Journal of Cleaner Production 70 (2014) 303e314

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Comparative studies on catalytic and non-catalytic co-gasification of

rubber seed shell and high density polyethylene mixtures
Bridgid Lai Fui Chin a, Suzana Yusup a, *, Ahmed Al Shoaibi b, Pravin Kannan b,
Chandrasekar Srinivasakannan b, Shaharin Anwar Sulaiman c
a
Biomass Processing Lab, Centre for Biofuel and Biochemical Research, Green Technology MOR, Department of Chemical Engineering, Universiti Teknologi
PETRONAS, Bandar Seri Iskandar, Tronoh 31750, Malaysia
b
Department of Chemical Engineering, The Petroleum Institute, P.O. Box 2533, Abu Dhabi, United Arab Emirates
c
Department of Mechanical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Tronoh 31750, Malaysia

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

Article history: The thermal degradation behavior of rubber seed shell, high density polyethylene waste, and the binary
Received 30 July 2013 mixtures of high density polyethylene and rubber seed shell (0.2:0.8 weight ratio) are compared in
Received in revised form pyrolysis, gasification, and catalytic gasification process at different heating rate of 10, 20, 30 and
15 February 2014
50 K min
1 in temperature range of 323e1173 K using thermogravimetric analysis equipment. It is
Accepted 16 February 2014
observed that there are one, two, and three stages of decomposition occurring in high density poly-
Available online 24 February 2014
ethylene, rubber seed shell, and the binary mixtures respectively regardless of the process involved. The
activation energies, EA and pre-exponential factor, A are generated using one step integral method based
Keywords:
Non-isothermal
on first order rate of reaction. Besides that, the synergistic effect on the binary mixtures is also inves-
Thermogravimetrical analysis tigated for the three different processes involved. It is found that the EA and A values for the binary
Catalytic mixtures are lower than the pure high density polyethylene but comparable to pure rubber seed shell
Kinetic regardless of the processes involved. In addition, it is also observed that the EA and A values are slightly
Rubber seed shells lower when catalyst is added in the binary mixtures compared to the absence of catalyst in the gasifi-
High density polyethylene cation process.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction molecules with different chain length through the random-chain

Plastic waste is not only said to be one of the major constituents
of municipal solid waste (MSW) but is also considered as one of the
most harmful components in MSW due to its non-biodegradable
properties which is inert to microbial degradation (Aboulkas
et al., 2007; Kumar et al., 2011). From the statistics, polyethylene
(PE) is reported to be the highest type of plastic consumption
amongst the other polyolefins which takes about 33% of the world
plastic consumption in year 2007 (CIPET, 2012). Among the poly-
ethylene types, high density polyethylene (HDPE) is said to provide
a major share of ethylene consumption structure recently with an
evidence increased in world demand up to 4.4% in year 2009
(Kumar et al., 2011). HDPE possess linear structure with repeating
unit of
(CH2eCH2)
, and contains the least degree of branching
compared to other types of PE, which gives an advantage for the
larger molecules in HDPE to be easily be broken down into smaller
* Corresponding author. Tel.: þ60 5 368 7642; fax: þ60 5 368 8205.
E-mail addresses: drsuzana_yusuf@petronas.com.my, drsuzana.yusuf.utp@
gmail.com (S. Yusup).
scission when heat is applied (Kumar et al., 2011). Finding an
alternative method for effective plastic recycling continues to be a
major barrier faced globally in replacement of conventional
methods specifically incineration and land filling which is losing its
significance due to its low operational cost effectiveness and
descending credibility towards the environment (Aznar et al.,
2006; Mumtaz et al., 2010). In solving the aforementioned prob-
lems, co-pyrolysis and co-gasification of plastic and biomass wastes
is said to have gained considerable interest recently as it does not
only subject to resolve the plastic waste disposal problems but
could be an alternative source of renewable energy which could
potentially convert these wastes to useful clean hydrocarbon fuel in
the substitution of fossil fuels which is becoming increasingly
scarce (Bosmans et al., 2013; Marin et al., 2002; Pinto et al., 2002).
Most publications report on the thermal degradation behavior
and kinetic parameters for individual component of MSW and bi-
nary mixtures of plastic and biomass waste under co-pyrolysis and
co-gasification condition. In contrast, no studies have been dedi-
cated to catalytic co-gasification of binary mixtures of plastic and

http://dx.doi.org/10.1016/j.jclepro.2014.02.039
0959-6526/Ó 2014 Elsevier Ltd. All rights reserved.
304 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314

biomass waste using thermogravimetric analysis (TGA). Saha and Table 1

Ghoshal (2006) investigated on the non-isothermal and Characteristics of the rubber seed shells (RSS) and high density polyethylene (HDPE).

