Chen Zhao, 2011
Chen Zhao, 2011
Chen Zhao, 2011
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
a r t i c l e
i n f o
Article history:
Received 20 August 2010
Revised 1 February 2011
Accepted 4 February 2011
Keywords:
Bio-oil
Phenol derivatives
Aqueous-phase catalysis
Hydrodeoxygenation
Palladium
Dual-functional catalysis
a b s t r a c t
The kinetics of the catalytic hydrodeoxygenation of phenol and substituted phenols has systematically
been investigated on the dual-functional catalyst system Pd/C and H3PO4 in order to better understand
the elementary steps of the overall reaction. The reaction proceeds via stepwise hydrogenation of the aromatic ring, transformation of the cyclic enol to the corresponding ketone, hydrogenation of the cycloalkanone to the cycloalkanol and its subsequent dehydration as well as the hydrogenation of the formed
cycloalkene. The presence of dual catalytic functions is indispensible for the overall hydrodeoxygenation.
The dehydration reaction is signicantly slower than the hydrogenation reaction and the keto/enol transformation, requiring a signicantly larger concentration of Brnsted acid sites compared to the available
metal sites for hydrogenation.
2011 Published by Elsevier Inc.
1. Introduction
Bio-oil, produced by pyrolysis or liquefaction of lignocellulosic
biomass, is a promising potential raw material for liquid energy
carriers and in particular liquid transportation fuels. It cannot be
used directly, because it contains a high concentration of oxygen,
and the presence of unsaturated and phenolic moieties makes it
instable [13]. In contrast to the conventional crude oil, which is
a mixture of hydrocarbons containing 98 wt.% carbon and hydrogen, 1.8 wt.% sulfur and only 0.1 wt.% oxygen [1], bio-oil is an
acidic (pH = 2.5) aqueous solution containing up to 50 wt.% oxygen
[4,5]. Such high oxygen values cause a rapid catalyst deactivation
in hydrodeoxygenation using sulde CoMo and NiMo catalysts
[6]. The highly active oxo-functionalized molecules also readily oligomerize, requiring advanced catalytic technology to directly
hydrodeoxygenate the crude bio-oil under mild conditions.
Bio-oil contains ca. 30 wt.% of lignin-derived phenolic components (phenols, guaiacols, and syringols) which are of high energy
density [2,3]. Hydrodeoxygenation (HDO) of such phenolic compounds to cycloalkanes has been reported using heterogeneous
metal sulde catalysts at moderate temperatures (573873 K)
with high-pressure hydrogen (1316 MPa) in xed bed reactors
[1,7]. However, the incorporation of sulfur into products over these
catalysts stimulated us to develop catalysts, which are not based
on suldes [1]. Combined with supported metal catalysts, water
Corresponding author. Fax: +49 89 28913544.
E-mail address: [email protected] (J.A. Lercher).
Present address: Department of Chemical Engineering, Aristotle University of
Thessaloniki, Thessaloniki 54124, Greece.
1
4-allyl-2,6-dimethoxy-phenol (Alfa Aesar, 98.0% GC assay), cyclohexanol (SigmaAldrich, 99.0% GC assay), 2-methoxycyclohexanol
(Alfa Aesar, 99.0% GC assay), palladium (II) nitrate hydrate (Strem
Chemicals, 99.9%-Pd), hydrogen (Air Liquide, >99.999%).
2.2. Commercial catalysts used
Pd/C (Aldrich, loading amount: 5 wt.%), Ru/C (Aldrich, loading
amount: 5 wt.%), Pt/C (Aldrich, loading amount: 5 wt.%), Rh/C (Aldrich, loading amount: 5 wt.%), Pd/C (Aldrich, loading amount:
1 wt.%).
2.3. Preparation of supported catalysts Pd/Al2O3, Pd/SiO2, and Pd/ASA
We synthesized 2 wt.% of Pd-based catalysts supported on alumina (Degussa), silica (Degussa), and amorphous-silicaalumina
(ASA, containing 20% of alumina) with incipient wetness impregnation using palladium (II) nitrate hydrate as Pd precursor, then
air-calcined at 573 K for 4 h and hydrogen-reduced at 588 K for
4 h [17].
