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Journal of the Energy Institute 88 (2015) 332e343

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Journal of the Energy Institute


journal homepage: http://www.journals.elsevier.com/journal-of-the-energyinstitute

TGA pyrolysis and gasication of combustible municipal solid waste


Shen Chen, Aihong Meng, Yanqiu Long, Hui Zhou, Qinghai Li, Yanguo Zhang*
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Key Laboratory for CO2 Utilization and Reduction Technology,
Department of Thermal Engineering, Tsinghua University, Beijing 100084, China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 2 July 2014
Received in revised form
26 July 2014
Accepted 28 July 2014
Available online 19 August 2014

It brings modeling, design and operation of thermochemical treatment systems a huge challenge for a
large variety in municipal solid waste (MSW) composition and differences in thermal behavior of MSW
components. The pyrolysis and gasication characteristics of 8 different combustible solid wastes, representing the most common components of MSW, were investigated using a thermogravimetric analyzer
(TGA). Their decomposed characteristics in different atmospheres (N2 and CO2) was analyzed and
compared, which identied as pyrolysis and gasication, respectively. The results showed that pyrolysis
characteristics of 8 materials were similar to their gasication with the temperature less than 600  C. The
pyrolysis degradation of eight materials was slight above 600  C, while the gasication degradation in
the range of 700e900  C was obvious because of the reaction between CO2 and char. The discrete
distributed activation energy method (DAEM) was applied to analyze kinetics of pyrolysis and gasication. When pre-exponential factor was given as 2.2  1013(s1), the activation energy of cellulose
decomposed reaction was approximately 176 kJ/mol, while the activation energy of the reaction between
CO2 and char was 327 kJ/mol.
2014 Energy Institute. Published by Elsevier Ltd. All rights reserved.

Keywords:
Municipal solid waste (MSW)
Pyrolysis
Gasication
Kinetics analysis

1. Introduction
The amount of municipal solid waste (MSW) in China has increased to 170.4 million tons by the end of 2012, which has resulted in
serious environment problems. The components of the MSW in China are complex and normally categorized into ve groups, including
food residue, paper, wood & bamboo, rubber & plastic and textiles. The proportion of combustible solid wastes in MSW is about 81.26%
on average [1]. In the thermochemical treatment methods, pyrolysis and gasication are regarded as efciently and validly ways to
recycle MSW [2e4]. Pyrolysis occur at anaerobic atmosphere, and always generates char, liquid and gas productions. While gasication
is the process in which carbonic compounds turn to synthesis gas (mixture of CO, H2, CH4, N2, CO2 and some low-molecular-weight
hydrocarbons). Pyrolysis and gasication technology can greatly reduce the volume and weight of MSW and produce synthesis gas
for further utilities [4]. Many researchers have studied effects of different factors, such as heating way or heating rate, atmospheres
[5,6], particle sizes [7,8], on the process of thermal degradations of MSW. They have used several different experimental apparatus, such
as TGA [9e12], xed bed [5,8,13] and uidized bed [14,15]. In all these studies, thermogravimetric analysis is the most commonly
applied technique.
Due to the enormous number of reactions and their unknown mechanisms, global reactions cannot be described by simple kinetic
models, but a too detailed approach cannot be followed either. So the Least Squares tting method of multiple experiments has become the
most direct and widely used approach to analyze thermogravimetric data [16e18]. Arrhenius parameters (activation energy, E, and preexponential factor, A) can be obtained by simple linear tting. There are two main methods of tting analysis: the one which considers
the three main components of biomass e cellulose, hemicellulose and lignin, so that the experimental DTG curve can be t with a weighted
sum of three independent, rst-order reactions. The second method is called the distributed activation energy method (DAEM), where the
process is modeled as an innite series of parallel, irreversible, rst-order reactions [19].

* Corresponding author.
E-mail address: zhangyg@tsinghua.edu.cn (Y. Zhang).
http://dx.doi.org/10.1016/j.joei.2014.07.007
1743-9671/ 2014 Energy Institute. Published by Elsevier Ltd. All rights reserved.

