Energy Conversion and Management 48 (2007) 11321139

www.elsevier.com/locate/enconman

Bio-syngas production from biomass catalytic gasication

Pengmei Lv
a

a,*

, Zhenhong Yuan a, Chuangzhi Wu a, Longlong Ma a,

Yong Chen a, Noritatsu Tsubaki b

Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, No. 2 Nengyuan Road, Tianhe, Wushan,
Guangzhou 510640, Peoples Republic of China
b
School of Engineering, Nagoya University, Gofuku, Toyama, Japan
Received 26 December 2004; received in revised form 23 April 2006; accepted 29 October 2006
Available online 12 December 2006

Abstract
A promising application for biomass is liquid fuel synthesis, such as methanol or dimethyl ether (DME). Previous studies have studied
syngas production from biomass-derived char, oil and gas. This study intends to explore the technology of syngas production from direct
biomass gasication, which may be more economically viable. The ratio of H2/CO is an important factor that aects the performance of
this process. In this study, the characteristics of biomass gasication gas, such as H2/CO and tar yield, as well as its potential for liquid
fuel synthesis is explored. A uidized bed gasier and a downstream xed bed are employed as the reactors. Two kinds of catalysts: dolomite and nickel based catalyst are applied, and they are used in the uidized bed and xed bed, respectively. The gasifying agent used is
an air-steam mixture. The main variables studied are temperature and weight hourly space velocity in the xed bed reactor. Over the
ranges of operating conditions examined, the maximum H2 content reaches 52.47 vol%, while the ratio of H2/CO varies between 1.87
and 4.45. The results indicate that an appropriate temperature (750 C for the current study) and more catalyst are favorable for getting
a higher H2/CO ratio. Using a simple rst order kinetic model for the overall tar removal reaction, the apparent activation energies and
pre-exponential factors are obtained for nickel based catalysts. The results indicate that biomass gasication gas has great potential for
liquid fuel synthesis after further processing.
 2006 Elsevier Ltd. All rights reserved.
Keywords: Syngas; Biomass; Catalytic gasication

1. Introduction
Syngas plays an important role as an intermediate in the
production of several industrial products, such as Fischer
Tropsch liquids, methanol and ammonia. Currently, syngas is produced from fossil fuels, mainly coal, natural gas
and naphtha. Syngas from renewable resources, such as
biomass, exhibits a promising prospective [17]. This is
because biomass is a CO2 neutral resource and is distributed extensively in the world. Several biomass to methanol
demonstration projects have been developed recently, such
as the Hynol project in the United States, the BioMeet and

Corresponding author. Tel.: +86 20 87057729; fax: +86 20 87057737.

E-mail address: lvpm@ms.giec.ac.cn (P. Lv).

0196-8904/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2006.10.014

Bio-Fuels projects in Sweden and the BGMSS project in

Japan [810]. Although more and more interest has been
focused on this subject, little study was found to address
this topic [1114]. Classifying the literature involved in this
subject, it can be found that three dierent routes of syngas
from biomass were studied. They were syngas from biomass-derived oil [11], syngas from biomass-derived char
[12,13] and syngas from reforming of biomass gasication
gas [14]. Panigrahi et al. [11] explored synthesis gas production from steam gasication of biomass-derived oil. Dierent gasifying agents, mixtures of CO2 and N2, H2, N2 and
steam were used. In their study, syngas (H2 + CO) ranged
from 75 to 80 mol%. Chaudhari et al. [12,13] investigated
synthesis gas production from biomass-derived char. Their
objective was to provide information on dierent optimum
conditions for producing gases for dierent applications.

P. Lv et al. / Energy Conversion and Management 48 (2007) 11321139

1133

Nomenclature
kinetic constant for tar elimination (m3 (Tb,wet)/
kg h)
A
pre-exponential factor for k (m3 (Tb,wet)/kg h)
R
gas constant (kJ/mol K)
E
apparent activation energy for overall tar removal (kJ/mol)
Q
gas ow rate [m3 (Tb,wet)/h]
T = Tb temperature measured in center of xed bed (C)

