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Catalysis
Science &Technology
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

Catalysis
Science & Technology
Cite this: Catal. Sci. Technol., 2012, 2, 113–118
www.rsc.org/catalysis
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
Published on 07 September 2011. Downloaded on 10/09/2014 18:20:29.
Received 13th May 2011, Accepted 7th August 2011
DOI: 10.1039/c1cy00169h
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.
1. Introduction
Among the potential routes for production of fuels and
chemicals from lignocellulosic biomass, fast pyrolysis accom-
panied by or followed by catalytic upgrading offers excellent
potential because the number of conversion steps is small and
the processing may be cost effective.1 Catalytic upgrading is
required because the pyrolysis products are characterised
by thermal and chemical instability, low heating values,
corrosiveness, and immiscibility with petroleum-derived fuels.2
Research on catalytic upgrading of bio-oils has focused on
cellulose-derived fractions,3 with less attention paid to
lignin-derived fractions—which offer attractive prospects for
production of aromatic chemicals such as phenolics.4 Lignin-
derived bio-oils can also be converted into fuels, with a key
processing challenge being the removal of oxygen—because
bio-oils derived from lignocellulose typically contain 35–40 wt%
oxygen.2,5 The literature of bio-oils conversion is largely lacking
in fundamental chemistry.6 The complexity of the feedstocks
limits the usefulness of the available data for predicting catalyst
performance. Even data characterising the reactions of indivi-
dual biomass-derived compounds7 are scarce, and the catalytic
reaction networks are largely limited to primary products or
products lumped into classes of similar compounds.8,9
Our goal was to determine a reaction network to account for
the reactions of a group of compounds prototypical of lignin and
compounds derived from it, incorporating the representative
aromatic rings, hydroxyl groups, keto groups, and ether
a
Department of Chemical Engineering and Materials Science,
University of California, Davis, Davis CA, USA.
E-mail: bcgates@ucdavis.edu; Fax: (+ 1) 530-752-1031
b
Department of Viticulture and Enology, University of California,
Davis, Davis CA, USA
w Electronic supplementary information (ESI) available: The details of
materials and methods, table showing product list from the catalytic
reactions of each of the prototypical compounds. See DOI: 10.1039/
c1cy00169h
This journal is c The Royal Society of Chemistry 2012
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PAPER
linkages—the compounds are guaiacol, anisole, 4-methylanisole,
and cyclohexanone. These reactants were converted in the
presence of a solid catalyst, platinum on g-Al2O3 (Pt/g-Al2O3).
2. Experimental
2.1 Catalytic reaction experiments
The Pt/g-Al2O3 catalyst (1 wt% Pt, Sigma-Aldrich) had a BET
surface area of 206  1 m2 g 1 and a platinum dispersion
determined by H2 chemisorption of 0.25.10 The catalyst was
used in powder form.
In the reaction experiments, carried out with a once-through
flow reactor with reactant vapors flowing at steady state, the
catalyst (0.001–0.100 g, mixed with particles of inert nonporous
a-Al2O3) was pre-treated in flowing gases at 573 K. The pre-
treatment gas, flowing at 100 mL min 1, was 30% H2/70% N2.
In a typical experiment, liquid reactant (guaiacol, flowing at
0.015 mL min 1, or anisole, 4-methylanisole, or cyclohexanone,
each flowing at 0.030 mL min 1) was vaporised into a gas stream
(30% H2/70% N2) flowing at 100 mL min 1 into the packed-bed
reactor. The reactor temperature was 573 K, and the pressure
was 140 kPa. The effluent was condensed at 283–288 K.
Analysis of the products in the liquid samples was
performed with a gas chromatograph (GC, Agilent 7890)
equipped with a mass selective detector (MSD, Agilent 5795)
and a flame ionisation detector. Analysis of the gas-phase
products was performed with a GC refinery gas analyser
(Agilent 7980). Details of the analysis are given in ESI.
Mass balance closures were typically greater than 95%.
3. Results
3.1 Oxygen removal in reactions catalysed by Pt/c-Al2O3
The products formed in the reactions catalysed by Pt/g-Al2O3
in the presence of H2 are listed in Tables 1 and 2. In the
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

Products formed in conversion Product Products formed in conversion Product

Reactant of prototypical reactant structure Reactant of prototypical reactant structure

Guaiacol Anisole (methoxybenzene) Guaiacol Catechol (benzene-1,2-diol)

(2-methoxyphenol)

3-Methylcatechol
Cyclohexanone (3-methyl-1,2-benzenediol)

3-Methylguaiacol
Phenol (2-methoxy-3-methylphenol)
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o-Cresol (2-methylphenol) 6-Methylguaiacol

(2-methoxy-6-methylphenol)

