JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY

Volume 38, Issue 5, October 2010

Online English edition of the Chinese language journal

Cite this article as: J Fuel Chem Technol, 2010, 38(5), 554559 RESEARCH PAPER

Fast pyrolysis of biomass for bio-oil with ionic liquid and

microwave irradiation
DU Jun1,*, LIU Ping1, LIU Zuo-hua1,2, SUN Da-gui1, TAO Chang-yuan1

1
College of Chemistry & Chemical Engineering, Chongqing University, Chongqing 400044, China
2
Key Laboratory of the Three Gorges Reservoir Region’s Eco-Environment, Ministry of Education, Chongqing University,
Chongqing 400044, China

Abstract: The pyrolysis of rice straw and sawdust under microwave irradiation was performed with ionic liquids (ILs)
1-butyl-3-methylimidazolium chloride and 1-butyl-3-methylimidazolium tetrafluoroborate as catalysts. With microwave heating for 20
min, the bio-oil yield from rice straw reached 38% and that from sawdust reached 34%. The effects of microwave heating time,
microwave power, and IL dosage on bio-oil yields were discussed. The chemical components in bio-oil were analyzed by gas
chromatography–mass spectroscopy technique. The main components in bio-oil are furfural, acetic acid, and 1-hydroxy-2-butanone,
and their contents mainly depend on the source of biomass and the type of IL used in pyrolysis.
Key words: biomass; pyrolysis; microwave; ionic liquid

Biomass is a renewable energy, which is an important
component of energy security strategy for the sustainable
development. The exploitation of biomass has attracted wide
attention since 1980[1]. The biomass energy utilization
techniques could be classified into three types[2–4]: direct
combustion, biochemical conversion, and thermochemical
conversion. Direct combustion includes stove combustion and
boiler combustion. The existing problem of direct combustion
is low thermal efficiency. Anaerobic fermentation and use of
biological enzymes are the main techniques for biomass
conversions. However, the rate of transformation is slow,
especially for lignocelluloses, and the waste liquids need
secondary treatment. Also, there still exist some difficulties in
mass production of enzymes. Thermochemical conversion of
biomass is a promising route for producing bio-oils and gases
with high heat values from the biomasses with low heat values.
But the bio-oils from the thermochemical conversion of the
biomass are of high oxygen content, poor stability, and
complicated components. Thus, upgrading of the pyrolyzed
vapor over zeolite catalyst has been performed to produce
liquid with a boiling point range comparable to gasoline. Some
research groups have focused their work on the catalyst and
the selection of heating source, as well as pyrolysis reaction
conditions. But the thermochemical conversion of biomass
usually needs a relatively higher temperature of more than
500qC to maximize the yields of total hydrocarbon products. It
is necessary to explore or establish a facile route for biomass
conversions for obtaining the maximum liquid yields.
As it has been revealed, the selection of heating source is an
important aspect for biomass pyrolysis[5]. Most research on
pyrolysis is conducted using the conventional heating methods.
For these methods, the first step is the heat transfer via
conduction, convection, or irradiation from the heating source
to increase the temperature of biomass[6]. Thus, the relatively
lower efficiency of the heating source remains an issue in
practical applications. Recently, with the development of
microwave heating technology, extensive attentions have been
focused on the application of microwave heating in biomass
pyrolysis[7,8]. Compared with traditional heating method,
microwave heating has shown some special results for biomass
pyrolysis. For example, the compositions of bio-oil produced
from microwave-assisted pyrolysis were different from those
obtained by conventional heating method[9,10].
To improve the yield of bio-oil, various catalysts or
additives were investigated in biomass pyrolysis[11–14]. Aho et
al[15] recently studied the influence of ZSM-5 zeolite structure
on bio-oil yields and compositions in a fluidized bed. They
found that three most dominant compounds in the bio-oil were
acetic acid, 1-hydroxy-2-propanone, and 2-methoxy-4-
methylphenol But only a few research focused on the
catalytic pyrolysis process combined with microwave heating
method. Chen et al[16] studied the effect of eight catalysts,