Wang et al. [14] studied syngas from reforming of biomass

gasication gas by adding of biogas.
From the above discussion, it was easily discovered that
few studies referred to syngas from direct gasication of
biomass. Hence, there is a need for a systematic study in
this direction. Therefore, the purpose of this study is to test
the feasibility of syngas from direct biomass gasication,
which is a more compact process because pure biomass
air gasication produces a gas with a low H2/CO ratio,
which is not suitable for further synthesis of liquid fuel.
Therefore, gasifying agents air and steam were used in this
study and common catalysts were applied to improve the
H2/CO ratio as well as to decrease tar yield.
2. Experimental section
2.1. Feed materials and catalysts
Pine sawdust obtained from a timber mill in Guangzhou
City, China, was used as the feedstock for experimental
runs. The particle size of this pine sawdust is between 0.3
and 0.45 mm. Its proximate and ultimate analyses are
reported in Table 1.
Calcined dolomite and nickel based catalysts were used
in the experiments, which were proved to be quite active for
tar elimination [1517]. The dolomite was rst crushed and
sieved to obtain a fraction with a particle sized 0.3
0.45 mm and then calcined in air at 900 C for 4 h. Its
chemical composition is presented in Table 2. Nickel based

Table 1
Proximate and ultimate analysis of pine sawdust
Moisture content (wt% wet basis)
Higher heating value (MJ/kg)
Proximate analysis (wt% dry basis)
Volatile matter
Fixed carbon
Ash
Ultimate analysis (wt% dry basis)
C
H
O
N
S

8
20.2
81.0
18.5
0.5
51.26
5.54
42.29
0.18
0.23

X
W

tar conversion, dimensionless

weight of catalyst in xed bed (kg)

Greek Symbols
o
tar concentration in ue gas (kg/m3)
s
space time, dened as W/Q [kg h/m3(Tb,wet)]

catalysts of Z409R were used in the catalytic reactor, which

were produced in Qilu PetroChemical Company, Shandong Province, China. Z409R is annular with a size of /
16 /6 6.06.8 mm and a composition of NiO P
22 wt%, K2O of 6.5 0.3 wt%.
2.2. Apparatus
The tests were performed in an atmospheric pressure,
indirectly heated, uidized bed gasication system, which
is shown schematically in Fig. 1. Its major components
are: a uidized bed gasier, a biomass feeder, a steam generator, an air compressor, a cyclone and a catalytic xed
bed reactor.
The reactor is made of 1Cr18Ni9Ti stainless steel pipe
and is externally heated by two electric furnaces. The total
height of the reactor is 1400 mm, with a bed diameter of
40 mm and a freeboard diameter of 60 mm. Along the total
height of the reactor, there are 5 temperature and pressure
taps for temperature and pressure detection. Below the
reactor, one air distributor is installed for better air distribution. The distributor is 3 mm in thickness and 25 holes
(i.d. 1 mm) are perforated uniformly in it. The biomass is
fed into the reactor through one screw feeder driven by a
variable speed metering motor. Air is used as the uidizing
agent and comes from the air compressor. Before the air
enters the reactor, it is preheated to 65 C for better performance. The steam of 154 C is produced in a steam generator (Model SZ0.015-0.40, Guangzhou Zhongli Boilers
Auxiliary Machine Co., Ltd., Guangdong, China). Before
the steam ows into the reactor above the biomass feeding
point, it is metered by a steam ow meter. The produced
gas ow exits the reactor, then passes through a cyclone,
which is heated to 200 C to prevent the tar contained in
the gas from condensing in it. The xed bed reactor is
externally heated by an electric furnace. Its length is
400 mm with an inner diameter of 38.5 mm.

Table 2
Chemical composition of uncalcined dolomite (wt%)
Sample

CaO

MgO

SiO2

Al2O3

Fe2O3

Loss

Total

Dolomite

31.2

19.5

2.35

0.34

0.24

46.15

99.78

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P. Lv et al. / Energy Conversion and Management 48 (2007) 11321139

Gas and tar
sampling
T

Valve
T
T,P

Cyclone

Gasifier

To
exhaust
burner

Fixed-bed
reactor
Gas and tar
sampling

Heators
T

Hopper

Steam
flowmeter

T,P

Steam
generator

Air distributor

Air
compressor
Gas
flowmeter

Fig. 1. Schematic diagram of biomass catalytic gasication for syngas production.