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

333

Due to complication of MSW components and their thermal reactions, pyrolysis and gasication of MSW still need to be investigated at a
universal basis to get much more basic data and gain well understanding on their mechanism. Our research group has been studying the
pyrolysis of MSW and proposed a pseudo-components method to clarify the pyrolysis of combustible MSW [20]. Here, we did further study
on pyrolysis and gasication of combustible MSW and tried to compare their different behavior with TGA and DAEM analysis.
2. Materials and methods
2.1. Materials and their characterization
According to China's MSW compositions categories, the 8 typical components, including Chinese cabbage, orange peel, poplar wood,
paper, PE, PS, PVC and polyester fabric, which represented the major part of the combustible MSW were studied on a TGA. Chinese cabbage,
orange peel and poplar wood represented biomass solid waste: the rst two represented fruit vegetable biomass and the last represented
wood biomass. All of them were dried at 105  C and ground to less than 0.25 mm. PE, PS and PVC, which were bought from Shanghai Yangli
Electromechanical Technology Co. Ltd. represented plastic solid wastes, and their particle sizes were about 75 mm. Paper was from supermarket and its particle sizes were cut to less than 0.5 mm. Polyester fabric was also cut into pieces rstly and then grounded into
occulent.
The proximate and ultimate analysis of the samples is shown in Table 1. As biomass product, paper has similar components as the three
biomass samples. Biomass contains various amounts of cellulose, hemicellulose, lignin and a small amount of other extractives. Cellulose is
generally the largest fraction, about 40e50% of the biomass by weight; the hemicellulose portion is 20e40% of the material by weight [21].
Paper is obtained from plants with high cellulose content, and the cellulose content of paper is about 90%, higher than the other three
natural biomasses. As shown in Table 1, these four samples had similar content in major elements. Their carbon contents and oxygen content
are about 45e50% and 41e49% respectively. C/H ratios of these four samples are around 8, and all of them contained a bit of sulfur. The xed
carbon contents of Chinese cabbage, orange peel and poplar wood are about 20%, while paper has the lowest xed carbon content, of about
10%.
Plastics (PE, PS and PVC) and polyester fabric with high heating values belong to articial polymers. Plastics account for 11.06% and
textiles accounts for 3.13% in MSW in China on average[1]. The high heating values of PE, PS, PVC and paper are 46.48 kJ/mol, 38.93 kJ/mol,
20.83 kJ/mol and 20.86 kJ/mol, respectively. The composition of articial polymers is relatively simple with high volatile matter and low ash.
As shown in Table 1, the volatile in PE and PS is more than 99% volatile and the ash is neglected. While PVC is different, it contains no oxygen
and the chlorine is about 56%, which results in great difference in thermal degradation process from PE and PS [10]. Fixed carbon content of
polyester fabric is much higher than plastics, while its ash content is slightly higher. In short, natural polymers including Chinese cabbage,
orange peel and poplar wood characterize with higher ash and xed carbon, while articial polymers (PE, PS, PVC and polyester fabric) have
lower ash content and higher volatile.
2.2. Experimental apparatus
Experiments of pyrolysis and gasication were performed by a NETZSCH STA 409C/3/F. Pure N2 with a ow rate of 100 ml/min was
used in the pyrolysis process, and pure CO2 with a ow rate of 100 ml/min was used in the gasication process. Temperature rose
from room temperature to 1000  C at a heating rate of 10  C/min. Repeated experiments showed that TG curves had good
reproducibility.
2.3. DAEM analysis
The DAEM based on the assumption that the system was consisted of a series of irreversible parallel 1st order reactions. The details were
elucidated by Miura [22,23] and many researchers have tried to simplify and improve the models. For a linear heating thermal degradation
process, change in the remaining percentage of sample, x, against temperature, T, was given by Miura [23].

Z
x

FE; Tf EdE

(1)

Table 1
Proximate and ultimate analysis of the samples.
Samples

Orange peel
Chinese cabbage
Poplar wood
Paper
PE
PS
PVC
Polyester fabric

Proximate analysis

Ultimate analysis

Ad%

Vd%

FCd%

St,daf%

Cdaf%

Hdaf%

Ndaf%

Odaf%

2.91
9.91
7.54
10.69
0.00
0.04
0.00
0.49

76.49
67.60
73.85
79.33
99.98
99.57
94.93
88.60

20.60
22.49
18.61
9.98
0.02
0.39
5.07
10.91

0.19
0.61
0.22
0.28
0.17
0.19
0.61
0.28

48.74
47.49
51.36
45.12
85.98
86.06
38.34
62.16

5.92
5.88
5.89
5.31
11.20
6.27
4.47
4.14

1.43
4.11
1.52
0.38
0.21
5.73
0.23
0.29

43.72
41.91
41.00
48.91
2.44
1.74
0
33.12

A: ash content; V: volatile matter content; FC: xed carbon content; d: dry basis.

