Syngas production by two-stage method of biomass catalytic pyrolysis

and gasication
Qinglong Xie
a
, Sifang Kong
a
, Yangsheng Liu
b,
, Hui Zeng
a,c,
a
School of Urban Planning and Design, Shenzhen Graduate School, Peking University, Shenzhen Key Laboratory of Circular Economy, Shenzhen 518055, China
b
College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China
c
College of Urban of Environmental Sciences, Peking University, Beijing 100871, China
a r t i c l e i n f o
Article history:
Received 11 November 2011
Received in revised form 5 January 2012
Accepted 7 January 2012
Available online 14 January 2012
Keywords:
Two-stage method
Biomass pyrolysis
Gasication
Kinetics
Nickel based catalyst
a b s t r a c t
A two-stage technology integrated with biomass catalytic pyrolysis and gasication processes was
utilized to produce syngas (H
2
+ CO). In the presence of different nickel based catalysts, effects of
pyrolysis temperature and gasication temperature on gas production were investigated. Experimental
results showed that more syngas and char of high quality could be obtained at a temperature of
750 C in the stage of pyrolysis, and in the stage of gasication, pyrolysis char (produced at 750 C)
reacted with steam and the maximum yield of syngas was obtained at 850 C. Syngas yield in this study
was greatly increased compared with previous studies, up to 3.29 N m
3
/kg biomass. The pyrolysis process
could be well explained by Arrhenius kinetic rst-order rate equation. XRD analyses suggested that for-
mation of Mg
0.4
Ni
0.6
O and increase of Ni
0
crystallite size were two main reasons for the deactivation of
nickel based catalysts at higher temperature.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Energy crises and environmental problems have led to an
increasing focus on renewable energy sources, alternative to tradi-
tional fossil fuels. Biomass is the only carbon-containing renewable
source, making it suitable for fuel production and chemical feed-
stock (Kantarelis and Zabaniotou, 2009). Among biomass utiliza-
tion technologies, thermochemical methods including pyrolysis
and gasication are currently most appropriate and widely com-
mercially used (Encinar et al., 2000). Syngas produced from bio-
mass pyrolysis and gasication is an important intermediate for
synthesis of large numbers of industrial products (e.g., methanol
and ammonia) (Chmielniak and Sciazko, 2003; Hamelinck and
Faaij, 2002; Tijmensen et al., 2002). Thus, maximizing the syngas
yield from biomass will largely promote the biomass utilization
with high efciency.
Up to date, research about syngas production from biomass
mainly focuses on gasication technologies. According to different
tar removal technologies involved, biomass gasication process
can broadly be divided into two approaches: primary methods
and secondary methods (Devi et al., 2003). In primary methods,
gasication process and tar elimination are carried out simulta-
neously in gasier; while in secondary methods, gas cleanup is
conducted in a separate reformer in downstream of the gasier.
The primary methods have gained much attention (Ahmed and
Gupta, 2009; Gransson et al., 2011; Karmakar and Datta, 2011;
Moghtaderi, 2007; Ueki et al., 2011). Ahmed and Gupta (2009)
examined steam gasication of cardboard using a batch reactor,
obtaining syngas of about 1.2 N m
3
/kg biomass at 600 C. Karmakar
and Datta (2011) studied steam gasication of rice husk in a uid-
ized bed reactor and generated syngas with a maximum yield
of 1.21 N m
3
/kg biomass and lower heating value (LHV) of 11.18
MJ/N m
3
at 750 C. Moghtaderi (2007) investigated steam gasica-
tion of pine sawdust catalyzed by Ni/Al
2
O
3
and observed a maxi-
mum H
2
yield of 1.6 N m
3
/kg biomass at 600 C. Although primary
methods eliminate the need for downstream cleanup, they cannot
effectively solve the purpose of tar reduction without affecting the
useful gas composition and heating value (Devi et al., 2003). As a
result, the syngas yields in primary methods will be relatively low
compared with those in secondary methods.
Extensive studies on secondary methods of biomass gasication
have also been conducted (Gao et al., 2009; Lv et al., 2007; Wang
et al., 2006; Xiao et al., 2011; Yang et al., 2010). By steam gasica-
tion of pine sawdust using an updraft gasier combined with a por-
ous ceramic reformer, Gao et al. (2009) obtained syngas with a
maximum yield of 1.72 N m
3
/kg biomass and lower heating value
(LHV) of 11.73 MJ/N m
3
at 950 C. Employing a uidized bed gasier
and a downstreamxed bed as the reactors, Lv et al. (2007) studied
catalytic gasication of pine sawdust and the maximum gas yield
reached 2.41 N m
3
/kg biomass at 850 C. Similarly, Xiao et al.
(2011) utilized primary uidized bed and secondary reforming
0960-8524/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2012.01.028

