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www.rsc.org/catalysis Volume 2 | Number 1 | January 2012 | Pages 1–228
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ISSN 2044-4753
COVER ARTICLE
Gates et al.
Catalytic conversion of compounds representative of lignin-derived bio-oils: a reaction network for guaiacol, anisole,
4-methylanisole, and cyclohexanone conversion catalysed by Pt/-Al2O3
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www.rsc.org/catalysis PAPER
Catalytic conversion of compounds representative of lignin-derived
bio-oils: a reaction network for guaiacol, anisole, 4-methylanisole,
and cyclohexanone conversion catalysed by Pt/c-Al2O3w
Ron C. Runnebaum,a Tarit Nimmanwudipong,a David E. Blockab and
Bruce C. Gates*a
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The conversion of compounds representative of lignin and lignin-derived bio-oils (guaiacol, anisole,
4-methylanisole, and cyclohexanone), catalysed by Pt/Al2O3 in the presence of H2 at 573 K is
described by a reaction network indicating a high selectivity for platinum-catalysed aromatic
carbon–oxygen bond cleavage accompanied by acid-catalysed methyl group transfer reactions.
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 113–118 113
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Table 1 Productsa formed with oxygen removal in the conversion of Table 2 Productsa formed without oxygen removal in the conversion
compounds representative of lignin and lignin-derived bio-oils of compounds representative of lignin and lignin-derived bio-oils
catalysed by Pt/g-Al2O3 in the presence of H2 catalysed by Pt/g-Al2O3 in the presence of H2
3-Methylcatechol
Cyclohexanone (3-methyl-1,2-benzenediol)
3-Methylguaiacol
Phenol (2-methoxy-3-methylphenol)
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Veratrole (1,2-dimethoxybenzene)
Anisole Benzene
(methoxybenzene)
Cyclohexene
Anisole Phenol
Cyclohexane
Cyclohexanone
4-Methylanisole Toluene
(1-methoxy-4- (methylbenzene)
methylbenzene)
2-Methylphenol
Cyclohexanone Benzene
4-Methylphenol
Cyclohexane
2,6-Dimethylphenol
Cyclohexene
a
A list of the trace products is given in the ESI.
4-Methylanisole 4-Methylphenol
114 Catal. Sci. Technol., 2012, 2, 113–118 This journal is c The Royal Society of Chemistry 2012
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This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 113–118 115
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Table 3 Pseudo-first-order rate constants characterising reactions in The data provide a comparison of the reactivities of the
the network of Fig. 4 various reactants. For example, the rate constants representing
Reaction the reactions of guaiacol and anisole to remove the methoxy
number group are 4.4 and 0.86 L (g of catalyst) 1 h 1, respectively.
(keyed to Rate This comparison indicates that the methoxy group becomes
Fig. 4) Reactant constanta Reaction class easier to remove when a hydroxy group is present in the ortho
1 Guaiacol 0.11 Hydrodeoxygenation position. The rate constant for removal of the methyl group
2 Guaiacol 4.4 Hydrodeoxygenation from the methoxy substituent is greater for anisole, 12 L
3 Guaiacol 6.5 Hydrogenolysis
4 Guaiacol 1.8 Transalkylation (g of catalyst) 1 h 1, than for guaiacol, 6.5 L (g of catalyst) 1 h 1.
5 Guaiacol 0.50 Bimolecular transalkylation
6 Guaiacol 0.21 Bimolecular transalkylation 4.2 Evaluation of the reaction network and comparison with
7 Guaiacol 0.26 Bimolecular transalkylation reported data
8 Anisole 12 Hydrogenolysis
9 Anisole 0.86 Hydrodeoxygenation A statement of the reaction network including the minor and
10 Anisole 2.8 Transalkylation trace products is presented in Fig. 5; we inferred this network
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Fig. 4 Reaction network accounting for formation of primary products determined from analysis of selectivity-conversion plots for the
conversion of individual reactants (shown in red), guaiacol, anisole, 4-methylanisole, and cyclohexanone, catalysed by Pt/g-Al2O3 in the presence
of H2 at 573 K. H2, as a reactant, is omitted for simplicity. Pseudo-first-order rate constants for the individual primary products formed in the
conversion of the individual reactants catalysed by Pt/g-Al2O3 are shown in Table 3; the numbers next to the arrows in this figure are keyed to the
list in Table 3.
116 Catal. Sci. Technol., 2012, 2, 113–118 This journal is c The Royal Society of Chemistry 2012
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Fig. 5 Reaction network for the conversion of lignin-derived compounds (each compound shown in red was used as a reactant) with H2 catalysed
by Pt/g-Al2O3 at 573 K and 140 kPa. HDO, hydrogenolysis, and hydrogenation (or dehydrogenation) reactions are represented by dashed green,
blue, and black arrows, respectively. Transalkylation reactions are represented by solid black arrows. H2 as a reactant is omitted for simplicity. The
representation in this network is simplified: for example, in transalkylation reactions in which two guaiacol molecules are involved (e.g., 2-guaiacol
- catechol + veratrole), the stoichiometry is not represented here.
the relatively low conversions observed in our experiments The data characterising the conversion of anisole and of
(e.g., 4-methylanisole gave negligible yields of anisole). The 4-methylanisole show that the conversions of reactants in
data are too few to identify reversible reactions involving trace homologous series give homologous products (e.g., benzene
products. and toluene, respectively). These results suggest that the data
The results indicate that methyl group transfer reactions may be extrapolated with some confidence to increasingly
were negligible when the methyl group was bonded to the higher homologues including those found in pyrolysis oils.13
aromatic ring; for example, only a trace of 2-methylanisole The results highlight the requirement of higher partial
was observed to form from 4-methylanisole. We contrast this pressures of H2 than we used when selective deoxygenation
observation with the relatively rapid methyl group transfer is a goal; for example, deoxygenated compounds such as
reactions occurring when the methyl group migrated from toluene and xylenes are valuable high-octane-number fuel
the methoxy group to the aromatic ring, as, for example, in the components. The data also point to potentially useful routes
formation of 2,4-dimethylphenol from 4-methylanisole. The for production of chemicals. For example (Fig. 5), the
data also imply the simultaneous occurrence of intermolecular products phenol and cyclohexanone could be useful as chemical
and intramolecular methyl group transfers; for instance, both intermediates.
2-methylanisole and o-cresol were identified as primary products The results also clearly demonstrate the value of metals as
in the reactions of anisole. Similarly, methylguaiacols (formed catalysts for HDO reactions. We suggest further that the
by intermolecular transalkylation) and 3-methylcatechol results presented here may be useful in guiding the conversion
(formed by intramolecular transalkylation) were identified as of lignin fractions produced in new processes for biomass
primary products in the conversion of guaiacol. conversion, such as those using molten salt catalysts.4,14
This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 113–118 117
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118 Catal. Sci. Technol., 2012, 2, 113–118 This journal is c The Royal Society of Chemistry 2012