isothermal decompositions of polyethylene sample from polypack Sample Ultimate analysis (wt%, dry ash basis) Proximate analysis (wt%,
under nitrogen atmosphere of 40e50 mL min
1 for temperature dry basis)
range of 303e873 K at different heating rates of 10, 15, 20 and C H N S Oa MC VM FCa Ash
25 K min
1. The activation energy, EA dependency on conversion, x
RSS 44.31 4.38 0.51 0.13 50.67 8.59 80.98 6.62 3.81
is compared with literature data and it is reported that the opti- HDPE 81.45 12.06 0.34 0.79 5.36 0.00 99.46 0.00 0.34
mum activation energy, EA dependencies of non-isothermal data at a
By difference.
15 K min
1 heating rate are best predicted using the isothermal
data. Aboulkas et al. (2008a) studied the thermal decomposition of
co-pyrolysis olive residue and polypropylene mixtures in 1:1 ratio 2. Experimental
in a nitrogen atmosphere of 60 mL min
1 for a range of temperature
between 300 and 975 K at different heating rates of 2, 10, 20, and 2.1. Materials and sample preparation
50 K min
1 and using Friedman isoconversional method to evaluate
the decomposition kinetics. It is found that the maximum degra- The raw materials used in this work are RSS from Vegpro
dation temperature of the binary mixture is higher compared to the Trading, Malaysia and HDPE plastic from Shen Foong Plastic In-
individual components alone. Thus, an increase in thermal stability dustries Sdn Bhd, Malaysia. These materials are ground and sieved
is expected. It is also found that the presence of polypropylene does to a particle size ranging from 0 to 710 mm. Homogenized HDPE/RSS
not significantly changed the apparent EA of thermal decomposi- blends in a weight ratio of 0.2/0.8 are prepared. The characteristics
tion of olive residue however the EA value for polypropylene in the of the materials used in this study are presented in Table 1. The
mixture is higher than that of the pure components. Chin et al. ultimate analysis and proximate analysis of the HDPE and RSS are
(2013a) investigated on the co-pyrolysis of rubber seed shell conducted in LECO CHNS-932 elemental analyzer and thermog-
(RSS) with HDPE (0.8:0.2 weight ratio) in an argon atmosphere of ravimetry analyzer EXSTAR TG/DTA 6300 (Seiko Instrument Inc.)
100 mL min
1 for a temperature range of 323e1173 K at different respectively. A commercial Nickel powder (index number 028-002-
heating rates of 10, 20, 30 and 50 K min
1 and the kinetic param- 01-4, Merck) is selected as a catalyst to be investigated in the cat-
eters are determined using one step integral method. It is found alytic gasification process for comparison of pyrolysis and gasifi-
that the EA and pre-exponential factor (A) values for the binary cation behavior of HDPE/RSS binary mixture. The amount of Nickel
mixture are lower than pure HDPE but slightly higher compared to powder used in the present study is 10% of the total weight of the
pure RSS. The estimated EA values for RSS, HDPE, and binary mix- HDPE/RSS binary mixture. The particle size of the Nickel powder is
tures of RSS and HDPE are in the range of 46.94e63.21, 242.13e in the range of w10 mm and the properties of the catalyst is pre-
278.14, and 49.14e83.11 kJ mol
1 respectively. Meanwhile, the sented in Table 2. The field emission scanning electron microscopic
estimated A for RSS, HDPE, and binary mixtures of RSS and HDPE (FESEM) images of the Nickel catalyst in 7000 and 10,000
are in the range of 3.20  106e1.31  108, 8.30  1018e1.05  1022, magnification determined using Zeiss Supra 55 VP are displayed in
and 3.47  106e6.78  108 min
1 respectively. It is also reported Fig. 1 to depict the surface physical morphology of Nickel powder. It
that the remaining residue increases with an increment of heating is observed that the surface morphology of Nickel powder is a
rate regardless the type of samples used. Chin et al. (2013b) studied flower-like shape with nanotips outspreading from the cores which
the gasification kinetics of RSS, HDPE, and their mixtures (20/80 are similar to the work reported by Bai et al. (2008) and Kim et al.
and 40/60 weight ratio of HDPE/RSS) at heating rate of 10 K min
1 (2004).
in the temperature range of 323e1173 K with argon gas supplied at
flowrate of 100 mL min
1 and steam injected at flowrate of 2.2. Experimental apparatus and procedure
300 mL h
1 into TGA using Criado and Coats-Redfern methods. The
predicted activation energy for RSS, HDPE, HDPE/RSS mixture (20/ The experiments are performed using thermogravimetry
80 weight ratio), and HDPE/RSS mixture (40/60 weight ratio) are analyzer EXSTAR TG/DTA 6300 (Seiko Instrument Inc.) as illustrated
385, 637, 177, and 175 kJ mol
1 respectively. Chin et al. (2013c) in Fig. 2. Approximately 5 mg of sample is placed on a ceramic
examined the thermal decomposition behavior, degradation tem- crucible in TGA under an inert atmosphere of argon. A flow rate of
perature, and maximum degradation rate of RSS, HDPE, and binary 100 mL min
1 of argon gas is fed into the system for 20 min at a
mixture of RSS and HDPE in the weight ratio of 20/80 (HDPE/RSS) at temperature of 323 K. Subsequently, all samples are heated from
different heating rates of 10, 20, 30, and 50 K min
1 within tem- 323 K to 1173 K at respective heating rates and temperatures are
perature range of 323e1173 K under non-isothermal gasification kept constant for 10 min. During heating, the TGA is used to mea-
conditions with injected steam at flowrate of 300 mL h
1. The sure mass variation of the materials and furnace temperature.
remaining solid residue after the gasification process for RSS, HDPE, Thermogravimetric curves are obtained at four heating rates (10,
and binary mixture of RSS and HDPE respectively are in the range of 20, 30, and 50 K min
1) within the temperature range of 323e
11.9e15.3, 0.4e2.8, and 7.3e12.2 wt%. The maximum degradation 1173 K. Steam is generated by a superheater at 383 K and is injected
rate achieved by the RSS, HDPE, and binary mixture of RSS and into the TGA at a flowrate of 300 mL h
1 when the temperature
HDPE respectively are in the range of 7.9e43.7, 26.7e116.7, and inside the TGA equipment reached to 383 K to avoid any occurrence
6.2e32.6 wt% min
1.
In this present work, a comparison of the thermal degradation Table 2
and kinetic parameters such as the activation energy (EA) and pre- Properties of Nickel powder.
exponential factor (A) of RSS, HDPE waste, and the HDPE/RSS XRF analysis
mixture (0.2:0.8 weight ratio) in pyrolysis, gasification, and cata- Ni (wt%) 96.79
lytic gasification process using thermogravimetric analysis (TGA) Impurities (wt%) 3.21
approach at different heating rate of 10, 20, 30 and 50 K min
1 in Surface properties
the temperature range of 323e1173 K using one step integral Mean pore size (nm) 6.2
method are investigated. In addition, the synergistic effects on the Pore volume (BJH) (cm3 g
1) 0.0016
BET surface area (m2 g
1) 0.78
binary mixture of RSS and HDPE are examined.
 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314 305