Received: 12-Mar-2010; Revised: 08-Jun-2010

* Corresponding author. Tel: 86-15723069821, E-mail: dujune@cqu.edu.cn
Copyright ” 2010, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
 DU Jun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(5): 554559
which included four inorganic sodium salts, iron sulfate,
phosphoric acid, TiO2, and HZS-5, on the performances of
microwave heating–assisted pyrolysis of pine wood sawdust.
The components in produced bio-oils were compared with
those in bio-oils obtained by traditional heating method. They
found that all the eight additives more or less increased yields
of solid products and decreased yields of gaseous products.
Until now, most research is focused on inorganic additives.
Research on the influences of catalysts or additives on the
performances of pyrolysis process is still in its infancy.
Research related with the screening of high-effect additives or
catalysts is one of the hotspot in biomass pyrolysis.
It has been noticed that room temperature ionic liquids (ILs)
have found their significant applications in many aspects, such
as green solvent, catalyst, microwave absorbent, etc. Rogers
reported the dissolution of cellulose in ILs and indicated that
ILs would be promising solvents for the chemical utilization of
biomass[17]. In 2007, Argyropoulos demonstrated that wood
biomass was readily soluble in various imidazolium-based ILs
under mild conditions[18]. With ILs as solvents or additives, the
hydrolysis or chemical transformation of glucose, fructose, and
cellulose to produce 5-hydroxymethylfurfural had also been
studied intensively[19–21]. Meanwhile, ILs can act as an
effective microwave absorbent because of their special
structure and properties. It could be predicted that when ILs
were used as additives for pyrolysis of biomass under
microwave irradiation, ILs would interact with biomasses in
large contact areas and absorb microwave energy effectively to
facilitate the pyrolysis of the biomass. However, few studies
have focused on the microwave pyrolysis of biomass with the
incorporation of ILs as catalysts or additives. The product
distribution under IL–microwave pyrolysis conditions deserves
further investigations.
To determine effective catalysts and microwave absorbents
for biomass pyrolysis, imidazolium-based ILs were used as
catalysts or additives in pyrolysis of biomass under microwave
irradiation. Two types of ILs were used for pyrolysis of rice
straw and sawdust biomasses under microwave irradiation.
The influences of ILs combined with microwave heating on
product yields were investigated. The compositions of bio-oils
were analyzed by gas chromatograph–mass spectroscopy
(GC–MS) technique, and the distributions of the products were
discussed.
Table 1 Ultimate analysis and component analysis of the biomass
Ultimate analysis w /%
Parameter
C H O N
Rice straw 48.87 5.84 44.38 0.74
Sawdust 45.15 4.78 35.49 0.39
1 Experimental
1.1 Biomass and catalyst
Two typical biomasses of rice straw and sawdust obtained
from the suburbs of Chongqing, China, were selected. The
component analysis and the ultimate analysis of the biomasses
were performed according to the method described by Xiong
et al[22]. The analysis results are listed in Table 1.
Two ILs, 1-butyl-3-methylimidazolium chloride (IL-C) and
1-butyl-3-methy-limidazolium tetrafluoroborate (IL-B), were
purchased from Henan Lihua Pharmaceutical Co., Ltd., with
purity of 99% and used without further purification.
1.2 Microwave heating pyrolysis procedures
The biomass samples were dried, milled, sieved, and
classified to obtain fractions of uniform particle size. The
samples with mean particle size of 80 Pm were collected for
use. Before pyrolysis, the biomass was pretreated with IL
aqueous solution. In a typical procedure, 1.0 g of IL was
dissolved in 34 mL of distilled water to make an aqueous
solution of IL. 10 g of dry rice straw or sawdust samples was
immersed in the prepared aqueous solution of IL at room
temperature for 2 h and then the mixture was heated mildly to
evaporate water and dried at 80qC to a constant weight. The
mixture with the IL/biomass ration of 0.1 was obtained. Using
the same procedures, mixtures with different ratios of
IL/biomass were prepared by changing the amount of IL added
in distilled water.
Fig. 1 Schematic layout of the microwave pyrolysis
