Bioresource Technology 127 (2013) 298–305

Contents lists available at SciVerse ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

The kinetic analysis of the pyrolysis of agricultural residue under

non-isothermal conditions
Chao Gai, Yuping Dong ⇑, Tonghui Zhang
Key Laboratory of High Efficiency and Clean Mechanical Manufacture, Department of Mechanical Engineering, Shandong University, Jinan 250061, PR China

h i g h l i g h t s

" Thermal decomposition characteristics of corn straw and rice husk.

" Characteristic parameters of TG–DTG curves of the samples are calculated.
" Variation of activation energy corresponding to different conversion fractions.
" Variation of reaction order corresponding to varied heating temperatures.

a r t i c l e i n f o a b s t r a c t

Article history: The study concerns the pyrolysis kinetics of agricultural wastes, corn straw (CS) and rice husk (RH). Ther-
Received 14 July 2012 mogravimetric experiments were carried out in a thermogravimetric analyzer under inert conditions, and
Received in revised form 20 September 2012 operated at different heating rates ranging from 5 to 40 K/min. As the increment of heating rates, the vari-
Accepted 21 September 2012
ations of characteristic parameters from the TG–DTG curves were determined. Iso-conversional Starink
Available online 29 September 2012
approach and Avrami theory were used to evaluate the kinetic parameters, including apparent activation
energy and reaction order. For the range of conversion fraction investigated (20–80%), the apparent acti-
Keywords:
vation energy of CS initially increased from 98.715 to 148.062 kJ/mol and then decreased to 144.387 kJ/
Biomass
Kinetics
mol afterwards, whilst the apparent activation energy of RH increased gradually from 50.492 to
Pyrolysis 88.994 kJ/mol. With varied temperatures (517–697 K), the corresponding value of reaction order was
Apparent activation energy increased from 0.288 and 0.359 to 0.441 and 0.692, along with a decrease to 0.306 and 0.445, respectively.
Reaction order Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction derived from agricultural wastes in rural areas, researchers have

A large number of agricultural wastes have not been properly uti-
lized in China every year. Corn and rice are the most widely cultivated
crop in China, especially in the eastern area of the country. Conse-
quently, as the agricultural waste of the two crops, corn straw and rice
husk are abundantly available every year. The National Bureau of Sta-
tistics of China (NBSC) has reported in China Statistical Yearbook that
the predicted availabilities of the two agricultural wastes are esti-
mated to be approximately 220 Mt/year (dry basis) and 100 Mt/year
(dry basis) respectively (National Bureau of Statics of China, 2009).
However, a majority of the two kinds of agricultural wastes is burned
in the farmland every year, which seriously pollutes the atmospheric
environment and wastes the various biomass resources.
In order to address this common problem brought by direct
burning, and promote the use of clean and highly efficient energy
⇑ Corresponding author. Tel./fax: +86 531 88392199.
E-mail address: dongyp@sdu.edu.cn (Y. Dong).
continuously paid special attention to convert agricultural wastes
into solid, liquid or gaseous fuels using thermochemical conversion
(TCC) technologies, which are summarized in Table 1. As for the
biomass gasification, it is an important technology for converting
wastes into combustible gas and subsequent use in power genera-
tion (Karmakar and Datta, 2011).
As a separate technology and the preliminary stage of combus-
tion and gasification, pyrolysis not only involves complicated
chemical processes, but also includes complex physical processes
such as heat transfer, mass transfer and their interactions. It has
a significant effect on the gasification process. According to White
et al. (2011), a thorough understanding of pyrolysis kinetics is vital
to supply guidance on the feasibility, design, and scaling of indus-
trial gasification reactors, as well as pave the way for optimizing
the operating conditions. In addition, as already discussed in a pre-
vious paper (Gai and Dong, 2012), during the gasification of agri-
cultural wastes, apart from the pollutants of particulate dust and
condensable tars, the detrimental element of sulphur and chlorine
in the feedstock are also released in several chemical forms in

