Waste Management 48 (2016) 275–284

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Kinetic modelling of RDF pyrolysis: Model-fitting and model-free

approaches
Özge Çepelioğullar ⇑, Hanzade Haykırı-Açma, Serdar Yaman
Istanbul Technical University, Faculty of Chemical and Metallurgical Engineering, Department of Chemical Engineering, 34469 Istanbul, Turkey

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

Article history: In this study, refuse derived fuel (RDF) was selected as solid fuel and it was pyrolyzed in a thermal ana-
Received 8 September 2015 lyzer from room temperature to 900 °C at heating rates of 5, 10, 20, and 50 °C/min in N2 atmosphere. The
Revised 11 November 2015 obtained thermal data was used to calculate the kinetic parameters using Coats-Redfern, Friedman,
Accepted 12 November 2015
Flylnn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods. As a result of Coats-Redfern
Available online 21 November 2015
model, decomposition process was assumed to be four independent reactions with different reaction
orders. On the other hand, model free methods demonstrated that activation energy trend had similari-
Keywords:
ties for the reaction progresses of 0.1, 0.2–0.7 and 0.8–0.9. The average activation energies were found
RDF
Pyrolysis
between 73–161 kJ/mol and it is possible to say that FWO and KAS models produced closer results to
Kinetics the average activation energies compared to Friedman model. Experimental studies showed that RDF
Model-fitting may be a sustainable and promising feedstock for alternative processes in terms of waste management
Isoconversional strategies.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Final disposal of the municipal solid wastes (MSW) has become
one of the urgent challenges that the modern societies have been
encountered as a result of population growth and the increasing
trend of consumption. This situation not only creates landfill prob-
lems and hazardous contents but also forces countries to struggle
against this problem by developing serious policies (Gallardo
et al., 2014; Materazzi et al., 2015). European Environment Agency
(EEA) highlighted that a well-planned waste management may
offer a way to cut greenhouse gas (GHG) emissions. In this respect,
one of the important targets of EEA for the year of 2020 is to recy-
cle 50% of the wastes (EEA, 2013a, 2013b). As a candidate country
to EU, Turkey also has to take significant precautions in terms of
waste management strategies. Istanbul as one of the crowded
metropolises in the world, amount of MSW accelerates drastically.
In 2005, produced MSW amount was reported almost 13,000
tonnes per day. Today, this amount is 17,000 tonnes per day and
Abbreviations: ASTM, American Society for Testing and Materials; DTG, Deriva-
tive Thermogravimetry; FT-IR, Fourier Transform Infrared Spectroscopy; FWO,
Flylnn-Wall-Ozawa method; KAS, Kissinger-Akahira-Sunose method; RDF, refuse
derived fuel; SEM, Scanning Electron Microscope; TG, Thermogravimetry.
⇑ Corresponding author.
E-mail addresses: cepeliogullar@itu.edu.tr (Ö. Çepelioğullar), hanzade@itu.edu.tr
(H. Haykırı-Açma), yamans@itu.edu.tr (S. Yaman).
predictions show that it will reach 31,500 tonnes per day by
2030. Final disposal methods in developing countries, including
Turkey, generally employ traditional methods due to their simplic-
ity and low cost (Istanbul Metropolitan Municipality, 2015; Kanat,
2010). TurkStat data showed that 54% of the municipal waste is
sent to sanitary landfills and 44% is dumped into municipality
dumpsites. 2% of the MSW was reported as composted or disposed
of by other methods (ETC/SCP, 2013). Even though the waste man-
agement in Turkey is improving, there are still some points that the
country should be strengthen especially about recycling by apply-
ing alternative technologies.
From the environmental stand point, there are many alternative
ways such as waste-to-energy/waste-to-products technologies
(including pyrolysis and gasification), composting and anaerobic
digestion instead of traditional disposal methods (Murphy and
McKeogh, 2004). Among these technologies, pyrolysis is known
as the common step of thermal processes that allows a detailed
characterization of thermal and kinetic behaviors that can be help-
ful for the further steps of the operation. Pyrolysis also results in
extraction of the energy content of the MSW in the form of pyrol-
ysis products and valuable chemicals (Efika et al., 2015). In litera-
ture, there are numerous studies about pyrolysis where MSW
derived from household wastes, plastic wastes, industrial or
agricultural wastes were selected as feedstock (Tursunov, 2014;
Zhou et al., 2014, 2015; Song et al., 2014). On the contrary to these

http://dx.doi.org/10.1016/j.wasman.2015.11.027
0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
276 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284

