J Therm Anal Calorim

DOI 10.1007/s10973-014-4215-3

Applicability of FraserSuzuki function in kinetic analysis

of DAEM processes and lignocellulosic biomass pyrolysis
processes
Zhicai Cheng Weixuan Wu Peng Ji
Xiaotong Zhou Ronghou Liu Junmeng Cai

Received: 20 July 2014 / Accepted: 27 September 2014

Akademiai Kiado, Budapest, Hungary 2014

Abstract In this work, a new method for fitting the

conversion rate curves of the distributed activation energy
model (DAEM) and lignocellulosic biomass pyrolysis
process was introduced. The method was based on the
curve fitting technique using the FraserSuzuki function.
Various simulated DAEM processes were analyzed. The
results showed that the conversion rate curve of one
DAEM process could be described well by a FraserSuzuki
function. According to the obtained parameters of the fitted
FraserSuzuki functions, the influences of the DAEM
parameters on the conversion rate curves of the corresponding DAEM processes can be quantitatively obtained.
The experimental data of the pyrolysis of cotton stalk,
oilseed rape straw, and rice straw were fitted by the Fraser
Suzuki mixture model which involves three individual
FraserSuzuki functions. It has been found that the Fraser
Suzuki mixture model can reproduce accurately the conversion rate curves of the pyrolysis of three lignocellulosic
biomass samples. The FraserSuzuki mixture model provides an approach to separate lignocellulosic biomass
pyrolysis into three parallel reactions which link to the
decomposition of hemicellulose, cellulose, and lignin,
respectively.
Keywords Lignocellulosic biomass  Pyrolysis 
Distributed activation energy model  FraserSuzuki
function  Kinetics  Fitting

Z. Cheng  W. Wu  P. Ji  X. Zhou  R. Liu  J. Cai (&)

Biomass Energy Engineering Research Center, Key Laboratory
of Urban Agriculture (South) Ministry of Agriculture, School of
Agriculture and Biology, Shanghai Jiao Tong University, 800
Dongchuan Road, Shanghai 200240, Peoples Republic of China
e-mail: jmcai@sjtu.edu.cn

Introduction
The pyrolysis kinetics of lignocellulosic biomass is usually
performed by means of thermogravimetric (TG) analysis
[1]. The pyrolysis of lignocellulosic biomass usually
involves several processes, which would result in some
mass loss steps observed in a TG curve or some peaks
observed in the corresponding differential thermogravimetric (DTG) curve [2]. Unfortunately, a very common
situation is that different processes of decomposition
overlap each other [1]. In general, those overlapped peaks
cannot be separated directly from the DTG curve. To solve
this problem, some researchers proposed the Logistic mixture model [35] and Weibull mixture model [611] to
separate peaks in the DTG curves. Recently, Perejon et al.
[12] found that the FraserSuzuki function can be used to
deconvolute a complex solid-state reaction into its individual processes. Findorakova et al. [13] successfully
deconvoluted the conversion rate curves of the thermal
decomposition of [Zn(2-Clbenz)2(caf)2]. Svoboda et al. [14]
investigated the applicability of the FraserSuzuki function
in the deconvolution of complex crystallization processes
and found that the deconvolution procedure could provide
reasonable, consistent, and accurate results. They also
obtained the correlation between the JohnsonMehlAvrami (JMA) model and parameters of the FraserSuzuki
function. Koga et al. [15] successfully used nine empirical
mathematical functions (including the FraserSuzuki
function, Weibull mixture model, and Logistic mixture
model) for the deconvolution of the DTG curves of the
thermal decomposition of co-precipitated zinc carbonates.
The distributed activation energy model (DAEM) has
proven to describe complex thermally activated solid-state
reactions very well [16], in particular, the pyrolysis of
lignocellulosic biomass and its major components [17, 18].