Fig. 1. FESEM images of Nickel powder a) 7000 and b) 10,000 magnification.

of condensation within the system. The equivalence ratios (ER) for Eqs. (2) and (3) are combined to provide a fundamental
the pyrolysis and gasification process are 0 and 0.25 respectively. expression of analytical methods to calculate kinetic parameters on
All experiments are repeated two or three times. the basis of TGA results as shown in Eq. (5).

dx
2.3. Kinetic theory ¼ A  f ðxÞ  e
EA =RT (5)
dt

A one step global pyrolysis and gasification process and a first Since linear heating rate, b is defined as shown in Eq. (6):
order rate equation model can be represented as shown in Eq. (1):
b ¼ dT=dt (6)
Solid/Volatiles þ Char (1)
Hence, Eq. (5) can be written as

1

where volatiles refer to the sum of the gas and tar and k is the
dx
pyrolysis or gasification rate constant whose temperature depen- ¼ A  e
EA =RT dT (7)
f ðxÞ b
dence is expressed by the Arrhenius equation, Eq. (2).
Rx
Introducing gðxÞ ¼ dx=f ðxÞ hence,
k ¼ Ae
EA =RT (2) 0

Zx ZTF

where EA is the activation energy (kJ mol
1), T is the absolute dx 1
gðxÞ ¼ ¼ A  e
EA =RT dT (8)
temperature (K), R is the gas constant (8.314 J K
1 mol
1) and A is f ðxÞ b
the pre-exponential factor (min
1). 0 TI
The rate of transformation from solid waste to volatile product is
described by the following expression: For first order reaction, f(x) ¼ 1
x meanwhile g(x) ¼
ln (1
x).
   
dx E 1 ART 2
¼ kðTÞf ðxÞ (3) ln½
lnð1
xÞ ¼
A þ ln (9)
dt R T bEA

where x, t, k(T), f(x) represent the conversion of the process, the
time, the rate constant and the reaction model respectively.
Conversion, x is defined as the normalized form of weight loss
data of decomposed sample and is defined as follows:
mi
ma
x ¼
mi
mf
By plotting a linear graph of ln[
ln(1
x)] versus 1/T, the value
of EA can be obtained by calculating the slope which represents the
eEA/R meanwhile the ln (ART2/bEA) represents the intercept-c.
Hence, the pre-exponential factor, A can be determined by taking
the temperature as Ta ¼ (T1 þ TF)/2 whereas the T1 and TF are the
initial and final temperature of the main mass loss in each stage
(4)
respectively.

where mi is the initial mass of the sample, ma is the actual mass of

the sample, and mf is the mass after pyrolysis or gasification. 3. Results and discussion

3.1. Analysis of thermal degradation behavior

3.1.1. Rubber seed shell (RSS)

Fig. 2. Process flow diagram of TGA-MS.
Figs. 3 and 4 depict the kinetic scheme of thermogravimetric
(TG) in wt% and derivative thermogravimetric (DTG) in wt% min
1
respectively for RSS involving two different processes which are
pyrolysis and gasification under four different heating rates of 10,
20, 30 and 50 K min
1. It is observed the curves in TG profiles
(Fig. 3) are asymmetric, and almost identical for all range of heating
rate studied. It is also seen that the TG profiles demonstrate a
temperature shift to the right as the heating rate increases in both
processes. Comparing the TG profiles for pyrolysis and gasification
306 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314

process, it is noticeable that both show similar trends with a slight

difference in wt% corresponding to temperature. The initial mass
loss starts slowly from temperature 380 K and 384 K for pyrolysis
and gasification process respectively which indicates water
removal through evaporation. Subsequently, a rapid mass loss oc-
curs from temperature 380 Ke660 K for pyrolysis process and
temperature from 384 K to 666 K for gasification process. The rapid
mass loss indicates the main devolatilization phase due to the
released of the volatiles and carbon from the RSS. The mass loss
decreased moderately from temperature 680 Ke990 K and from
temperature 684 Ke960 K for pyrolysis and gasification respec-
tively followed by a constant mass loss until temperature of 1200 K.
From the DTG profiles (Fig. 4), two peaks are distinguished
which indicates the RSS undergoes major weight losses in two
stages regardless of the processes involved. Fig. 4 shows the two
peaks become more pronounced from smooth baseline or over-
lapping of the two peaks as heating rate increases from 10 to
50 K min
1 as it is speculated to be linked to the slow decompo-
sition of lignin in the RSS. This further explained that lignin is more
stable compared to cellulose and hemicellulose and the degrada-
tion of lignin takes place at higher temperature and had been
evidently shown in both TG and DTG profiles by previous re-
searchers (Chin et al., 2013a; Yao et al., 2008). The existence of the
two peaks in the DTG profiles are linked with two groups of main
reaction and this behavior is consistent with the results reported by
Aboulkas et al. (2008a) and Chin et al. (2013a) on the co-pyrolysis of

