Zeolites, synthesis, characterizations and

applications

Sandip Chakrabarti
1
 Framework Structure of Zeolite

SiO4 AlO4

General formula of Zeolite: Ax/n[Si1-xAlxO2].mH2O

A: Metal cation of valence n.
2
 Use of Zeolite

Ion exchange
Air separation
Drying agent
Separation of solvents
Sulpher removal from natural gas
Catalytic cracking
(gasoline production)
Xylene isomerisation
Butene isomerisation
3
 Commercial Adsorbent
Applications
• Purification
• Drying: Cracked gas, Insulation windows,
refrigerant
• CO2 removal: Natural Gas, Cryogenic Air Sepns.
• Sulfur Removal: sweetening of natural gas &
liquefiedpetroleum gas
• Bulk Separations
• n/i paraffins (LTA)
• Xylenes (PAREX: FAU)
• Olefins separations
• O 2 from air (LTA)
• Sugar Separations 4
 Metal
Aluminosilicate/ Metal
Silicoaluminophosohate Aluminosilicate Metal Phosphate

Inorganic compounds
Hybrid Framework Metal Silicates
with open architecture

Metal Sulphates
Metal Selenates
Silica

5
 “Molecular Sieve” Synthesis

HighAluminaMaterials: Atmospheric 60’s

e.g. Zeolite X, Y, A, L, ...

Hydrothermal
High Silica Materials:Autoclave; 70’s
Templates e.g. ZSM-5, ZSM-11

AlPO4, SAPO4, MeAPO4 Ti-silicates 80’s

MesoporousMaterials, Membranes, 90’s

6
.........................................
 Synthesis

Metal salt + HCl/HF/ H2C2O4/HOAc + As2O5/As2O3/H3AsO4 +

Organic Amine + H2O/n-Hexanol/THF/n-Butanol.

Temperature: 60 to 250 oC
Pressure: 1 to 10 bar 7
 Schematic Representation of The Formation
of Crystals in Hydrothermal method

Teflon liner
Stainless
Steel Jacket

Gel Product
(Crystals ?)

Before heat treatment After heat treatment

8
 100
Presence of
Organic Moiety
80

Low Angle

Wight Loss (%)

Region 60

40
Intensity (a.u.)

20
200 400 600 800
Thermogravimetric
o
Temperature ( C)
analysis (TGA)

10 20 30 40 50 1.2

2
1.0

Powder X-ray

Transmittance
0.8

Diffraction
0.6

0.4

Infrared Spectroscopy 0.2

4000 3000 2000 1000
9
-1

(IR) Wavenumber (cm )

Single crystal structure determination by X-ray

X-ray tube
(Mo K-)

CCD-detector

10
Oxidation: Loss of electrons and increase in oxidation number

Or,

Gain of oxygen and /or a loss of hydrogen

CrO2Cl2
ArCH3 ArCHO

11
 Catalyst

Increases the rate of approach to equilibrium of a chemical

reaction without being substantially consumed in the reaction.

12
 Heterogeneous catalysts

Advantages over Homogeneous catalysts

Easy to separate, handling and recovery.

Can be regenerated and re-used.

Environmental friendly

Disadvantages over Homogeneous catalysts

Enantio and regio selectivity are far

behind from homogeneous catalysts.

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Pore-size regimes and representative inorganic materials

Pore-size Actual pore size

regimes (Å)

Microporous 4 to 20

Mesoporous >20 to 100

Macroporous >100

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Brönsted acid sites and Shape selectivity

are the main features of zeolite catalysis

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 The Active Surface
Lewis Acidity: Cations, Al3+ BröenstedAcidity: Protons

H
Si

O
Al

Bi-functional: Acid + Metal Function (Highly Dispersed Pt, Rh, ....)