334

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

0
A
FE; T exp@ 
b

ZT

1
eE=RT dT A

(2)

Where, E(kJ/mol) represented the activation energy of the rst order reaction. T( C) was the temperature of the thermal process. A(s1) was
the pre-exponential factor. b( C/min) was heating rate. E/RT was denoted by x and equation (2) was rewritten as

0
1
11
0
Z x
x
AE
e
e
AE
pxA

dxAA exp@ 
FE; T exp@  @
bR x
bR
x
0

(3)

And the function p(x) approximate to px ex =x2 [22], then the above formula expressed as:



ART 2 E=RT
e
FE; T exp 
bE

(4)

Here, f(E) was a distribution function of the activation energy to represent the differences in the activation energies of many rst-order
irreversible reactions and the activation energies were always assumed to follow a Gaussian distribution. As a valid alternative, a discrete
distribution of activation energy was proposed by Giuntoli et al. [19], in which the integral in (1) was substituted by a sum of a nite number
of parallel reactions. This model was chosen because even though the activation energies which were found were not directly related to the
actual reacting functional groups [24], it provided a more effective visualization of the results and an additional degree of freedom to the
method [22].
It supposed that the global reaction of the process was consisted a limited number of irreversible reactions. The activation energy of
number i reaction was Ei and its proportion was P(Ei). Then formula (1) was rewritten as:

n
X

FEi ; TPEi

(5)

i1

P
Where, P(Ei) satised ni1 PEi 1.
We used a MATLAB program to analyze the TG curves of the processes thermal degradation at heating rate of 10  C/min and t them
with several rst-order reactions. Another common assumption used in DAEM is all the rst-order reactions sharing the same preexponential factor. It is debated because of the so called compensation effect and the pre-exponential factor appearing to depend
on the activation energy [25]. In many kinetic papers, the pre-exponential factor and activation energy are given as a couple but they
both vary on a wide range. In order to have a reliable comparison between different fuel conversion kinetics, the pre-exponential factor
can be xed at a reasonable value allowing instead of depending on the activation energies and the distribution shape. In this paper, we
chose to follow the common practice and xed the pre-exponential factor at the value of 2.2  1013(s1) [19,26,27]. It was reported by
Vamvuka, D. [28] that when tting three parallel rst order reactions, a pre-exponential factor of 101e101(s1) was usually used for
the lignin pseudo-component, which was much smaller than the value of pre-exponential we used in our model calculation. On this
occasion, the physic-chemical meaning of the pre-exponential factor was already lost here.
In this paper, we chose a discrete distribution of the activation energies for the thermal processes because we considered it more
suitable to represent the heterogeneous nature of the solid wastes. According to former research, it suggested that the activation energy
distribution of the thermal process of MSW was 100e400 kJ/mol. With MATLAB program developed by ourselves, a set of linear equations
are solved to get the nonnegative least-squares solution to obtain the discrete distribution of activation energy in the section of 0e600 kJ/
mol with an interval of 2 kJ/mol. Furthermore, reactions with proportions below 1% were ignored. Therefore, activation energy

12

100

Chinese cabbage (N2)


Poplar wood (N2)

10

Mass [wt%]

60

6
40

4
20

Mass Loss Rate [wt%/min]

Orange peel (N2)


80

200

400

600
o

800

0
1000

Temperature [ C]
Fig. 1. TG and DTG curves of pyrolysis of Chinese cabbage, orange peel and poplar wood (N2).

