Energy & Fuels 2006, 20, 2717-2720 2717

Upgrading Bio-oil over Different Solid Catalysts

Qi Zhang,*,†,‡ Jie Chang,† TieJun Wang,† and Ying Xu†
Guangzhou Institute of Energy ConVersion, Chinese Academy of Sciences, Guangzhou 510640, China, and
Department of Thermal Science and Energy Engineering, UniVersity of Science and Technology of China,
Hefei 230027, China

ReceiVed May 18, 2006. ReVised Manuscript ReceiVed August 24, 2006

Solid acid 40SiO2/TiO2-SO42- and solid base 30K2CO3/Al2O3-NaOH were prepared and compared with
catalytic esterification activity according to the model reaction. Upgrading bio-oil by solid acid and solid base
catalysts in the conditioned experiment was investigated, in which dynamic viscosities of bio-oil was lowered
markedly, although 8 months of aging did not show much viscosity to improve its fluidity and enhance its
stability positively. Even the dehydration by 3A molecular sieve still kept the fluidity well. The density of
upgraded bio-oil was reduced from 1.24 to 0.96 kg/m3, and the gross calorific value increased by 50.7 and
51.8%, respectively. The acidity of upgraded bio-oil was alleviated by the solid base catalyst but intensified
by the solid acid catalyst for its strong acidification. The results of gas chromatography-mass spectrometry
analysis showed that the ester reaction in the bio-oil was promoted by both solid acid and solid base catalysts
and that the solid acid catalyst converted volatile and nonvolatile organic acids into esters and raised their
amount by 20-fold. Besides the catalytic esterification, the solid acid catalyst carried out the carbonyl addition
of alcohol to acetals. Some components of bio-oil undertook the isomerization over the solid base catalyst.