123

Z. Cheng et al.
Table 1 Ultimate analysis results of lignocellulosic biomass samplesa
Sample

C/%

Cotton stalk

N/%

S/%

O /%

Ash/
%

43.750 6.290

0.536

0.260

47.007

2.157

Oilseed rape
straw

41.390 5.430

0.254

0.429

48.134

4.363

Rice straw

37.895 5.781

0.585

0.408

49.785

5.546

Dry basis

By difference

H/%

Table 2 Chemical analysis results of lignocellulosic biomass

samplesa
Sample

Cellulose/%

Hemicellulose/%

Lignin/%

Cotton stalk

34.54

12.30

42.08

Oilseed rape straw

47.16

24.31

22.52

Rice straw

42.29

27.43

16.00

Dry basis

However, in the literature, the applicability of the Fraser

Suzuki function in the kinetic description of DAEM processes and lignocellulosic biomass pyrolysis processes is
still missing. Therefore, the aim of this study is to analyze
some data sets of simulated DAEM processes and some
experimental data sets of lignocellulosic biomass pyrolysis
using the FraserSuzuki function.

Materials and experimental details

The lignocellulosic biomass samples used in this work
were cotton stalk, oilseed rape straw, and rice straw. The
cotton stalk sample was taken from a farm in Jiangxi
Province, China, in 2013. The oilseed rape and rice straw
samples were collected from a farm located in Anhui
Province, China, in 2013. All samples were prepared following the standard ASTM E1757-01 [19]. Ultimate analysis results of the lignocellulosic biomass samples are
listed in Table 1.
The pyrolysis kinetic experiments were carried out with
a thermogravimetric analyzer (SDT Q600, TA Instruments,
USA) on samples of around 5 mg. A heating rate of
20 K min-1 was used, and the temperature ranged from
room temperature to 973 K. The samples were evenly
spread in an alumina sample crucible without lid. Pyrolysis
runs were performed under nitrogen atmosphere, and the
flow rate of nitrogen was 50 mL min-1.
The chemical compositions of the lignocellulosic biomass samples were obtained in accordance with the standard NREL/TP-510-42618 [20] and listed in Table 2. The

123

results show that the cotton stalk sample contains the

highest lignin content and the oilseed rape straw sample
contains the highest cellulose content, while the rice straw
sample contains the highest hemicellulose content.

FraserSuzuki function
The FraserSuzuki function, an exponential function, was
originally developed by Fraser and Suzuki for the resolution of overlapping bands [21, 22]. This function was
usually used for signal processing and data analysis in
chromatography [23, 24]. In this work, the FraserSuzuki
function was used to describe the DAEM processes and
lignocellulosic biomass pyrolysis processes. The Fraser
Suzuki function can be expressed as
(
 
 )
da
ln 2
T p 2
h exp  2 ln 1 2s
;
1
dT
s
w
where a is the conversion degree, T is the temperature, da/
dT is the conversion rate, and h, s, p, and w are the
parameters.
In order to better understand the physical meanings of h,
s, p, and w, a parametric study of the FraserSuzuki
function was carried out. Figure 1 shows the influences of
the parameters on the function curve. From Fig. 1, it can be
obtained that the parameter p is the position parameter, the
parameter w is related to the function curve width, the
parameter h is the height parameter, and the parameter s is
the shape parameter. The FraserSuzuki function curve is
left-skewed if s \ 0 and is right-skewed if s [ 0.
For fitting the data of the DAEM processes and lignocellulosic biomass pyrolysis processes to the FraserSuzuki
function, some estimation of the function parameters is
required. The nonlinear optimization method was
employed to perform this task. The minimum of the
residual sum of squares was sought in order to obtain the
best fit. In this work, DataFit, a professional curve fitting
(nonlinear regression) and data plotting software developed
by Oakdale Engineering [25], was used for the implementation of the nonlinear optimization.

Application to DAEM processes

The DAEM assumes that the decomposition mechanism
takes a large number of independent, parallel, first-order or
nth-order reactions with different activation energies,
which can be represented by a distribution function [26].
The DAEM equations for the nonisothermal processes are
given below:

Applicability of FraserSuzuki function in kinetic analysis

8


 1=1n
RT A
R1
E
>
>
< 1  0 1  1  n T0 exp 
f EdE
dT
b

 RT  
a
RT A
R1
>
E
>
:
1  0 exp  T0 exp 
dT f EdE
b
RT

n 6 1
2
n1

8



 n=1n
Z T
>
R
A
E
>
> 1 A exp  E
exp

f EdE
1


1

n

dT
<
0 b
da
RT
RT
T0 b 




Z T
R1 A
dT >
E
A
E
>
>
exp


exp 
dT f EdE
:
0 b
RT
RT
T0 b

where A is the frequency factor, E is the activation energy,

E0 is the mean of activation energy distribution, R is the
universal gas constant, n is the reaction order, T0 is the
initial temperature, T is the temperature, b is the heating
rate, and f(E) is the activation energy distribution. Usually,
f(E) is taken to be a Gaussian distribution with a mean
activation energy, E0, and a standard deviation, r [27, 28].
"
#
1
E  E 0 2
f E p exp 
4
2r2
2pr