Prior to each test, an amount of 120 g/(kg h1) biomass calcined dolomite mixed with 30 g silica sand (0.2
0.3 mm) were put in the gasier. Since calcined dolomite
is soft, it erodes during the test and is eluted out of the
bed with the ue exit gas. Therefore, some calcined dolomite was mixed with the pine sawdust carefully by hand
and continuously fed into the gasier to attain a steady
state. The feeding rate of calcined dolomite was determined by preliminary test. At the end of each test, calcined dolomite left in the gasier is separated and
measured. Thus, the weight percent of calcined dolomite
in the gasier bed during operation can be known, and
it is about 6571 wt% over the ranges of experimental
conditions examined.

Electric
heating

The measurement accuracy for the gas ow meter, temperature sensor, manometer, steam ow meter is 0.06
N m3/h, 10 C, 0.25 kPa, 0.05 kg/h, respectively.
To ensure the reliability of the test data, each experiment was repeated 2 times and the results had good agreement. The data reported in this paper is average values of
the two times.
2.3. Gas and tar analysis
The cool, dry, clean gas was sampled using gas bags and
analyzed on a gas chromatograph (Model GC-2010, Shimadzu, Japan), which is tted with a GS carbon plot
column (30 m 0.530 mm 3.00 lm), ame ionization

Quartz fiber filter

Steel tube

Volume flow meter

Silica gel

Ice bath

Cool bath

Gas washing bottles content CH2C 2

Fig. 2. Schematic diagram of tar sampling system.

P. Lv et al. / Energy Conversion and Management 48 (2007) 11321139

detector (FID) and thermal conductivity detector (TCD),

and standard gas mixtures are used for quantitative
calibration.
The tar sampling line is shown in Fig. 2. Dichloromethane cooled to approximately 10 C is used to condense
and collect the tar.
A gas chromatograph HP-4890 is used to analyze the tar
sample. The operating conditions are: 30 m 0.25 mm
0.25 lm, HP-5 capillary column; carrier gas, N2; temperature program: 75 C (hold 5 min) to 285 C at 3 C/min
(hold 40 min); injector and detector temperature, 280 C.

1135

rst increases and then decreases with temperature and

reaches the maximum value of 4.45 at the temperature of
750 C, as shown in Fig. 3. Fig. 3 indicates that the value
of H2/CO ranges between 3.11 and 4.45, a quite high ratio.
Fig. 3 also indicates that temperature is an important factor for controlling H2/CO ratio
CO H2 O CO2 H2 41 kJ=mol

CH4 H2 O CO 3H2  206 kJ=mol

C H2 O CO H2  131 kJ=mol

2
3

C CO2 2CO  172 kJ=mol

3. Results and discussion

3.1. Eects of dierent xed bed reactor temperature
4.6

As listed in Table 3, run no. 1, the operating conditions

in the uidized bed were kept constant, while the temperature in the catalytic reactor was varied to perform a series
of tests. In Table 3, equivalence ratio is dened as the
actual oxygen to fuel ratio divided by the stoichiometric
oxygen to fuel ratio needed for complete combustion.
The experimental results are presented in Table 4.
Table 4 shows that the content of H2 exhibits an increasing trend with temperature. This is an expected result
because most H2 production reactions are endothermic.
The content of CH4 decreases with temperature because a
higher temperature strengthens the steam reforming reaction of CH4. The content of CO rst decreases and then
increases with temperature, which indicates reactions (1)
(4) happen simultaneously in the process. As a result of
the variation trend of H2 and CO, the ratio of H2/CO also

4.4

Value of H2/CO

4.2
4.0
3.8
3.6
3.4
3.2
3.0
650

700

750

800

850

Temperature ()
Fig. 3. Eect of temperature on the value of H2/CO.

Table 3
Operating conditions in the uidized bed reactor
Run no.

Biomass feed rate (kg/h)

0.47
Air (N m3/h)
0.65
Steam (kg/h)
0.4
Equivalence ratio
0.30
Gasier bed outlet gas composition(dry, inert-free, vol%)

Run no.

0.54
0.65
0.4
0.25

Steam-to-biomass ratio
Calcined dolomite feeding rate (g/h)
Calcined dolomite in the gasier (g)
Gasier bed temperature (C)

0.85
14
56
800

0.75
16
65
800

Run no.