Corresponding authors. Tel./fax: +86 10 62751756.

E-mail addresses: yshliu@pku.edu.cn (Y. Liu), zengh@szpku.edu.cn (H. Zeng).
Bioresource Technology 110 (2012) 603609
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j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
xed bed to investigate steam gasication of waste biomass with
Ni/BCC as catalyst and obtained syngas with a yield of 2 N m
3
/kg
biomass and LHV of 14 MJ/N m
3
at about 600 C. Secondary meth-
ods are effective in reducing tar content and improving syngas yield,
but additional equipments required will increase the investment.
Despite the large number of studies on syngas production, in
most cases, the processes of pyrolysis and gasication are con-
ducted at the same temperature. However, effects of temperature
on syngas production may differ in these two completely distinct
processes. Therefore, if pyrolysis and gasication processes can
be separated and investigated, respectively, effect of temperature
on syngas yield in each process will be clearer, and the optimum
parameters for syngas yield would be found accordingly.
In this study, pyrolysis and gasication processes were sepa-
rately conducted using the same apparatus with the presence of
catalysts, and effect of temperature on syngas yield was considered,
respectively in each process. The purpose of this study is to explore
the optimum temperature for both pyrolysis and gasication pro-
cesses, thereby maximizing syngas yield. The mechanismof catalyst
deactivation in higher temperature was also investigated.
2. Methods
2.1. Materials and catalysts
The pine sawdust was obtained from Shaoguan City in
Guangdong Province, China. Its physico-chemical properties includ-
ing proximate and element analyses are shown in Table 1. The high
content of cellulose and low content of ash favor the pyrolysis
process and syngas production. According to the elemental analysis,
the chemical formula of the rawmaterial that derives is CH
1.72
O
0.61
.
Prior to its use, the sawdust samples were ground using a rotary
cutting mill and then screened to limit the particle size smaller than
0.3 mm. Afterwards, these ground samples were dried for 24 h at
105 0.5 C.
The catalysts used in the experiments were primarily nickel
based catalysts. Five types of nickel based catalysts were chosen,
i.e., Z402,Z405,Z409,Z412 and Z413, which were commercially
available from Qilu PetroChemical Company in Shandong Province,
China. The catalyst supports for Z402 and Z405 are MgOnAl
2
O
3
(n = 12) and CaOnAl
2
O
3
(n = 12), respectively, and a-Al
2
O
3
act
as the support for the catalysts including Z409,Z412 and Z413.
The mass contents of the active component of Ni for these ve cat-
alysts are (wt.%): 12.6, 10.1, 17.3, 11.0 and 11.0, respectively. In
order to further improve the catalytic activities, ve catalysts were
Table 1
Characteristics of pine sawdust (dry basis).
Biomass
sample
Proximate analysis/% Elemental analysis/% Component analysis HHV
a
(MJ/kg) LHV
b
(MJ/kg)
Moisture Volatile Ash Fix carbon C H O N S Cellulose Hemicellulose Lignin
Pine sawdust 13.43 73.45 2.01 11.11 42.74 6.11 34.88 0.14 0.70 56.85 15.16 12.70 16.71 15.00
a
Higher heating value.
b
Lower heating value.
Table 2
Comparison of nickel based catalysts with mineral catalysts in biomass pyrolysis at 800 C.
Catalyst Gas yield (N m
3
/kg biomass) Syngas (% v/v) H
2
/CO BET surface area of char (m
2
/g) Micropore volume of char (10
2
N cm
3
/g)
Dolomite 0.49 25.14 0.60 17.00 1.88
Olivine 0.51 37.27 0.67 7.24 0.66
Z402 + Z405 0.63 87.63 0.90 14.28 1.38
Z405 + Z409 0.64 83.09 0.92 20.33 1.59
Z412 + Z413 0.56 83.26 0.94 46.42 5.49
10
15
20
25
30
35
40
45
50
55
60
65
70 a
GAS LIQUID SOLID
600 650 700 750 800 850 900
5
10
15
20
25
30
35
40
45
50
55
60
65
70
Y
i
e
l
d
(
w
t
-
%

