i s r e p o r t e d t o e x p l a i n t h e ion-exchange
o c c u r e d i n the m i x t u r e HZSM-5 + ZnO t h r o u g h s o l i d s t a t e r e a c t i o n a b o v e 500 c.

REFERENCES
1. S.M. C s i c s w y , J. C a t a l . 17(1970)207
2 , M . S . SCLJlfell, Appl. C a t ; l l . 32(1987)1
3. J.A. J o h n s o n a n d G . K . Miller, P a p e r OM-84-45, NFRA Rrin. M e e t i n g , March 1904,
San O n t o n i o .
4. C.D. W a ~ n e r , L.E. Davis, V.V. Z e l l e r , J.A. T a y l o r , R.H. Raymond a n d L.H. Gale,
 Surface and Interface Analysis 3(1981)211
5. B.D. Mcnicol, J. Catal. 46(1977)438
6. N.Y. Topsoe, Karsten Pedersen, and E.G. Derauane, J. Catal. 70(1981)41
7. J.R. Anderson, K. Foger, T. Mole, R.A. Rajadhyaksha, and J.V. Sander,
J . Catal. 50(1979)114
8. K.H. Rhee, V.U.S. Rao, J.M. Stencel, G . A . Melson and J.E. Crawford
ZEOLITES 3 (19833337
9. E.M. L o k , B.K. Marcus, and C.L. Angell, ZEOLITES 6(1986)185
10. Y.Yang, Fu Zaihui and Guo Xiexian, submitted to J. Catal.(chinese)
1 1 . A.V. Kucherov and A.A Slinkin, ZEOLITES 7(1987)38
12. Y.Yang, Fc; Zaihui, Wang Limin, Deng Maicun and Guo %iexian, submitted to
J. Catal. (Chinese)
 859

AUTHOR INDEX

A
Andreev, A. 315 Coudurier, G. 61 5
Auroux, A. 377 Coughlin, P. K 1
Aust, E. 49 5
D
B Decyk, P. 305
Ball, W. J. 271 Deng, M. 849
Barlow, G. E. 827 Derewinski, M. 305
Barthomeuf, D. 429 Dimitrov, C. 91
Beck, I. 469 Doyemet, J. Y. 153
Beer, M. 469 Ducarme, V. 615
Bekkum, H. van 519 Dwyer, J. 39,271
Ben Taarit, Y. 377
t
Beran, 5. 347
Echoufi, N. 377
Beyer, H. K. 635 Ernig, G. 495
Bezouhanova, C. 91 Erneis, C. A 365
Boddenberg, B. 533 779
Endoh, A.
Borbely, G. 635
Bragin, 0. V. 143 F
Fajula, F. 61
Bulow, M. 505
Burrneister, R. Fiedler, K. 439
533
Figueras, F. 61
C Forster, H. 355,545,575
Caro, J. 505 Frede, W. 545
Carson, R. 39 Freude, D. 42 1
Cartlidge, 5. 389 849
Fu, 2 .
Catlow, C.R.A. 409 Fyfe, C. A. 827
Chang, N. 5. 223,231
Chao, K. 1. 19 G
Garforth, A. A. 271
Chen, C.C. 223
23 1 Geerts, H. 72 1
Chen, L. Y.
Chen, P. Y. 223,231 Gies, H. 827
223,231 Giordano, G. 281
Chu, 5. J.
Chu, Y. F. 749 Girrbach, U. 399
223,231 Gnep, N. 5. 153
Chuang, T. K.
Grillet, Y. 625
Colbourn, E. A. 409
Cooke, E. M. 39 Grobet, P. J. 72 1
Cotterman, R. L. 389 Grodzicki, M. 575
 860