Fig. 4. DTG curves for RSS at different heating rates for (a) pyrolysis and (b) gasifi-
cation process.

olive and polypropylene and co-pyrolysis of RSS and HDPE

respectively. For the first peak to occur in the pyrolysis process, the
temperature was increased from 484 K at 10 K min
1 to 626 K at
50 K min
1. As for the gasification process, the temperature was
increased from 505 K at 10 K min
1 to 636 K at 50 K min
1.
Meanwhile, the second peak occurred at temperature 600e695 K
and 616e701 K for pyrolysis and gasification process respectively.
The first peak is said to be linked to hemicellulose and some lignin
in the RSS whereas the second peak is said to be linked to cellulose
and HDPE (Chin et al., 2013a; Font et al., 1991). In contrast, few

Table 3
Degradation temperature, amount of residue, and maximum degradation rate
values of RSS for pyrolysis, and gasification process.

Process Heating Degradation temperature Residue Maximum

rate T1/Tmax/TF (K) (wt%) degradation
(K min
1) rate (wt% min
1)
First stage Second stage

Pyrolysis 10 484/579/600 600/624/652 15.3 7.9

20 504/589/600 600/633/663 14.5 15.7
30 523/602/615 615/647/679 12.2 25.4
50 525/616/629 629/660/695 11.9 43.7

Gasification 10 505/584/616 616/630/661 8.6 6.8

20 516/598/618 618/646/693 0.8 15.2
30 520/609/621 621/657/694 0.5 24.8
Fig. 3. TG curves for RSS at different heating rates for (a) pyrolysis and (b) gasification
50 523/618/636 636/668/701 0.2 43.6
process.
 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314 307

Fig. 6. DTG curves for HDPE at different heating rates for (a) pyrolysis and (b) gasifi-
Fig. 5. TG curves for HDPE at different heating rates for (a) pyrolysis and (b) gasifi- cation process.
cation process.

maximum mass loss for each stage respectively generated from

the curves in the DTG profiles. It is observed that the residual
researchers had reported on similar temperature range of the weight of the sample decreased as the temperature and heating
thermal decomposition of lignin, hemicellulose, and cellulose. rate increased. A similar behavior is seen when compared with
Becidan et al. (2007) found out that hemicellulose decomposed at other published literature data on pyrolysis of biomass (Aboulkas
temperatures between 473 and 648 K, cellulose decomposed at et al., 2008a,b; Chin et al., 2013a; Khan et al., 2011). The occur-
temperatures between 548 and 653 K, and lignin is decomposed rence of this phenomenon has been previously described by
gradually in a wider range of temperatures between 453 and 823 K other authors (Bilbao et al., 1997; Rotliwala and Parikh, 2011;
under pyrolysis conditions. The findings by Chin et al. (2013a) Sampath and Babu, 2006). They stated that the thermal
showed that hemicelluloses decomposed at temperatures be-
tween 410 and 637 K, cellulose decomposed at temperatures be-
tween 537 and 690 K, and lignin decomposed at temperature Table 4
between 318 and 1200 K under pyrolysis condition. Degradation temperature, amount of residue, and maximum degradation rate
From the DTG profiles, it is also observed that an increment of values of HDPE for pyrolysis, and gasification process.
lateral shift in temperature of the maximum temperature for the Process Heating Degradation Residue Maximum
first and second peak occurs as the heating rate increases. This rate (K min
1) temperature (wt%) degradation
behavior is due to the thermal lag in the decomposition from the T1/Tmax/TF (K) rate (wt% min
1)
combined effects of the heat transfer at different heating rates, First stage
kinetics of the decomposition and heat conductive property of the Pyrolysis 10 651/754/792 3.0 31.8
biomass particles (Aboulkas et al., 2008a; Khan et al., 2011; Zhang 20 659/767/790 2.1 56.9
et al., 2009). 30 670/773/799 1.8 78.4
The data extracted from the DTG profiles are summarized in 50 677/781/812 0.1 130.5
Table 3 and comparison is made between both pyrolysis and Gasification 10 682/748/776 2.7 26.7
gasification processes on the degradation temperatures, 20 691/761/794 2.5 47.3
remaining residue, and maximum degradation rate for RSS. TI, TF, 30 693/764/794 1.6 73.5
50 694/776/811 1.2 116.7
and Tmax represent the initial, final, and temperature of the
308 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314
Fig. 7. TG curves for binary mixture of HDPE and RSS (0.2:0.8 weight ratio) at different
heating rates for (a) pyrolysis, (b) gasification, and (c) catalytic gasification process.
hysteresis is influenced by the heating rate hence increase of the
heating rate will increase the thermal hysteresis which results in
both TG and DTG curves to be shifted to a higher temperature.
Moreover, higher heating rate will lead to an increase of mass
volatilization at the core of the sample which will transform the
solid residue structure with an increased yield of the liquid and
gaseous fractions.
Fig. 8. DTG curves for binary mixture of HDPE and RSS (0.2:0.8 weight ratio) at
different heating rates for (a) pyrolysis, (b) gasification, and (c) catalytic gasification
process.
The solid residue left for RSS at the temperature of 1200 K is in
the range of 11.9e15.3 and 0.2e8.6 wt% for pyrolysis, and gasifi-
cation process respectively. It is observed that the solid residue left
in gasification process is much lesser compared to pyrolysis process
in the range of heating rate studied. The observation is due to the
higher conversion of solid to gaseous products occurring in the
gasification process as compared to the pyrolysis process at a higher
temperature.
 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314 309

Table 5
Degradation temperature, amount of residue, and maximum degradation rate values of RSS-HDPE mixture for pyrolysis, gasification and catalytic gasification process.