1. Introduction emulsification,7-97-9 steam reforming,1010 extracting chemicals

Biomass, despite containing a low carbon content, is clean,
because biomass has a negligible content of sulfur, nitrogen,
and ash, which gives a lower emission of SO2, NOx, and soot
than that of conventional fossil fuels. Besides, zero emission
of CO2 can be achieved because CO2 released from biomass
will be resolved into the plants by photosynthesis quantitatively.
Biomass fast pyrolysis for bio-oil production has aroused great
attention and interest extensively in recent years for the excess
consumption of fossil fuels and high efficiency of the biomass
pyrolysis technique. Energy crisis and fuel tension make the
biomass fast pyrolysis a more important area of research.1,2 Bio-
oil from biomass fast pyrolysis is mainly produced from biomass
residues in the absence of air, atmospheric pressure, a low
temperature (450-550 °C), high heating rate (103-104 °C/s),
and short gas residence time, to crack into short-chain molecules
and be cooled to liquid rapidly. However, bio-oil has deleterious
properties of high viscosity, thermal instability, corrosiveness,
and chemical complexity, which set up many obstacles to their
applications. The recent upgrading techniques are hydro-
deoxygenation,3-53-5 catalytic cracking of pyrolysis vapors,66
* To whom correspondence should be addressed. Telephone: 086-020-
87057787. Fax: 086-020-87057789. E-mail: zhangqi@ms.giec.ac.cn.
† Chinese Academy of Sciences.
‡ University of Science and Technology of China.
(1) Czernik, S. R.; Bridgwater, A. V. Overview of applications of biomass
fast pyrolysis oil. Energy Fuels 2004, 18, 590-598.
(2) Bridgwater, A. V.; Peacocke, G. V. C. Fast pyrolysis processes for
biomass. Renewable Sustainable Energy ReV. 2000, 4, 1-73.
(3) Pindoria, R. V.; Lim, J. Y.; Hawkes, J. E. et al. Structural
characterization of biomass pyrolysis tars/oils from eucalyptus wood
wastes: Effect of H2 pressure and samples configuration. Fuel 1997, 76,
1013-1023.
(4) Pindoria, R. V.; Megaritis, A.; Herod, A. A. et al. A two-stage fixed-
bed reactor for direct hydrotreatment of volatiles from the hydropyrolysis
of biomass: Effect of catalyst temperature, pressure and catalyst ageing
time on product characteristics. Fuel 1998, 77, 1715-1726.
from the bio-oils, etc. In this paper, solid acid and solid base
catalysts were prepared and compared with upgrading the bio-
oil properties by catalytic esterification and the mechanism
involved in it was investigated.
2. Experimental Section
2.1. Catalysts Preparation. Titanium solution was prepared by
stirring the mixture of Ti(OBu)4, EtOH, H2SO4, and H2O in some
proportion, and TiO2 powder was obtained after aging, drying, and
milling the titanium gel. Mixing SiO2 (Degussa A-380) with TiO2
powder by 40 wt % in ethanol, impregnating in H2SO4 (1 M), and
being calcined in 400 °C, the solid acid catalyst 40STS were
prepared. Milling the mixture of K2CO3 and Al2O3 by 30 wt %
together, impregnating in NaOH (1 M) solution, and drying, the
solid base catalyst 30KAN was prepared after the calcination in
500 °C under the protection of nitrogen atmosphere.
2.2. Esterification. The model reaction of esterification with
ethanol and acetic acid by a molar ratio of 2.5:1 was carried out in
the three-neck flask equipped with a thermometer, reflux condenser,
and magnetic stirrer. The catalyst was used by 5 wt % of the
reaction solution, which was sampled at a 20 min interval and
(5) Senol, O. I.; Viljava, T. R.; Krause, A. O. I. Hydrodeoxygenation of
methyl esters on sulphided NiMo/γ-Al2O3 and CoMo/γ-Al2O3 catalysts.
Catal. Today 2005, 100, 331-335.
(6) Nokkosmaki, M. I.; Kuoppala, E. T.; Leppamaki, E. A. et al. Catalytic
conversion of biomass pyrolysis vapours with zinc oxide. J. Anal. Appl.
Pyrolysis 2000, 55, 119-131.
(7) Chiaramonti, D.; Bonini, M.; Fratini, E. et al. Development of
emulsions from biomass pyrolysis liquid and diesel and their use in engines.
Part 1: Emulsion production. Biomass Bioenergy 2003, 25, 85-99.
(8) Chiaramonti, D.; Bonini, M.; Fratini, E. et al. Development of
emulsions from biomass pyrolysis liquid and diesel and their use in engines.
Part 2: Tests in diesel engines. Biomass Bioenergy 2003, 25, 101-111.
(9) Ikura, M.; Stanciulescu, M.; Hogan, E. Emulsification of pyrolysis
derived bio-oil in diesel fuel. Biomass Bioenergy 2003, 24, 221-232.
(10) Takanabe, K.; Aika, K.; Seshan, K. et al. Sustainable hydrogen from
bio-oil-steam reforming of acetic acid as a model oxygenate. J. Catal. 2004,
227, 101-108.