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

335

distributions were obtained and different numbers of parallel reactions of the thermal degradation processes of the samples were gotten
to t the DTG curves.
3. Results and discussion
3.1. Pyrolysis and gasication of biomass solid wastes
As biomass, the main components of Chinese cabbage, orange peel, poplar wood and paper are cellulose, hemicellulose and lignin so that
their thermal decomposed processes are similar, as shown in Figs. 1,2 and 3. Actually, pyrolysis or gasication of biomass can be seen as a
combined process consisting of individual processes of cellulose, hemicellulose and lignin [10,29]. At nitrogen atmosphere, DTG curve of
cellulose pyrolysis had one peak and the mass loss of cellulose pyrolysis mainly occurred between 300  C and 400  C, while hemicellulose
had two close peaks and the mass loss mainly occurred between 210  C and 400  C. The mass loss of lignin pyrolysis occurred in a large
temperature range and most mass loss occurred between 280 and 400  C [30]. As shown in Fig. 1, the main mass loss of three samples,
Chinese cabbage, orange peel and poplar wood, mainly occurred between 200  C and 400  C. The TG curves were all atten and the mass
loss was slight with temperature above 600  C, because the procedure of solid organic pyrolysis and devolatilization was almost completed
below 600  C and char formed above 600  C [31]. As mentioned above, the component of paper was relatively simple and mainly cellulose,
so its DTG curve of pyrolysis had only one peak as cellulose pyrolysis and the main mass loss of paper occurred at 300e400  C, as shown in
Fig. 3.
At CO2 atmosphere, the thermochemical behavior of paper was very close to its pyrolysis below 400  C, while there was another peak at
800e900  C in DTG curve of gasication, obviously differed from that of pyrolysis. The same appeared in TG curves of Chinese cabbage,
orange peel and poplar wood. As shown in Fig. 2, their main mass loss occurred at 200e400  C and the TG curves almost stayed at in
temperature range of 500e700  C, then above 700  C three samples all show apparent mass reduction and a peak appeared on the DTG
curves.
The biomass-CO2 gasication process is represented by three global reaction steps. The rst step involves heating and drying of the
biomass. The second step involves pyrolysis of the dried biomass to release volatile organic matter and create char. The third step involves
oxidation of the char by CO2 to produce CO and it is called Boudouard reaction [32]. The Fig. 4 represented the DSC curves of three biomass
samples and we could nd that there was an upgrade from the temperature of 700  C in each curve. And char gasication with CO2 is an
endothermic process which corresponds to the change of the DSC curves. Combining the TG curves and DSC curves of these three biomass,
we can conclude that the mass loss above 700  C at the gasication processes of biomass samples was caused by the Boudouard reaction
C(s) CO2 / 2CO, which could be evidenced by Gibbs free energy calculation [33]. Based on their HSC calculation, the Boudouard reaction
initiates at the temperature of 720  C [33] and it agrees well with our experimental results.
To compare the processes of pyrolysis and gasication, temperature range of main mass loss and peaks of DTG curves of four samples in
two atmospheres are listed in Table 2. At the temperature range of 150e500  C, thermal degradation in two atmospheres exhibited similar
characteristics for all samples respectively. The peaks of DTG curves had no great differences in two atmospheres. It suggested that below
500  C CO2 had no signicant inuence on the thermal degradation process compared with N2. Above 600  C mass loss of four samples was
slight at nitrogen atmosphere while all of them had a signicant mass decay between 700  C and 900  C. That's because the Boudouard
reaction initiated at about 720  C which resulted in the decreasing of char.
3.2. Pyrolysis and gasication of plastics and textile
Fig. 5 shows the thermal decomposition of PE, PS and PVC at two atmospheres. Pyrolysis and gasication processes of PE and PS were
very similar, in which the mass loss occurred in a narrow temperature range. At the N2 atmosphere the temperature peaks of DTG curves of
PE and PS were 477  C and 417  C, respectively, while they turned to 473  C and 413  C at the CO2 atmosphere, a little lower than the former.

12

100

Chinese cabbage (CO2)


Poplar wood (CO2)

10

Mass [wt%]

60

6
40

4
20

Mass Loss Rate [wt%/min]

Orange peel (CO2)


80

200

400

600

800

0
1000

Temperature [ C]
Fig. 2. TG and DTG curves of gasication of Chinese cabbage, orange peel and poplar wood (CO2).