16
 Chemical composition and properties of
zeotype molecular sieves

Chemical composition Properties

Zeolite (SiIV-O-AlIII-O-SiIV)- Negatively charged framework, hydrophilic, with ion

H+ or M+ exchange and acid sites.
Silicates SiIV-O-SiIV-O-SiIV Neutral framework, hydrophobic, without ion exchange
and acid sites.
ALPO AlIII-O-PV-O-AlIII Neutral framework, hydrophilic, without ion exchange
and acid sites.
SAPO (SiIV-O-AlIII-O-PV)- Negatively charged framework, hydrophilic, with ion
H+ or M+ exchange and acid sites.

17
Pore dimensions of zeolites and critical dimensions of
some hydrocarbons
0.4 Zeolite A Linear paraffins

Erionite

Critical molecular dimension, nm

Ferrierite
Average Channel size, nm

0.5 Benzene
2-methyl-substituted
ZSM-5 olifins
o-Xylene

aromatics
0.6

Higher
Offretite

Mordenite
0.7

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Faujasite Napthalene
 Some reactions performed by ZSM-5

Ethyl benzene
from benzene:

Xylenes
production:

ZSM-5

p-xylene
from toluene and
ethylene

19
Dwyer, Catalysis of Organic Reactions, P. 39, Chemical Industries no. 5, Dekker, New York (1981)
 Preparation of synthetic gasoline

Red-hot Cu/Zn
CH4 (or C) + H2O H2 + CO CH3OH
coke oxide

ZSM-5
nCH3OH (CH2)n + nH2O

Hölderich et al, Angew. Chem. Int. Ed. Engl. 1988, 27, 226 20
Dehydration of methanol

21
Sinclair et al, J. Chem. Soc. Faraday Trans. 1977, 93, 333
Sequence of steps for immobilization of ferroceny-based ligand on MCM-41

22
Thomas et al, J. Mol. Catal. A 1999, 141, 139
Thomas Angew.Chem. Int. Ed. Engl. 1999, 38, 3588 23
 The allylic amination of cinnamyl acetate with benzylamine

Catalyst Conversion Straight Branched (%)

(%) chain product (%) ee
(%)
3 76 99 + - -
Jonson et al,
Chem, 7 98 98 2 43
Commum. 6 99 + 49 51 >99
1999, 1167 24
The term ‘ee’ the highest possible enantiomeric excess
Synthesis and Characterization of Zeolite Membranes

Zeolite is a porous material with a particular size

Porous ceramic substrate is used as the support of membrane

Layers of zeolite crystals are deposited on the substrate

Zeolite membranes are synthesized by hydrothermal method

Characterization is done by using SEM, TEM, XRD, XRF,

XPS and FTIR techniques.

25
Tubular Zeolite Membrane and its Microstructures

T. Kyotani et. al., Anal. Sci., 2006, 22, 317

26
Application of Tubular Zeolite Membrane
in Separation of Solvent Mixtures

27
 Schematic Representation of
Solvent Mixture Separating Unit

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Solvent Mixtures Separated using Zeolite A Membrane
Ethanol – Water mixture

Ethanol – Water mixture (Acetic acid impurity)

Isopropyl alcohol – Water mixture

n-Butanol – Water mixture

THF – Water mixture

Acetonitrile – Water mixture

Pyridine – Water mixture

Pyridine – ammonia – water mixture 29

 Steps Followed for the Experiments
with Zeolite Membrane

Sealing of zeolite membrane with SS adaptor

Reference ethanol – water (water ~10 wt%) experiment at

75 oC (Opening experiment)

Pervaporation and vapor permeation experiments

with solvent mixtures

Reference ethanol – water (water ~10 wt%) experiment at

75 oC (Closing experiment)

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 Types of Studies Conducted with
Sealed Zeolite Membranes

Performance studies: Indicates separating

capability of membrane

Endurance studies: Life of the membrane

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 Important Performance Parameters

Permeation Flux (Q): Amount of sample permeates

through per unit area of membrane in per unit time
(unit: kgm-2h-1)

Separation factor (α): Indicates the separation capability

of the membrane in the particular feed mixture.

Incase of binary mixtures: αA/B = (YA/YB)/(XA/XB)

XA = Concentration of component A in feed mixture

XB = Concentration of component B in feed mixture
YA = Concentration of component A in permeate mixture
YB = Concentration of component B in permeate mixture
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