d /dT/K1

0.012
0.009
0.006

0.010

h = 0.005 K1
h = 0.0075 K1
h = 0.01 K1

0.008

h = 0.0125 K1
h = 0.015 K1
p = 600 K
w = 40 K
s = 0.3

n1

0.006
0.004

h = 0.01 K1
p = 550 K
p = 575 K
p = 600 K
p = 625 K
p = 650 K
w = 40 K
s = 0.3

0.002

0.003

0.000

0.000
450

The simulated DAEM data were analyzed. However, the

DAEM equations have no exact analytical solution. So, the
simulated DAEM data were obtained from the numerical
calculations of Eqs. (2) and (3). In this work, Mathematica, a computational software program used in many scientific, engineering, mathematical, and computing fields
based on symbolic mathematics [29], was used for the
implementation of the numerical calculations of the DAEM
equations. The following four numerical examples for
simulated DAEM processes were used.

d /dT/K1

0.015

n 6 1

500

550

600

650

700

450

500

550

T/K

d /dT/K1

0.008
0.006
0.004

0.010
h = 0.01 K1
p = 600 K
w = 20 K
w = 30 K
w = 40 K
w = 50 K
w = 60 K
s = 0.3

0.008

d /dT/K1

0.010

0.006
0.004

0.002

0.002

0.000

0.000

450

500

550

600

650

700

T/K

600

T/K

650

700

450

h = 0.01 K1
p = 600 K
w = 40 K
s = 0.5
s = 0.3
s = 0.1
s = 0.1
s = 0.3
s = 0.5

500

550

600

650

700

T/K

Fig. 1 Parametric study of the FraserSuzuki function

123

Z. Cheng et al.
Table 3 Parameter values of fitted FraserSuzuki functions for simulated DAEM processes together with corresponding correlation coefficients
(Example 1)
DAEM process

h/K-1
13.64

R2

FraserSuzuki function parameters

-1

-1

-1

-1

p/K

s , E0 = 185.4 kJ mol , r = 3.5 kJ mol , b = 20 K min , and

A = 10
n = 1.00

-2

1.799 9 10

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, and

n = 1.25

w/K

627.52

-1

-1.853 9 10

51.23

0.9998

1.652 9 10-2

628.26

-1.211 9 10-1

56.04

0.9997

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, and

n = 1.50

1.522 9 10-2

628.68

-5.285 9 10-2

60.83

0.9994

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, and

n = 1.75

1.409 9 10-2

628.89

1.379 9 10-2

65.44

0.9990

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, and

n = 2.00

1.311 9 10-2

628.98

7.691 9 10-2

69.83

0.9984

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, and

n = 2.25

1.226 9 10-2

628.99

1.360 9 10-1

73.99

0.9970

Table 4 Parameter values of fitted FraserSuzuki functions for simulated DAEM processes together with corresponding correlation coefficients
(Example 2)
DAEM process

R2

FraserSuzuki function parameters

h/K-1

p/K

w/K

E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

A = 1010.64 s-1

1.064 9 10-2

770.02

-4.911 9 10-2

86.93

0.9991

E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

A = 1011.64 s-1

1.209 9 10-2

716.55

-5.099 9 10-2

76.49

0.9991

E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

A = 1012.64 s-1

1.362 9 10-2

669.83

-5.220 9 10-2

67.94

0.9992

E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

A = 1013.64 s-1

1.522 9 10-2

628.68

-5.283 9 10-2

60.83

0.9993

E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

A = 1014.64 s-1

1.689 9 10-2

592.17

-5.302 9 10-2

54.86

0.9993

E0 = 185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

A = 1015.64 s-1

1.861 9 10-2

559.58

-5.282 9 10-2

49.81

0.9994

Table 5 Parameter values of fitted FraserSuzuki functions for simulated DAEM processes together with corresponding correlation coefficients
(Example 3)
DAEM process