0960-8524/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2012.09.089
 C. Gai et al. / Bioresource Technology 127 (2013) 298–305
Table 1
Classification scheme of thermochemical conversion of agricultural wastes for fuels.
Conversion temperature TCC technology Major products Major pollutants
Low temperatures Pyrolysis Bio-char
Intermediate temperatures Pyrolysis Bio-oil
High temperatures Pyrolysis Bio-gas
High temperatures Gasification Syngas
Low temperatures Hydrothermal liquefaction Bio-oil
terms of gaseous compounds or bounded to the ash. In terms of the
potential technologies of syngas cleaning, it can generally be di-
vided into two categories including treatments during gasification
and gas cleaning after gasification. Undoubtedly, gasifier design
parameters and operating parameters have effect on the formation
of those pollutants during gasification. Therefore, in order to min-
imize the formation of such pollutants during the gasification pro-
cess, the knowledge of pyrolysis kinetics is also needed, which is
usually investigated by the thermogravimetric analysis (TGA).
TGA can be carried out under isothermal or non-isothermal con-
ditions. The main disadvantage of the traditional isothermal meth-
od is that there is a small mass-lose before reaching the desired
temperature, causing a certain error when investigate the pyrolysis
reaction mechanism of the solid state. Therefore, non-isothermal
method has become a widespread analytical technique in recent
decades due to the high sensitivity to experimental noise compared
to isothermal methods. Characteristic parameters of the sample can
be obtained from the TG and DTG curves during the TGA experi-
ments; then in order to investigate the pyrolysis mechanism, the ki-
netic parameters of pyrolysis reactions can be calculated using the
characteristic parameters, including apparent activation energy E,
pre-exponential factor A, reaction order n and reaction model f(a).
Assessing these kinetic parameters of pyrolysis of the sample rely
on different mathematical approaches.
Many mathematical approaches have been developed to calcu-
late the kinetic parameters, in terms of Coats–Redfern (Daood
et al., 2010), Freeman and Carroll method (Font and Williams,
1995), et al. These methods are usually based on the preliminary
assumption of a certain reaction order and reaction model, such
as mampel, nucleation, autocatalytic, diffusional and contracting
geometry, et al. Then the apparent activation energy and pre-
exponential factor are calculated simultaneous, but not separately.
Consequently, these approaches are viewed as the model-fitting
method. This kind of method often employs the single and simple
reaction model during the reaction process, which can result in a
substantial divergence; this discrepancy results from the difference
between the ideal reaction model and actual heterogeneous
reaction process consisting of series of parallel and sequential reac-
tions. Besides, the values of E and A will vary greatly on condition
that different reaction model is preliminary assumed; but the two
parameters can always get good linear regression between each
other. This manifestation of ‘kinetic compensation effect’ could
result in some difficult in determining the accurate reaction model,
since more than one reaction model can be obtained using this
method. Therefore, adopting the model-fitting method may bring
about the highly uncertain values of the kinetic parameters.
In respect to these faults of the model-fitting method, another
approach called model-free method has been more widespread
employed to assessing the pyrolysis kinetics of the solid state in
recent years, such as Friedman (Aboyade et al., 2011), Flynn–