Groenenboom, C.J. 99 Kornatowski, J. 567

Guisnet, M. 153 Krings, P. 70 1
Guo, X. 849 Kubelkova, L. 347
Gutsze, A. 567
H L
Haas, J . 295,337 Laktit, A. 469
Haber, J. 305 Lambret, M. 61
Harris, I.M. 271 Laniecki, M. 2 59
Hashimoto, K. 48 5 Lechert, H. 29,91
Hilgert, W. 49 5 Leonhardt, W. 69 1
Hinchliffe, A. 39 Lercher, J. A. 585
Hoelderich, W.F. 193 Leslie, M. 409
Howes, M. L. 389 Leu, L. J. 19
Huizinga, T. 365 Li, Huong-Xin 735
Hulsters, P.De 759 Lillerud, K. P. 769
Hunger, M. 42 1 Lin, D.H. 615
Huybrechts, D. R. 163 Liphard, M. 673

I M
Ignatzek, E. Macedo, A. 115
315
Iliev, V. Mallmann, A. de 429
315
Inoue, K. Marcilly, Ch. 115
80 1
Martens, J.A . 49,72 1,735
J Masuda, T. 485
Jacobs, J. M. 163,211 Mavrodinova, V. 29
Jacobs, P. A. 49,163,211,721,735 McAteer, C. H. 27 1
Jacquinot, E. 115 Mentzen, B. F. 477
Jentys, A. 585 Mersmann, A. 62 5
Jiru, P. 281 Mbsztiros-Kis, A. 251,711
Johnson,J. A. 45 1 Miasnikov, P. 63 5
Minachev, Kh. M. 143
K
Minchev, Ch. 29
Kallo, D. 241,711
Monaci, R. 595
Kanazirev, V. 29
Morbidelli, M. 595
Kawase, M. 485
Mroczek, U. 81
Kennedy, G. J. 827
Mucsi, Gy. 71 1
Keweshan, C. F. 749
Muhl, J. 469
Kim, J.-H. 71
Muller, U. 399,625
Kiricsi, I. 3 55
Myrdal, R. 327
Kokotailo, G. T. 82 1,827,843
Kolboe, St. 327
 861

N Rombi, E. 595
Namba, 5 . 71 Rouquerol, F. 625
Nanne, J. M. 365 Rouquerol, J. 62 5
Nastro, A. 28 1 R6zsa, P. 635
Nenova, V. 91 Rozwadowski, M. 567
Nishimiya, K. 779 5
Novakova. J. 347 Sax, 8.-M. 69 1
Schirmer, W. 439
0 Schmidt, F. 735
Occelli, M. L. 127 Schollner, R. 81 1
Olah, 1. 71 1 Schubert, 5. 735
O'Malley, P. J. 39 S~h~lz-Ekl~ G.f f , 315
Onyestyak, Gy. 241 Schwuger, M. J. 673
Ooteghem, H. v. 21 1 iebik, R. 347
Oroskar, A.R. 45 1 Shamshoum, E. 5. 1
P Shi, Z.C. 377
Pan, Dongfeng 62 5 Shpiro, E.S. 143
Papp Jr., J. 241,711 Siegel, H. 81 1
Parton, R.F. 163,211 SmieSkov6, A. 347
Pasztor, C. T. 827 Solinas, V. 595
Pellet, R. J. 1 Spaeth, G. 533
Penchev, V. 29 Stach, H. 439
Peters, G. 545 Steinberg, K.-H. 81,421
Pfeifer, H. 42 1 Steinwandel, J. 295,337
Philippaerts, J. 555,759 Stencel, J. M. 127
Plog, c. 295,337 Stocker, M. 769
Polanek, P. 399 Stork W. H. 1. 365
Post, M. F. M. 365 Strobl, H. 827
Suckow, M. 439
R
Raatz, F. 115 T
Rabo, J. A. 1 Takaishi, T. 779
Rees, L.V.C. 66 1 Tasi, Gy. 355
ReiB, G. 607 Tielen, M. 49,72 1
Riekert, L. 82 1,843 TiBler, A. 399,82 1,843
Rohl-Kuhn, B. 505 Tkachenko, 0. P. 143
Roeher, F. 81,421 Trautwein, A. X. 735,789
Roland, E. 645 Trifir6, F. 28 1
862