h/K-1
13.64

-1

R2

FraserSuzuki function parameters

-1

-1

p/K

s , r = 3.5 kJ mol , b = 20 K min , n = 1.50, and

A = 10
E0 = 175.4 kJ mol-1

-2

1.586 9 10

A = 1013.64 s-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

E0 = 185.4 kJ mol-1

w/K

595.57

-2

-4.957 9 10

58.44

0.9994

1.522 9 10-2

628.68

-5.285 9 10-2

60.83

0.9993

A = 1013.64 s-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

E0 = 195.4 kJ mol-1

1.464 9 10-2

661.74

-5.568 9 10-2

63.23

0.9992

A = 1013.64 s-1, r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.50, and

E0 = 205.4 kJ mol-1

1.409 9 10-2

694.75

-5.851 9 10-2

65.66

0.9992

Example 1 Let A = 1013.64 s-1, E0 = 185.4 kJ mol-1,

r = 3.5 kJ mol-1, b = 20 K min-1, and n = 1.0, 1.25,
1.50, 1.75, 2.00, and 2.25. The values of A, E0, r, and b

123

were taken from the literature [30], which were used to

describe the pyrolysis kinetics of cellulose. Example 2 The
parameter values in this example are identical to those in

Applicability of FraserSuzuki function in kinetic analysis

Table 6 Parameter values of fitted FraserSuzuki functions for simulated DAEM processes together with corresponding correlation coefficients
(Example 4)
r/kJ mol-1

h/K-1
13.64 -1

-1

-1

-1

p/K
-2

1.677 9 10

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, b = 20 K min-1, n = 1.50, and r = 3.5 kJ mol-1

1.522 9 10-2

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, b = 20 K min-1, n = 1.50, and r = 5.5 kJ mol-1

A = 1013.64 s-1, E0 = 185.4 kJ mol-1, b = 20 K min-1, n = 1.50, and r = 7.5 kJ mol-1

A = 10

R2

FraserSuzuki function parameters

s , E0 = 185.4 kJ mol , b = 20 K min , n = 1.50, and r = 1.5 kJ mol

w/K

629.43

-2

-8.393 9 10

54.86

0.9986

628.68

-5.283 9 10-2

60.83

0.9993

1.333 9 10-2

627.79

-2.341 9 10-2

69.90

0.9997

1.156 9 10-2

627.02

-3.452 9 10-3

80.86

0.9999

0.020

Simulated data
F-S predicted curve

d /dT/K1

d /dT/K1

n = 1.0

0.015
0.010

0.010

0.005

0.005
0.000

Residuals/K1

Residuals/K1

0.015 n = 1.25
Simulated data
F-S predicted curve

0.0005
0.0000
0.0005
500

550

600

650

700

0.000
0.0005
0.0000
0.0005
500

550

600

T/K

n = 1.5
Simulated data
F-S predicted curve

0.010

750

n = 1.75
Simulated data
F-S predicted curve

0.010

0.005

0.000
0.0005
0.0000
0.0005
500

550

600

650

700

750

800

Residuals/K1

Residuals/K1

0.005

0.000
0.0005
0.0000
0.0005
500

550

600

650

T/K

700

750

800

T/K

0.015

0.0125
n = 2.0
Simulated data
F-S predicted curve

0.010

0.005

n = 2.25
Simulated data
F-S predicted curve

0.0100

d /dT/K1

d /dT/K1

700

0.015

d /dT/K1

d /dT/K1

0.015

650

T/K

0.0075
0.0050

0.000
0.0005
0.0000
0.0005
500

550

600

650

700

750

800

T/K

Fig. 2 Simulated kinetic curves (dots, A = 1013.64 s-1, E0 =

185.4 kJ mol-1, r = 3.5 kJ mol-1, b = 20 K min-1, and n = 1.0,
1.25, 1.5, 1.75, 2.0, and 2.25) fitted with the FraserSuzuki function

Residuals/K1

Residuals/K1

0.0025
0.0000
0.0005
0.0000
0.0005
500

550

600

650

700

750

800

850

T/K

(solid lines). The residuals between the simulated data and the curve
predicted by the FraserSuzuki function are plotted underneath the
figures. (Example 1)