10.1021/ef060224o CCC: $33.50 © 2006 American Chemical Society

Published on Web 10/14/2006
2718 Energy & Fuels, Vol. 20, No. 6, 2006
Figure 1. Catalytic activity of solid catalysts in the model reaction.
Table 1. Acetic Acid Conversion over Different Catalysts in Partial
Reflux Esterification
no catalyst solid acid/ solid base/
catalysts (%) 40STS (%) 30KAN (%)
acetic acid conversion 15 100 23.7
measured quantitatively by NaOH standard solution titration and
analysis by GC2010 (Shimadzu, FID, N2 carrier gas, column: DB-
1HT 30 m × 0.25 mm × 0.1 µm). By the titration method, the
acetic acid conversion was calculated by applying the equation:
conversion ) (1 - V/V0) × 100%, in which V and V0 are the
volumes of the standard NaOH solution consumed in neutralizing
0.5 mL solution sampled in the process and at the beginning of the
reaction to change the phenolphthalein indicator pink, respectively.
The conversion was also measured by the internal standard method
through GC2010, with isoamyl acetate as the internal standard, and
the results of the measurements were kept consistent mutually.
2.3. Characterization of Bio-oil. The dynamic viscosity was
measured with WFY-108D viscometers (GB/T265-88), and gross
calorific value was measured using a WGR-1 calorimetric bomb
(ASTM D4809). The water content was determined by the Karl
Fischer titration (ASTM D1744, GB11146-89), which was per-
formed by using Metrohm 787 KF Titrino. The acidity was
evaluated by a PHC-3C precision pH-meter from the Shanghai REX
Instrument Factory.
Gas chromatography-mass spectrometry (GC-MS; GC, HP5890;
MSD, HP5972A) was conducted to analyze the composition of bio-
oil. The separation was realized on a column of DB-5MS, 30 m ×
0.25 mm × 0.25 µm, and the oven temperature program was 40
°C (holding for 5 min) at 6 °C/min to 295 °C (holding for 10 min).
3. Results and Discussion
3.1. Catalytic Activity of the Solid Acid and Solid Base
Catalysts on Model Esterification. First, in partial reflux
esterification with only the reflux in 20 min, the conversion of
acetic acid in 1 h was shown in Table 1.
The solid acid catalyst nearly converted all of the acetic acid
into esters and showed higher catalytic activity, and the solid
base catalyst exhibited better activity than no catalyst, although
it was not as high as the solid acid catalyst. To clarify the
relation of the conversion with time, total reflux esterification
was carried out.
The conversion of acetic acid in the total reflux reactor of
catalytic esterification over different catalysts was described in
Figure 1. The solid acid catalyst 40STS presented high activity,
and acetic acid conversion rose with time remarkably and
reached 84% in 80 min, approaching the 88% of equilibrium
conversion. The solid acid catalyst could accelerate the esteri-
fication greatly; however, the conversion over the solid base
catalyst 30KAN was low.
Zhang et al.
Figure 2. Effect of catalytic esterification on bio-oil viscosity. (a)
Before and (b) after dehydration by 3A molecular sieve.
3.2. Effect of Catalytic Esterification on the Properties of
Bio-oil. The bio-oil studied was obtained by fast pyrolysis of
biomass in the fluidized bed of 2 m × 70 mm, with two screw
feeders, two cyclones, a condenser, and an electric heater, and
the specific operation conditions were illustrated in the litera-
ture.11 The feedstock of pyrolysis was rice husks, and the bio-
oil was held in a refrigerator for 1 month before its esterification.
The bio-oil was a dark brown, free-flowing liquid with a
distinctive smoky odor. The esterification was carried out in
the flask with ethanol/bio-oil ) 2.5 by volume ratio and 5 wt
% catalyst, and the reaction temperature was maintained in 50
°C for 5 h to avoid coke formation. Some properties of bio-oil
were changed by catalytic esterification and detailed as follows.
3.2.1. Effect of Catalytic Esterification on Viscosity. The
dynamic viscosity curves with temperature of bio-oils were
illustrated in the Figure 2. At 20 °C, the dynamic viscosity of
bio-oils was lowered from 48.56 to 4.81 and 6.09 mm2/s
catalyzed by 40STS and 30KAN, respectively. With the
dehydration of 3A molecular sieve, the dynamic viscosity of
raw bio-oil increased by 2.49-fold, that catalyzed over the solid
acid catalyst only increased by 7.3%, and that catalyzed over
the solid base catalyst was nearly unchanged. On the other hand,
the fluidity of upgraded bio-oil was kept well and the viscosity
fluctuation with temperature was weakened. The dehydration
by 3A molecular sieve did not make the upgraded bio-oils much
more viscous. The catalytic esterification stabilized the bio-oil
positively and enhanced the fluidity of bio-oil despite dehydra-
tion by 3A molecular sieve.
The partially dehydrated original and upgraded bio-oils were
sealed in bottles and held still in a refrigerator under about 5
°C for 8 months, and the dynamic viscosities were measured
and showed in Table 2.
All of the dynamic viscosities of partially dehydrated original
and upgraded bio-oils increased to some extent after 8 months
(11) Zheng, J.-l.; Zhu, X.-f.; Guo, Q.-x. et al. Thermal conversion of
rice husks and sawdust to liquid fuel. Waste Manage. 2006, in press.
Upgrading Bio-oil oVer Different Solid Catalysts Energy & Fuels, Vol. 20, No. 6, 2006 2719

Figure 3. GC-MS spectroscopy of bio-oil and upgraded bio-oils. (a) Raw bio-oil, (b) upgraded bio-oil by the solid acid catalyst, and (c) upgraded
bio-oil by the solid base catalyst.