Wall–Ozawa (Ounas et al., 2011) and Kissinger–Akahira–Sunose
(Damartzis et al., 2011) approach. In this method, the apparent
activation energy can be calculated at the same fraction conversion
of the sample in multiple TG curves, without assuming the reaction
model. Hence this approach eliminates the phenomenon of ‘kinetic
299
Typical decontamination technology Refs.
Ash, toxic organic pollutants Hexane extraction solvent Bernardo et al. (2012)
Corrosiveness of the oil Hydro treating Ozawa (1965)
Tars Catalytic converting Chen et al. (2003)
Tars, dust Catalytic converting. Dedusting Karmakar and Datta (2011)
Corrosiveness of the oil Hydro treating Toor et al. (2011)
compensation effect’. And it is also called the iso-conversional
approach, since the apparent activation energy obtained by this
approach is a function of the extent of conversion. Multistep
reaction mechanism of the pyrolysis kinetics can be obtained from
the knowledge of the relationship between apparent activation
energy and conversion degree. Besides, it is adequate to evaluate
the reaction kinetics over a wider temperature region.
Therefore, it is more reliable for analyzing the thermal data
using the multi-heating rate methods together with iso-conver-
sional approaches in recent years. Iso-conversional approaches
have been increasingly used to investigate the thermal decomposi-
tion kinetics of varied materials such as cattle manure (Otero et al.,
2011), sensitive plants (Wongsiriamnuay and Tippayawong, 2010)
or municipal solid waste (Liu et al., 2009).
In terms of the studies of pyrolysis kinetics of corn straw and
rice husk, most investigations adopt the model-fitting method,
and usually take the first-order reaction as the presumed reaction
model. Some other researches generally assume a certain reaction
order (e.g. normally range from zero-order to three-order) and a
particular reaction model. However, just as the former discussion,
the pyrolysis of the solid-state sample is a complicated physical
and chemical process. Not only does the reaction order may vary
greatly during the reaction process, but such significant difference
may also exist in the reaction model preliminary selected. There-
fore, the main objective of this study is to investigate the variation
of pyrolysis kinetics of corn straw and rice husk at different con-
version fractions and reaction temperature. It is hoped that the
pyrolysis kinetics of agricultural wastes obtained in the current
study can give a better and more comprehensive understanding
of the pyrolysis process, as well as to help establish the kinetic
model of biomass gasification for design and scaling of industrial
gasification reactors.
2. Methods
2.1. Raw material properties
As typical kinds of agricultural residues, corn straw and rice
husk were selected to carry out thermogravimetric experiments.
They were both locally available materials. Before the pyroylsis
tests, the samples were air-dried, crushed and then sieved. The
fraction 20–40 mesh was used as power samples for the experi-
mental runs. As for the properties of the applied feedstocks, the
methods of proximate and ultimate analysis are described by Gai
and Dong (2012). The proximate, ultimate and biochemical analy-
ses of the corn straw and rice husk are listed in Table 2.
2.2. TGA experiments
Thermogravimetric experiments were performed using a ther-
mogravimetric analyzer (TGA-SDTA 851e, METTLER TOLEDO),
which detects the mass-loss signal with a resolution of 0.1 lg. In
order to avoid the heat-transfer limitation generated by the sample
itself, a small sample mass of 10 mg was placed in the pan of the
300 C. Gai et al. / Bioresource Technology 127 (2013) 298–305