123

Z. Cheng et al.
0.0125

0.0125

A = 1010.64 s 1
0.0100

0.0075

d /dT/K1

Simulated data
F-S predicted curve

0.0050

0.0050
0.0025

0.0000

0.0000

0.0005
0.0000

0.0005
600

Simulated data
F-S predicted curve

0.0075

0.0025

Residuals/K1

Residuals/K1

d /dT/K1

0.0100

A = 1011.64 s 1

0.0005
0.0000

0.0005

650

700

750

800

850

900

600

650

700

T/K
A = 1013.64 s 1

A = 1012.64 s 1
0.0150

Simulated data
F-S predicted curve

d /dT/K1

0.0125
0.0100

0.0075

0.0075

0.0050

0.0050

0.0025

0.0025

0.0000

0.0000

Residuals/K1

d /dT/K1
Residuals/K1

Simulated data
F-S predicted curve

0.0100

0.0005

0.0005

0.0000

0.0000

0.0005

0.0005
550

600

650

700

750

500

550

600

T/K
0.0200

A = 1014.64 s 1

700

750

0.0100
0.0075
0.0050

Simulated data
F-S predicted curve

0.0150

d /dT/K1

Simulated data
F-S predicted curve

0.0125

A = 1015.64 s 1

0.0175

0.0150

0.0125
0.0100
0.0075
0.0050

0.0025

0.0025

Residuals/K1

0.0000
0.0005
0.0000

0.0005
500

650

T/K

0.0175

d /dT/K1

800

0.0175

0.0150
0.0125

Residuals/K1

750

T/K

0.0000
0.0005
0.0000

0.0005

525

550

575

600

625

650

675

700

T/K

475

500

525

550

575

600

625

650

T/K

Fig. 3 Simulated kinetic curves (dots, E0 = 185.4 kJ mol-1,

r = 3.5 kJ mol-1, n = 1.5, b = 20 K min-1, and A = 1010.64,
1011.64, 1012.64, 1013.64, 1014.64, and 1015.64 s-1) fitted with the

FraserSuzuki function (solid lines). The residuals between the

simulated and FraserSuzuki function predicted data are plotted
underneath the figures. (Example 2)

Example 1, except for n = 1.50 and A = 1010.64, 1011.64,

1012.64, 1013.64, 1014.64, and 1015.64 s-1. Example 3 The
parameter values in this example are identical to those in
Example 1, except for n = 1.50 and E0 = 175.4, 185.4,
195.4, and 205.4 kJ mol-1. Example 4 The parameter
values in this example are identical to those in Example 1,
except for n = 1.50 and r = 1.5, 3.5, 5.5, and
7.5 kJ mol-1. Conversion rate curves for DAEM processes

were simulated by assuming the above kinetic parameters

and fitted using the FraserSuzuki function. Tables 36
show the fitted FraserSuzuki function parameters for
Examples 14, respectively. The corresponding correlation
coefficients are also included in the tables. Figures 25
show the simulated curves for DAEM processes and the
resulting fitting curves using the FraserSuzuki function. It
is quite clear from the figures and tables that the Fraser

123

Applicability of FraserSuzuki function in kinetic analysis

0.0175

0.0150 E0 = 185.4 kJ mol1

0.0125
0.0100

d /dT/K1

E0 = 175.4 kJ mol1
Simulated data
F-S predicted curve

0.0075

0.0125
0.0100

0.0050

0.0025

0.0025

0.0000

0.0000

0.0005
0.0000

0.0005
500

550

600

650

700

Simulated data
F-S predicted curve

0.0075

0.0050

Residuals/K1

Residuals/K1

d /dT/K1

0.0150

0.0005
0.0000
0.0005
500

550

600

T/K

E0 = 195.4 kJ mol1

d /dT/K1

0.0125

Simulated data
F-S predicted curve

0.0100
0.0075

0.0100

750

0.0050

0.0025

0.0025

0.0000

0.0000

0.0005
0.0000
600

650

700

750

800

T/K

Simulated data
F-S predicted curve

0.0075

0.0050

Residuals/K1

d /dT/K1

0.0125

Residuals/K1

700

1
0.0150 E0 = 205.4 kJ mol

0.0150

0.0005
550

650

T/K

0.0005
0.0000
0.0005
600

650

700

750

800

T/K

Fig. 4 Simulated
kinetic
curves
(dots,
A = 1013.64 s-1,
r = 3.5 kJ mol-1, b = 20 K min-1, n = 1.5, and E0 = 175.4,
185.4, 195.4, and 205.4 kJ mol-1) fitted with the FraserSuzuki

function (solid lines). The residuals between the simulated and

FraserSuzuki function predicted data are plotted underneath the
figures. (Example 3)

Suzuki function fits the simulated curves very well.