o
f

d
r
y

b
i
o
m
a
s
s
)
c
GAS LIQUID SOLID
Temperature ( )
15
20
25
30
35
40
45
50
55
60
GAS LIQUID SOLID
Y
i
e
l
d
(
w
t
-
%

o
f

d
r
y

b
i
o
m
a
s
s
)
b
Fig. 1. Effects of temperature on the major products distribution in pine sawdust
catalytic pyrolysis process. (a) Z402 + Z405, (b) Z405 + Z409, and (c) Z412 + Z413.
604 Q. Xie et al. / Bioresource Technology 110 (2012) 603609
combined into three groups for experimental use. These combina-
tions were Z402 + Z405, Z405 + Z409, Z412 + Z413, and the mass
ratio of two catalysts in each group equaled 1:1. According to prac-
tical experience, these combinations were proved to be more appli-
cable to syngas production than each individual catalyst. Prior to
application, the catalysts were rst ground using a ball mill to
achieve a particle size smaller than 3 mm, and then reduced in
the atmosphere of H
2
at 800 C for 3 h. In addition, two mineral
catalysts were also selected for comparison: dolomite and olivine.
The two catalysts were rst crushed to obtain a fraction with a par-
ticle sized 0.150.2 mm and then calcined in mufe at 900 C for
4 h.
2.2. Apparatus
The pyrolysis and gasication processes were examined in the
same system. The major components include carrier gas and steam
generator, tube furnace reactor, gas condenser and purier, ow
meters and gas collecting bag.
The reactor is made of quartz tube which is externally heated by
an electric furnace (Model OTF-1200X, Hefei Kejing Materials
Technology Co. Ltd., Anhui, China). Its length is 100 mm with an in-
ner diameter of 42 mm. In the stage of pyrolysis, the biomass sam-
ple (2.00 g) was rst loaded in a small quartz boat, which was put
on the left side of the tube. The carrier gas (pure N
2
) was pumped
into the system to expel all the air in it. When the temperature of
furnace reached the designated value, the quartz boat was quickly
pushed into the middle of the tube, and the reaction occurred.
Flowing through the condenser and lter, the product gas would
be puried, and was then collected into sampling bags made of alu-
minum (volume 15 L, Shanghai Eler Co. Ltd., Shanghai, China) for
ofine analysis. The ow and volume of product gas were mea-
sured by the rotameter (Model LZB-3, Yuyao Industrial Automation
Instrument and Meters Factory, Zhejiang, China) and the wet meter
(Model LMP-1, Changchun Automobile Filter Co. Ltd., Jilin, China),
respectively. When it came to the gasication process, these proce-
dures were repeatedly conducted, and the only difference was that
the valve of carrier gas was closed and steam produced in the
steam generator (Model DZFZ-0.4, Shanghai Diye Ironing Equip-
ment Manufacturing Co. Ltd., Shanghai, China) was pumped into
the tube to react with pyrolysis product in the quartz boat.
The measurement accuracies for temperature sensor, rotameter
and wet meter are 1 C, 0.025 N L/min, 0.02 L, respectively.
These accuracy numbers were obtained from the manufacturers.
2.3. Gas and char analysis
Ofine gas analysis was performed using an Agilent Technologies
6890Ngas chromatograph (GC) equipped with thermal-conductivity
detector (TCD). Gas samples were introduced to GC through a six-
way valve with the sample loop of 1 mL. The two columns used were
Plot Q and Molesieve with heliumas carrier gas. Among them, Plot Q
was used to analyze CO
2
and light hydrocarbons, while Molesieve
was used for CO,H
2
and CH
4
analysis. The column temperature of
the gas chromatograph was set at 40 C, and the analysis retention
time was 38 min. The standard gas mixture used for the calibration
of the method was CO,CO
2
,H
2
,CH
4
,C
2
H
4
and C
2
H
6
1% v/v balanced
in helium and the volume concentration was calculated by an exter-
nal standard method. The produced gas was mainly composed of
CO,CO
2
,H
2
,CH
4
, and a small amount of light hydrocarbons. Light
hydrocarbons joined as C
m
H
n
with the exception of CH
4
due to its
higher concentration.
BET surface area and pore size distribution of the pyrolysis char
were determined by N
2
adsorption using a JW-BK static nitrogen
adsorption instrument. The sample was degassed at 105 C for
5 h in high vacuum before measurement.
2.4. Catalyst characterization
The X-ray powder diffraction (XRD) patterns, obtained on a Sie-
mens D500 X-ray diffractometer instrument with a CuKa radiation
at 40 kV and 30 mA, were used to identify the major phases pres-
ent in the nickel based catalysts.
3. Results and discussion
3.1. Comparison of nickel based catalysts with mineral catalysts
In order to investigate the performance of catalysts, three kinds
of nickel based catalysts and two mineral catalysts (dolomite
and olivine) were tested in pyrolysis experiments. As shown in
Table 2, at the temperature of 800 C, all the nickel based catalysts
600 650 700 750 800 850 900
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
c
Temperature ( )
Y
i
e
l
d
(
N
m
3
/
k
g