Nomenclature

A pre-exponential factor (min
1) R universal gas constant (8.3145 Jmol
1K
1)

a conversion R2 correlation coefficient
b heating rate (K min
1) t time (min)
E activation energy (kJ/mol
1) T temperature (K)
f(a) function expressing dependence of the reaction rate on Tm the temperature at maximum reaction rate (K)
the conversion x equivalent form of E/RT
g(a) integrated reaction model W0 initial weight of the sample (mg)
k reaction rate constant (min
1) Wf final weight of the sample (mg)
n order of the reaction Wt weight of the sample at a given time (mg)
p(x) integral function

studies, a different form of MSW which is known as refuse derived
fuel (RDF) was selected for this study. RDF is obtained as a result of
different operations such as composting, shredding, wind shifting
and screening, magnetic and eddy-current separation for more
manageable and storable form of wastes fuel. It contains pelletized
or fluffy MSW that remains after the removal of noncombustible
materials such as ferrous materials, glass, grit, and other
noncombustible materials (Sever Akdağ et al., 2016; Kara, 2012;
Kara et al., 2009). EU Directives such as Landfill Directive
1999/31/EC; Waste Incineration Directive 2000/76/EC and The
Renewable Energy Directive 2001/77/EC that came into force
within the years increased the share of RDF in waste-to-energy
technologies. In this respect, most of EU countries use RDF in co-
incineration process or industrial applications (coal or cement
plants) as alternative fuel. Use of RDF in industrial processes offers
more flexibility than incineration and provides a large number of
ecological advantages. Therefore, some EU countries view RDF as
part of their strategy to help them fulfil the requirements and com-
mitments of Kyoto protocol (Gendebien et al., 2003). As a candi-
date country to EU, although the legislation process is still on
progress, RDF use is very welcomed especially in cement industry
as an alternative fuel. RDF compositions may show differences
according to different regions since it is derived from MSW. Table 1
summarizes some of the studies in the literature that employed
RDF as solid fuel together with its varying fractions. On the other
hand, its high calorific value and more predictable features are
some of the superiorities of RDF compared to other solid fuels such
as waste biomass species (Gendebien et al., 2003). Even though,
there are some studies about the pyrolysis of RDF in literature
(Hwang et al., 2014; Blanco et al., 2013, 2014; Zhou and Yang,
2015; Singh et al., 2012; Seo et al., 2010), the fewness in the studies
about detailed thermal and kinetic investigations are remarkable.
Especially, kinetic modelling constitutes as one of the significant
aspects of thermal decomposition, since kinetic data may affect
the reactor selection, optimization of the reactor design and oper-
ating conditions at the step of design and implementation (Saha
et al., 2008). For instance, Bosmans et al. (2014) used RDF pro-
cessed from excavated landfill waste in order to decompose in
TGA. Experiments were carried out with a heating rate of 10 °C/
min until 800 °C in N2 atmosphere. 1st order independent reaction
model was applied to obtained data and the assumption of four
possible reactions was modelled by MATLABÒ. The authors claim
that they found a model that fits well to the measured data from
degradation of both the lignocellulosic and the plastics fractions
in the waste material. In another study (Seo et al., 2010), sub-
bituminous coal, RDF and their blends were selected as feedstock.
The pyrolysis characteristics of the raw materials and their blends
were investigated under isothermal and non-isothermal condi-
tions. During isothermal experiments, the reactor was heated to
a desired temperature (500–800 °C) under N2 flow while non-
isothermal experiments were carried out until 900 °C with a heat-
ing rate of 15 °C/min. The kinetic modelling of the materials was
employed for both isothermal and non-isothermal data. The first
order reaction assumption resulted in high correlation coefficient
and four first order reactions at different temperature ranges well
represented the data of RDF. These authors determined that the
activation energy obtained from isothermal experiments was
lower than that from the non-isothermal experiments. In addition,
it was concluded that the increase of RDF ratio in the blend caused
a linear decrease in the activation energy. Grammelis et al. (2009)
also investigated pyrolysis and combustion behaviors of tetrapack,
RDF and fractions of each waste for a detailed comparison.
Devolatilization experiments were conducted with a heating rate
of 20 °C/min until 1000 °C in He atmosphere and first order inde-
pendent reaction model was applied to pyrolysis data. Pyrolysis
mechanism of RDF was modelled by employing four independent

