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Kinetic analyses of biomass pyrolysis using the distributed

activation energy model
Taro Sonobe, Nakorn Worasuwannarak

The Joint Graduate School of Energy and Environment, King Mongkuts University of Technology Thonburi,
126 Pracha-Uthit Road, Bangmod, Tungkru, Bangkok 10140, Thailand
Received 21 February 2006; received in revised form 26 January 2007; accepted 8 May 2007
Available online 6 June 2007

Abstract
The pyrolysis behaviors of several agricultural residues have been investigated by using thermogravimetric analysis. The evolving rates
of the gaseous products during the pyrolysis such as H2, CH4, H2O, CO and CO2 were also measured by the TG-MS techniques. Without
any assumption and mathematical tting, we could obtain the very proper kinetic parameters (the distribution curve of activation energy,
f(E), and the activation energy dependent frequency factor, k0(E)) of biomass pyrolysis by utilizing the distributed activation energy
model (DAEM) proposed by Miura and Maki [Miura K, Maki T. Energ Fuel 1998;12:864]. The peaks of f(E) curve for rice straw, rice
husk, corncob and cellulose were found to be 170, 174, 183, and 185 kJ/mol, respectively. The k0 value increased from an order of 1011 to
an order of 1018 s1, while E increased from 120 to 250 kJ/mol. The catalytic eects of alkali and alkaline earth metals during the pyrolysis play a major role in the variation of f(E) curve among the dierent biomass species.
2007 Elsevier Ltd. All rights reserved.
Keywords: Biomass; Pyrolysis; Kinetic analysis

1. Introduction
A satisfactory understanding of biomass pyrolysis can
give rise to a dramatic development of biomass conversion
process. Since pyrolysis is the rst step of biomass conversion such as gasication, liquefaction, carbonization, and
combustion, its sound understanding is signicant for the
eective use of biomass. For engineering applications,
knowledge of the pyrolysis kinetics is essential for predicting the pyrolysis behavior of biomass materials as well as
designing the suitable reactor. Recently, numerous
researchers have investigated the pyrolysis kinetics of biomass, cellulose, lignin, and coal [16]. Antal and Varhegyi
reviewed the state of the art for the cellulose pyrolysis
kinetics [13]. They nally suggested an endothermic reaction governed by a rst-order reaction with the activation
energy of 238 kJ/mol for cellulose pyrolysis [1,2]. At pres*

Corresponding author. Tel.: +66 2470 8309x4150; fax: +66 2872 6978.
E-mail address: nakorn_w@jgsee.kmutt.ac.th (N. Worasuwannarak).

0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.05.004

ent, most of the researchers have assumed the independent

parallel decompositions of hemicellulose, cellulose, and lignin for biomass pyrolysis [18]. Teng and Wei assumed a
combination of four independent parallel reactions for rice
hull pyrolysis and assigned a single value of activation
energy and pre-exponential constant to each reaction
[4,5]. Manya et al. also assumed a set of three independent
parallel reactions for sugarcane bagasse and waste-wood
pyrolysis [6]. In these models, the authors have assumed
that there is no interaction between three components:
hemicellulose, cellulose, and lignin, and regard these components as single homogeneous material [16]. However,
it is surprising to note that the single represented values
of activation energy and pre-exponential constant are
assigned even though the biomass structure consists of
the complex organic material, where hemicellulose, cellulose and lignin are cross-linked and have various kinds of
chemical bonds and minerals in their chemical structures
[912]. Low rank coal, which has abundant oxygen-bearing
functional groups such as OH and COOH, can start the