b
i
o
m
a
s
s
)
H
2
CO CH
4
CO
2
Total
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
b
H
2
CO CH
4
CO
2
Total
Y
i
e
l
d
(
N
m
3
/
k
g

b
i
o
m
a
s
s
)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
a
Y
i
e
l
d
(
N
m
3
/
k
g

b
i
o
m
a
s
s
)
H
2
CO CH
4
CO
2
Total
Fig. 2. Effect of temperature on major gases yield in pine sawdust catalytic
pyrolysis process. (a) Z402 + Z405, (b) Z405 + Z409, and (c) Z412 + Z413.
Q. Xie et al. / Bioresource Technology 110 (2012) 603609 605
presented better performance than the mineral catalysts in both
gas yield and char quality. The result is consistent with previous
studies (Asadullah et al., 2003; Li et al., 2009; Magrini-Bair et al.,
2007; Tomishige et al., 2004; Yung et al., 2010). Therefore, nickel
based catalysts were chosen as the catalysts for the following
experiments.
3.2. Effect of temperature on pyrolysis products
Catalyzed by nickel based catalysts, pyrolysis experiments were
carried at a temperature range of 600900 C to examine effect of
temperature on products distribution between gas, liquid and solid
phases. As Fig. 1 shows, for three catalysts, the variation trends of
gas, liquid or solid fraction yield during the sawdust pyrolysis were
much similar with an increase of temperature. The yield of solid
fraction was almost kept stable as temperature increased. When
the temperature was higher than 500 C, solid fraction had a very
low content of volatile matter (Kantarelis and Zabaniotou, 2009),
so no further (or negligible) devolatilization took place. The varia-
tion curves of yield with temperature for liquid and gas fractions
were nearly opposite. When temperature was below 700 C, gas
productionwas increased, while liquidproductiondecreased. When
temperature was at 700850 C, high gas yield was obtained and
there was an optimum temperature at which maximum gas yield
was observed (for Z402 + Z405, Z405 + Z409 and Z412 + Z413 were
Table 3
Pine sawdust catalytic pyrolysis-produced gas characteristics.
Temperature
(C)
Z402 + Z405 Z405 + Z409 Z412 + Z413
Syngas
(% v/v)
H
2
/
CO
LHV
(MJ/
Nm
3
)
HHV
(MJ/
Nm
3
)
Syngas
(% v/v)
H
2
/
CO
LHV
(MJ/
Nm
3
)
HHV
(MJ/
Nm
3
)
Syngas
(% v/v)
H
2
/
CO
LHV
(MJ/
Nm
3
)
HHV
(MJ/
Nm
3
)
600 56.15 0.70 10.80 11.72 58.56 0.53 11.39 12.28 54.49 0.48 11.06 11.91
650 61.53 0.90 11.09 12.09 64.25 0.71 11.85 12.85 60.93 0.70 11.59 12.58
700 82.26 0.85 14.01 15.24 75.53 0.81 13.46 14.64 74.63 0.78 13.46 14.62
750 81.39 0.89 14.00 15.25 75.80 0.85 13.33 14.51 83.35 0.77 14.75 16.01
800 87.63 0.90 14.48 15.77 83.09 0.92 13.87 15.11 83.26 0.94 13.46 14.67
850 79.26 1.00 12.32 13.44 65.91 0.80 10.64 11.54 91.75 0.97 14.31 15.60
900 83.54 1.24 11.01 12.07 67.36 1.07 9.68 10.57 84.49 1.09 12.52 13.69
600 650 700 750 800 850 900
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
Y
i
e
l
d
(
N
m
3
/
k
g