The ASA support was prepared from a gel formed at pH 7.5 by
mixing a solution of acetic acid and AlCl36H2O in distilled water
(pH = 1.5) with a solution containing sodium silicate in NH4OH
(pH = 12). The gel was then thoroughly washed with a diluted solution of ammonium acetate to eliminate Na+ cations, dried at 393 K
overnight at ambient atmosphere, and then calcined at 943 K for
2 h in owing air (100 ml min1).
2.4. Catalyst characterization
2.4.1. Surface areas and pore diameters
The surface areas and pore diameters were determined from
nitrogen adsorption measurements carried out at 77 K on a PMI
automated BET sorptometer. The samples were rst outgassed at
523 K for 20 h before measurements. The surface area, micropore
and mesopore distributions were calculated according to the BET
and BJH theories [18].
2.4.2. H2 chemisorption
The Pd catalysts were activated in vacuum at 588 K for 1 h and
then cooled to 313 K. A hydrogen adsorption isotherm (chemisorption together with physisorption) was subsequently measured at a
pressure range from 1 to 40 kPa. Then, the sample was outgassed at
the same temperature for 1 h to remove the physisorbed H2, followed by measuring another adsorption isotherm (physisorption).
The concentration of chemisorbed hydrogen on the metal was
determined by extrapolating the isotherm to zero hydrogen pressure and using the value to estimate the dispersions of the metal
on the supports. Besides H2 chemisorption, we also calculated
the Pd dispersion from a TEM micrograph (Fig. S1). The dispersion
of the 5 wt.% Pd/C calculated from the TEM measurement was 52%,
which is very similar to the 55% derived from the H2 chemisorption, showing that hydride formation and H2 uptake into the bulk
of Pd do not take place under the used conditions.
2.5. Measurements of catalytic reactions
2.5.1. Aqueous-phase HDO of bio-derived phenolic compounds
The HDO reactions were optimized by varying the pH of the
aqueous solution (neutral, acidic, basic), the metal (Pd, Pt, Ru,
Rh), the catalyst support (C, Al2O3, SiO2, ASA), as well as by varying
the reaction temperature (423, 473, 523 K). The reaction conditions
used are noted in the footnotes of the tables. In a typical experiment, phenol or other lignin-derived monomers (0.0106 mol),
H3PO4-H2O solution (80 ml, 0.5 wt.%, pH = 2.1), and Pd/C (0.040 g,
5 wt.%) were added into an autoclave (Parr, Series 4843, 300 ml).
Then, the autoclave was pressured with 5 MPa H2 (ambient temperature). Reactions were conducted at 473 K for 0.5 h with a stirring speed of 1000 rpm. After cooling to ambient temperature, the
organic products were extracted by ethyl acetate. The organic
phase and aqueous phase were both analyzed by a gas chromatograph (GC, Shimadzu 2010, ame ionization detector) with a HP-5
capillary column (30 m 250 lm). A gas chromatographmass
spectrometer combination (GCMS, Shimadzu QP 2010S) was used
to identify the organic compounds. Internal standards (i.e., 2-isopropylphenol for the organic phase and acetone for the aqueous
phase) were used to determine the liquid product concentration
and carbon balance. The calculations of conversion and selectivity
were based on carbon mole basis. Conversion = (the amount of aromatic ring change during reaction/total amount of aromatic
ring) 100%. Selectivity = (C atoms in each product/total C atoms
in the products) 100%. The carbon balance in the liquid
phase for all reported experiments was better than 95 3% in this
work.
The composition of the gas phase was determined by GC (HP
6890) equipped with a plot Q capillary column (30 m 250 lm)
with thermal conductivity detector (TCD). We found 99% hydrogen
and trace amounts of CO2 and methanol in the gas phase, so in this
work only the changes in the liquid phase were considered.
2.5.2. Kinetic study of phenol hydrodeoxygenation network
The kinetic study of the aqueous-phase hydrodeoxygenation of
phenol to cyclohexane was divided into four steps: (i) phenol
hydrogenation to cyclohexanone, (ii) cyclohexanone hydrogenation to cyclohexanol, (iii) cyclohexanol dehydration to cyclohexene, and (iv) cyclohexene hydrogenation to cyclohexane. These
reactions were carried out at 473 K in the batch autoclave reactor.