Process Heating rate Degradation temperature T1/Tmax/TF (K) Residue (wt%) Maximum degradation
(K min
1) rate (wt% min
1)
First stage Second stage Third stage

Pyrolysis 10 465/592/614 614/637/671 671/746/773 16.0 7.2

20 479/601/621 621/649/677 677/755/785 14.7 14.6
30 493/613/627 627/657/693 693/765/794 12.3 20.3
50 494/621/635 635/668/704 704/777/802 9.6 32.1

Gasification 10 499/584/606 606/632/661 661/735/764 12.8 6.2

20 504/603/618 618/649/677 677/751/778 11.6 13.4
30 514/607/623 623/655/683 683/756/788 8.1 18.7
50 527/625/641 641/670/700 700/765/800 7.3 32.6

Catalytic gasification 10 490/572/596 596/623/653 653/712/740 1.2 6.0

20 502/591/612 612/636/670 670/735/781 0.4 9.3
30 505/602/621 621/647/701 701/743/776 0.3 16.2
50 509/621/639 639/666/701 701/760/795 0.1 30.6

under different heating rates. It is observed that all the curves in

Fig. 9. Variation of DW for binary mixture of RSS and HDPE (0.2:0.8 weight ratio) at
different heating rates for pyrolysis process.
3.1.2. High density polyethylene (HDPE)
Figs. 5 and 6 present the kinetic scheme of TG and DTG
respectively for HDPE in the process of pyrolysis and gasification
both TG and DTG profiles show an almost identical trend in the
range of heating rates studied when compared with pyrolysis and
gasification process.
From the TG profiles (Fig. 5), the thermal degradation for HDPE
starts at 651e677 K and ends at 790e812 K for pyrolysis mean-
while the thermal degradation starts at 682e694 K and ends at
776e811 K for gasification. It is found that the initial thermal
degradation for HDPE starts at a lower temperature for gasification
process compared to pyrolysis process. In comparing the initial
thermal degradation temperature between HDPE and RSS, the
former takes place at a much higher temperature compared to the
latter. In another words, the weight loss of HDPE is lower
compared to RSS at lower temperature. According to Zhou et al.
(2006), this phenomenon occurred due to low fixed carbon and
ash content in the HDPE compared to RSS. In RSS, the fixed carbon
and ash content is higher than HDPE by 6.62 wt% and 2.48 wt%
respectively.
From the DTG profiles (Fig. 6), it is observed that there is only
one peak which indicates one step of thermal degradation occur-
ring in the range of heating rate studied. And also, HDPE displayed a
narrow degradation temperature intervals compared with RSS.
Several studies reported similar trend observed from the thermal
decomposition of HDPE from the DTG curves (Aboulkas et al.,

Fig. 10. Variation of DW for binary mixture of RSS and HDPE (0.2:0.8 weight ratio) at Fig. 11. Variation of DW for binary mixture of RSS and HDPE (0.2:0.8 weight ratio) at
different heating rates for gasification process. different heating rates for catalytic gasification process.
310 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314

Fig. 12. Experimental and calculated remaining solid residue for (a) RSS, (b) HDPE, and (c) HDPE/RSS mixture.

2008a; Cai et al., 2008; Chin et al., 2013a). It is also observed that
the DTG profiles displaced to higher temperature as heating rate
increases.
Table 4 shows the degradation temperatures, remaining residue
and maximum degradation rate for HDPE in pyrolysis and gasifi-
cation process. The remaining residue and maximum degradation
rate for HDPE achieved from both processes does not show much
difference in values. With comparison to RSS, it is observed that
higher maximum degradation rate can be achieved in HDPE. Hence,
this shows that HDPE degrades easily and faster at higher tem-
perature compared to RSS. This attributes to the different structure
and composition possess in both HDPE and RSS. HDPE are typically
composed by very high volatile matter fraction (>99%), low ash
content (<1%), and absence of fixed carbon.
3.1.3. Binary mixtures of RSS and HDPE
Figs. 7 and 8 present the kinetic scheme of TG and DTG
respectively for HDPE/RSS binary mixture (0.2/0.8 mass ratio) in the
process of pyrolysis, gasification, catalytic gasification under
different heating rates.
From the TG profiles (Fig. 7), great similarities are observed in
the profile trends except for the slight difference in the remaining
solid residue corresponding with temperature when observations
are made from three different types of processes involved.
From the DTG profiles (Fig. 8), the binary mixtures of HDPE and
RSS exhibits three peaks which conclude three steps of thermal
degradation which takes place in the range of heating rate studied.
For the first step of thermal degradation in the pyrolysis process,
the temperature was increased from 365 K at 10 K min
1 to 635 K at
 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314 311