Tsutsumi, K 779 W
Tuleuova, G. J. 143 Wang, L. 849
Tvarurkova, 2. 281 Wichterlovd, B. 347
TupB, M. 281 Wisniewski, K.E. 567
Wohrle, D. 315
U
Y
Unger, K.K. 399,625
Yan, Y. 555,759
Upadek, H. 70 1
Yang, Y. 849
Yashima, T. 71
v
Yoshida, A. 80 1
Valyon, J. 251
Vansant, E. F. 555,749,759 2
Vasina, T. V. 143 Zaikovskii, V.I. 143
Vedrine, J.C. 61 5 Zakharieva-Pencheva,0. 575
Verbiest, J. 759 Zibrowius, B. 505
Vetrivel, R. 409 Ziethen, H. M. 735,789
Voogd, P. 519 Zidlek, M. 305
 863

SUBJECT I N D E X *

A
Ab initio calculations 409 -,AlP0,-5 625
Acetophenones, shape ,-based catalysts 1
selective formation of 163 Anisole 21 1
Acetylacetone 72 1
Aromatic, skeletal
Acetylene 24 1 rearrangementsof 1
Acidity 19,39,305,377 Aromatic hydrocarbons 495,505,843
Active centers 29 Aromatisation 91,271
Acid sites 389,409,485,585 -, of alkanes 143
Acylation 163 -, of propane 849
Adsorption 439,451,469,585,
595,811,843 B
- of aromatics 843 Basicity 429
-,calculation of Beckmann rearrangement
potentials of 567 of anilines 193
-, concentration dependence Benzene 533
of coefficients 495
-,adsorption of 585
-,dynamics of 115
Beta 115
-,gas chromatigrophic
investigation of 545 Bifunctional catalysis 49,153
-, heats of 779 Bimetallic pentasil catalyst 143
-,isotherms 567 Boron-nitrogen compounds 555
Brensted acidity 409
-I technica processes
Of of 439 Builder systems 673
-, pressure swing 607 Butane, conversion of 271
-,selective 645 Butene, conversion of 27 1
-, theory 439
-,vacuum swing 607
C
Alkaline X and Y zeolites 595 ,C
, olefins 281
Alkyl amines 193 C, aromatic isomerization 347
Al kylation 71,211 Calorimetry 377
-, of aromatics 163 Carbocations 355
-, of aromatic amines 193 13C NMR 505
-,of heteroaromatics 193 Chemical vapor deposition 749
-, of phenolic compounds 163 Chiral hydrogenation catalysts 163
2 7 ~ MAS
1 NMR 271,721 Chromatographic experiments 495
Aluminas 99 Clinoptilolite 71 1
Aluminophosphate 39 Clay 163

* Note:
page numbers refer to the first page of the respective contribution
864

co 429 F
Co(ll)-phthalocyanine,
NaX encaged 315 FAPO-5 735
Co-builder 70 1 Faujasite 115,429,533
Computer simulation 769 Faujasite-typezeolites 789
Concentration dependence 495 -,as adsorbents 451
Cresol formation 223 Ferrierite 71
C rystaI Iite size 615 Fire retardant materials 635
Crystallinity of zeolite catalysts 127 Fluidized cracking
catalysts (FCC) 99,127
Cyclocondensations 193
Fries rearrangement 163
D FTIR-PAS 759
Dealumination 61,377, 389, G
645,72 1,769
-,effect on adsorption GalH-ZSM-5 catalyst 153,271
on ZSM-5 567 Galliation 779
-, Of ZSM-5 567 Gas chromatographic investigation
Degradation model 81 1 of adsorption states 545
Dehydrosulphurization 305 Gas oil 469
Desorption 477 Gas sorption 555,759
Diels Alder synthesis 163 Gibbsite 63 5
Diffusion 505,519,615 H
Diffusion coefficients 495 Heat conductivity 635
Diffusivities 533 Heating plants 295
Dimerization 91 Heats of adsorption 779
Disilanation 759 Hexadecane cracking 389
Disproportionation 61 n-Hexane, conversion of 365
DTA 80 1 High resolution adsorption 625
E H-mordenite 759
Enzyme mimic 163 2HNMR 505,533
EPR spectroscopy 315,735,789 Hydration on transition
metal zeolites 241
Erionite 39,81,421,769
- of acetylene 24 1
-, as adsorbent 451
Hydrocarbons, transformation
Ethanethiol 305 into carbocations 355
-,oxidation of 315 Hydroconversion 81
Ethylation 61 Hydrogen 545
Ethylbenzene dehydrogenation 19 Hydrogenation activity
Ethylbenzene oxidation 315 of nickel 347
Exhaust emission 295,337 Hydrogen transfer 115
Hydrothermal stability 127,801
Hydrothermal treatment 81 1
 865