experimental setup
1. nitrogen gas cylinder; 2. gas flow meter; 3. domestic microwave oven;
4. condensing unit; 5. gas collecting bag
Component analysis w /%
S cellulose hemicellulose lignin
0.07 35.00 25.00 12.00
0.03 48.00 15.00 32.00
 DU Jun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(5): 554559
The pyrolysis of biomass was conducted in a domestic
microwave oven (WD850B, Galanz, China) with the
maximum output power of 850 W and frequency of 2.45 GHz.
Two holes (Ɏ20 mm) for gas inlet and gas outlet were made
on the back board of the oven. For each pyrolysis experiment,
5.0 g of biomass pretreated with IL was put into a 250 mL
three-neck round-bottom flask equipped with nitrogen inlet
and vent tubes, and 2 g of SiC was placed on the top of the
mixture to increase microwave absorption. Then, the flask was
placed in the microwave oven (Fig. 1). Before microwave
heating, the flask was purged for 10 min with nitrogen at a
constant flow rate of 20 mL/min to remove the air inside and
then the microwave generator was turned on. The liquid
bio-oil formed was collected in a cooling bath, and the gaseous
products were collected in a gas bag. After microwave heating,
nitrogen was kept for certain time to bring all the residual
gaseous products into the gas bag. Most of the liquid bio-oil
was collected in the cooling bath, but some of the liquid
bio-oil remained in the reaction flask. Thus, the amount of
liquid bio-oil produced (ml, g) was evaluated by the sum of the
weight increased in the cooling bath and the weight of the
residual liquid in the flask. The amount of gaseous products
(mg, g) was determined by subtracting the weight of nitrogen
from the total weight of the gas collected in the bag. If the
initial amount of biomass was m0 (g), the yields of bio-oil and
gas were calculated as follows:
ml
wl u 100%
m0
mg
wg u100%
m0
After each pyrolysis reaction, IL was recovered by
extraction with distilled water as follows. The entire residue
was transferred into a 250 mL beaker by adding distilled water
and then the flask was rinsed three times with small amount of
distilled water. The total amount of distilled water used was
a100 mL. After 0.5 h of static extraction in the beaker, the
residue was filtrated and the filtrate was first heated at 50qC to
evaporate water and residual bio-oil and then dried with
Fig. 2 Effects of microwave power on bio-oil yields under microwave irradiation for 20 min
(a): IL-C/Rice straw 0.15 and IL-C/Sawdust
: Rice straw; : Sawdust
infrared light at a80qC for 12 h to obtain a viscid liquid of IL.
1.3 Bio-oil analysis
The components of bio-oil were analyzed by GC–MS
(GC6890/MS5973, Agilent). The bio-oil products were first
filtrated with a microporous membrane, and the clear liquid
portion was then diluted with ethanol before GC–MS analysis.
The carrier gas is helium at a constant flow rate of 1 mL/min.
The initial oven temperature was 50qC kept for 2 min, then
raised to 100qC with a heating rate of 30qC/min, and then
programmed to rise from 100qC to 290qC with a heating rate
of 5qC/min and maintained at 290qC for 20 min. The
temperatures of injection port and transfer line were 290qC and
270qC, respectively. The compositions in gaseous products
were not determined.
2 Results and discussion
2.1 Yields of bio-oil and gaseous product
The experimental results revealed that the yield of both
bio-oil and gaseous product depended obviously on the
microwave power and microwave heating time. The effect of
microwave power on bio-oil yield was examined in the range
of 160–800 W (Fig. 2). Only a small amount of bio-oil was
produced when microwave power was lower than 480 W. As
microwave power increased to 640 W, bio-oil yield from rice
straw reached 38% and that from sawdust reached 18%, with
IL-C as catalyst (Fig. 2(a)). Meanwhile, with IL-B as catalyst
under the same microwave power, the bio-oil yield from rice
straw reached 32% and that from sawdust reached 24% (Fig.
2(b)). It also indicated that the bio-oil yield from rice straw
reached a stable value as microwave power increased above
640 W. Because the highest microwave power of the domestic
microwave oven was 800 W, pyrolysis at higher microwave
power was not performed.
0.35; (b): IL-B/ Rice straw 0.50 and IL-B/Sawdust 0.35
 DU Jun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(5): 554559