H2

CH4

CO

CO2

C2

Gas yield (N m3/kg biomass, wet basis)

Tar yield (g/kg biomass)

1
2

38.38
38.13

7.02
7.48

24.89
26.06

27.62
26.20

2.09
2.14

1.56
1.54

13.85
19.05

Table 4
Experimental results of dierent xed bed temperature at the condition of run no. 1
Reactor temperature (C)
Dry, inert-free, gas composition (vol%)
H2
CH4
CO
CO2
C2
Gas yield (N m3/kg biomass) (wet basis)
Tar yield (g/kg biomass) (wet basis)

650
46.28
5.24
14.89
32.16
1.42
1.87
6.43

700
49.33
4.89
12.28
32.81
0.69
2.12
5.53

750
49.65
4.37
11.15
34.37
0.46
2.15
4.42

800
50.23
4.3
12.3
32.56
0.6
2.24
4.29

850
52.47
2.9
14.82
29.65
0.16
2.41
2.35

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P. Lv et al. / Energy Conversion and Management 48 (2007) 11321139

Table 5
Experimental results of dierent reactor WHSV (h1) at the condition of run no. 2, Tb = 700 C
WHSV (h1)

10.7

7.2

5.4

4.3

3.6

3.1

2.7

Dry, inert-free, gas composition (vol%)

H2
CH4
CO
CO2
C2
Gas yield (N m3/kg biomass) (wet basis)

42.84
6.59
20.35
28.62
1.61
1.86

46.67
5.67
17.35
29.42
0.9
1.97

47.61
5.18
16.44
30.12
0.66
2.01

47.62
4.79
16.87
30.08
0.65
2.09

47.84
5.12
15.93
30.18
0.94
2.13

48.93
5.14
15.33
29.99
0.62
2.19

49.09
4.72
14.78
30.73
0.64
2.22

3.2. Experimental results of dierent Weight Hourly Space

Velocity (WHSV)
Weight hourly space velocity (WHSV) is dened as the
mass ow rate of biomass fed to the gasier divided by
the mass of catalyst in the catalytic reactor. Keeping the
operating conditions listed in Table 3, run no. 2 constant,
the experimental results of dierent WHSVs in the catalytic
reactor is presented in Table 5. As shown in Table 5, the
content of H2 shows an upward trend with increasing residence time, while the content of CH4 and CO decreases
with increasing residence time. The content of CO2 has lit-

3.4

Tb=700
Tb=800

3.2

Value of H2/CO

3.0
2.8
2.6
2.4
2.2
2.0
1.8

tle change. The above phenomena indicate that applying

more catalysts is favorable for H2 production.
The value of H2/CO for two dierent temperatures in
the xed bed reactor is shown in Fig. 4. For the temperatures of 700 C and 800 C, the values of H2/CO vary
between 2.11 and 3.32, 1.87 and 2.78, respectively. Fig. 4
indicates that the ratio of H2/CO increases with residence
time. This is an obvious result, which can be seen from
Table 5. Another phenomena found from Fig. 4 is that
the ratio of H2/CO at 700 C is higher than that at
800 C. This result is in accordance with the conclusion
drawn from Fig. 3. That is, there exists a maximum value
of H2/CO for the dierent temperatures. This is possibly
caused by the water gas shift reaction (1) being exothermic;
so a higher temperature is not favorable for CO consumption, which lowers the CO transformation rate, which
results in a smaller value of H2/CO.
Observing Fig. 4, we can also nd that there appears an
extraordinary decrease in the H2/CO ratio at WHSV just
higher than 4 h1. This can be explained by the residence
time being shorter than the minimum time needed for some
secondary reactions of biomass gasication gas to proceed
when WHSV is higher than 4 h1. This results in a slight
increase of H2 content and, thus, makes a quite small increment of H2/CO ratio when WHSV is higher than 4 h1.
3.3. Comparison of dierent routes for bio-syngas production

10

12

Table 6 lists a comparison of the dierent routes for biosyngas production and process D represents this study. As
Table 6 indicates, process A yields the least hydrogen,

-1

Weight Hourly Space Velocity (h )

Fig. 4. Eect of WHSV on the value of H2/CO.