According to the obtained parameters of the fitted Fraser
Suzuki functions, the influences of the DAEM parameters on
the conversion rate curves of the corresponding DAEM
processes can be quantitatively obtained. In the literature,
those influences can only be qualitatively determined
[18, 31]. As an example, the obtained results of Example 1
present the influences of the reaction order on the DAEM. It can
be seen that with the increasing reaction order in the DAEM,
the height parameter h decreases, the position parameters
p slightly increases, the width parameter w increases, and the
shape parameter s increases from negative to positive.

processes can be described well by the FraserSuzuki

function according to the above analysis results. Therefore, the pyrolysis kinetics of lignocellulosic biomass can
be described by the following FraserSuzuki mixture
model:
(
 
 )
3
dw X
ln 2
T  pi 2


hi exp  2 ln 1 2si
; 5
dT
wi
si
i1

Application to biomass pyrolysis processes

Lignocellulosic biomass contains three major components:
cellulose, hemicellulose, and lignin [32]. Many researchers reported that the pyrolysis of lignocellulosic biomass
can be regarded as a weighted sum of the pyrolysis of
cellulose, hemicellulose, and lignin [17, 18, 33, 34]. The
pyrolysis kinetics of these biomass components can be
described well by using the DAEM [35]. And the DAEM

where -dw/dT is reaction rate obtained from the DTG

curve of lignocellulosic biomass pyrolysis and the subscript
i is the related value of the ith FraserSuzuki function.
The DTG curves of the pyrolysis of cotton stalk, oilseed
rape straw, and rice straw were analyzed by the above
FraserSuzuki mixture model. The corresponding model
parameters were optimized by using DataFit and shown in
Table 7. The overlays of the experimental data, model
prediction, and its individual components for the pyrolysis
of cotton stalk, oilseed rape straw, and rice straw are shown
in Figs. 68, respectively. The corresponding correlation
coefficients (R2) between the experimental data and the
model prediction have also been included in those figures.
It is evident from Figs. 68 that the fittings are perfect (for

123

Z. Cheng et al.
0.0175

0.0150
0.0125

0.0125

d /dT/K1

d /dT/K1

0.0150

0.0100
0.0075

Simulated data
F-S predicted curve

0.0000

0.0000

Residuals/K1

Residuals/K1

= 3.5 kJ mol1

0.0025

Simulated data
F-S predicted curve

0.0025

0.0075
0.0050

= 1.5 kJ mol1

0.0050

0.0100

0.0005
0.0000
0.0005

0.0005
0.0000

0.0005

550

600

700

650

550

600

650

T/K

700

T/K

0.0150
0.0100

0.0075
= 5.5 kJ mol1

0.0050
0.0025

0.0050

= 7.5 kJ mol1

Simulated data
F-S predicted curve

0.0000

0.0005
0.0000
0.0005
500

0.0075

0.0025

Simulated data
F-S predicted curve

0.0000
Residuals/K1

d /dT/K1

0.0100

Residuals/K1

d /dT/K1

0.0125

0.0005
0.0000

0.0005

550

600

650

700

750

500

550

600

T/K

650

700

750

T/K

Fig. 5 Simulated kinetic curves (dots, A = 1013.64 s-1, E0 =

185.4 kJ mol-1, b = 20 K min-1, n = 1.50, and r = 1.5, 3.5, 5.5,
and 7.5 kJ mol-1) fitted with the FraserSuzuki function (solid lines).