336

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343


40

100
Paper (CO )
Paper (N )

80

Mass [wt%]

60

24

40

16
20

Mass Loss Rate [wt%/min]

32

0
0

200

400

600

800

1000

0
1200

Temperature [ C]
Fig. 3. TG and DTG curves of pyrolysis (N2) and gasication (CO2) of paper.

6
Chinese cabbage
orange peel
poplar wood
paper

DSC [mW/mg]

-3

-6

-9

200

400

600

800

1000

Temperature [ C]
Fig. 4. DSC curves of gasication of biomass solid waste.

Table 2
Thermal decomposition process of Chinese cabbage, orange peel, poplar wood and paper.
Atmosphere

Sample

Temperature range/ C

Temperature peaks of DTG/ C

Mass loss/wt%

Residue/wt%

CO2

Chinese cabbage

150e500
700e1000
150e500
700e1000
150e500
700e1000
150e500
700e1000
150e500
700e1000
150e500
700e1000
150e500
700e1000
150e500
700e1000

248,311
791
235,332
824
345
830,936
354
848
157,253,313
no peak
229,333
no peak
161,345,490
701
350
no peak

50.42
28.77
60.64
23.47
62.78
22.56
80.36
9.5
52.88
10.73
60.32
2.49
61.71
3.17
81.08
5.14

14.51

Orange peel
Poplar wood
Paper
N2

Chinese cabbage
Orange peel
Poplar wood
Paper

8.43
6.57
5.91
27.38
30.15
30.77
6.94

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

337

100
PE (CO )
PS (CO )
PVC (CO )

80

PE (N )
PS (N )

Mass [wt%]

60

PVC (N )

40

20

200

400

600

800

1000

Temperature [ C]

a)
30
PE(CO )
PS(CO )

25

PVC(CO )

Mass Loss Rate [wt%/min]

PE(N )
20

PS(N )
PVC(N )

15

10

200

400

600

800

1000

Temperature [ C]

b)
Fig. 5. TG and DTG curves of pyrolysis and gasication of PEPS and PVC: a) TG; b) DTG.

Pyrolysis and gasication of PVC both could be divided into two stage, which occurred at the temperature range of 250e380  C and
400e550  C respectively. At the N2 atmosphere, the temperature peaks of DTG curves of PVC were 287  C and 467  C, and they changed to
299  C and 469  C at the CO2 atmosphere. Comparing TG curves of PVC at two atmospheres, it could nd that at the range of 250e380  C CO2
promoted the thermal decomposition process.

40

100
Terylene (CO )
Terylene (N )

35

80

25

60

20
40

15
10

20

5
0

200

400

600

800

0
1000

Temperature [ C]
Fig. 6. TG and DTG curves of pyrolysis and gasication of polyester fabrics.

Mass Loss Rate [wt%/min}

Mass [wt%]

30

338

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

Table 3
Calculation results of DAEM for 8 samples.
Samples

Atmosphere

Number of parallel reactions

Pmax(%)

E(Pmax)

Chinese cabbage

N2
CO2
N2
CO2
N2
CO2
N2
CO2
N2
CO2
N2
CO2
N2
CO2
N2
CO2

27
23
27
25
17
20
11
4
1
1
1
1
6
6
4
7

19.39
17.49
22.07
17.91
31.34
27.25
76.87
76.65
100
100
100
100
32.12
47.34
85.16
73.60

171
171
177
179
181
183
183
185
223
221
205
203
167
169
211
211

Orange peel
Poplar wood
Paper
PE
PS
PVC
Polyester fabrics

40

Distribution [%]

32

24

16

0
100

150

200

250

300

350

400

E [kJ/mol]

a)
0.10
Experimental
Fitted

Mass Loss Rate [wt%/min]

0.08

0.06

0.04

0.02

0.00
200

400

600

800

1000

Temperature [ C]

b)
Fig. 7. Activation energy distribution, DTG and tted curve of poplar wood pyrolysis: a) activation energy distribution; b) DTG and tted curve.

kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol
kJ/mol

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

339

40

Distribution [%]

32

24

16

0
100

150

200

250

300

350

400

E [kJ/mol]

a)
0.10
Experimental
Fitted

Mass Loss Rate [wt%/min]

0.08

0.06

0.04

0.02

0.00
200

400

600

800

1000

Temperature [ C]

b)
Fig. 8. Activation energy distribution, DTG and tted curve of poplar wood gasication: a) activation energy distribution; b) DTG and tted curve.