Hydroxyarenes, oxidation of 163 Metathesis 2 59

Hydroxylation 163 Methylation of toluene 485
Hydroxyl groups 42 1 Methylnaphthalene isomers 595
H-zeolites 749 3-Methyl pentane 519,615
H-ZSM-5Zeolite 91,485,519 MFI structure 365,505
-.
acid sites of 585 M FlIsorbate systems 477
MlBK synthesis 23 1
I
Microcalorimetry, acidity
Infrared spectroscopy 39,355,365, measurements by 377
429,545,585
Mo (n-C H I,
, reaction
-, of hydration on transition withk-t 251
metal zeolites 241
Model of degradation 81 1
-,of Mo-fixed HY 251
Model reactions 153
Intermediates of
aromatization 91 Modeling of technical
separation processes 439
Intracrystal line diffusion 485
Modified ZSM-5 223,231
Ion exchange 66 1
Mossbauer spectroscopy 735,789
Iridium /zeolite X catalysts 327
Mo IHY 251
Iron carbonyls 789
Mo 1 H-ZSM-5 catalyst 27 1
IR spectroscopy 39,355
Molecular dynamics 533
lsomerisations 193
Molecular orbitals 39
lsomorphoussubstitution 365
Molecular sieves 439,607
L Molybdenum carbonyl 2 59
Laser Raman spectroscopy 127 Mordenite 16,81,533
Lattice structure 42 1 -,as adsorbent 45 1
Laundry detergent 673 Mullite and orthovanadates
Liquid detergent 69 1 formation 127
Low temperature m-xylene conversion 29
microcalorimetry 625 N
LZ 132 zeolite 281
n-Alkanes 81
M n-Hexane 519
Mass spectroscopy 789 Nickel incorporation 347
Mechanism, of alkylation of NiHZSM-5 catalyst 347
phenolic compounds 163
Nitrogen-containing organic
-,of aromatization of intermediates 99
propane and propene 153
Nitrogen oxide removal 295
-, propylene, ethylene and
methanol reaction Nitrous oxide 575
over LZ 132 281 NMR spectrometry 271,421,469,827
Metal doped zeolites 295 -, of '3c 505
Metal traps 99 -,of2H 505,533
Metha no1transformation 281 Nobel metal doped zeolites 337
866

NO, selective reduction of 327 Precursor gels 66 1

NO, pollution control 327 Pre-injection of water 80 1
0 Pressure swing adsorption 607
1,7-0ctadiene, conversion of 271 Probe molecules in
microcalorimetry 377
'*O-exchange 779
2-propanol 91
Offretite 61,769
Propane, aromatization of 153
Olefins 533
Propene 91
-,skeletal rearrangementsof 1
Oligomerisations 193 Q
Omega 115 Quadricyclane norbornadiene,
valence isomerization of 315
O/N replacement reactions 193
Quantum chemical calculations 575
Optical brighteners 673
Quantum mechanical calculations
Oxidaton reactions 193 of acidic properties 409
-,of hydroxyarenes 163 R
Oxygenates 163
Rietveld refinements 477
Oxygen-containing substrates 163
Resins, comparison with
Oxygen, separation from air 607 zeolites 45 1
P s
Palladium / ZSM-5 23 1 SAPO-5 19
Paraffins, skeletal -, catalytic activity of 29
rearrangements of 1
-, comparison with
n-Paraffins, extraction of 439 dealuminated H-Y 29
Paraffin isomerisation 49 Secondary building units 39
Parex, separation process 439 Selective extraction 439
Particle size 69 1 Self-diffusion 505
Phase transition 82 1 Separation of
Phenol 21 1 methylnaphthalenes 595
-,methylation of 223 Separation technology 439,451
Phenolic compounds, Sewage treatment 71 1
alkylation of 163 Shape selective catalysts 163,749
Photoacousticspectroscopy 555 Shape selectivity 71,163,399,485
Phosphate 701,711 Shaping of zeolite materials 645
Platinum /zeolite systems, MAS NMR 271,721
acidity and basicity of 429
Si incorporation 19
-,state of Pt in 143
SIMS 337
PoIyca rboxylates 673,701
Solid-state NMR 769
Pore-opening reduction 749 Solid-state reactions
Potential energ in zeolites 347,849
distribution [AAP) 625 Sorbex, separation technology 451
PdRSM - 5 231
Sorption 519,827
 867