Table 6
Comparison of dierent routes for bio-syngas production
Process

A [11]

B [13]

C [14]

Feedstock
Gasifying agent
Reforming method
Use of catalyst
Typical gas composition (dry, inert-free,
mol%)
H2
CO
CO2
CH4
Others
Range of H2/CO

Biomass-derived oil
H2 and N2

No

Biomass-derived char
Steam

No

Biomass-derived gas
Air-steam
Biogas or CH4 reforming
Yes

Biomass
Air-steam

Yes

33.3
29.0
4.9
17.0
15.8
1.152.41

70.0
14.8
14.1
1.1

4.07.0

57.64
36.62
3.07
2.38

1.421.57

52.47
14.82
29.65
2.9
0.16
1.874.45

P. Lv et al. / Energy Conversion and Management 48 (2007) 11321139

while process B produces a maximum H2 content and

thereby the highest H2/CO ratio. Processes C and D produce comparable H2 quantities. From Table 6, we can
know that the H2/CO ratio is quite high from direct biomass catalytic gasication. Process D has the highest content of CO2, which is caused by the catalytic activity of
nickel catalysts on the water gas shift reaction (1). This
can be settled by controlling operation conditions and

1137

modifying the nickel catalyst to make it have low selectivity

on the WGSR. The advantage of process D is that it produces syngas in one step, while the other processes need
two steps. This means it has more compact equipment
and may be more economically viable.
Based on the above analysis, it can be concluded that
biomass catalytic gasication has great potential for syngas
production and has a good economic outlook.

Fig. 5. Gas chromatogram of tar sample in the inlet of xed bed reactor.

Fig. 6. Gas chromatogram of tar sample in the exit of xed bed reactor.

1138

P. Lv et al. / Energy Conversion and Management 48 (2007) 11321139

4.4
4.2
4.0

ln(k)

3.8
3.6
3.4
3.2
3.0
0.00090

0.00095

0.00100

0.00105

0.00110

1/T(1/K)

Acknowledgements

Fig. 7. Arrhenius plot for tar catalytic cracking.

3.4. Tar yield analysis and kinetic model construction for tar
cracking
Figs. 5 and 6 show the gas chromatogram of tar samples
taken from the inlet and outlet of the xed bed reactor,
respectively. It is obvious that both the species and the
quantity of tar are reduced greatly in the presence of nickel
based catalysts.
Although there are hundreds of species in the tar sample, in order to simplify the analysis, all the species are treated as a single one lump. This approach has been accepted
by many institutions working worldwide in catalytic hot
gas cleaning [18]. It uses the following single rst order
kinetic equation:


d@
k@
dt

which can be used in integrated form, working under piston or plug ow conditions, as
k  ln1  X =s

Also, for k, it abides by the Arrhenius equation as

k A expE=RT
Eq. (7) can be further transformed as


E 1
lnk lnA 
R T

catalytic gasication, which is favorable for methanol or

DME synthesis. However, besides H2 and CO, there is also
a lot of CO2 and CH4 in the gases, which needs to be
decreased through modifying the catalysts and controlling
operating conditions. The maximum H2 content reaches
52.47 vol%. An appropriate temperature (750 C for the
current study) and more catalyst are more favorable for
getting a higher H2/CO ratio.
From the comparison of this technology with others, it
can be seen that great potential exists for syngas production from direct biomass gasication.
A single one lump model is perfect for tar destruction
analysis. Applying this model, E and A can be determined
as 51 kJ/mol and 14476 (m3 (Tb,wet)/kg h), respectively.

Eq. (8) is linear. By applying k (determined by Eq. (6)) and

T to it; the values of E and A can be determined. A calculation result for the condition listed in Table 4 is presented
in Fig. 7, which shows good linearity. The E and A values
determined by Fig. 7 are 51 kJ/mol and 14476 (m3 (Tb,wet)/
kg h), respectively. This value of E is in near agreement
with Aznar et al.s experimental data, 58 kJ/mol [18].
4. Conclusion
The results show that quite a high ratio of H2/CO, ranging between 1.87 and 4.45, can be obtained from biomass

The nancial support received from the National Natural Science Foundation of China (Project No. 50576100),
Guangdong Province Key Laboratory Open Foundation
(Project No. 50610117) and Guangdong Province Natural
Science Foundation (Project No. 003045) is gratefully
appreciated.
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