50 K min
1. Meanwhile, the temperature increased was from 343 K

at 10 K min
1 to 641 K at 50 K min
1 for the gasification process.
Furthermore, the temperature was increased from 338 K at
10 K min
1 to 635 K at 50 K min
1 for the catalytic gasification
process. This step of thermal degradation is attributed to the
decomposition of hemicellulose. For the second step, the thermal
degradation temperature starts between 614 and 704 K, 606e
700 K, 596e701 K for pyrolysis, gasification, and catalytic gasifi-
cation respectively and is attributed to the decomposition of cel-
lulose. For the third step, the thermal degradation temperature
starts between 671 and 802 K, 661e800 K, and 653e795 K for
pyrolysis, gasification, and catalytic gasification respectively and is
attributed to the decomposition of lignin and HDPE.
Table 5 summarized the degradation temperature, remaining
residue and maximum degradation rate for HDPE/RSS mixture in
pyrolysis, gasification, and catalytic gasification process. At tem-
perature of 1200 K, the remaining solid residue after the catalytic
gasification is within 0.1e1.2 wt% and is greatly lower compared to
net pyrolysis with 9.6e16.0 wt% and gasification with 7.3e12.8 wt%
process in the range of heating rate studied. With the relative
comparison between the single component and binary mixtures, it
is seen that the range of the remaining residue attained in single
component of RSS and HDPE is much lower compared to the HDPE/
RSS mixtures in both pyrolysis and gasification process. Since the
weight percentage of RSS is much higher compared to HDPE in the
mixture, hence the fixed carbon and ash content in the mixture will
be relatively higher compared to HDPE which results to a high
amount of remaining residue.
In order to further illuminate the occurrence of synergistic ef-
fects between the HDPE and RSS samples, the difference of weight
loss (DW) is defined in Eq. (10) are investigated in each process. DW
is also known as the extent of the synergistic effects during the
process.

DW ¼ Wmixture
ðx1 W1 þ x2 W2 Þ (10)

where Wmixture is the weight loss of the binary mixture of HDPE and
RSS (wt%), xi is the weight fraction of each material in the mixture,
and Wi is the weight loss of each material in the same mixture at
respective operating conditions (wt%).
Figs. 9e11 illustrate the variation of DW with temperature for
the HDPE/RSS mixture in pyrolysis, gasification, and catalytic
gasification process respectively. For the pyrolysis process (Fig. 9), it
is observed that the DW is in the range of 1.7e4.2 wt% before 520 K.
For the gasification process (Fig. 10), it is seen that the DW for
HDPE/RSS mixture is in the range of 0.1e3.0 wt% before 645 K. For
the catalytic gasification process (Fig. 11), it is depicted that the DW
is in the range of 0.5e2.1 wt% before 518 K. At this phase, the DW is
considered minimal as it indicates that the plastic has not decom-
Fig. 13. Arrhenius plot of ln[
ln(1
x)] versus 1/T at 10 K min
1 for (a) RSS, (b), HDPE
(c) RSS-HDPE mixtures in pyrolysis process.
posed and also there is no interaction between the biomass and
plastic. This phase also shows that the DW is not equal to zero and

Table 6
Kinetic evaluation for RSS during pyrolysis, and gasification process.

Process Heating rate (K min
1) Activation energies, EA Pre-exponential factor, A Correlation coefficient Fitted Equation
(kJ mol
1) (min
1) (R2)

First stage Second stage First stage Second stage First stage Second stage First stage Second stage
6 8
Pyrolysis 10 50.29 61.14 9.90  10 1.02  10 0.9794 0.9960 y ¼
6049x þ 9.295 y ¼
7354x þ 11.527
20 49.08 63.21 6.65  106 1.31  108 0.9790 0.9993 y ¼
5903x þ 8.834 y ¼
7603x þ 11.758
30 46.94 57.12 3.20  106 3.15  107 0.9656 0.9929 y ¼
5646x þ 8.203 y ¼
6870x þ 10.321
50 50.17 57.33 5.05  106 7.03  107 0.9616 0.9852 y ¼
6034x þ 8.658 y ¼
6896x þ 10.910

Gasification 10 45.38 77.75 3.80  106 2.71  109 0.9558 0.9947 y ¼
5458x þ 8.382 y ¼
9352x þ 14.821
20 46.72 59.82 4.20  106 7.49  107 0.9623 0.9686 y ¼
5619x þ 8.451 y ¼
7195x þ 11.164
30 46.05 68.44 2.85  106 2.81  108 0.9522 0.9908 y ¼
5538x þ 8.072 y ¼
8232x þ 12.560
50 47.18 64.02 3.17  106 1.01  108 0.9525 0.9918 y ¼
5675x þ 8.136 y ¼
7700x þ 11.469
312 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314

Table 7
Kinetic evaluation for HDPE during pyrolysis, and gasification process.