T. Sonobe, N. Worasuwannarak / Fuel 87 (2008) 414421

interactions between macro-molecular components to form

the cross-linking from low temperature at around 200 C
under pyrolysis [13,14]. It has been well known that hemicellulose, cellulose and lignin also have abundant oxygenbearing functional groups [12]. Recently, we observed the
signicant interactions between model compounds of cellulose and lignin during the pyrolysis [15]. The interactions
contributed to a decrease in tar yields but an increase in
char yields. Moreover, these single reaction models have
a critical limitation to consider any heterogeneous chemical
reactions and interactions such as catalytic eects during
pyrolysis. This is because alkali metals should inuence
the particular chemical bonds to decrease the bond energy,
and they are also distributed in biomass structure inhomogeneously [12]. Therefore, it is more suitable to consider the
inhomogeneous reaction for well understanding the biomass pyrolysis reaction.
A simplied model known as distributed activation
energy model (DAEM) for determining kinetic parameters
for complex reactions such as coal pyrolysis reaction has
been proposed by Miura et al. [16,17]. This model assumes
a set of irreversible rst-order reactions that have dierent
activation energies. The DAEM has been widely used to
analyze complex reactions such as pyrolysis of various
ranks of coal and other fossil fuels [1619]. This simplied
model does not require a priori assumption and mathematical model tting for obtaining the kinetic parameters.
Only a set of experimental data obtained at three dierent
heating proles are required [16,17].
In the present study, we aim at obtaining the proper
kinetic parameters which can predict the global devolatilization behavior of biomass pyrolysis without any mathematical model tting and assumptions in particular
reference to the DAEM which assumes a set of irreversible
rst-order reactions that have dierent activation energies
and frequency factors.

2. Experimental
2.1. Materials
The materials selected for this study were rice straw, rice
husk, corncob, and cellulose (microcrystalline powder,
Sigma Aldrich). The agricultural residues were locally
available materials and their ultimate and proximate analyses are shown in Table 1. After milling and sieving into

415

Table 2
Elemental analysis of alkali and alkaline earth metals in biomass (mg/gsample)
Samples

Na (mg/gsample)

Mg (mg/gsample)

K (mg/gsample)

Ca (mg/gsample)

Rice
straw
Rice
husk
Corncob

1.01

1.84

16.79

4.84

0.21

0.58

5.37

1.67

0.76

0.05

7.26

1.04

less than 74 lm in diameter, the samples were dried in

vacuo at 70 C for 24 h before the experiments. The elemental analysis of alkali and alkaline earth metals in biomass samples was performed by Inductively Coupled
Plasma-Mass Spectrometry (Agilent, 7500a ICP-MS).
The ne samples were digested with 5 mL of HNO3 (Suprapure, 65% v/v, Merck) and made up to 25 mL with ultrapure water at 18.2 mO, using Anton Paar Microwave
Digester (Anton Paar) [20]. All analyses are performed
three times and the detection limit for each element was
dened as triple standard deviation of blank. Table 2 shows
the results of elemental analysis of alkali and alkaline earth
metals in biomass samples.
2.2. TG-MS analysis during the pyrolysis
The pyrolysis experiments were performed in a sensitive
thermobalance (PerkinElmer, Pyris 1 TGA) at a heating
rate of 10 C/min up to a nal temperature of 900 C
under the helium ow rate of 50 ml/min. A quadrupole
mass spectrometer (PerkinElmer, Clarus 500 MS) coupled to the thermobalance was used for the evolved gas
analysis. To avoid secondary reactions, a probe was placed
very close to the sample pan of the thermobalance in the
direction of the gas ow. The transfer lines between the
TGA and the MS were heated to 200 C in order to avoid
cold points and thus prevent the condensation of the gaseous products. The signals for mass numbers of
2, 15, 18, 28, and 44 were continuously detected. Then the
mass numbers were converted to the concentrations of
H2, CH4, H2O, CO, and CO2 by referring to the calibration curves constructed using standard gas. The evolving
rates of the gaseous products were estimated from the
measurements.
Fine particles of less than 74 lm and small samples of
around 5 mg were used to ensure uniform heating of the

Table 1
Ultimate (wt%, daf.) and proximate analyses (wt%, dB.) of rice straw, rice husk, corncob, and cellulose
Samples

Ultimate analyses (wt% daf.)

Proximate analyses (wt% dB)

O (dierent)