b
i
o
m
a
s
s
)
Temperature ( )
H
2
-Gasification CO-Gasification
H
2
+CO-Gasification H
2
+CO-Pyrolysis+Gasification
Fig. 3. Effects of char obtained from different pyrolysis temperature on major gases
yield in char gasication process. Gasication temperature: 750 C, catalyst:
Z402 + Z405.
1/T (1/K)
0.00090 0.00095 0.00100 0.00105 0.00110 0.00115 0.00120
l
n

(
k
)
-6.8
-6.6
-6.4
-6.2
-6.0
-5.8
-5.6
Z402+Z405 Z405+Z409 Z412+Z413
Fig. 4. Arrhenius plots for syngas production in pine sawdust catalytic pyrolysis
process. Temperature range: 600800 C.
Table 5
Kinetic parameters for syngas production in catalytic pyrolysis.
Catalyst Kinetic equation R
2
E (kJ/mol) k
0
(10
3
s
1
)
Z402 + Z405 ln(k) = 4000.8
(1/T) 2.0472
0.9267 33.26 129.10
Z405 + Z409 ln(k) = 2945.1
(1/T) 3.1861
0.9679 24.49 41.33
Z412 + Z413 ln(k) = 2692.2
(1/T) 3.4567
0.8247 22.38 31.53
Table 4
BET surface area and miropore volume of pyrolysis char.
Temperature
(C)
Z402 + Z405 Z405 + Z409 Z412 + Z413
BET surface area
(m
2
/g)
Micropore volume
(10
2
N cm
3
/g)
BET surface area
(m
2
/g)
Micropore volume
(10
2
N cm
3
/g)
BET surface area
(m
2
/g)
Micropore volume
(10
2
N cm
3
/g)
600 55.83 6.46 52.59 5.88 50.22 6.80
650 48.14 5.16 47.14 5.74 45.69 5.30
700 48.69 5.60 38.65 4.06 47.03 6.81
750 55.60 7.31 53.98 5.93 50.76 6.85
800 14.28 1.38 20.33 1.59 46.42 5.49
850 23.23 1.85 27.13 2.20 47.59 6.45
900 38.51 4.24 16.21 1.31 16.83 1.51
606 Q. Xie et al. / Bioresource Technology 110 (2012) 603609
at 700, 800 and 700 C, respectively). Further temperature increase
resulted in decline of gas production.
The main reaction occurred during the catalytic pyrolysis pro-
cess was thermal cracking of the biomass. Thermal cracking is an
endothermic reaction which is favored by the rose of temperature
(Encinar et al., 2000), indicating the increase of gas production and
decrease of liquid production with an increase of temperature.
However, when temperature reached above 800 C, yield of gas
fraction was found to decline due to the decrease of catalyst activ-
ity resulting from sintering at high temperature (Sehested et al.,
2006; Yung et al., 2010; Hashemnejad and Parvari, 2011). There-
fore, the optimum temperature range for catalytic pyrolysis of pine
sawdust to produce more gas is 700850 C.
Major gases (H
2
,CO,CO
2
,CH
4
) yieldwas alsoaffectedby temper-
ature, as shown in Fig. 2. There was also an optimum temperature
for each catalyst at which the maximum overall gas production
was obtained. For Z402 + Z405, Z405 + Z409 and Z412 + Z413, the
optimun temperatures are 800, 800 and 850 C, and their corre-
sponding gas yields are 0.720, 0.685, 0.726 N m
3
/kg biomass (dry
basis), respectively. It is obvious that effects of temperature on
major gas yields were also related with the catalyst activities.
The lower heating value of the produced gas was calculated by
the following equation (Lv et al., 2004; Yang et al., 2006).
LHV 30CO 25:7H
2
85:4CH
4
151:3C
m
H
n