Fig. 3 Effects of microwave irradiation times on bio-oil yields from rice straw (a) and sawdust (b) under microwave power of 800 W
(a): IL-C/Rice straw 0.15 and IL-B/Rice straw 0.50; (b) IL-C/Sawdust 0.30 and IL-B/Sawdust 0.35
: bio-oil (IL-C); : bio-oil (IL-B); : gas (IL-C); : gas (IL-B)

Fig. 4 Effects of IL dosages on bio-oil yields under microwave power of 800 W for 20 min irradiation
: Rice straw; : Sawdust

The variations of bio-oil yields with different microwave
irradiation times were investigated. As shown in Fig. 3(a),
bio-oil yields obtained from rice straw reached a stable value
after 20 min of microwave heating with IL-C or IL-B catalyst.
But an initiation time was observed when IL-B was used as
catalyst. A bio-oil yield of lower than 8% was observed for
pyrolysis of rice straw and sawdust in the first 2 min of
microwave heating. For saw dust, when IL-B was used as
catalyst, the bio-oil yield increased rapidly after 8 min of
microwave heating and did not reach a stable value after 20
min of microwave heating. Obviously, an initiation time for
producing bio-oil was needed when IL-B was used as catalyst
in pyrolysis of biomass.
42% from rice straw was obtained when the ratio of IL-C/rice
straw reached 0.15. On the other hand, when IL-B was used as
catalyst, the yield of bio-oil from rice straw was lower than
that from sawdust. Thus, IL-C catalyst facilitated the pyrolysis
of rice straw and IL-B favors that of sawdust. These two ILs
possess the same cation but different anions. It was deduced
that anions in ILs played an important role on the pyrolysis of
biomass. Biomass of sawdust contains 32% lignin, which is
higher in comparison with 12% in rice straw. Thus, the
chemical compositions of biomasses should be another reason
for this result.
2.3 Analysis of chemical composition