TG and DTG curves of pyrolysis and gasication of polyester fabrics are shown in Fig. 6. At N2 atmosphere, the main mass loss of polyester
fabrics occurred at a narrow temperature range (375e475  C), and the temperature peak of DTG curve was 438  C. At CO2 atmosphere, the
main mass loss occurred at 370e500  C, and the temperature peak was 432  C. Below 450  C, the thermal decomposition processes was
similar, while there was an apparent mass loss above 700  C at CO2 atmosphere and the temperature peak of DTG curve was 951  C. From the
previous analysis, it suggested that it was caused by the Boudouard reaction of CO2 and char.
3.3. Kinetic analysis
Some detailed calculation results of discrete distribution for activation energy (DAEM) are listed in Table 3. It shows that the numbers of
parallel reactions of biomass solid wastes were much larger than that of plastics and textile. The most signicant reason was that components of biomass were more complicated than the others. More parallel reactions were needed to represent the global reaction of
biomass, while one rst-order reaction could describe the thermal process of plastics like PE and PS because their component was simple.
The parameter Pmax denoted the proportion of the parallel reaction with highest proportion value and having greatest effect on the reaction of the whole thermal decomposition process.
Figs. 7 and 8 show the distribution of activation energy, DTG curves and tted curves with parallel reactions of poplar wood at N2 and CO2
atmosphere, respectively. It indicated that reactions with lower activation energy initiated at low temperature and reactions with high
activation energy occurred at high temperature. At N2 atmosphere, activation energies of poplar wood pyrolysis concentrated at the range of
150e220 kJ/mol and the reactions mainly occurred at temperature range of 200e520  C. The activation energy with the highest proportion
was 181 kJ/mol, whose relevant reaction occurred at 250e390  C. While activation energy of cabbage mainly distributed in the range of

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343


20

20

16

16

Distribution [%]

Distribution [%]

340

12

12

100

150

200

250

300

350

400

100

150

200

E [kJ/mol]

300

350

400

300

350

400

b)
20

20

16

Distribution [%]

Distribution [%]

a)
25

15

10

250

E [kJ/mol]

12

100

150

200

250

300

350

400

100

150

200

250

E [kJ/mol]

E [kJ/mol]

c)

d)

Fig. 9. Activation energy distribution of pyrolysis and gasication: a) Chinese cabbage (N2); b) Chinese cabbage (CO2); c) orange peel (N2); d) orange peel (CO2).

120e250 kJ/mol, and the relevant reactions occurred at 150e500  C. The reaction at the maximum of Chinese cabbage's DTG curve was with
activation energy of 181 kJ/mol. The major reactions of orange peel with E distributed in the range of 120e230 kJ/mol occurred at
180e500  C and the reaction at the maximum of DTG curve was with E of 177 kJ/mol, as shown in Fig. 9.
At CO2 atmosphere, parallel reactions of poplar wood with E of 150e250 kJ/mol mainly occurred at 200e550  C. The activation energy
with the highest proportion was 183 kJ/mol. The reaction with E of 327 kJ/mol happening at 700e900  C was considered as Boudouard
reaction of CO2 and char. Based on the activation energy distribution of Chinese cabbage, poplar wood and orange peel, it suggested that the
activation energy of Boudouard reaction was around 327 kJ/mol when the pre-exponent factor was xed at the value of 2.2  1013(s1). It
was reported by Sircar, I. [32] that activation energies for pinewood char-CO2 reaction from these studies varied between 141 kJ/mol and
263 kJ/mol. Di Blasi [34] reported a similarly large range of variation of kinetic rate parameters for the global char-CO2 reaction for other
types of biomass. It was recognized that char preparation procedures, biomass ash content, and experimental methods affect char mass-loss
rates and may explain the variations in measured kinetic rate parameters.
Comparing to other three biomass solid wastes, components of paper were relatively simple, which also showed in the activation energy
distribution, as shown in Fig. 10. At N2 atmosphere, the activation energy with the highest distribution was 183 kJ/mol, which was regarded
as the cellulose decomposition reaction. At CO2 atmosphere, AE with the highest distribution was 185 kJ/mol. The AE of the reaction of CO2
and carbon happening at 700e900  C was 331 kJ/mol, which agreed well with the former analysis for Boudouard reaction. From analysis
above, it suggested that the cellulose decomposition at two atmosphere could both be characterized by the activation energy of 176 kJ/mol
with the pre-exponent factor at value of 2.2  1013(s1) and it agreed well with the study of Giuntoli [19]. In the process of gasication at CO2
atmosphere, the activation energy of Boudouard reaction, C(s) CO2 /2CO, was around 327 kJ/mol.
As mentioned above, three plastics, PE, PS and PVC showed similar thermal decomposition characteristics at N2 and CO2 atmospheres,
respectively. For PE and PS, thermal decomposition processes, both pyrolysis and gasication, could be described by a rst-order reaction.
The activation energies of two thermal processes of PE and PS at different atmospheres were very close, and CO2 almost had no inuence on
the thermal decomposition process. The activation energy distribution of PVC pyrolysis and gasication was shown in Fig. 11, and the
distributions at two atmospheres showed no obvious differences. Combining the distribution of activation energy and DTG curves of PVC,
we could nd the major difference appeared at 250e380  C. Thermal decomposition of PVC could be divided into two major stage occurred