Volatile matter

Fixed carbon

Ash

Rice straw
Rice husk
Corncob
Cellulose

44.2
47.4
45.5
44.4

6.2
6.7
6.2
6.8

0.8
0.8
1.3
0.0

48.8
45.1
47.0
48.8

71.6
68.9
82.2
96.3

14.5
11.1
16.9
3.7

13.9
20.0
0.9
0.0

T. Sonobe, N. Worasuwannarak / Fuel 87 (2008) 414421

samples. For the kinetic analysis of the pyrolysis reactions,

the weight changes accompanying the pyrolysis were measured by used of the thermobalance (PerkinElmer, Pyris 1
TGA) under three dierent heating rates (a) of 2, 5 and
10 K/min in a nitrogen atmosphere. A separate blank
run was conducted using an empty pan under each heating rate and this was used for baseline correction during
the pyrolysis of samples. The measured weighttime relationships were converted to the relationships of V/V*
vs. T.
2.3. Theoretical background
The so-called distributed activation energy model
(DAEM) has been widely used to analyze complex reactions such as pyrolysis of fossil fuels. The model, originally
proposed by Vand [21], assumes an innite number of irreversible rst-order parallel reactions with dierent activation energy E to occur simultaneously, where the
dierence in activation energies is represented by a distribution function f(E). Miura et al. have recently proposed
two methods to estimate f(E) and k0(E), a dierential
method [16] and an integral method [17], from a set of
three TG experiments at dierent heating rates without
assuming k0 value and functional form for f(E). Although
both methods are the same in principle, the integral
method is more accurate and does not need a tedious differentiation step.
When the model is used to analyze biomass pyrolysis,
change in the total volatiles, V, against time, t, is given
by


Z t
Z 1

E=RT
1  V =V
exp k 0
e
dt f E dE
1

Figs. 1 and 2 show the thermogravimetric (TG) and the

derivative thermogravimetric (DTG) curves for rice straw,
rice husk, corncob, and cellulose as a function of temperature. All the curves are on a dry and ash free basis (daf.).
The devolatilization of biomass samples starts at above
180 C and it is completed by 600 C. As can be seen in
the sharp devolatilization process, the DTG curves for biomass present two overlapping peaks. It has been well
known that lignocellulosic biomass mainly consists of cellulose, hemicellulose, and lignin [912], and these compositions signicantly inuence the biomass pyrolysis process
[911]. As can be seen in Fig. 2, the second peaks of
DTG curve for biomass well correspond with the peak of
DTG curve for cellulose. Since cellulose is the dominant compound among the composition of lignocellulosic

1.0
0.9
Cellulose
0.8

Using Eq. (3), we can estimate both E and k0 from the

Arrhenius plot of ln(a/T2) vs. 1/T at the selected V/V* values for dierent a values. The relationship between V/V*
vs. E could be obtained by plotting the V/V* value against
the corresponding E value. The distribution curve of the
activation energy, f(E), can be obtained by simply dierentiating the V/V* vs. E relation by resorting to Eq. (2). No
assumptions are required for the functional forms of f(E)
and k0(E).

Rice husk

0.6
0.5
0.4
Rice straw

0.3
0.2

He, 50ml/min
o

10 C/min

Corncob

0.0
200

300

400

500

600

Te mper ature [ C]

Fig. 1. TG curves for rice straw, rice husk, corncob, and cellulose.

0.0

In this simplied model, the Arrhenius equation can be described as follows:

 
 
a
k0R
E
3
ln
0:6075 

ln
2
E
RT
T

0.7

0.1

where V* is the eective volatile content of the biomass,

f(E) is the normalized distribution curve of the activation
energy representing the dierences in the activation energies of many reactions, and k0 is the frequency factor corresponding to the E value. Equation (1) was simplied to
Eq. (2) by Miura et al. [16].
Z 1
Z Es
f E dE
f E dE
2
V =V  1 
Es

3.1. TG-MS analysis during the pyrolysis of biomass

-0.5
-1.0
DTG [mg/min]

3. Results and discussion

Weight loss [wt%, daf.]

416

-1.5
Rice straw
-2.0

Rice husk
Corncob

-2.5
-3.0
-3.5

He, 50ml/min

Cellulose

10 C/min

-4.0
200

300
400
500
o
Temperature [ C]

600

Fig. 2. DTG curves for rice straw, rice husk, corncob, and cellulose.

T. Sonobe, N. Worasuwannarak / Fuel 87 (2008) 414421

x10

Cellulose

0.6
1.0

0.4
CO
CO2

H2

0.2

Weight loss [w/w 0, daf.]

0.8

H2O

0.5

2.0

CH4
0.0

0.0
600

300
400
500
o
Temperature [ C]

Rice straw

0.8

1.5
0.6
H2O

1.0

0.4

CO
0.5

CH4
H2

0.2

CO2
0.0
200

300
400
500
o
Temperature [ C]

0.0
600

Rice husk

0.6
H2O

1.0

0.4

CO
0.5

CO2

CH4

0.0
200

300
400
500
o
Temperature [ C]

H2

0.2

0.0
600

Weight loss [w/w 0, daf.]