Table 2. Dynamic Viscosity Change of Partially Hydrated Original Table 4. Properties of Raw and Upgraded Bio-oils after
and Upgraded Bio-oils after 8 Months of Aging Storage Dehydration by 3A Molecular Sieve
dynamic viscositya upgraded upgraded
(partially hydrated bio-oils) (mm2/s) raw bio-oil by bio-oil by
properties bio-oil solid acid solid base
original upgraded bio-oil upgraded bio-oil
bio-oil by solid acid by solid base pH 3.58 1.12 5.54
density (kg/m3) 1.26 0.96 0.93
fresh 120.7 5.161 6.077
H2O content 26.34 11.21 11.02
aged for 8 months 135.6 7.645 7.783
gross calorific value (kJ/kg) 16 752.8 24 975.5 24 478.1
a Measured at a temperature of 20 °C.
Table 5. Percent Area of Acids and Esters in Bio-oil and Upgraded
Table 3. Properties of Raw and Upgraded Bio-oils Bio-oils
upgraded upgraded percent area
original bio-oil by bio-oil by organic acids
properties bio-oil solid acid solid base (nonvolatile) esters
pH 2.60 1.12 5.93 bio-oil 10.0 1.33
density (kg/m3) 1.24 0.96 0.97 upgraded bio-oil by solid acid 12.82 28.00
H2O content 29.79 13.60 12.35 upgraded bio-oil by solid base 12.55 18.46
gross calorific value (kJ/kg) 15 834.7 23 868.7 24 034.9
to 13.6 and 12.35% over 40STS and 30KAN, separately,
of aging storage. The dynamic viscosity of original bio-oil indicating that esterification might be involved.
increased by 14.9 mm2/s, and those of upgraded bio-oils by solid The pH value of upgraded bio-oil catalyzed by the solid acid
acid and solid base catalysts increased by 2.484 and 1.706 mm2/ catalyst was lowered from 2.60 to 1.12 for the catalyst
s, separately, whose absolute mounting magnitude were far acidification, while the pH value of upgraded bio-oil catalyzed
lower than the original one, which indicated the improved by the solid base catalyst rose to 5.93. The density decreased;
stability over time. dynamic viscosity was one-tenth of that of raw bio-oil; and gross
calorific value increased by 50.7 and 51.8%, respectively.
3.2.2. Effect of Catalytic Esterification on Other Proper- The dehydrated bio-oils by 3A molecular sieve were described
ties. The properties of bio-oils were shown in Table 3. The in Table 4.
addition of solution diluted the bio-oil, and the water content The dehydration decreased the water contents of raw and
was lowered. The esterification should follow the equation: upgraded bio-oils over 40STS and 30KAN by 11.6, 17.6, and
RCOOH + R′-OH f RCOOR′ + H2O. On the basis of the 10.8%, respectively, and increased the gross calorific value by
ethanol addition and stoichiometric calculation, the water content 5.8, 4.4, and 1.8%, separately. The 3A molecular sieve
in the upgraded bio-oil should be 11.45% if esterification did influenced the upgraded bio-oil over the solid acid catalyst more
not occur in the reactor but, actually, water contents increased and did not make much difference on the density. All of the
2720 Energy & Fuels, Vol. 20, No. 6, 2006
Table 6. Corresponding Components in Raw and Upgraded Bio-oils by the Solid Acid Catalyst
components
in raw bio-oil
formic acid f
formic acid f formic acid anhydride f
butanedioic acid f
1,2-benzenedicarboxylic acid f
Table 7. Corresponding Components in Raw and Upgraded Bio-oils by the Solid Base Catalyst
components
in raw bio-oil
butanedioic acid f
1,2-benzenedicarboxylic acid f
3-methyl-1,2-benzenediol f
3,5-dimethylbenzoic acid f
above results indicated that the direct and simple physical
dehydration was not effective and ideal in upgrading the bio-
oil, which can be taken as an assistant method.
3.3. Effect of Catalytic Esterification on the Composition
of Bio-oil. Bio-oil is a complex mixture highly oxygenated with
a great amount of large-size molecules, which nearly involve
all species of oxygenated organics, such as esters, ethers,
