Professional Documents
Culture Documents
2717
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
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 Biooil 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 hydrodeoxygenation,3-53-5 catalytic cracking of pyrolysis vapors,66
* To whom correspondence should be addressed. Telephone: 086-02087057787. 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 fixedbed 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.
Zhang et al.
no catalyst
(%)
solid acid/
40STS (%)
solid base/
30KAN (%)
15
100
23.7
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
and Upgraded Bio-oils after 8 Months of Aging Storage
dynamic viscositya
(partially hydrated bio-oils) (mm2/s)
fresh
aged for 8 months
a
original
bio-oil
upgraded bio-oil
by solid acid
upgraded bio-oil
by solid base
120.7
135.6
5.161
7.645
6.077
7.783
Measured at a temperature of 20 C.
Table 3. Properties of Raw and Upgraded Bio-oils
properties
original
bio-oil
upgraded
bio-oil by
solid acid
upgraded
bio-oil by
solid base
pH
density (kg/m3)
H2O content
gross calorific value (kJ/kg)
2.60
1.24
29.79
15 834.7
1.12
0.96
13.60
23 868.7
5.93
0.97
12.35
24 034.9
properties
raw
bio-oil
upgraded
bio-oil by
solid acid
upgraded
bio-oil by
solid base
pH
density (kg/m3)
H2O content
gross calorific value (kJ/kg)
3.58
1.26
26.34
16 752.8
1.12
0.96
11.21
24 975.5
5.54
0.93
11.02
24 478.1
bio-oil
upgraded bio-oil by solid acid
upgraded bio-oil by solid base
organic acids
(nonvolatile)
esters
10.0
12.82
12.55
1.33
28.00
18.46
Zhang et al.
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
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