The reaction conditions were as follows: (i) phenol (12.5 g), Pd/C
(1 wt.%, 0.020 g), 5 MPa H2; (ii) cyclohexanone (60 g), Pd/C
(1 wt.%, 0.020 g), 5 MPa H2; (iii) cyclohexanol (140 g), H3PO4-H2O
(0.5 wt.%, 80 ml), 5 MPa N2; (iv) cyclohexene (50 g), Pd/C (1 wt.%,
0.020 g), 5 MPa H2.
After reaction, ethyl acetate was used to extract the organic
phase and the extract was analyzed by GC and GCMS using the
internal standard 2-isopropylphenol. As the aqueous-phase HDO
reaction is a two-phase process, the real-time sampling during
reaction is very difcult. Thus, the conversion/selectivity data as
a function of reaction time were collected from separate batch
experiments with varying duration.
Turnover frequencies (TOFs) were determined as initial reaction
rates when the conversion was below 10%, dened as mole of consumed reactant per mole of surface Pd atom (or per mole of H+) per
hour.
2.5.3. Kinetic study of anisole, catechol, and guaiacol
hydrodeoxygenation conversion
The kinetic study of anisole, catechol, or guaiacol was carried
out as follows. The reactant (0.016 mol) was mixed with 0.5 wt.%
H3PO4H2O solution (80 ml) and 5 wt.% Pd/C (0.020 g), and then
such mixture was hydrodeoxygenated at 423 K and 5 MPa H2 with
a stirring speed of 1000 rpm. After reaction, ethyl acetate was used
to extract the organic phase, and the liquid products including
aqueous phase and organic phase were analyzed through GC and
GCMS with internal standards (i.e., 2-isopropylphenol for the organic phase and acetone for the aqueous phase). As mentioned in
Section 2.5.2, the conversion/selectivity data versus reaction time
were collected from the corresponding separate batch experiments
with varying duration.
2.5.4. Aqueous-phase HDO of phenolic mixture and catalyst recycle
Resembling the HDO of bio-oil, reaction of a phenolic monomer
mixture (3.38 g) containing 2-methoxy-4-n-propylphenol (0.83 g,
10
0.005 mol), 4-n-propylphenol (0.68 g, 0.005 mol), 4-hydroxy-3methoxyphenylacetone (0.90 g, 0.005 mol) and 4-allyl-2,6-dimethoxyphenol (0.97 g, 0.005 mol), Pd/C (0.080 g, 5 wt.%), and
H3PO4H2O solution (80 ml, 0.5 wt.%) was carried out at 523 K
and 5 MPa H2 (ambient temperature) for 0.5 h, stirred at
1000 rpm. After reaction, the other treatments were kept the same
as mentioned in Section 2.5.1.
To test the catalyst recyclability, the rst run for hydrodeoxygenation of the phenolic mixture was carried out at 523 K and
5 MPa H2 (ambient temperature) for 2 h, stirred at 1000 rpm. After
reaction, the Pd/C catalyst was separated by decantation, followed
by sequential washing with ethyl acetate and water, and drying at
393 K for 2 h. The catalyst was then reused in the next catalytic recycle run without any further treatment.
3. Results
3.1. Catalyst characterization
The main physicochemical properties of the Pd catalysts are
compiled in Table 1. The surface area of 1 wt.% Pd/C (934 m2 g1)
or 5 wt.% Pd/C (845 m2 g1) was much higher than that of 2 wt.%
Pd/SiO2 (174 m2 g1), Pd/Al2O3 (92 m2 g1), and Pd/ASA
(269 m2 g1). The pore diameter in Pd/C was 3.6 nm, while those
in the other three materials Pd/SiO2, Pd/Al2O3 and Pd/ASA were
1418 nm as compiled in Table 1. In agreement with the higher
surface area of the carbon support, the dispersion of Pd in 5 wt.%
Pd/C calculated from H2 chemisorption data (55%) was much higher than that of Pd supported on Al2O3 (12%), SiO2 (24%), and ASA
(40%).
Table 2
Aqueous-phase hydrodeoxygenation of phenol.a
Catalyst
T (K)
Solvent
Conv. (%)
Table 1
Textural properties of the Pd-supported catalysts.