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

conversion of each of the reactants individually with H2, we

observed dozens of products. The data determine conversions Methylcyclohexanone
and selectivities of the products that were formed in relatively
high yields at conversions o 10%. Conversion of the four
individual reactants as a function of time on stream, shown in 2,4-Dimethyphenol
Fig. 1, demonstrates similar rates of catalyst deactivation.
Plots of selectivity as a function of conversion (e.g., Fig. 2)
demonstrate which of the major products are primary and
2,4,6-Trimethylphenol
which are not; the methodology for these determinations is
summarised in the papers by Bhore et al.11
The data show that one of the dominant classes of reactions
Tetramethylphenol
observed with guaiacol, anisole, and 4-methylanisole was
transalkylation. Reported results indicate that with HY zeolite
catalyst, transalkylation was the only kinetically significant
Cyclohexanone Cyclohexanol
reaction class.10,12 This observation implies that the alumina
support in Pt/g-Al2O3 catalysed the transalkylation reactions.
The other important reaction classes observed with Pt/g-
Cyclohexenone
Al2O3 (but only when H2 was a coreactant) were hydrogenation
(e.g., the conversion of cyclohexanone to cyclohexanol and of
benzene to cyclohexene), dehydrogenation (e.g., the conversion Phenol
of cyclohexanone to phenol and hydrogen), and hydrogenolysis a
A list of the trace products is given in the ESI.
(e.g., the reaction of guaiacol to give catechol and methane).

114 Catal. Sci. Technol., 2012, 2, 113–118 This journal is c The Royal Society of Chemistry 2012
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Fig. 1 Change in conversion of anisole (K), 4-methylanisole (m),

cyclohexanone (n), and guaiacol (‘) during operation of a flow
reactor. Reactants were fed individually and all conversions were
catalysed by Pt/g-Al2O3 in the presence of H2 at 573 K. The WHSV,
in units of (g of reactant)/(g of catalyst  h), of the feed streams was
chosen to achieve similar initial conversions: anisole, 18; 4-methyl-
anisole, 17; cyclohexanone, 160; and guaiacol, 20.

There was no evidence of hydroxylation reactions under

our experimental conditions; for example, anisole was not
observed to produce guaiacol.
C–O bond cleavage reactions that removed oxygen from the
organic reactant were observed, as were C–O bond cleavage
reactions that did not remove oxygen from the organic
reactant. The former are categorised as hydrodeoxygenation
(HDO) and the latter as hydrogenolysis. In the HDO
reactions, oxygen was removed as methanol or water
(exemplified by the reaction of 4-methylanisole to give toluene
and methanol). In contrast, in hydrogenolysis, one of the
products was an alkane (as in the reaction of anisole to give
phenol and methane). In the conversion of cyclohexanone,
HDO was observed, but, because of the lack of substitutents
such as methyl, hydrogenolysis was not.
The observation of these three reaction classes when the
catalyst was the supported metal and not when it was the
zeolite demonstrates that they were catalysed by the platinum.
Fig. 2 (a) Selectivity for the formation of phenol (K), anisole (J),
and benzene (.) in the conversion of guaiacol. (b) Selectivity for the
formation of 4-methylphenol (B) and toluene (E) in the conversion of
4-methylanisole. Each conversion was catalysed by Pt/g-Al2O3 in the
presence of H2 at 573 K. Data for each product were fitted with a
straight line and extrapolated to zero conversion; intercepts of regres-
sion lines significantly different from zero selectivity at zero conversion
(determined with 95% confidence limits) indicate primary products, in
this case phenol, anisole, 4-methylphenol, and toluene.
conversions were kept low in almost all of our experiments
to simplify the analyses, we lack the data to determine the
reaction orders precisely and use pseudo-first-order kinetics
as a matter of convenience. The rate constants are summarised
in Table 3.

3.2 Identification of primary reactions and determination of

kinetics: first step towards elucidation of reaction networks
The data determine quantitative conversions and selectivities
of the products that were formed in relatively high yields at
conversions o 10%.
In the conversion of guaiacol with H2, phenol and anisole
are primary products, and benzene was a non-primary
product, as shown by the plot of Fig. 2a. The plot of Fig. 2b
shows that 4-methylphenol and toluene are primary products
in the reactions of 4-methylanisole and H2. (We emphasise
that the designations of primary and non-primary products
are empirical and do not provide details about intermediates
that were too reactive to be detected.) Fig. 3 Conversion of guaiacol to give phenol (n) and conversion of
The data also determine approximate kinetics of the anisole to give benzene (K); both conversions were catalysed by
primary reactions. As illustrated by the data of Fig. 3, which Pt/g-Al2O3 in the presence of H2 at 573 K. The term Xi represents
are typical, the reactions are satisfactorily represented as the conversion to product i. WHSV is weight hourly space velocity.
first-order in the organic reactant. However, because the The vertical scale is logarithmic.