Table 2
Proximate, ultimate and biochemical analyses of the CS and RH.

Proximate analysis (wt.% dba) Ultimate analysis (wt.% dafb) Biochemical analysis (daf b)
Corn straw Rice husk Corn straw Rice husk Corn straw Rice husk
Fixed carbon 13.21 13.85 Carbon 43.83 41.56 Cellulose 36.4e 29.2f
Ash 11.80 18.91 Hydrogen 5.75 5.23 Hemicelluloses 22.6e 20.1f
Volatile matter 75.0 64.27 Oxygend 45.01 39.75 Lignin 16.6e 18.2f
Moisture (arc) 6.57 7.26 Nitrogen 0.97 0.59 Extractives 7.82e 6.71f
a
Dry basis.
b
Dry and ash free basis.
c
As received basis.
d
By difference.
e
Ref. White et al. (2011).
f
Ref. Mansaray and Ghaly (1999).

Z T  
thermobalance, which was enough to fill the pan due to the low E E
exp  dT ¼ ð0:00484e1:0516u Þ ð4Þ
bulk density of the ground samples. Afterwards, experiments were T0 RT R
carried out at heating rates of 5, 10, 20 and 40 K/min, respectively.
Samples were firstly held at 298 K for 1 min and then heated to Substituting of Eq. (4) into Eq. (3), and then taking the logarithm
1073 K at the specific heating rate. After that, samples were held of both sides result in the expression for the FWO integral iso-con-
at 1073 K for 1 min. For suppressing mass transfer effect to a min- versional method (Ozawa, 1965):
imum, pure nitrogen (99.99% purity) was used as the carrier gas,  
and it was kept at a steady flow rate of 80 mL/min during all exper- AE E E
ln bi ¼ ln  2:315  0:4567 ¼ C 0  0:4567 ð5Þ
iments. Under each test of heating rate, a separate blank run was RGðaÞ RT RT
carried out for baseline correction, using an empty pan. In terms of the Kissinger–Akahira–Sunose (KAS) method, the
employed empirical approximation is the following expression:
2.3. Theory
Z T  
E Eb
As the typical kind of heterogeneous solid-state reaction, the exp  dT ¼ ð6Þ
T0 RT RAT
primary pyrolysis process of biomass is represented by the follow-
ing reaction scheme: Biomass ? char + (volatiles + gases) (Kumar Substituting of Eq. (6) into Eq. (3), and then taking the logarithm
Sadhukhan et al., 2009). The global kinetics of the biomass pyroly- of both sides result in the expression for the KAS integral iso-
sis reaction can be described as: conversional method (Kissinger, 1957):
!  
da bi Ak R Ek Ek
¼ kðTÞf ðaÞ ð1Þ ln ¼ ln  ¼ CK  ½i ¼ 1; 2; 3; 4; 5; 6 ð7Þ
dt T 2pi Ek RT pi RT pi
where a is the fraction of conversion, a = (W0  Wt)/(W0  W1) (W0 According to the Starink method (Starink, 1996), the approxi-
and W1 are sample masses at the beginning and at the end of mass mate expression of FWO method (Eq. (5)) and KAS method (Eq.
loss reaction, respectively. Wt is the sample mass at time t/temper- (7)) can both be transformed into the same general formula as:
ature T). f(a) is the differential function of conversion. T is the tem-  
perature, k(T) is the rate constant which is described by Arrhenius b BE
ln ¼ CS  ð8Þ
equation, k(T) = A exp(E/RT) (A is the pre-exponential factor, E is TS RT
the apparent activation energy, R is the gas constant (8.314 J/ Where for the FWO method (Eq. (7)) s = 0, B = 0.4567; for the
(mol K)).Eq. (1) can be converted into Eq. (2) expressed as: KAS method (Eq. (9)) s = 2, B = 1. After a further exact analysis by
    Starink, the parameters of s and B has been adjusted to s = 1.8,
da A E
¼ exp  f ðaÞ ð2Þ B = 1.0033, respectively. Besides, it has been verified by Starink
dT b RT
that the precision of apparent activation energy calculated by this
Where b is the linear heating rate (b = dT/dt) and it is a constant. method is higher than those of FWO method and KAS method.
Carry out the integration of the both sides of Eq. (2), and it can Hence the Starink method can be described as:
 
be further integrated into: b E
ln ¼ C S  1:0037 ð9Þ
Z a  Z T     T 1:8 RT
da A E A
¼ GðaÞ ¼ exp  dT ¼ pðxÞ ð3Þ
0 f ðaÞ b T0 RT b For a given conversion fraction, a, the points of ln(b/T1.8) versus
1/T at different temperature heating rates can be fitted to a straight
Where p(x) in Eq. (3) is known as the temperature integral. line, and the slope of the line corresponds to 1.0037E/R. Hence
Although it does not have an exact analytical solution in closed- the apparent activation energy E can be calculated from the slope
form, it can be approximately represented via different empirical of the straight line.
interpolation formulas in terms of Doyle, Agrawal, Gorbatchev Reaction order is also a significant parameter to investigate the
and Frank–Kameneskii approximation. pyrolysis characteristic of biomass, besides apparent activation
The Flynn–Wall–Ozawa (FWO) method and Kissinger–Akahira– energy. In order to calculate the reaction order, Avrami theory
Sunose (KAS) method are the two most common model-free (Ruitenberg et al., 2001) was used in this study, and it can be
methods of determination of kinetic parameters. The empirical described as:
approximation used by the Flynn–Wall–Ozawa (FWO) method is
Doyle’s approximation (Doyle, 1961): kðTÞ
a ¼ 1  exp ð10Þ
bn
 C. Gai et al. / Bioresource Technology 127 (2013) 298–305 301