Sorption complex 575 2

Spillover 81 Zeolite A 545,661,673,691,701
Statistical thermodynamics 545 -, as adsorbent 45 1
Steaming 389 -, heat conductivity of 63 5
Storage test 69 1 Zeolite BETA 49
Structure modification 555,759,843 Zeolite CSZ-1 389
Structure stability 39 Zeolite/Fe (111)
Surface analysis 337 composite material 71 1
Zeolite L, as adsorbent451 45 1
T
Zeolite mordenite 555
Technical white oil 469
-, as adsorbent 45 1
TPD, of NO from I r o n
X-zeolite 327 Zeolite NaA 645
Template-free zeolite Zeolite NaY 645
synthesis 399 Zeolite Omega 115
Thermal analysis 735 Zeolite Ultrastable Y 21 1
The r ma I stab iIit y 127 Zeolite X 305,661
Terminal silanol groups 749 -, heat conductivity of 63 5
Thermogravimetry 615 Zeolite Y 49,259,305,595,721
Theoretical studies -,hydrogen form, reaction
of zeolite acidity 409 with Mo (n-C,H,), 49
Three-way-catalyst 337 Zeolite ZSM-3 49
Time-resolved XRD 477 Zeolite ZSM-5 71,211,223,305, 399,
Transition metal forms 575 61 5,625,645,779,821,843,849
Trimerization 91 -, as adsorbent 45 1
-,characterization by IR 585
U
-,control of catalytic
uSY 80 1 activity of 399
-, catalytic activity of 21 1 -, large crystals of 567
UV-VIS spectroscopy 355 - modified by alkaline 231
-,tem late-free
W
Vacuum swing adsorption 607
E
synt esis of 399
Zeolite ZSM-1 1 71,211,779
Vanadium contaminants 127
Zeolite ZSM-20 49
VGO cracking 115
Zeolite 13X 469
Viscosity 69 1
Zeolites, commercial
W importance of 645
Waste water 711 Zeolites, production
technology of 645
X
XRD 80 1
X ray photoelectron
spectroscopy 127,143
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 8 69

STUDIES IN SURFACE SCIENCE AND CATALYSIS

Advisory Editors: B. Delmon, Universit6 Catholique de Louvain, Louvain-la-Neuve,Belgium

J.T. Yates, University of Pittsburgh, Pittsburgh, PA, U.S.A.

Volume 1 Preparation of Catalysts I.Scientific Bases for the Preparation of Heterogeneous