Table 1
RDF compositions in the literature.a

Cozzani et al. Reza et al. Materazzi et al. Krüger et al. Hogland and Marques Kara
(1995) (2013) (2015) (2014) (2003) (2012)b
Paper, board or card 65.0–70.0 26.0 22.2 10.0 35.0–42.0 17.1
Textile 8.0–12.0 2.9 9.9 20.0 – 66.0
Organic fraction – – 14.3 – – –
Plastics 1.5–2.5 19.1 8.0 22.0 18.0–43.0 3.6
Plastic films or bags 14.0–16.0 33.2 – – 13.3
Wood, rubber or leather 4.0–6.0 6.2 – 1.0 –
Non-ferrous materials, glass, 0.5–1.5 – 4.0 – 0.9 –
inerts
Composites – – 5.0 – –
Fine particles – 1.3 1.6 22.0 – –
Combustible materials – – – – 4.0–14.0 –
Calorific value (MJ/kg) – 15.8 26.8 – 19.6 16.7
a
Some of the important fractions were listed in the table, therefore summation may not give 100.
b
RDF fraction for this study was employed from Kara (2012).
 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284
reactions with first order. Singh et al. (2012) pyrolyzed waste
materials, woody waste biomass, scrap tire, RDF and waste plastic
in two different thermal analyzers which are TGA-FTIR and
TGA-MS. Decomposition experiments were carried out from room
temperature to 900 °C with a heating rate of 25 °C/min in N2 atmo-
sphere. Coats-Redfern integral method with first order reaction
assumption was employed. The pyrolysis mechanism was
modelled for two stages which were between 240–380 °C and
410–500 °C with high R2 values as 0.998 and 0.999, respectively.
In this respect, additional added value of this study is based on
the selection of the fuel in terms of local availability and its future
sustainability. Therefore in this study, RDF was selected as feed-
stock for pyrolysis process. After the pretreatment and characteri-
zation steps, RDF was pyrolyzed in a thermal analyzer at different
heating rates (5, 10, 20, 50 °C/min.) until 900 °C in the nitrogen
atmosphere. The obtained data was used to characterize the ther-
mal behaviors of RDF at high temperature regions. In addition, both
model-free and model-fitting kinetic approaches (Lu et al., 2009;
Brems et al., 2011; Oyedun et al., 2014; Özveren and Özdoğan,
2013) were applied to thermal data in order to determine the
kinetic parameters such as activation energy and pre-exponential
factor.
2. Experimental
2.1. Preparation of RDF
RDF used in this study was provided from ISTAÇ Co. Compost
and Recovery Plant in Istanbul-Turkey and the main fractions were
identified as textile (66%), paper (17.1%) and plastic derivatives
(13.3%).
The feedstock was first dried in open containers under labora-
tory conditions and then in an oven at 60 °C to prevent some struc-
tural changes at micro-level. After drying process, raw material
was grinded, sieved to the particle size less than 250 lm and par-
ticles were shaken very well to make a more uniform distribution
of the particles. After the preparation step, characterization tests
were carried out.
2.2. Characterization of RDF
Characterization studies of RDF were carried out by applying
proximate, ultimate and component analyses as well as determina-
tion of the calorific value. The proximate analysis was carried out
in TA Instruments SDTQ600 model thermal analyzer equipment.
This equipment has 0.1 lg balance sensitivity, a temperature range
of up to 1500 °C platinum/platinum–rhodium thermocouples, and
temperature sensitivity of 0.001 °C. The reference material used as
the benchmark in this equipment is thermally inactive alumina.
About 10 mg of fuel was placed in platinum pans and then the
heating was programmed according to ASTM standards. In spite
of the fact that it is highly difficult to take a representative sample