4:2=1000 MJ=N m
3
1
while the higher heating value was calculated using the following
correlation (Li et al., 2004).
HHV 12:63CO 12:75H
2
39:82CH
4

63:43C
m
H
n
=100 MJ=N m
3
2
where [H
2
],[CO],[CH
4
] and [C
m
H
n
] are the molar fractions of
H
2
,CO,CH
4
and C
m
H
n
in the produced gas.
As shown in Table 3, the LHV and HHV of produced gases at this
temperature range (600900 C) varied from 9.7 to 14.7 MJ/N m
3
and 10.616.0 MJ/N m
3
, respectively. From Fig. 2 and Table 3, the
conclusion could be made that the optimum temperature range
for catalytic pyrolysis of pine sawdust is 700850 C.
Char was the major component of solid fraction produced in the
pyrolysis process, which then reacted with steam in the gasica-
tion process to produce more syngas. Therefore, the property of
pyrolysis char is another important factor affecting the ultimate
syngas production. Table 4 shows the BET surface area and micro-
pore volume of pyrolysis char. It can be found that for each cata-
lyst, the pyrolysis char achieved the maximum BET surface area
and micropore volume at 750 C. Large surface area and mircopore
volume provide more sites for char to react with steam, therefore
favoring the syngas production during gasication process.
To further examine effects of pyrolysis char on gasication
products, chars produced at different pyrolysis temperatures were
gasied at 750 C, and Z402 + Z405 was employed as the catalyst.
As shown in Fig. 3, the maximum yields of H
2
and H
2
+ CO were
both obtained at the pyrolysis temperature of 750 C, at which
the optimum char quality was observed. In addition, the total yield
of H
2
+ CO produced in pyrolysis and gasication processes also
achieved the maximum value at 750 C.Considering both the gases
yield and char quality, the optimum temperature of pine sawdust
catalytic pyrolysis is 750 C.
3.3. Kinetic model for syngas production in pyrolysis process
The objective of sawdust thermochemical conversion was to ob-
tain more syngas with higher heating value. The kinetics of reac-
tions emerging in the conversion inevitably produced effect on
the yield and quality of syngas, so it is necessary to study the reac-
tion kinetics. The following classical equation is often used for the
kinetic interpretation of the thermal decomposition of wood and
its components (Capart, 1991):
dq=dt kq 3
q refers to the weight percentage of raw material in time t. Eq. (3)
can be used in the form of an equation of AvramiErofeev type,
applicable to materials whose porosity changes during the reaction,
as
K ln1 X=s 4
X refers to the weight percentage of syngas in time s.
Also, for k, it abides by the Arrhenius equation as
k k
0
expE=RT 5
Pre-exponential factor (k
0
) is in s
1
, whereas activation energy (E) in
kJ mol
1
.
Eq. (5) can be further transformed as
lnk lnk
0
E=RT 6
Eq. (6) is linear. By applying k (determined by Eq. (4)) and T to it, the
values of E and k
0
can be determined. The curves lnk lnk
0