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

341

80

Distribution [%]

60

40

20

0
100

150

200

250

300

350

400

300

350

400

E [kJ/mol]

a)
80

Distribution [%]

60

40

20

0
100

150

200

250

E [kJ/mol]

b)

Fig. 10. Activation energy distribution of pyrolysis and gasication of paper: a) pyrolysis; b) gasication.

at 250e380  C and 380e550  C, respectively. The rst stage of decomposition characterized by activation energy of 160e190 kJ/mol was
related to the release of the high amount of chlorine [10] and CO2 could slightly promote the process.

4. Conclusions
Pyrolysis and gasication of 8 different combustible solid wastes, Chinese cabbage, orange peel, poplar wood, paper, PE, PS, PVC
and polyester fabric, were analyzed by TGA and compared. At low temperature range (<500  C), the pyrolysis characteristics
of biomass solid wastes were similar to their gasication processes. While at high temperature range (>700  C), Boudouard reaction
of CO2 and carbon took place, which resulted in high conversion efciencies at the CO2 atmosphere than at the N2 atmosphere.
Pyrolysis and gasication processes of PE and PS looked very similar, of which the mass loss occurred at a narrow
temperature range. Thermal decomposition of PVC could be divided into two major stages occurred at 250e380  C and 380e550  C,
respectively. CO2 could slightly promote the rst stage of PVC decomposition which was related to the release of the high amount
of chlorine.
The discrete distributed activation energy model was applied to analyze the pyrolysis and gasication of the eight materials mentioned
above. It showed that the discrete DAEM was valid and the tted curves by different reactions agreed well with the DTG curves. Thermal
decomposition processes of biomass were complicated and the global reactions consisted of much more parallel reactions than that of
plastics. Activation energies of biomass thermal decomposition distributed at 150e220 kJ/mol and the cellulose decomposition at two
atmosphere could both be characterized by activation energy of 176 kJ/mol with the pre-exponent factor xed at the value of 2.2  1013(s1).
In the process of gasication at CO2 atmosphere, the mass loss above 700  C at the gasication processes of biomass samples is caused by the
Boudouard reaction: C(s) CO2 / 2CO, and the activation energy of this reaction was around 327 kJ/mol.

342

S. Chen et al. / Journal of the Energy Institute 88 (2015) 332e343

40

Distribution [%]

32

24

16

160

180

200

220

240

220

240

E [kJ/mol]

a)
50

Distribution [%]

40

30

20

10

160

180

200

E [kJ/mol]

b)
Fig. 11. Activation energy distribution of pyrolysis and gasication of PVC: a) pyrolysis; b) gasication.

Acknowledgments
The nancial support from National Basic Research Program of China (973 Program, No. 2011CB201502) and National Natural Science
Foundation of China (No. 21376134) is gratefully acknowledged.
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