Catalyst
Pore diameter
(nm)
Dispersion
(%)
Metal loading
(wt.%)
Pd/C
Pd/C
Pd/Al2O3
Pd/SiO2
Pd/ASA
934
845
92
174
269
3.7
3.6
16
18
14
51
55
12
24
40
1
5
2
2
2
Pd/C
Pd/Al2O3
Pd/SiO2
Pd/ASA
Pd/C
Pd/Al2O3
Pd/SiO2
Pd/ASA
Pd/C
Pd/Al2O3
Pd/SiO2
Pd/ASA
Pd/C
Pd/Cb
Pd/C
Pd/C
Pt/C
Ru/C
Rh/C
473
473
473
473
473
473
473
473
473
473
473
473
423
423
473
523
473
473
473
H2O
H2O
H2O
H2O
NaOHH2O
NaOHH2O
NaOHH2O
NaOHH2O
CH3COOHH2O
CH3COOHH2O
CH3COOHH2O
CH3COOHH2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
100
82
87
96
100
72
55
72
100
88
95
100
100
100
99
100
100
100
100
Selectivity (C%)
Cyclo
Hexane
Cyclo
Hexanol
Cyclo
Hexanone
0
0
0
0
0
0
0
0
75
20
20
21
0
1
85
98
86
88
92
98
72
62
73
97
69
53
64
20
20
13
24
74
94
10
1
13
10
7
2
28
38
27
3
31
47
36
2
56
64
53
25
4
4
0
0
1
0
a
Reaction conditions: phenol (1.0 g, 0.0106 mol), H2O (80 ml), H3PO4H2O
(0.5 wt.%, 80 ml), CH3COOHH2O (5 wt.%, 80 ml), NaOHH2O (0.05 wt.%, 80 ml), Pd/
C (5 wt.%, 0.040 g), Rh/C (5 wt.%, 0.040 g), Ru/C (5 wt.%, 0.040 g), Pt/C (5 wt.%,
0.070 g), Pd/Al2O3 (2 wt.%, 0.10 g), Pd/SiO2 (2 wt.%, 0.10 g), Pd/ASA (2 wt.%, 0.10 g),
5 MPa H2, 0.5 h, stirred at 1000 rpm.
b
Reaction time: 1 h.
11
Table 3
Aqueous-phase dehydration of cyclohexanol.a
T (K)
Catalyst
Solvent
Conv. (%)
473
473
473
373
393
423
433
453
473
473c
Pd/C
Pd/C
H2O
H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
H3PO4H2O
0
1.2
98
0
0.1
1.2
2.3
8.6
95
93
Selectivity (C%)
Cyclohexene
Cyclohexanone
0
0
99.9b
0
62
69
83
95
99.9
100
0
100
0.1
0
38
31
17
5.0
0.1
0
a
Reaction conditions: cyclohexanol (1.06 g, 0.0106 mol), Pd/C (5 wt.%, 0.04 g),
H2O (80 ml), H3PO4H2O (0.5 wt.%, 80 ml), 5 MPa H2 (ambient temperature), 0.5 h,
stirred at 1000 rpm.
b
Cyclohexane selectivity.
c
Repeat of the experiment carried out with H3PO4 at 473 K.
the mineral acid H3PO4 at 373 K, cyclohexanol was stable with zero
conversion in water solvent (Table 3). From 393 to 453 K, the dehydration conversion of cyclohexanol over H3PO4 increased from 0.1%
to 8.6%. The apparent activation energy, calculated from the data
presented in Table 3 for the aqueous-phase cyclohexanol dehydration with H3PO4, was 120 kJ mol1. At 473 K, cyclohexanol was
quantitatively dehydrated to cyclohexene within half an hour in
the presence of H3PO4 (Table 3). In previous studies, cyclohexanol
was dehydrated to cyclohexene with 80% yield over Lewis acid alumina at 603623 K [32], or it was dehydrated by Brnsted liquid
acids, such as sulfuric acid and phosphoric acid, and by solid acids
in the liquid phase at 403473 K in the absence of solvents [33,34].
In the aqueous phase, water as solvent inhibits cyclohexanol dehydration with respect to the chemical equilibrium, because it is also
a reaction product. Thus, the reaction temperature has to be increased to 473 K in water compared to 403 K with sulfuric acid
without a solvent. Catalyzed by the Pd/C and H3PO4 dual-functional components, phenol was rapidly and quantitatively hydrodeoxygenated to cyclohexane (Table 3). In summary, cyclohexane
formation from phenol requires dual-functional catalysis, i.e., the
presence of hydronium ions for dehydration at appropriate temperatures, and a metallic function able to hydrogenate in the presence of water.