0.8

1.5

2.0

1.0
Corncob

0.8

1.5
0.6
1.0

H2O
0.4

CO
0.5

CO2

CH4

H2

0.2

500

0.0
600

0.0
200

300

400

Weight loss [w/w 0, daf.]

1.0

Evolving rate [mol/(min g-sample, daf.)]

2.0

x10

-3

x10

1.0

-3

200

Evolving rate [mol/(min g-sample, daf.)]

1.0

Weight loss [w/w0, daf.]

-3

x10
Evolving rate [mol/(min g-sample, daf.)]

2.0

1.5

Evolving rate [mol/(min g-sample, daf.)]

of Na, Mg, K, and Ca elements compared with rice husk

and corncob. So, the early formation of oxygenated gases
for rice straw is probably inuenced by the large amount
of alkali and alkaline earth metals. This nding is neatly
consistent with the work of Anker et al. [22]. Moreover,
what is particularly noticeable in the biomass devolatilization behaviors is that each biomass sample shows the dierent devolatilization behaviors during the pyrolysis while
they show the similar elemental compositions as seen in
Table 1. This feature is very unique among the solid fuels
such as coal [2326]. It has been well known that the devolatilization behaviors of coal can be predicted from the
elemental composition and the 13C NMR structural
parameters of coal by using the FG-DVC model,
FLASH-CHAIN, and the CPD model [2326]. Denitely,
biomass cannot be represented by a single homogeneous
material. Therefore, it is necessary for deep understanding
of the biomass devolatilization to consider the physical texture (e.g. the distribution of hemicellulose, cellulose, lignin,
and minerals in biomass) and chemical structures (e.g.
functional groups and chemical bonds) simultaneously.
-3

biomass [12], it can therefore suggest that the large peak of

the DTG curve for biomass samples is closely related to
decomposition of their own cellulose.
Fig. 3 shows the gas formation rates (H2, CH4, H2O,
CO, CO2) of (a) cellulose, (b) rice straw, (c) rice husk,
and (d) corncob. The feature common to all the samples
is that the evolving behaviors of CH4, H2O, CO, and
CO2 are well accompanied by the sharp decomposition
seen in the DTG curves (Fig. 2). However, the H2 formation behavior is not accompanied by the sharp decomposition. Of particular interest is that the most dominated gas
formation is H2O for all biomass samples. As seen in
Fig. 3b, for rice straw, the formation rate of oxygenated
gases such as H2O, CO and CO2 starts quite early at
150 C and shows two distinctive peaks at 180 C and
300 C. On the other hand, for rice husk and corncob,
the formation rates of oxygenated gases start late at
200 C and show the closely overlapped two peaks. Furthermore, for pure cellulose, those formation rates start
at high temperature of about 300 C. As seen in Table 2,
rice straw contains the signicantly higher concentration

417

Temperature [ C]

Fig. 3. Gas formation rates (H2, CH4, H2O, CO, CO2) of (a) cellulose, (b) rice straw, (c) rice husk, and (d) corncob.

418

T. Sonobe, N. Worasuwannarak / Fuel 87 (2008) 414421

As will be discussed later, the discrepancies of the devolatilization among biomass samples are considered due to
the dierences in physical and chemical structures of the
biomass.

3.2. Kinetic analysis of biomass pyrolysis using DAEM

Fig. 4 shows the relationships of V/V* vs. T for rice
straw measured at a = 2, 5, and 10 K/min as a representa-13.5

1.0
Rice straw

0.9

Rice straw
-14.0

10 K/min
-1

0.6

5 K/min

ln(a/T ) [(sK) ]

0.7
V/V [ - ]

v/v*=0.05
0.1

0.8

0.5
0.4

2 K/min

-14.5

0.3

0.2

0.125
0.15

0.4
0.5

-15.0

0.6

-15.5

0.3
0.2

0.7

-16.0

0.1

2 K/min
5 K/min
10 K/min

0.8

-16.5
-3
1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 x10

0.0
400

500

600
700
Temperature [K]

800

-1

1/T [K ]

Fig. 5. Arrhenius plot of a/T2 vs. 1/T at selected V/V* values for rice
straw.

Fig. 4. V/V* vs. T relationship measured at a = 2, 5, and 10 K/min for rice

straw.