Where a, b and k(T) are the same parameters described in Eq. (1),
and as the exponent of b, n represents the reaction order.
Taking the double logarithm and transposing, Eq. (10) is trans-
formed into the following equation:
E
lnð lnð1  aÞÞ ¼ ln A   n ln b ð11Þ
RT
For a given temperature, T, the points of ln(ln(1a)) versus lnb
at different temperature heating rates can be fitted to a straight
line, and the slope of the line corresponds to n. Thus, the reaction
order can be deduced from the slope of the straight line.

3. Results and discussion

3.1. Thermal decomposition characteristics of CS and RH

The TG (Thermogravimetric) and DTG (Differential Thermo-

gravimetric) curves of CS and RH at different heating rates from
5 to 40 K/min are illustrated in Fig.1 and Fig.2. It can be observed
that the two samples resembled each other in TG–DTG curves,
which both presented two comparatively large losses of weight.
As a whole, the entire thermal decomposition process of the corn
straw sample is later than that of rice husk, whereas the mass-loss
extent of the corn straw is greater than that of rice husk. As sug-
gested by Kumar et al. (2008), the percentage of residual weight
after the whole thermal decomposition process is mainly deter-
mined by the total content of ash and fixed carbon. Therefore, it
can account for the greater mass-loss extent of the corn straw,
since the total content of ash and fixed carbon of corn straw is
smaller than that of rice husk, as presented in Table 2.
To be specific, the first segment of mass loss ranged from 298 K Fig. 2. DTG curves for the pyrolysis of CS (a) and RH (b) at heating rates of 5, 10, 20,
40 K/min.
to approximately 400 K. Such loss in mass originates majorly from
the increase of heating temperature, which promote the loss of

water and light volatile compounds in the tested sample, as

Fig. 1. TG curves for the pyrolysis of CS (a) and RH (b) at heating rates of 5, 10, 20,
40 K/min.
pointed out by Mansaray and Ghaly (1999). Hence it was a stage
of small mass loss since the low moisture content of those two
samples. Then, there was a negligible mass loss within a small tem-
perature range after the first stage. Afterwards, the second segment
of mass loss started about 500 K and ended at around 800 K. As it
can be seen from the TG–DTG curves, those two samples both
underwent a major weight loss during this stage. According to
the biochemical analysis illustrated in Table 2, the content of lignin
and extractives in the two tested samples are similar. However, the
difference in the fraction of cellulose and hemicelluloses between
two kinds of feedstock is relatively greater, which indicates that
the different properties of the pyrolysis process between corn
straw and rice husk are mainly affected by the percentage of cellu-
lose and hemicelluloses.
In order to describe the properties of the pyrolysis process of
these samples under the effect of varied heating rates, some char-
acteristic parameters calculated from the TG–DTG curves are listed
in Table 3. Ti: the initial thermal decomposition temperature at any
stage, K; Tf: the final thermal decomposition temperature at any
stage, K; Tp: the corresponding temperature of the peak rate of
weight loss, K; DTGmax: the maximum weight loss rate at any
stage, %/K; HTZ: the full temperature width at half-maximum of
the value of DTGmax, K; ML: the total mass loss at any stage, %.
It can be seen from Table 3, Fig.1 and Fig.2 that the entire
decomposition process was shifted to higher temperature zone as
the temperature heating rate was increased from 5 to 40 K/min.
From the view of Tp parameter, during the first mass loss stage of
corn straw and rice husk, the value of Tp was increased from
341 K and 321 K to 379 K and 345 K, respectively. As for the second
stage of weight loss, the corresponding value of Tp was increased
from 609 K and 569 K to 667 K and 619 K, respectively. In addition,
302 C. Gai et al. / Bioresource Technology 127 (2013) 298–305

Table 3
Characteristic parameters of CS and RH during the pyrolysis process.