Process Heating rate (K min
1) Activation energies, EA (kJ mol
1) Pre-exponential factor, A (min
1) Correlation coefficient (R2) Fitted Equation

First stage

Pyrolysis 10 278.14 1.05  1022 0.9694 y ¼
33454x þ 44.045

20 269.63 1.03  1021 0.9688 y ¼
32431x þ 42.156
30 266.42 7.41  1020 0.9758 y ¼
32045x þ 41.347
50 242.13 8.30  1018 0.9721 y ¼
29123x þ 37.128

Gasification 10 216.31 6.48  1017 0.9503 y ¼
26018x þ 34.461

20 212.41 2.16  1017 0.9577 y ¼
25548x þ 33.371
30 208.17 9.71  1016 0.9575 y ¼
25039x þ 32.512
50 191.35 6.96  1015 0.9608 y ¼
23015x þ 29.765

similar observations had been reported by few researchers (Cai
et al., 2008; Rotliwala and Parikh, 2011; Zhou et al., 2006).
For the pyrolysis process, the DW increased significantly from
temperature 520 Ke650 K and thereafter reduced drastically until
775 K. After DW increases gradually to 1000e1160 K and it seems to
stabilize. For the gasification process, the DW reduced slowly from
temperature 690e760 K and thereafter increased gradually from
temperature 746e792 K. For the catalytic gasification process, a
slight difference in trend is observed when comparison is made
with the pyrolysis and gasification process which is due to the
existence of Nickel powder in the HDPE/RSS mixture. More peaks
are illustrated in this process.
It is found that the DW attained at the end of the temperature of
1200 K for pyrolysis, gasification, and catalytic gasification is 9.5e
14.3, 0.07e3.7, and 3.0e6.5 wt% respectively. It is observed that the
obtained value of DW with the presence of catalyst process is
higher compared to in the absence of catalyst for the gasification
process. Other than tar cracking, catalyst accelerates the conversion
of solid to gaseous products in respect to steam reforming methane
and the water gas shift reactions as shown in Eqs. (11) and (12).
Both reactions are in endothermic reaction.
Watergas shift reaction : CþH2 O/COþH2 O ðþ131:3 MJ=kmolÞ
(11)
Steam reforming methane reaction : CH4 þ H2 O/CO þ 3H2
ð þ 206:3 MJ=kmolÞ
(12)
3.2. Error analysis for the remaining solid residue
Fig. 12(a)e(c) shows the calculated and experimental remaining
solid residue for RSS, HDPE, and HDPE/RSS mixture in the three
processes involved. It is observed that slight differences are shown
within the experimental error range. The remaining solid residue
for RSS, HDPE, HDPE/RSS mixture are in polynomial second order
relationship with an increased of heating rate. The values of the
standard deviation and error percentage obtained for these feed-
stocks are less than 2 and 5% respectively. The correlation coeffi-
cient, R2 value greater than 90% are evidently obtained in these
three samples regardless of the processes involved.
3.3. Determination of kinetic parameters
The kinetic parameters such as activation energy (EA) and pre-
exponential factor (A) of RSS, HDPE, HDPE/RSS mixtures are
determined by assuming that the solid fuel pyrolysis and gasifica-
tion are generated using one step integral method. Fig. 13(a)e(c)
displays the typical Arrhenius plot of ln[
ln(1
x)] versus 1/T for
RSS, HDPE, HDPE/RSS mixtures and catalytic HDPE/RSS mixtures
respectively at heating rate of 10 K min
1 in pyrolysis process.
Similar trend is observed at higher heating rate in all samples
regardless of the process involved. The value of EA can be obtained
by calculating the slope and the value of A can be attained by
calculating the intercept-c.
The estimated EA and A values for these samples are summa-
rized in Tables 6e8 for RSS, HDPE, and HDPE/RSS mixtures
respectively. The number of EA and A values obtained are based on
the number of stages of major weight loss occurring in each sample
for the entire temperature range. Hence, there are one, two, and
three set of different EA and A values for HDPE, RSS, and HDPE/RSS
respectively.
It is observed that the EA and A values for the binary mixture are
lower to pure HDPE but almost comparable to pure RSS. It is
noteworthy that the presence of HDPE does not change the values
of both EA and A in the mixture significantly. Similar observation
had been noted by few researchers from their obtained kinetic
parameters for co-pyrolysis of biomass and plastic mixtures
(Aboulkas et al., 2008b). It is further explained that this phenom-
enon is attributed to the influence of the char on the radical
degradation mechanism of the plastic (Aboulkas et al., 2008b).
Higher EA involving in the reaction requires either high tempera-
ture or long reaction time in order to generate more energy from
the surroundings (Aboulkas et al., 2008b; Lázaro et al., 1998). It is
also seen that both the EA and A values has minimal to negligible
effect when comparison is made between the pyrolysis and gasi-
fication process. For HDPE/RSS mixtures, the EA values are in the
range of 32.49e56.44 and 25.85e52.14 kJ mol
1 whereas the A
values are in the range of and 3.20  105e3.02  107 and
9.46  104e1.31  107 min
1 for gasification and catalytic gasifi-
cation respectively. From the aforementioned results, it is observed
that the range of values for both EA and A are slightly lower in
the catalytic gasification process compared to the gasification
process.
4. Conclusions
The thermal degradation behavior of three different processes
namely co-pyrolysis, co-gasification, and catalytic co-gasification
are investigated utilizing rubber seed shell (RSS), high density
polyethylene (HDPE), and its mixtures in thermogravimetric anal-
ysis (TGA) under non-isothermal condition. It is found that from the
derivative thermogravimetric (DTG) curves displayed one, two, and
three stages of major decomposition for HDPE, RSS and HDPE/RSS
mixtures regardless of the processes involved. The synergistic ef-
fects of gasification and catalytic gasification of HDPE/RSS mixtures
are determined. It is found that the maximum value of DW of 3.9e
13.8 wt%, 2.3e4.6 wt%, and 5.7e11.8 wt% can be achieved in py-
rolysis, gasification, and catalytic gasification process respectively
 B.L.F. Chin et al. / Journal of Cleaner Production 70 (2014) 303e314 313