E=RT for three nickel based catalysts are presented in Fig. 4,

which shows good linearity. The E and k
0
values determined by
Fig. 4 are listed in Table 5. These values ranged between those re-
ported by Barooah and Long (1976) (18.0 kJ/mol) and Fong and Ross
(1980) (45.1 kJ/mol).
3.4. Effect of temperature on gasication products
After pyrolysis, steam was pumped into the quartz tube to react
with pyrolysis char which was obtained at 750 C, thereby syngas
was further produced. The reaction temperature is also an impor-
tant factor with regard to the composition of nal syngas.
700 750 800 850 900
0.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
H
2
CO H
2
+CO
Y
i
e
l
d
(
N
m
3
/
k
g

b
i
o
m
a
s
s
)
Temperature ( )
Fig. 5. Effect of temperature on major gases yield in pyrolysis-char gasication
process. (char resulting from sawdust pyrolysis at 750 C), catalyst: Z402 + Z405,
gasifying agent: steam.
Table 6
Inuence of gasication temperature on char elemental composition.
Temperature (C) C (wt.%) H (wt.%) O
a
(wt.%) Ash (wt.%)
700 48.11 3.12 30.54 15.53
750 31.73 2.89 25.22 37.51
800 13.28 2.33 8.85 72.91
850 4.35 1.20 6.80 85.16
900 1.80 0.93 3.75 91.04
a
By difference.
Q. Xie et al. / Bioresource Technology 110 (2012) 603609 607
Gasication experiments were carried out at temperatures be-
tween 700 and 900 C, and the results were shown in Fig. 5. H
2
and CO yields drastically increased from 1.31 to 2.25 N m
3
/kg bio-
mass and from 0.22 to 0.54 N m
3
/kg biomass, respectively, when
temperature rose from 700 to 850 C. H
2
and CO yields both began
to decrease with temperature over 850 C.A simplied model that
explains gases evolution during gasication is described as follow-
ing (Fryda, 2006):
CCO
2
!2CO DH 173:8kJ=mol Boudouard reaction 7
CH
2
O!COH
2
DH 132kJ=mol Water-gas shift reaction 8
COH
2
O!CO
2
H
2
DH 41:2kJ=mol Water-gas shift reaction 9
CH
4
H
2
O!CO3H
2
DH 206kJ=mol Methane steamreforming 10
Since reactions (7)(10) are all endothermic reactions, higher
temperature favored gasication of char when the temperature
was below 850 C. The maximum syngas yield was obtained at
850 C, i.e., 2.78 N m
3
/kg biomass. The decrease of gas yield with
temperature over 850 C may be due to catalyst deactivation
caused by sintering. Therefore, the optimum temperature of pyro-
lysis char gasication is 850 C. Furthermore, under optimum con-
ditions, the total yield of syngas produced in pyrolysis and
gasication processes could achieve 3.29 N m
3
/kg biomass, with
LHV and HHV calculated by Eqs. (1) and (2) up to 9.6 and
10.9 MJ/N m
3
, respectively. Compared with previous studies, much
higher syngas yield was obtained in this study, favoring synthesis
of liquid fuels in subsequent processes.
The elemental analyses of char resulting from steam gasica-
tion at different temperatures were given in Table 6. As tempera-
ture increased from 700 to 900 C, the carbon content decreased
from 48.11% to 1.80%, while ash content rose from 15.53% to
91.04%, indicating that higher temperature signicantly reduced
carbon content and increased ash content in the char.
3.5. Catalyst characterization
To investigate the relation between the decrease of gas yield
and catalyst deactivation at high temperature, catalyst character-
ization was analyzed. Catalysts (Z402 + Z405) before and after
the gasication process at different temperatures were analyzed
with X-ray diffraction to determine effect of temperature on cata-
lyst structure (Fig. 6a). The main nickel phase emerging in the fresh
catalyst was metallic nickel, Ni
0
(2h = 44.5, 51.9 and 76.3), and
little nickel oxide (NiO) (2h = 62.8 and 75.3). Nickelmagnesium
compound Mg
0.4
Ni
0.6
O (2h = 37.2, 43.2 and 79.1) can be ob-
served in all ve catalysts after gasication.
For fresh catalyst, nickel phase existed mainly in the form of Ni
0
with little or no NiO, which indicated that the H
2
-reduction treat-
ment was sufcient to reduce NiO. The post-reaction samples
showed the presence of Ni
0
as well as NiO. It should be noted that
Mg
0.4
Ni
0.6
O was also seen in all post-reaction samples and its
intensity was generally increased as gasication temperature rose.
Fig. 6b and c showed a part of XRD patterns of post-reaction cat-
alysts and corresponding areas under the peak at 37.2, which was
700 750 800 850 900
14
15
16
17
18
19
20
d
N
i
0