Sample Stage I Stage II

Ti (K) Tf (K) Tp (K) DTGmax (%/K) HTZ (K) ML (%) Ti (K) Tf (K) Tp (K) DTGmax (%/K) HTZ (K) ML (%)
CS
5 298 422 341 0.098 36 9.12 443 769 609 0.481 57 66.32
10 298 435 349 0.091 39 8.31 457 794 628 0.449 61 66.51
20 298 448 365 0.081 43 7.36 462 832 645 0.426 68 65.73
40 598 471 379 0.078 49 6.49 476 868 667 0.412 73 65.87
RH
5 298 367 321 0.184 19 9.98 389 753 569 0.433 42 54.82
10 298 378 328 0.176 20 9.05 393 767 582 0.416 45 55.17
20 298 388 333 0.167 23 8.49 443 785 598 0.404 51 54.59
40 298 394 345 0.160 25 7.28 457 803 619 0.391 53 54.76

some other parameters also got higher values through the whole lated energy of activation and the square of correlation coefficient
thermal decomposition process of the two samples, including Ti (r2) are listed in Table 4. As the result of ANOVA analysis, the values
(i.e. refer in particular to the stage II) and Tf. This may have been of standard deviation (SD) are also listed in Table 4, in addition to
due to the fact that with the increment of heating rate, the time the regression analysis adopted.
consumed in reaching the settled final temperature is lesser. Con- It can be seen from Table 4 that the apparent activation energy
sequently, the heat transferred from the heating furnace within the of the two samples both varied greatly with different conversion
thermo-gravimetric instrument to the tested sample is limited, fractions, instead of keeping constant. And they showed varied var-
which may bring about a discrepancy between the recorded tem- iation trends. To be specific, as the increase of conversion fraction
perature and the actual sample temperature. In other words, the from 20% to 80%, the apparent activation energy of corn straw
reaction extent represented by horizontal axis and vertical axis of underwent the process of a slight fall to 144.387 kJ/mol after a rise
TG–DTG curves synchronously recorded by the computer are actu- from 98.715 to 148.062 kJ/mol, whereas the apparent activation
ally not coincided. In terms of the parameter of HTZ for the two energy of rice husk increased gradually from 50.492 to 88.994 kJ/
samples, it always increased with the increase of heating rates. mol. The different energies of activation at different conversion
This may also have been due to the heat-transfer limitation men- fractions suggest that the pyrolysis of corn straw and rice husk
tioned above. should proceed with varied reaction mechanisms.
However, not all characteristic parameters are increasing. The The data in Table 4 also demonstrate that the average value of
maximum weight loss rate DTGmax for both corn straw and rice the apparent activation energy of corn straw is 129 kJ/mol, which
husk were found to decrease a certain value. Specifically, with
the heating rate increased from 5 to 40 K/min, as for the corn
straw, the value of DTGmax was decreased from 0.098%/K for
the first segment and 0.481%/K for the second segment to
0.078%/K and 0.412%/K, respectively. As for the rice husk, the cor-
responding value of DTGmax was decreased from 0.184%/K and
0.433%/K to 0.160%/K and 0.391%/K, respectively. Biagini et al. Bia-
gini et al. (2008) carried out thermogravimetric experiment of
three biomass residues (e.g. rice husks, olive cake, cacao shells).
It was found that the maximum weight loss rate of three kinds
of sample all decreased with the heating rate increasing from
5 K/min to 100 K/min. Ptáček et al. (2011) investigated the kinetic
parameters of the thermal decomposition of kaolinite and reported
the same variation trend that the maximum weight loss rate grad-
ually decreased as the heating rate was increased from 1 to 40 K/
min. Therefore, taking into account the differences in the proper-
ties of the tested sample and operating conditions, the result in
the current study showed similar trends to the results published
in literature.
The data in Table 3 also showed that the parameter of ML for
two samples both appeared a narrower fluctuation with different
heating rates. According to Jeguirim and Trouvé (2009), this is be-
cause the total mass loss at any stage is mainly determined by the
essential component of the tested sample, which is not affected by
the heating rate.