The overall reaction pathway for the aqueous-phase hydrodeoxygenation of phenol to cyclohexane proceeds via an initial
metal-catalyzed aromatic ring hydrogenation and naphthenic alcohol dehydration and then metal-catalyzed cycloalkene hydrogenation (Fig. 1) [15].
12
OH
OH
Pd/C, H2
Pd/C, H2
H+
TOF1
TOF2
TOF3
Pd/C, H2
TOF4
Fig. 1. Reaction pathway for aqueous-phase phenol of hydrodeoxygenation on dual-functional catalysts of Pd/C and H3PO4 at 473 K.
Table 4
Aqueous-phase hydrodeoxygenation of bio-derived phenolic monomers with Pd/C and H3PO4 catalysts at 523 K.a
Reactant
Conv. (%)
Selectivity (C%)
CH3OH
Cycloalcohol/ketone
100
98
1.3
100
96
3.6
HO
100
87
12
H3CO
100
78b
10
10
100
80c
10
9.2
100
66
3.0
6.7
7.2
17
99
65
3.5
5.0
7.4
18
100
71
3.1
5.2
8.2
12
92
58
3.1
5.6
12
21
HO
HO
HO
HO
H3CO
HO
H3CO
HO
H3CO
HO
H3CO
HO
OCH3
HO
H3CO
a
Reaction conditions: phenol (1.0 g, 0.0106 mol) or other phenolic monomers (0.0106 mol), Pd/C (5 wt.%, 0.040 g), H3PO4-H2O (0.5 wt.%, 80 ml), 5 MPa H2 (ambient
temperature), 0.5 h, stirred at 1000 rpm.
b
Includes isomerization products: methylcyclopentane (selectivity: 1.8%) and 1,2-dimethylcyclopentane (selectivity: 4.6%).
c
Includes isomerization products: ethylcyclopentane (selectivity: 2.2%) and 2-methyl-1-ethylcyclopentane (selectivity: 7.6%).
copy (ICP-AES) analysis of the organic phase and the aqueous solution after each cycle did not show even traces of leached Pd
(detection limit: 1 lg/mL). Nearly quantitative conversions and
very high selectivities (ca. 80% cycloalkanes and 8% methanol)
were also obtained in the two subsequent recycle experiments (Table 5). The stable catalyst recycle performance indicates that the Pd
active sites have not changed (no changes in the Pd dispersion or
Pd leaching).
4. Discussion
4.1. Kinetics of the phenol hydrodeoxygenation network
The elementary reactions for the aqueous-phase phenol hydrodeoxygenation network are divided into four processes (Fig. 1), (i)
phenol hydrogenation to cyclohexanone on Pd/C, (ii) cyclohexa-
13
Selectivity (C%)
4-n-Propylphenol: 100
2-Methoxy-4-n-propylphenol: 92
4-Hydroxy-3-methoxyphenylacetone: 100
4-Allyl-2,6-dimethoxyphenol: 82
CH3OH
Cycloalcohol/ketone
64
3.0
3.2
8.0
20
80
3.6
5.0
9.0
1.7
Run 2
4-n-Propylphenol: 100
2-Methoxy-4-n-propylphenol: 98
4-Hydroxy-3-methoxyphenylacetone: 100
4-Allyl-2,6-dimethoxyphenol: 87
73
2.5
3.1
8.4
12
Run 3
4-n-Propylphenol: 100
2-Methoxy-4-n-propylphenol: 88
4-Hydroxy-3-methoxyphenylacetone: 95
4-Allyl-2,6-dimethoxyphenol: 79
67
1.7
1.7
7.5
21
a
Reaction conditions: the phenolic monomer mixture (3.4 g) contains 2-methoxy-4-n-propylphenol (0.83 g, 0.005 mol), 4-n-propylphenol (0.68 g, 0.005 mol), 4-hydroxy3-methoxyphenylacetone (0.90 g, 0.005 mol), and 4-allyl-2,6-dimethoxyphenol (0.97 g, 0.005 mol), Pd/C (0.080 g, 5 wt.%), H3PO4-H2O solution (80 ml, 0.5 wt.%), 523 K, 5 MPa
H2 (ambient temperature), 0.5 h, stirred at 1000 rpm.