aldehydes, ketones, phenols, organic acids, and alcohols. The
analysis on the composition of bio-oil and upgraded bio-oil was
illustrated in the spectroscopy of Figure 3.
The bio-oil consisted of nonvolatile components, such as
furfural, benzoic acid, benzene dicarboxylic acid, and other
organic acid. Most of the components identified were the
phenols and the derivatives with methyl, methoxy, propenyl,
ketones, and aldehydes groups attached, and nearly all of the
functional groups confirmed the existence of oxygen. The
comparison on the spectroscopy was shown in Table 5 and
validated the remarkable variation on the composition of bio-
oils considering the source material.11 For example, the obvious
peaks at time ) 35.00 min in b and c did not appear in a, and
according to analysis results, they are signals of 1,2-benzene-
dicarboxylic acid and bis(2-ethylhexyl)ester, which did not exist
in the raw bio-oil. The area of esters was increased by 20-fold
over the solid acid catalyst, including esters based on volatile
acids, such as formate and acetate, and by 12.9-fold over the
solid base catalyst. The evidence proved that 40STS presented
the high esterification activity and both solid acid and base
catalysts can convert organic acid to esters by catalytic esteri-
fication.
The composition transformation of bio-oils was shown in
Tables 6 and 7. The organic acid reacted with alcohol not only
to esters but also to acetals by nucleophilic addition over the
solid acid catalyst. Besides esterification, isomerization happened
over the solid base catalyst based on the component variation.
Zhang et al.
in upgraded bio-oil by solid acid
ethane,1,1′,1′′-[methylidynetris(oxy)]tris-
acetic acid, diethoxy-,ethyl ester
butanedioic acid, diethyl ester
1,2-benzenedicarboxylic acid, diethyl ester
in upgraded bio-oil by solid alkali
butanedioic acid, diethyl ester
1,2-benzenedicarboxylic acid, diethyl ester
2-methyl-1,3-benzenediol
2,3-dimethylbenzoic acid
4. Conclusions
(1) Both the solid acid catalyst 40STS and the solid base
catalyst 30KAN can catalyze the model esterification of ethanol
and acetic acid. 40STS achieved higher catalytic activity on
esterification than 30KAN. (2) The catalytic esterification
stabilized the bio-oil with lowered dynamic viscosity and
enhanced fluidity, which was sustained after the dehydration
by 3A molecular sieve and aging for 8 months as well. (3) The
upgraded bio-oils were observed with density decreased from
1.24 to 0.96 kg/m3, and the gross calorific value increased by
50.7 and 51.8% over 40STS and 30KAN, respectively. The pH
value of upgraded bio-oil over the solid acid catalyst was
lowered from 2.60 to 1.12 for the catalyst acidification, while
the pH value of upgraded bio-oil over the solid base catalyst
rose to 5.93. The water content was lowered from 29.79 to 11.21
and 11.02% by catalytic esterification over solid acid and solid
base catalysts, separately, and partial dehydration by 3A
molecular sieve. (4) The analysis on the composition proved
that catalytic esterification occurred over both solid acid and
solid base catalysts, and the proportion of esters in the upgraded
bio-oils increased remarkably, by 20-fold over the solid acid
catalyst. Both volatile and nonvolatile acids can be converted
to esters over the 40STS catalyst, indicating its high activity.
(5) Over the solid acid catalyst, the organic acid reacted with
alcohol not only to esters but also to acetals by nucleophilic
addition. Besides esterification, isomerization happened over the
solid base catalyst based on the component variation.
Acknowledgment. The authors thank the National Natural
Science Foundation of China (50476090) and the Natural Science
Foundation of Guangdong Province (04000378) for financial
support.
EF060224O