2.2 Influence of IL dosages on bio-oil yields
The effects of catalyst dosages on the bio-oil yield are
shown in Fig. 4. It shows that there were no bio-oil and gas
produced without IL under microwave heating. When IL-C
was added as catalyst (Fig. 4(a)), the bio-oil yield from rice
straw was higher than that from sawdust. A maximum yield of
The bio-oils obtained from the catalytic pyrolysis of
biomasses under microwave irradiation were of reddish brown
in color. Previous studies indicated that the bio-oil was a
mixture of organic compounds, which was mainly composed
of acid, phenol, aldehyde, ketone, ester, macromolecule
saccharide, etc[23]. The compounds identified by GC–MS in
this study are listed in Table 2.
 DU Jun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(5): 554559
Table 2 Main compounds in bio-oil identified by GC–MS
Retention
Compound
time t /min IL-C/RS
2.15 1-Butanol
2.56 Propionic acid
2.74 Acetic acid
3.73 Furfural
3.17 1-Hydroxy-2-butanone
3.70 3-Methoxy-1-butanol
4.13 Furfuryl alcohol
4.25 Acetylacetone
5.55 5-Methyl furfural
6.19 2-Methyltetrahydrofuran
8.13 Dimethyl glutarate
Note: The bio-oil samples examined by GC–MS were obtained under microwave power of 640 W and irradiation time of 20 min
RS: Rice straw; SD: Sawdust
A semiquantitative analysis was accomplished by means of
the relative percentage of chromatographic area of each
compound except for ethanol and 1-butyl-3-methylimidazole.
It was found that furfural, acetylacetone, and
1-hydroxy-2-butanone were the three main compounds in
bio-oil from rice straw. Furfural was likely derived from
hemicelluloses via an intermediate like xylose. In bio-oils from
sawdust, acetic acid content was found to be relatively higher.
But no acetic acid was found from pyrolysis of rice straw
using IL-C or IL-B catalyst.
Total ion chromatogram graphs showed that the components
and their contents in bio-oil varied with the sources of biomass
and the types of ILs. We noticed that (a) furfural was the main
component in bio-oil when IL-C was used as catalyst. When
IL-B was used as catalyst with the same biomass source, the
content of furfural was lower than that when IL-C was used as
catalyst. For example, from rice straw biomass, the furfural
content was around 17.9% in bio-oil obtained with catalyst
IL-B, but the furfural content was 43.5% in bio-oil obtained
with catalyst IL-C. The fact indicated that anions in ILs played
an important role in determining the formation of furfural in
bio-oil, but the reaction mechanism remains unrevealed and it
is under our further investigation. (b) The dominant
component was acetic acid in bio-oil from the pyrolysis of
sawdust.
Compared with conventional pyrolysis, when catalyzed by
zeolite, ketones and phenols were the dominating groups of
compounds from the pyrolysis of pine biomass. The three most
dominant compounds in the bio-oil are acetic acid,
1-hydroxy-2-propanone, and 2-methoxy-4-methyl-phenol[15].
But the distributions of the compounds in bio-oil obtained by
pyrolysis under microwave irradiation were concentrated in a
narrow range, especially in bio-oils from sawdust biomass
with the dominant compounds of acetic acid and furfural
(Table 2). It could be suggested that the pyrolysis of biomass
Area /%
0.3 IL-B/RS 0.3 IL-C/SD 0.5 IL-B/SD 0.5
8.2
6.3
49.4 55.5
43.5 17.9 35.8 12.1
8.0
8.0
6.0
15.5
5.5
10.4
5.74
was proceeded in a rapid way and was comparable to the flash
pyrolysis in microwave pyrolysis. The microwave energy was
centered in the polar molecules and resulted in the breaking of
polymer molecules in an irregular way to form uniform
products. Meanwhile, in this catalytic pyrolysis with
microwave heating, the secondary reactions could be reduced
to minimum.
3 Conclusions
Fast pyrolysis of biomass for bio-oil under microwave
heating was feasible. Under the optimum condition of
microwave power of 640 W in 20 min of microwave
irradiation, the maximum bio-oil yield of 38% was obtained
from rice straw with IL-C/biomass ratio of 0.15 (g/g) and 34%
from sawdust with IL-B/biomass ratio of 0.40 (g/g).
ILs showed positive effect on the catalytic pyrolysis of
biomass under microwave heating. A rapid formation of
bio-oil was obtained in 2 min when catalyzed by IL-C, and an
initiation time of a8 min was observed for the pyrolysis of
biomass when catalyzed by IL-B.
The catalytic activities of ILs varied to some degree with the
source of biomass. IL-C mostly facilitated the pyrolysis of rice
straw and IL-B favored that of sawdust.
The distributions of compounds in bio-oil produced from
catalytic pyrolysis of rice straw and sawdust were different.
Furfural was the component produced in largest amount from
rice straw, whereas acetic acid was the preponderant
component produced from sawdust catalyzed by IL-C or IL-B.
The IL catalytic microwave pyrolysis method provided a
facile and effective route for biomass pyrolysis. The yields of
liquid bio-oil and the distributions of the chemical components
in bio-oils differed from those obtained by conventional
heating method with inorganic additives. Some possible
mechanisms for the formation of the bio-oil are presented in
 DU Jun et al. / Journal of Fuel Chemistry and Technology, 2010, 38(5): 554559
this study, but the details of the interactions between ILs and
biomasses are under further research.
Acknowledgment: The authors are grateful for the financial
support from Key Laboratory of the Three Gorges Reservoir
Region’s Eco-Environment, Ministry of Education, China. The
authors also thank Ms. Liu Y P at Lab Center of Chemistry,
Chongqing University, for GC–MS measurement.
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