TOF1 for
phenol
hydrogenation
(h1)
TOF2 for
cyclohexanone
hydrogenation
(h1)
TOF3 for
cyclohexanol
dehydration
(h1)
TOF4 for
cyclohexene
hydrogenation
(h1)
6.2 103
1.2 104
15
>9 106
10.0
Phenol hydrogenation to cyclohexanone
8.0
6.0
4.0
2.0
0.0
0
20
40
60
80
100
120
Time (min)
Fig. 2a. Aqueous-phase hydrogenation of phenol to cyclohexanone as a function of
time. Reaction conditions: phenol (12.5 g), Pd/C (1 wt.%, 0.020 g), 473 K, 5 MPa H2,
stirred at 1000 rpm.
10.0
1
8.0
6.0
4.0
2.0
0.0
0
20
40
60
80
100
120
Time (min)
Fig. 2b. Aqueous-phase hydrogenation of cyclohexanone to cyclohexanol as a
function of time. Reaction conditions: cyclohexanone (60 g), Pd/C (1 wt.%, 0.020 g),
473 K, 5 MPa H2, stirred at 1000 rpm.
1
Cyclohexanone conversion
(%)
Table 6
Turnover frequencies for aqueous-phase phenol hydrodeoxygenation network.
10.0
Cyclohexanol dehydration
8.0
6.0
4.0
2.0
0.0
0
20
40
60
80
100
120
Time (min)
Fig. 2c. Aqueous-phase dehydration of cyclohexanol to cyclohexene as a function of
time. Reaction conditions: cyclohexanol (140 g), H3PO4-H2O (0.5 wt.%, 80 ml),
473 K, 5 MPa N2, stirred at 1000 rpm.
14
80
Conversion (%)
(a)
60
60
40
40
20
20
0
0
50
100
150
OCH3
OH
H+/H2O
H2/Pd
hydrogenation
hydrogenation
+ CH3OH
(b)
OH
O
OH
cyclohexanol
H+
60
60
40
40
20
50
100
Time (min)
150
0
200
150
100
90
80
70
60
50
40
30
20
10
0
200
100
80
60
40
20
0
0
50
100
Time (min)
dehydration
OH
methanol
cyclohexanone
ketone/enol isomerization
OH
Conversion (%)
hydrogenation
methoxycyclohexane
OH
H+
H2
80
20
(c)
H2
Pd
Pd
hydrogenation
ketone/enol isomerization
dehydration
Conversion
OH
OH
2H2
hydrogenation H2/Pd
Selectivity (C%)
Conversion (%)
80
H2/Pd
OH
OCH3
0
200
Pd
hydrogenation
Conversion
2-hydroxycyclohexanol
cyclohexanol
2-hydroxycyclohexanone
cyclohexanone
(c)
OH
OH
OCH3
H2
Pd
hydrogenation
Pd
hydrogenation
ketone/enol isomerization
H+, hydrolysis
H+, hydrolysis
OH
O
methoxycyclohexane
2-hydroxycyclohexanone
OCH3
OCH3
2H2
OH
Conversion
Selectivity (C%)
(b)
+ CH3OH
Pd
hydrogenation
ketone/enol isomerization
Time (min)
100
2H2
+ CH3OH
hydrolysis
80
Selectivity (C%)
(a)
100
CH3OH
OH
CH3OH
H2
Pd
methanol
cyclohexanol
cyclohexanone
2-methoxycyclohexanone
2-methoxycyclohexanol
H+, dehydration
Pd, H2, hydrogenation
H+, dehydration
ketone/enol isomerization
O
OH
CH3OH
H2
Pd
hydrogenation
CH3OH
15
1
dehydration followed by hydrogenation and the other via hydrogenation followed by dehydration. This dual pathway may explain
why cyclohexanone behaves as a primary product. Cyclohexanone
is in turn hydrogenated to cyclohexanol (Fig. 4b). Note that we cannot rule out, however, that in a rst step, only one double bond of
catechol is hydrogenated and that this diol undergoes acid-catalyzed elimination of water to phenol, which subsequently is then
partially hydrogenated to cyclohexanone [38].
Hydrogenation of the most representative phenolic monomer,
guaiacol, with adjacent methoxy and hydroxy functional groups
at the aromatic ring led to a variety of products including cycloalkanone, cycloalkanol, aromatics, and methanol at 423 K (Fig. S2).