1.0

1.0

Cellulose

0.9

0.8

0.8

0.7

0.7

0.6

0.6

V/V [-]

0.5

V/V [-]

0.9

0.4

0.4
0.3

0.2

0.2

0.1

0.1

0.0

0.0

120

140 160 180 200 220

Activation Energy [kJ/mol]

240

120

160

180

200

220

240

1.0
0.9

Rice husk

0.8

0.8

0.7

0.7

0.6

0.6
V/V [-]

0.5

140

Activation Energy [kJ/mol]

1.0

V/V [-]

0.5

0.3

0.9

Rice straw

0.4

0.5
0.4

0.3

0.3

0.2

0.2

0.1

0.1

0.0

Corncob

0.0
120

140

160

180

200

220

Activation Energy [kJ/mol]

240

120

140 160 180 200 220

Activation Energy [kJ/mol]

240

Fig. 6. The V/V* vs. E relationship estimated from the Arrhenius plot for cellulose, rice straw, rice husk, and corncob.

T. Sonobe, N. Worasuwannarak / Fuel 87 (2008) 414421

k 0 aebE a; b are constants

It is obvious that k0 value cannot be assumed as a constant

for the pyrolysis of biomass.
Utilizing the f(E) and k0(E) obtained by DAEM, the calculated TG curves could be obtained as shown in Fig. 9
without any mathematical tting techniques. As can be
seen in Fig. 9, both the experimental curves and the calcu-

1.0
0.9
Rice straw

0.8

(Epeak =170 kJ/mol)

Cellulose
(Epeak =185 kJ/mol)

f(E) [mol/kJ]

0.7
Rice husk

0.6

(Epeak =174 kJ/mol)

0.5
0.4
Corncob

0.3

(Epeak =183 kJ/mol)

0.2
0.1
0.0
150
200
Activation Energy [kJ/mol]

250

Fig. 7. f(E) curves estimated for rice straw, rice husk, corncob, and
cellulose.

10
10
10
10
10

19
18
v/v*=0.155
(Corncob)

17
16

v/v*=0.704
(Corncob)
v/v*=0.278
(Rice straw)

15

-1

k 0 [s ]

tive result for this study. The eective volatile content of

biomass V* at 600 C was independent on heating rate in
this study. The curve is shifted to the higher temperature
when increasing the heating rate. The Arrhenius plot of
a/T2 vs. 1/T was performed to obtain activation energy E
at each selected level of V/V* and the results are shown
in Fig. 5. Utilizing Eq. (3), the activation energy E at
selected level of V/V* are determined from the Arrhenius
plot. Since the activation energy is very sensitive to the linearity of the ln(a/T2) vs. 1/T relationship, these lines were
carefully drawn in the same plot while having a so-called
R2 to be above 0.99 in this study. The relationship between
V/V* vs. E could be obtained by plotting the V/V* value
against the corresponding E values as shown in Fig. 6.
When the curves were dierentiated graphically by E,
f(E) curves for biomass could be obtained as shown in
Fig. 7. The peaks of the f(E) curve appear at
170, 174, 183, and 185 kJ/mol for rice straw, rice husk,
corncob, and cellulose, respectively, and the activation
energy E spreads from 120 to 250 kJ/mol.
Then, the k0 value corresponding for each E value could
be calculated by utilizing Eq. (3). Fig. 8 shows the k0 vs. E
relationship estimated for rice straw, rice husk, corncob,
and cellulose. The k0 value increased from an order of
1011 to an order of 1018 s1, while E increased from 120
to 250 kJ/mol. The following compensation eect is
approximately held between k0 values and E values for biomass, where a and b are constants dependent on reaction
system [16].

419

10
10
10
10
10

14
13
12
11

v/v*=0.734
(Rice straw)

Rice straw
Rice husk
Corncob
Cellulose

10

150
200
Activation Energy [kJ/mol]

250

Fig. 8. k0 vs. E relationship estimated for rice straw, rice husk, corncob,
and cellulose.