for the studied heating rates. The estimated values of activation

11.370
12.153
13.436

4622x þ 6.335
energy (EA), and pre-exponential factor (A) for RSS, HDPE, and

9.652

5.664
5.917
7.660
6.164

3109x þ 4.575

4995x þ 7.040

5200x þ 7.215
HDPE/RSS mixtures are determined using one step integral method

þ
þ
þ
þ

þ
þ
þ
þ
based on first order rate of reaction. The findings show that the EA

6667x

8246x

8924x

4784x

9997x

4164x

5512x

4481x
Third stage
and A values for the binary mixture are lower than in pure HDPE but
comparable to pure RSS. For HDPE/RSS mixtures, the EA values are
in the range of 32.49e56.44 and 25.85e52.14 kJ mol
1 whereas the

¼
¼
¼
¼

¼
¼
¼
¼

¼
¼
¼
¼
y
y
y
y

y
y
y
y

y
y
y
y
A values are in the range of and 3.20  105e3.02  107 and
10.658 9.46  104e1.31  107 min
1 for gasification and catalytic gasifi-

10.187

10.320
8.885
8.448

9.863
9.327
8.690

9.480
9.089
7.482
8.485
cation respectively. From the aforementioned results, it is observed
that the range of values for both EA and A are slightly lower when
þ
þ
þ
þ

þ
þ
þ
þ

þ
þ
þ
þ
Second stage

6912x

6127x

5910x

7134x

6789x

6665x

6440x

6120x

6257x

6271x

5277x

6011x
catalyst is added in the mixture when comparison is made with the
absence of catalyst in the gasification process.
¼
¼
¼
¼

¼
¼
¼
¼

¼
¼
¼
¼
y
y
y
y

y
y
y
y

y
y
y
y
Acknowledgments
11.372
9.526
9.003
8.709

6.894
7.070
7.075
6.923

7.394
7.198
7.614
7.703
This work is carried out under financial support of Petroleum
Institute, United Arab Emirates and Universiti Teknologi PETRONAS,
Fitted Equation

þ
þ
þ
þ

þ
þ
þ
þ

þ
þ
þ
þ
Malaysia. The authors also gratefully acknowledge Shen Foong

6285x

6239x

6137x

7988x

4784x

5034x

5129x

5068x

5108x

5200x

5486x

5607x
First stage

Plastic Industries Sdn Bhd, Malaysia for sponsoring HDPE samples

for this research.
¼
¼
¼
¼

¼
¼
¼
¼

¼
¼
¼
¼
y
y
y
y

y
y
y
y

y
y
y
y

Abbreviations
0.9662
0.9656
0.9664
0.9656

0.9503
0.9539
0.9544
0.9548

0.9859
0.9716
0.9842
0.9572
Third
stage
Correlation coefficient (R2)

MSW municipal solid waste

PE polyethylene
Second

0.9652
0.9857
0.9808
0.9838

0.9958
0.9942
0.9959
0.9920

0.9964
0.9977
0.9754
0.9864

RSS rubber seed shell

stage

HDPE high density polyethylene

TG thermogravimetric
First stage

TGA thermogravimetric analysis

0.9804
0.9852
0.9824
0.9752

0.9526
0.9507
0.9544
0.9606

0.9518
0.9536
0.9533
0.9572

MS mass spectrometer
DTG derivative thermogravimetric
MC moisture content
Third stage

106
107
108
108

105
105
106
105

104
106
106
105

VM volatile matter
FC fixed carbon














4.58
8.32
1.78
6.78

3.20
4.05
2.70
5.17

9.46
1.06
1.31
5.32
Pre-exponential factor, A (min
1)

ER equivalence ratio
T temperature (K)
Kinetic evaluation for RSS-HDPE mixture during gasification, and catalytic gasification process.

TI initial temperature of the main mass loss (K)

107
106
107
107

107
107
107
106

107
106
106
106

TF final temperature of the main mass loss (K)

Second















stage

Tmax maximum temperature of the main mass loss (K)

4.19
7.36
1.29
1.68

3.02
1.92
1.12
6.86

1.31
8.81
1.87
4.95

Ta middle temperature of the main mass loss (K)

EA activation energy (kJ mol
1)
107
106
106
107

105
106
106
105

106
106
106
106

A pre-exponential factor (min
1)
















gas constant (8.314 J mol
1 K
1)

stage

R
First

1.28
3.47
5.92
7.46

8.76
1.38
1.06
9.25

1.45
1.66
2.57
2.71

XRF X-ray fluorescence

FESEM field emission scanning electron microscopic
55.43
68.56
74.20
83.11

32.49
34.62
45.83
37.26

25.85
41.53
43.23
38.43
Third
stage

DW difference of weight loss (wt%)

Activation energies, EA

Wmixture weight loss of the binary mixtures of HDPE and RSS (wt%)
xi weight fraction of each material in the mixture
Second

57.47
50.94
49.14
59.31

56.44
55.41
53.54
50.88

52.02
52.14
43.87
50.00
stage

Wi weight loss of each material in the same mixture (wt%)

x degree of conversion of the process
(kJ mol
1)

b heating rate (K min
1)

52.25
51.87
51.02
66.42

39.77
41.85
42.64
42.14

42.43
43.23
45.61
46.62
stage

R2
First

correlation coefficient

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