The primary product was the intermediately hydrogenated 2methoxycyclohexanone (t = 0, selectivity = 100%) (Fig. 3c). Also, in
this case, the fastest step is the metal-catalyzed hydrogenation of
the aromatic ring and not the acid-catalyzed hydrolysis of the
methoxy group. The initial TOF for guaiacol hydrogenation on Pd/
1
1
C at 423 K exceeded 1500 molguaiacol molsurf:Pd h . In comparison
with anisole, which has only a single methoxy group and which
is easily hydrolyzed at 423 K in water, the lower rate of the methoxy group hydrolysis of guaiacol may be caused by the stabilization of the carbocation transition state through electron donation
by the adjacent hydroxyl groups, preventing its further hydrolysis
to methanol. Note that Kanetake et al. reported that under more
drastic conditions, i.e., in supercritical water at 653673 K, guaiacol can be hydrolyzed and pyrolyzed to catechol, methanol, phenol,
and char [39].
The hydrogenated intermediate 2-methoxycyclohexanone is
converted to cyclohexanone and methanol via two routes
(Fig. 4c). One is based on sequential methoxy hydrolysis followed
1100 molanisole molsurf:Pd h . The results also imply that the alkyl CO bond of an aryl alkyl ether (anisole) is much easier to hydrolyze
than that of a dialkyl ether (methoxy-cyclohexane), which is in line
with the ndings of the hydrolysis of benzyl phenyl ether [36] and
diphenyl ether [37]. Hence, with a single methoxy group at the aromatic ring, anisole can be catalytically hydrolyzed and directly
hydrogenated at the same time on the dual-functional catalyst system Pd/C and H3PO4 (Fig. 4a).
Catechol having two adjacent hydroxyl groups on the aromatic
ring is an important constituent from lignin depolymerization and
also an intermediate in the guaiacol or syringol conversion. When
Pd/C and a mineral acid were jointly used as catalysts for catechol
hydrodeoxygenation, it was rapidly hydrogenated at the aromatic
ring leading to 2-hydroxycyclohexanone (t = 0, selectivity = 80%)
(Fig. 3b). The TOF for catechol hydrogenation on Pd/C at 423 K ex1
1
ceeded 3500 molcatechol molsurf:Pd h . Subsequently, 2-hydroxycyclohexanone was rapidly converted to cyclohexanone (s = 0,
selectivity = 20%) via two parallel routes of sequential alcohol
dehydration/alkene hydrogenation (minor pathway) and ketone
hydrogenation/alcohol dehydration (major pathway) (Fig. 4b). It
was shown in a separate experiment that 1,2-cyclohexanediol
was dehydrated to cyclohexanone at 92% yield at 523 K with Pd/
C and H3PO4 in 10 min (Table S3). Note that the dehydration rate
of 1,2-cyclohexanediol was signicantly lower at 423 K. It was
shown from Fig. 3b that cyclohexanone was then slowly hydrogenated to cyclohexanol, eventually reaching nearly 30% selectivity.
Thus, the catechol conversion proceeds in the rst step via hydrogenation, as initial metal-catalyzed partial aromatic hydrogenation
to form 2-hydroxycyclohexanone, and then, it was subsequently
converted to cyclohexanone via two parallel pathways: one via
OH
OH
R
OCH3
2H2
Pd
R1
hydrogenation
OH
H+
hydrolysis
H2
+
CH3OH -H2O/H
hydrogenation R1
R1
OH
CH3OH
or
CH3OH
R1
or
R1
CH3OH
OH
Pd
dehydration
OH
R
or
-H2O/H+
R1
or
dehydration
R1
ketone/enol isomerization
R1
OCH3
O
OH
OH
H2
Pd
hydrogenation
ketone/enol isomerization
R1
OCH3
demethoxygenation R1
CH3OH
R1
H2
CH3OH
Pd
hydrogenation
R1
R1
R=H, OCH3
R1=alkyl
Fig. 5. Proposed overall reaction pathway for hydrodeoxygenation of bio-derived phenolic monomers to cycloalkanes with Pd/C catalyst and H3PO4 component [15].
16
Catalyzed by acids, cycloalkanes undergo carbon skeletal isomerization to the extent of 610%. For example, n-propylcyclohexane
was isomerized to n-butylcyclopentane via ring contraction and
proton transfer and to 2-methylpropylcyclopentane via 1,3-carbon
backbone transformation.
[18]
[19]
[20]
[21]
[22]
5. Conclusions
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]