c
r
y
s
t
a
l
l
i
t
e

s
i
z
e

(
n
m
)
Temperature ( )
700 750 800 850 900
3000
3500
4000
4500
5000
5500
6000
c
M
g
0
.
4
N
i
0
.
6
O

a
r
e
a

a
t

3
7
.
2

a
.
u
.
)
Temperature ( )
R
2
=0.9399
36 37 38 39 40 41 42
Blank
900
850
800
750
700
Mg
0.4
Ni
0.6
O
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
2 2
b
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
Blank
900
850
800
750
700
NiO A
NiO
A
A
Ni
Ni
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Ni
a
Fig. 6. (a) XRD patterns for Z402 + Z405 before and after gasication at different temperatures, with nickel phases labeled as: Ni (cubic Ni
0
), NiO (NiO), and A (Mg
0.4
Ni
0.6
O).
(b) XRD patterns for the Mg
0.4
Ni
0.6
O phase on post-reaction catalysts, with fresh catalyst as comparison. (c) Areas of the Mg
0.4
Ni
0.6
O phase on post-reaction catalysts, under
the peak at 37.2; and (d) Ni
0
crystallite sizes on post-reaction catalysts.
608 Q. Xie et al. / Bioresource Technology 110 (2012) 603609
attributed to Mg
0.4
Ni
0.6
O. The intensity and area of the Mg
0.4
Ni
0.6
O
phase were observed to increase as temperature rose from 700 to
900 C, which demonstrated an increasing amount of nickel inter-
acted with the support to form the spinel Mg
0.4
Ni
0.6
O. Moreover,
there was a good linear relationship between area of the
Mg
0.4
Ni
0.6
O phase and temperature, as shown in Fig. 6c. The nickel
incorporation into the spinel phase reduced the amount of Ni
0
which was the active component of the catalyst, thus the catalyst
activity was decreased. As shown in Fig. 6a, the formation of NiO
phase may also be responsible for the loss of catalyst activity dur-
ing the gasication process.
The Ni
0
crystallite sizes in post-reaction catalysts were shown in
Fig. 6d. The Ni
0
size was increased from 149 at 700 C to 193 at
900 C, which corresponded to a 22.8% decrease in the nickel sur-
face area from a geometric argument. The result indicated that
some sintering occurred during reaction at higher temperature,
which also resulted in the catalyst deactivation, and the higher
reaction temperature would cause the more serious sintering.
4. Conclusion
In this study, two-stage catalytic pyrolysis and gasication of
pine sawdust has been applied to investigate effects of pyrolysis
temperature and gasication temperature on syngas production.
Results illustrated that higher temperature was needed in the gas-
ication process (850 C) than in the pyrolysis process (750 C) to
maximize syngas yield, and the maximum syngas yield could
achieve up to 3.29 N m
3
/kg biomass (dry wt.), much higher than
previous studies. Catalyst characterization analyses indicated that
formation of Mg
0.4
Ni
0.6
O and increase of Ni
0
crystallite size were
two main reasons for catalyst deactivation. Further study should
focus on the industrialization of the technique.
Acknowledgements
The authors would like to express their great appreciation to
the National Science Foundation of China (grants 21077002 and
20877002) and the Double-Hundred Talents Program of Shenz-
hen Municipal Government for the nancial support to this study.
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