The residuals between the simulated and FraserSuzuki function

predicted data are plotted underneath the figures. (Example 4)

Table 7 Parameter values of fitted mixed FraserSuzuki functions for cotton stalk, oilseed rape straw, and rice straw
FS function

Parameter value

Cotton stalk

Oilseed rape straw

Rice straw

h/K-1

2.888 9 10-3

2.478 9 10-3

2.903 9 10-3

p/K

592.79

561.17

581.65

-6.089 9 10-2

3.320 9 10-1

-4.649 9 10-3

w/K
2

-1

83.00

4.266 9 10

3.774 9 10-3

p/K

635.99

608.60

595.73

-6.552 9 10-2

-5.120 9 10-2

-5.592 9 10-2

h/K-1

-3

34.55

-3

43.02

41.75

9.698 9 10-4

5.242 9 10-4

6.888 9 10-4

p/K

639.75

677.13

638.05

1.982 9 10-1

-6.394 9 10-2

-6.784 9 10-3

w/K

243.65

264.01

291.28

all lignocellulosic biomass samples, the R2 values are

higher than 0.998).
The separation into three individual component functions by the FraserSuzuki mixture model provides a

123

90.70

3.635 9 10

h/K

w/K
3

82.62

method to separate three parallel reactions involved in

the process of lignocellulosic biomass pyrolysis.
According to the temperature range of each individual
component process, it can be approximately concluded

Applicability of FraserSuzuki function in kinetic analysis

0.007

0.006
Experimental data
F-S predicted curve
F-S 1
F-S 2
F-S 3

0.004
0.003

Experimental data
F-S predicted curve
F-S 1
F-S 2
F-S 3

0.006

dw/dT/K1

dw/dT/K1

0.005

R 2 = 0.9989
0.002

0.005
0.004
0.003

R 2 = 0.9995

0.002
0.001

Residual/K1

Residual/K1

0.001
0.000
0.0002
0.0000

0.0002
450

0.000
0.0002
0.0000

0.0002
400

500

550

600

650

700

750

800

850

Fig. 6 Overlay of experimental DTG curve of cotton stalk (dots) at

the heating rate of 20 K min-1 and the corresponding FraserSuzuki
function used for fitting the experimental curve (solid line). Residuals
are plotted underneath the figure. The correlation coefficient has been
included in the figure

600

700

800

900

1000

T/K

900

T/K

500

Fig. 8 Overlay of experimental DTG curve of rice straw (dots) at the

heating rate of 20 K min-1 and the corresponding FraserSuzuki
function used for fitting the experimental curve (solid line). Residuals
are plotted underneath the figure. The correlation coefficient has been
included in the figure

Conclusions
0.006

Experimental data
F-S predicted curve
F-S 1
F-S 2
F-S 3

dw/dT/K1

0.005
0.004
0.003

R 2 = 0.9991

0.002

Residual/K1

0.001
0.000
0.0002
0.0000

0.0002
450

500

550

600

650

700

750

800

850

900

T/K

Fig. 7 Overlay of experimental DTG curve of oilseed rape straw

(dots) at the heating rate of 20 K min-1 and the corresponding
FraserSuzuki function used for fitting the experimental curve (solid
line). Residuals are plotted underneath the figure. The correlation
coefficient has been included in the figure

that the first, second, and third processes correspond to

the decomposition of hemicellulose, cellulose, and lignin,
respectively. The traditional kinetic models are easier to
apply on those individual component processes obtained
by the FraserSuzuki mixture model than on the raw TG
data for lignocellulosic biomass pyrolysis. The further
kinetic analyses of those component processes will be
our next work.

In this work, the possibility of applying the FraserSuzuki

function for the fitting of the conversion rate curves of the
DAEM processes and the lignocellulosic biomass pyrolysis
processes was investigated. Several sets of DAEM processes
were simulated and analyzed. It can be found that the conversion rate curve of a DAEM process can be fitted well by
one FraserSuzuki function. According to the obtained
parameters of the fitted FraserSuzuki functions, the influences of the DAEM parameters on the conversion rate curves
of the corresponding DAEM processes can be quantitatively
obtained. Moreover, the DTG curves of the pyrolysis of
cotton stalk, oilseed rape straw, and rice straw were fitted by
the FraserSuzuki mixture model involving three individual
FraserSuzuki functions. The results showed that the curves
calculated by the FraserSuzuki mixture model were in
agreement with the experimental data.
Acknowledgements Financial support was obtained from School of
Agriculture and Biology, Shanghai Jiao Tong University (Grant No.
NRC201101). The authors would like to acknowledge Professor Lius
A. Perez-Maqueda for his help in the parameter estimation of the
FraserSuzuki function and Miss Lu Wang for providing TG data.

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