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 network of Fig. 4
Reaction
number
(keyed to
Fig. 4) Reactant
1 Guaiacol
2 Guaiacol
3 Guaiacol
4 Guaiacol
5 Guaiacol
6 Guaiacol
7 Guaiacol
8 Anisole
9 Anisole
10 Anisole
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The data provide a comparison of the reactivities of the
various reactants. For example, the rate constants representing
the reactions of guaiacol and anisole to remove the methoxy
group are 4.4 and 0.86 L (g of catalyst) 1 h 1, respectively.
Rate This comparison indicates that the methoxy group becomes
constanta Reaction class easier to remove when a hydroxy group is present in the ortho
0.11 Hydrodeoxygenation position. The rate constant for removal of the methyl group
4.4 Hydrodeoxygenation from the methoxy substituent is greater for anisole, 12 L
6.5 Hydrogenolysis
1.8 Transalkylation (g of catalyst) 1 h 1, than for guaiacol, 6.5 L (g of catalyst) 1 h 1.
0.50 Bimolecular transalkylation
0.21 Bimolecular transalkylation 4.2 Evaluation of the reaction network and comparison with
0.26 Bimolecular transalkylation reported data
12 Hydrogenolysis
0.86 Hydrodeoxygenation A statement of the reaction network including the minor and
2.8 Transalkylation trace products is presented in Fig. 5; we inferred this network

11 Anisole 0.039 Transalkylation

12 Anisole 0.14 Bimolecular transalkylation
by recognising which compounds were primary products and
13 4-Methylanisole 0.76 Hydrodeoxygenation by using our chemical judgment of the most likely pathways
14 4-Methylanisole 4.2 Hydrogenolysis for formation of the minor and trace compounds by presuming
15 4-Methylanisole 2.2 Transalkylation that the important reaction classes are methyl group transfer,
16 Cyclohexanone 77 Dehydrogenation
17 Cyclohexanone 5.5 Hydrogenation hydrodeoxygenation, hydrogenolysis, and hydrogenation.
18 Cyclohexanone 0.05 Hydrodeoxygenation The network of Fig. 5 provides a more complete description
a
Rate constants unit in L (g catalyst) 1
h 1. than that given in Fig. 4, but it is not quantitative. The
inference that the most important reaction classes are
hydrodeoxygenation, transalkylation, hydrogenolysis, and
4. Discussion hydrogenation is in good agreement with earlier reports,8
but the results provide detailed new evidence of the reactions.
4.1 Combined reaction network
This is a more detailed representation of the catalytic reactions
The data form the basis for determining a reaction network to of lignin-derived compounds than any reported.
summarise the quantitative results, as shown in Fig. 4. This As represented in Fig. 5, for example, the data show that
network shows all the primary products formed from each some of the reactions are reversible (e.g., cyclohexanone
reactant. produces phenol), but others appeared to be irreversible at

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
(e.g., 4-methylanisole gave negligible yields of anisole). The
data are too few to identify reversible reactions involving trace
products.
The results indicate that methyl group transfer reactions
were negligible when the methyl group was bonded to the
aromatic ring; for example, only a trace of 2-methylanisole
was observed to form from 4-methylanisole. We contrast this
observation with the relatively rapid methyl group transfer
reactions occurring when the methyl group migrated from
the methoxy group to the aromatic ring, as, for example, in the
formation of 2,4-dimethylphenol from 4-methylanisole. The
data also imply the simultaneous occurrence of intermolecular
and intramolecular methyl group transfers; for instance, both
2-methylanisole and o-cresol were identified as primary products
in the reactions of anisole. Similarly, methylguaiacols (formed
by intermolecular transalkylation) and 3-methylcatechol
(formed by intramolecular transalkylation) were identified as
primary products in the conversion of guaiacol.
The data characterising the conversion of anisole and of
4-methylanisole show that the conversions of reactants in
homologous series give homologous products (e.g., benzene
and toluene, respectively). These results suggest that the data
may be extrapolated with some confidence to increasingly
higher homologues including those found in pyrolysis oils.13
The results highlight the requirement of higher partial
pressures of H2 than we used when selective deoxygenation
is a goal; for example, deoxygenated compounds such as
toluene and xylenes are valuable high-octane-number fuel
components. The data also point to potentially useful routes
for production of chemicals. For example (Fig. 5), the
products phenol and cyclohexanone could be useful as chemical
intermediates.
The results also clearly demonstrate the value of metals as
catalysts for HDO reactions. We suggest further that the
results presented here may be useful in guiding the conversion
of lignin fractions produced in new processes for biomass
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

Conclusions
In summary, the reaction network of Fig. 5 represents our
data well, accounting quantitatively for the kinetically impor-
tant reaction classes. This reaction network is much more
extensive than any reported for the catalytic conversion of
lignin-derived compounds. The data show that the hydro-
genolysis reactions (including HDO) are kinetically significant
under our operating conditions and require a metal function
and H2. Transalkylation reactions occur in the presence of an
acid such as our catalyst support (g-Al2O3), which is not active
for oxygen removal reactions. Thus, the identification of the
roles of the acid and metal functions in the bifunctional
catalyst implies an opportunity to optimize the catalyst for a
particular application by balancing these functions and opti-
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mizing processes for the conversion of lignin-derived bio-oils
to fuels and chemicals.
Acknowledgements
We thank Jennifer Heelan of the University of California,
Davis, for help with the analytical instrumentation. Support of
this work was provided by Chevron Technology Ventures, a
division of Chevron USA, Inc. An Agilent Technologies
Foundation Research Project Gift provided a GC7890
Refinery Gas Analyzer. Tarit Nimmanwudipong thanks the
Fulbright Foundation for an Open Competition scholarship.
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This journal is c The Royal Society of Chemistry 2012