3.2. Variation of apparent activation energy of CS and RH

In this study, to estimate the dependence of apparent activation

energy on the conversion fraction during the major pyrolysis pro-
cess, seven levels of conversion fraction varying from 20% to 80%
were employed at different heating rates of 5, 10, 20 and 40 K/
min. Based on the model-free of Starink method, the regression Fig. 3. Regression lines to apparent activation energy proposed by Starink method
lines of corn straw and rice husk are illustrated in Fig.3. The calcu- for CS (a) and RH (b) at heating rates of 5, 10, 20, 40 K/min.
 C. Gai et al. / Bioresource Technology 127 (2013) 298–305 303

Table 4
Slope, apparent activation energy (E) and correlation coefficient (r2) deduced from Starink method for CS and RH.

Sample Conversion (%) Slope E (kJ/mol) r2 SD Sample Conversion (%) Slope E (kJ/mol) r2 SD
CS 20 11.918 98.715 0.994 0.012 RH 20 6.096 50.492 0.991 0.017
30 14.239 117.942 0.989 0.022 30 7.412 61.398 0.999 0.002
40 15.853 131.312 0.987 0.022 40 8.295 68.713 0.998 0.002
50 17.345 143.667 0.984 0.027 50 9.234 76.489 0.998 0.001
60 17.522 145.136 0.978 0.033 60 9.958 82.488 0.989 0.001
70 17.875 148.062 0.984 0.045 70 10.598 87.784 0.995 0.003
80 17.432 144.387 0.993 00.032.015 80 10.744 88.994 0.997 0.006
Average 129 79

is higher than that of rice husk, 79 kJ/mol. Since the value of appar-
ent activation energy represents the minimum energy required to
break the chemical bonds between atoms, which means the higher
value of the apparent activation energy, slower is the reaction. It is
a parameter indicating the reactivity and sensitivity of overall reac-
tion rate. Consequently, the reactivity of pyrolysis of rice husk with
relatively lower apparent activation energy is higher than that of
corn straw. It explains the experimental result that the entire ther-
mal decomposition process of the corn straw sample is later than
that of rice husk, which is indicated in Section 3.1.
Aboyade (2011) carried out non-isothermal kinetic analysis of
the pyrolysis of corn cobs in the heating rate range of 10–50 °C/
min. It was reported that the apparent activation energy in the
0.1–0.8 conversion interval ranged from 75–130 kJ/mol. Thus, the
result in this study showed the similar range to those obtained
in the present study in spite of the small property differences be-
tween corn cob and corn straw. Sharma and Rajeswara Rao
(1999) investigated the kinetics of pyrolysis of rice husk under
non-isothermal conditions in nitrogen. The experiments were con-
ducted at different temperature heating rates from 5 to 100 K/min,
and the energies of activation calculated was found to range from
72.7 to 97.1 kJ/mol. Taking into account the differences in the
experimental conditions, the result of 79 kJ/mol in this study
showed good agreement with the conclusion published in the
literature.
Researchers have also paid special attention to investigate the
three biochemical composition of biomass, including cellulose,
hemicellulose and lignin. As suggested by Huang et al. (2011),
the apparent activation energy of cellulose, hemicellulose and lig-
nin is generally about two hundreds, one hundreds and tens kJ/
mol, respectively. Thus, it indicates that property of the biomass
Fig. 4. Regression lines to reaction order proposed by Avrami theory for CS (a) and
is also a key factor determining the variation of apparent activation RH (b) at heating rates of 5, 10, 20, 40 K/min.
energy in the pyrolysis process.