Catalysts. Proceedings of the First International Symposium, Brussels, October 14-
17,1975
edited by B. Delmon, P.A. Jacobs and G. Poncelet
Volume 2 The Control of the Reactivity of Solids. A Critical Survey of the Factors that
Influence the Reactivity of Solids, with Special Emphasis on the Control of the
Chemical Processes in Relation to Practical Applications
by V.V. Boldyrev, M. Bulens and B. Delmon
Volume 3 Preparation of Catalysts 11. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Second International Symposium, Louvain-la-Neuve,
September 4-7, 1978
edited by B. Delmon, P. Grange, P. Jacobs and G. Poncelet
Volume 4 Growth and Properties of Metal Clusters. Applications to Catalysis and the
Photographic Process. Proceedings of the 32nd International Meeting of the Soci6t6
de Chimie Physique, Villeurbanne, September 24-28, 1979
edited by J. Bourdon
Volume 5 Catalysis by Zeolites. Proceedings of an International Symposium, Ecully (Lyon),
September 9-1 1, 1980
edited by B. Imelik, C. Naccache, Y. Ben Taarit, J.C. Vedrine, G. Coudurier and
H. Praliaud
Volume 6 Catalyst Deactivation. Proceedings of an International Symposium, Antwerp,
October 13- 15, 1980
edited by B. Delmon and G.F. Froment
Volume 7 New Horizons in Catalysis. Proceedings of the 7th International Congress on
Catalysis, Tokyo, June 30-July 4, 1980. Parts A and B
edited by T. Seiyama and K. Tanabe
Volume 8 Catalysis by Supported Complexes
by Yu.1. Yermakov, B.N. Kuznetsov and V.A. Zakharov
Volume 9 Physics of Solid Surfaces. Proceedings of a Symposium, Bechyiie, September 29-
October 3, 1980
edited by M. LazniEka
Volume 10 Adsorption a t the Gas-Solid and Liquid-Solid Interface. Proceedings of an
InternationalSymposium, Aix-en-Provence, September 2 1-23, 198 1
edited by J. Rouquerol and K.S.W. Sing
Volume 1 1 Metal-Support and Metal-Additive Effects in Catalysis. Proceedings of an
International Symposium, Ecully (Lyon), September 14-1 6, 1982
edited by B. Imelik, C. Naccache, G. Coudurier, H. Praliaud, P. Meriaudeau,
P. Gallezot, G.A. Martin and J.C. Vedrine
Volume 12 Metal Microstructures in Zeolites. Preparation - Properties - Applications.
Proceedings of a Workshop, Bremen, September 22-24, 1982
edited by P.A. Jacobs, N.I. Jaeger, P. Jird and G. Schulz-Ekloff
Volume 13 Adsorption on Metal Surfaces. An Integrated Approach
edited by J. Benard
Volume 14 Vibrations a t Surfaces. Proceedings of the Third International Conference,
Asilomar, CA, September 1-4, 1982
edited by C.R. Brundle and H. Morawitz
870