of 10 mg from a bulk, the limitations of the thermal analyzer
necessitated this and to check the repeatability of the results the
experiments were repeated three times. Component analysis of
RDF was carried out analytically. Elimination of extractives to get
the extractive-free bulk was performed in accordance with ASTM
D1105 (2013). At the beginning, 10 g of sample (<0.250 mm) was
extracted with benzene-ethanol (1:2, v/v) mixture for 4 h in soxh-
let extractor according to TAPPI, T264 om-97 (TAPPI, 1997). In the
following step, sample was extracted with ethanol (95%) for 4 h in
order to remove benzene. Then, the extracted bulk was washed
with ethanol, hot and cold distilled water, respectively. The yield
of extractives was calculated from the loss in the mass. The deter-
mination of holocellulose and lignin was carried out using this
277
extractive-free sample. For lignin analysis, 1 g of extractive-free
sample was treated with sulfuric acid solution and washed with
hot distilled water, dried and weighted. The lignin content was cal-
culated in accordance with the ‘‘van Soest’s Method” (van Soest,
1963). For the holocellulose isolation 2–5 g of extractive-free sam-
ple was treated with the mixture of NaClO2, acetic acid and water
according to ‘‘Wise’s Chlorite Method” (Wise et al., 1946). Ultimate
analysis was also performed in order to determine the elemental
composition of the fuels using Leco TruSpecÒ CHN model with S
module an elemental analyzer. On the other hand, gross calorific
value of the fuel was determined by IKA2000 model calorimeter.
Results are given in Table 2. In addition to these, surface morphol-
ogy was investigated using a SEM FEI Quanta Feg 250 model
equipment. Determination of the functional groups in the structure
was completed by FT-IR analysis using a Perkin Elmer Spectrum
equipment. FT-IR and SEM results are given in Figs. 1 and 2.
2.3. Pyrolysis experiments in thermal analyzer
Pyrolysis experiments were conducted using a TA Instruments
SDTQ600 model thermal analyzer equipment. The fuel was pyrol-
ysed from room temperature to 900 °C at different heating rates
(5, 10, 20, 50 °C/min.) in N2 atmosphere with a flow rate of
100 mL/min. This nitrogen flow ensured an inert atmosphere on
the sample during the run, while the small amount of sample
and the slow heating rate ensured that the heat transfer limitations
can be ignored.
3. Results and discussion
3.1. Characterization of the raw material
One of the important parameters that affect the yield of the
thermal system is the moisture content of the chosen fuel. As
can be seen from Table 2, the moisture content of RDF was deter-
mined as 7.1% which seems appropriate for the system. Addition-
ally, ash yield is another point, since it has negative impact on
the systems. The ash content of RDF was determined as 15.6%
which seemed considerably higher compared to other solid fuels
such as biomass. However, this was an expected outcome, since
RDF is the residual organic part along with some inorganics of
municipal solid wastes and known with its high calorific
value despite the fact that high ash content. Even though the
Table 2
Proximate, ultimate and component analysis results (%wt, dry basis).
Proximate analysis
Moisture (as received) 7.1
Volatiles 71.5
Ash 15.6
Fixed C* 12.9
Component analysis
Extractives 10.2
Lignin 27.4
Holocellulose 62.3
Ultimate analysis (dry ash free)
C 58.0
H 7.3
N 1.2
S 0.7
Oa 32.8
H/Cb 1.50
O/Cb 0.42
Calorific value (MJ/kg) 17.7
a
Calculated by difference.
b
Atomic molar ratio.
278 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284