lated curves for every sample at three dierent heating rates

well correspond each other. It was found that the activation energy of biomass pyrolysis is widely distributed, i.e.
from 120 to 250 kJ/mol, and each reaction step of V/V*
has corresponding activation energy during the biomass
pyrolysis.
If we look carefully in Fig. 7, the broad f(E) curve of
corncob includes the sharp f(E) peak of cellulose, on the
contrary, the sharp f(E) peaks of rice straw and rice husk
keep away from the celluloses peak. Those distributions
of f(E) curves are varied with biomass species and the sharp
f(E) peak of pure cellulose has the highest activation energy
at 185 kJ/mol among the samples. This variation of f(E)
curve is probably brought about by the dierences in physicochemical composition as well as alkali and alkaline earth
metals concentration in each biomass species. As seen in
Table 2, rice straw contains signicantly higher amounts
of alkali and alkaline earth metals compared with rice husk
and corncob. The f(E) peaks of rice straw show the lowest
activation energy at 170 kJ/mol among the samples. However, the f(E) peaks of corncob shows the higher activation
energy at 183 kJ/mol compared with rice husk of 174 kJ/
mol, while corncob contains higher alkali metals (Na and
K), but less alkaline earth metals (Mg and Ca). This indicates that the variation of f(E) peaks cannot be explained
by only alkali and alkaline earth metals concentration in
biomass. It is also necessary to consider the interaction of
biomass components: cellulose, hemicellulose, and lignin
during the pyrolysis. However, the concentration of alkali
and alkaline earth metals is signicant for the variation
of f(E) peaks. The f(E) peak of rice straw shows the lowest
activation energy due to the large amount of alkali and
alkaline earth metals while that of cellulose shows the highest activation energy due to neither catalytic eects of alkali
and alkaline earth metals nor the interaction with other
components. So, the catalytic eects of alkali and alkaline
earth metals during the pyrolysis play a major role in the
variation of f(E) curve among the dierent biomass species.

420

T. Sonobe, N. Worasuwannarak / Fuel 87 (2008) 414421

1.0

1.0
10 K/min

0.8

0.8
10 K/min

V/V [-]

0.6

0.6
5 K/min

V/V [-]

5 K/min

2 K/min

0.4

0.4

2 K/min

Cellulose
0.2

Rice straw
0.2

Exp.
Calc.

0.0

Exp.
Calc.

0.0
400

500
600
700
Temperature [K]

800

400

1.0

600
700
Temperature [K]

800

1.0

0.8

0.8
10 K/min

10 K/min

0.6

0.6

5 K/min

V/V [-]

5 K/min

V/V [-]

500

2 K/min

0.4

2 K/min

0.4

Rice husk
0.2

Corncob
0.2
Exp.
Calc.

Exp.
Calc.

0.0

0.0
400

500

600
700
Temperature [K]

800

400

500

600
700
Temperature [K]

800

Fig. 9. Experimental and Calculated TG curves at a = 2, 5, and 10 K/min for cellulose, rice straw, rice husk, and corncob.

4. Conclusion
The pyrolysis behaviors of several agricultural residues
have been investigated by using thermogravimetric analysis. The evolving rates of the gaseous products during the
pyrolysis such as H2, CH4, H2O, CO and CO2 were also
measured by the TG-MS techniques. The feature common
to all the samples was that the evolving behaviors of CH4,
H2O, CO, and CO2 were well accompanied by the sharp
decomposition seen in the DTG curves. However, the H2
formation behavior was not accompanied by sharp decomposition. Of particular interest was that the most dominated gas formation was H2O for all biomass samples.
Moreover, by comparing the ultimate analyses with the
devolatilization behaviors, it was found that biomass cannot be represented by a single homogeneous material. This
is because each biomass showed quite dierent devolatilization behaviors while they showed the similar elemental
composition.
For kinetic analysis, we could obtain the very proper
kinetic parameters (the distribution curve of activation
energy, f(E), and the activation energy dependent frequency factor, k0(E)), of biomass pyrolysis by utilizing a

distributed activation energy model (DAEM) without any

assumption and mathematical tting. The peaks of f(E)
curve for rice straw, rice husk, corncob and cellulose were
found to be 170, 174, 183, and 185 kJ/mol, respectively. The
k0 value increased from an order of 1011 to an order of
1018 s1, while E increased from 120 to 250 kJ/mol. The
catalytic eects of alkali and alkaline earth metals during
the pyrolysis play a major role in the variation of f(E) curve
among the dierent biomass species.

Acknowledgement
The authors acknowledge Professor Pierre Joulain from
the Laboratoire de Combustion et de Detonique, CNRS,
for his valuable comments on the manuscript.
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