Volume 15 Heterogeneous Catalytic Reactions Involving Molecular Oxygen

by G.I. Golodets
Volume 16 Preparation of Catalysts Ill. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Third International Symposium, Louvain-la-Neuve,
September 6-9, 1982
edited by G. Poncelet, P. Grange and P.A. Jacobs
Volume 17 Spillover of Adsorbed Species. Proceedings of an International Symposium, Lyon-
Villeurbanne, September 12-1 6, 1983
edited by G.M. Pajonk, S.J. Teichner and J.E. Germain
Volume 18 Structure and Reactivity of Modified Zeolites. Proceedings of an International
Conference, Prague, July 9-13, 1984
edited by P.A. Jacobs, N.I. Jaeger, P. Jirb, V.B. Kazansky and G. Schulz-Ekloff
Volume 19 Catalysis on the Energy Scene. Proceedings of the 9th Canadian Symposium on
Catalysis, Quebec, P.Q., September 30-October 3, 1984
edited by S. Kaliaguine and A. Mahay
Volume 20 Catalysis by Acids and Bases. Proceedings of an International Symposium,
Villeurbanne (Lyon), September 25-27, 1984
edited by B. Imelik, C. Naccache, G. Coudurier, Y. Ben Taarit and J.C. Vedrine
Volume 2 1 Adsorption and Catalysis on Oxide Surfaces. Proceedings of a Symposium,
Uxbridge, June 28-29, 1984
edited by M. Che and G.C. Bond
Volume 22 Unsteady Processes in Catalytic Reactors
by Yu.Sh. Matros
Volume 23 Physics of Solid Surfaces 1984
edited by J. Koukal
Volume 24 Zeolites: Synthesis, Structure, Technology and Application. Proceedings of an
International Symposium, Portoroi-Portorose, September 3-8, 1984
edited by B. Driaj, S.HoEevar and S. Pejovnik
Volume 25 Catalytic Polymerization of Olefins. Proceedings of the International Symposium
on Future Aspects of Olefin Polymerization, Tokyo, July 4-6, 1985
edited by T. Keii and K. Soga
Volume 26 Vibrations at Surfaces 1985. Proceedings of the Fourth International Conference,
Bowness-on-Windermere, September 15-1 9, 1985
edited by D.A. King, N.V. Richardson and S. Holloway
Volume 27 Catalytic Hydrogenation
edited by L. Cerveng
Volume 28 New Developments in Zeolite Science and Technology. Proceedings of the 7th
International Zeolite Conference, Tokyo, August 17-22, 1986
edited by Y. Murakami, A. lijima and J.W. Ward
Volume 29 Metal Clusters in Catalysis
edited by B.C. Gates, L. Guczi and H. Knozinger
Volume 3 0 Catalysis and Automotive Pollution Control. Proceedings of the First International
Symposium, Brussels, September 8-1 1, 1986
edited by A. Crucq and A. Frennet
Volume 3 1 Preparation of Catalysts IV. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Fourth International Symposium, Louvain-la-Neuve,
September 1-4, 1986
edited by B. Delmon, P. Grange, P.A. Jacobs and G. Poncelet
Volume 32 Thin Metal Films and Gas Chemisorption
edited by P. Wissmann
Volume 33 Synthesis of High-silica Aluminosilicate Zeolites
by P.A. Jacobs and J.A. Martens
Volume 34 Catalyst Deactivation 1987. Proceedings of the 4th International Symposium,
Antwerp, September 29-October 1, 1987
edited by B. Delmon and G.F. Froment
 87 1

Volume 35 Keynotes in Energy-Related Catalysis

edited by S. Kaliaguine
Volume 36 Methane Conversion. Proceedings of a Symposium on the Production of Fuels and
Chemicals from Natural Gas, Auckland, April 27-30, 1987
edited by D.M. Bibby, C.D. Chaney, R.F. Howe and S.Yurchak
Volume 37 Innovation in Zeolite Materials Science. Proceedings of an International
Symposium, Nieuwpoort, September 13-1 7, 1987
edited by P.J. Grobet, W.J. Mortier, E.F. Vansant and G. Schulz-Ekloff
Volume 38 Catalysis 1987. Proceedings of the 10th North American Meeting of the Catalysis
Society, San Diego, CA, May 17-22, 1987
edited by J.W. Ward
Volume 39 Characterization of Porous Solids. Proceedings of the IUPAC Symposium (COPS I),
Bad Soden a. Ts., April 26-29, 1987
edited by K.K. Unger, J. Rouquerol, K.S.W. Sing and H. Kral
Volume 40 Physics of Solid Surfaces 1987. Proceedings of the Fourth Symposium on Surface
Physics, Bechyne Castle, September 7-1 1, 1987
edited by J. Koukal
Volume 4 1 Heterogeneous Catalysis and Fine Chemicals. Proceedings of an International
Symposium, Poitiers, March 15-17, 1988
edited by M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, C. Montassier and
G. PBrot
Volume 42 Laboratory Studies of Heterogeneous Catalytic Processes
by E.G. Christoffel, revised and edited by 2. Pa61
Volume 43 Catalytic Processes under Unsteady-State Conditions
by Yu. Sh. Matros
Volume 44 Successful Design of Catalysts - Future Requirements and Development.
Proceedingsof the Worldwide Catalysis Seminars, July, 1988, on the Occasion of
the 30th Anniversary of the Catalysis Society of Japan
edited by T. lnui
Volume 45 Transition Metal Oxides. Surface Chemistry and Catalysis
by H.H. Kung
Volume 46 Zeolites as Catalysts, Sorbents and Detergent Builders. Applications and
Innovations. Proceedings of an InternationalSymposium, Wurzburg, September 4-8,
1988
edited by H.G. Karge and J. Weitkamp
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