3.3. Variation of reaction order of CS and RH
During the major pyrolysis process, in order to evaluate the
dependence of reaction order on temperature, seven levels of tem-
perature were also employed at four temperature heating rates of
5, 10, 20 and 40 K/min. Adopting the Avrami theory, the regression
lines of corn straw and rice husk are shown in Fig. 4 and the calcu-
lated reaction order is listed in Table 5. The corresponding values of
r2 and SD are also presented in Table 5.
It can be seen from Table 5 that the Avrami theory is suitable for
determining the kinetic parameter of reaction order, based on the
data of r2 calculated. The reaction order of corn straw and rice husk
both differed greatly rather than remained constant. However,
they showed the same variation trend. With varied temperatures
(517–697 K), the reaction order of corn straw was first increased
from 0.288 to 0.441 and then decreased to 0.306. As for the rice
husk, it increased from 0.359 to 0.692 and decreased to 0.445
afterwards.
Consequently, it can be observed that the varying currents of
apparent activation energy and the reaction order for corn straw
and rice husk are different. From the view of the varied mathemat-
ical mutual relation of the two kinetic parameter for the two sam-
ples, it can be further affirmed that the pyrolysis reaction
mechanisms of corn straw and rice husk are obviously different.
To determine this relationship of the two kinetic parameter and
the reaction mechanism, a kinetic analysis of elementary reaction
is required, which is recommended for further study.
The data in Table 5 also show that the mean value of the reac-
tion order of corn straw and rice husk is 0.365 and 0.539, respec-
tively. Vuthaluru (2004) investigated the pyrolytic behavior of
coal/biomass blends using thermogravimetric analysis. It was
found that the orders of reaction were in the range of 0.21–1.6,
with different blend ratios of coal/biomass. In terms of the 0:100
blends for coal/wood waste and coal/wheat straw, the correspond-
ing reaction orders were 0.42 and 0.52, respectively. Hence the re-
sults of reaction order obtained in the current paper were in a
similar range with the results published in literature. It also indi-
cates that the pyrolysis kinetics is greatly affected by the type
and composition of the biomass feedstock (Sanchez-Silva et al.,
2012).
304 C. Gai et al. / Bioresource Technology 127 (2013) 298–305

Table 5
Slope, reaction order (n) and correlation coefficient (r2) deduced from Avrami theory for CS and RH.

Sample Temperature (K) Slope n r2 SD Sample Temperature (K) Slope n r2 SD

CS 517 0.288 0.288 0.991 0.002 RH 497 0.359 0.359 0.951 0.002
547 0.328 0.328 0.996 0.001 517 0.448 0.448 0.922 0.003
577 0.364 0.364 0.991 0.003 537 0.559 0.559 0.989 0.002
607 0.391 0.391 0.989 0.004 557 0.656 0.656 0.994 0.009
637 0.441 0.441 0.984 0.007 577 0.692 0.692 0.995 0.014
667 0.434 0.434 0.993 0.003 597 0.619 0.691 0.991 0.016
697 0.306 0.306 0.996 0.001 617 0.445 0.445 0.977 0.017
Average 0.365 0.539

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lulose, cellulose and lignin, Li et al. (2008) simulated the corn straw
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4. Conclusions
TGA of CS and RH indicates that the two samples both showed
two relatively large weight losses. The characteristic parameters of
Tp, Ti, Tf, HTZ, DTGmax and ML were found to have inconsistent
variation trends. With conversion fraction increasing from 20% to
80 %, the apparent activation energy of CS initially increased from
98.715 to 148.062 kJ/mol and then decreased to 144.387 kJ/mol; as
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reaction order of CS ranged from 0.288 to 0.441, and 0.359 to
0.692 for RH.
Acknowledgements
Financial support for this study that has been provided by
Shandong Provincial Natural Science Foundation of China
(2009ZRA01100 and ZR200EZ001) and National Science and
technology support program (2010BAC66B02, 2011BAD15B05-05
and 2011YQ120039) is gratefully acknowledged.
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