Fig. 1. FT-IR spectrum of RDF.

Fig. 2. SEM image of RDF (750X and 3000X).

composition of RDF may vary from region to region, generally the attributed to ethers, esters, alcohols or other compounds contain-
ash contents of RDF in the literature were between 10%–17% (Singh ing CAO single bonds. RDF gave fairly a large band in this range
et al., 2012; Seo et al., 2010; Bosmans et al., 2014; Grammelis et al., resulting from the CAO bonds due to its high oxygen content. In
2009; Cozzani et al., 1995). The fuel was characterized with vola- addition, strong CAH stretches were observed in the FT-IR spec-
tiles content of 71.5%. Cellulose which is the main and the most trum between 1050–1150 cm
1. The peak at around 870 cm
1 in
abundant component in the biomass has different forms. In this RDF’s spectrum could be the indicator of CACl bonds in the struc-
study, the amount of holocellulose (summation of cellulose and ture. SEM analysis was also applied to investigate the surface char-
hemicellulose) was determined as 62.3%. In addition, lignin and acteristics of the fuel and the results can be seen from Fig. 2. At first
extractives contents were determined as 27.4% and 10.2%. In addi- look, it can be confirmed that the surface morphology of the fuel is
tion, the higher O content leads to higher reactivity during the amorphous and heterogeneous. The shape and the size of the par-
thermal processes. This situation generally results in ignition at ticles on the surface were not uniformly distributed. In addition,
lower temperatures. As can be seen from Table 2, RDF had a high long fibers were the most noticeable points in RDF’s SEM image
O content of 32.8%. This situation may create fast volatile release and this is convenient with the cylindrical shapes encountered
during thermal process. for biomass species.
Fig. 1 shows the FT-IR spectrum of RDF. The large intense band
between 3600–3200 cm
1 indicates the presence OAH coming
from the moisture content of the fuel. The OAH peak was followed
by strong and asymmetric CAH stretches between 2950–
2850 cm
1 which were caused by the alkyl groups in the structure.
C@C peaks that are the indicators of the aromatics were observed
at nearly 1600 cm
1. Lignin is the only aromatic constituent in bio-
mass and the strong band of C@C for lignin-rich RDF is in good
agreement with this fact. RDF had another C@C peak at
1416 cm
1 and this was followed by CAH stretch at 1317 cm
1.
The region of the infrared spectrum from 1200 to 700 cm
1 is
called the fingerprint region. This region is notable for the large
number of infrared bands. Many different vibrations, such as
CAO, CAC and CAN single bond stretches, CAH bending vibrations,
and some bands due to benzene rings are found in this region.
According to this, the peaks between 1050–1260 cm
1 can be Fig. 3. TG curves of RDF at different heating rates.
 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284 279

3.2. Thermal decomposition characteristics of RDF at different heating Table 3

rates Significant peak temperatures and the amounts of residues at different heating rates.

Heating rate Peak dW/dt (%/min) Residue (%)

TG and DTG curves for each heating rate are given in Figs. 3 and (°C/min) temperature (°C)
4 and Table 3 also shows the important peak temperatures 5 38 0.70 20.1
together with the amounts of residues after pyrolysis. Even though, 322 3.01
thermal decomposition behaviors followed the same pathways at 437 0.71
647 0.36
first sight, important differences occurred in detailed. To begin
with, the first weight loss regions in DTG curves can be attributed 10 37 0.87 13.7
298 3.15
to moisture release from the structure. Until 120 °C, the recorded 441 3.27
weight losses were almost the same for all heating rates as approx- 683 1.01
imately 7% of the initial weight. As the heating rate increased, 20 57 2.20 11.3
weight loss rates also increased and the recorded weight loss rates 323 11.04
were 0.70%/min, 0.84%/min, 2.20%/min and 4.94%/min, for 5, 10, 20 50 72 4.94 9.1
and 50 °C/min respectively. After the moisture removal, the main 337 3.34
structure started to decompose due to increasing temperature.
Since, RDF is a heterogeneous material, its degradation at high
temperature region took place in two main steps which are known maximum peak temperatures were observed at 322 °C (11.04%/
as the decomposition of the cellulosic components (250–400 °C) min) and 337 °C (30.34%/min) for the heating rates of 20 and
and the plastics (450–500 °C) (Seo et al., 2010). The peaks that rep- 50 °C/min, respectively. It is obvious that the weight loss rates
resent these decomposition steps were clearer for 5 and 10 °C/min were really high for these heating rates compared to the lower
rather than the faster heating rates. For 5 °C/min, the decomposi- heating rates. The varying heating rates also affected the comple-
tion started above 180 °C and had a maximum peak at 322 °C with tion of the process. For 5 and 10 °C/min, the weight losses were
a rate of 3.01%/min due to cellulose and hemicellulose decomposi- continued to be recorded until the final temperature. In contrast,
tions. This weight loss continued until 349 °C and above this tem- the decomposition process almost completed between 700–
perature weight loss rate slightly slowed down. RDF lost almost 750 °C for 20 and 50 °C/min. Final residues showed that the
half of its initial weight. This first step can be attributed to the vola- increase in the heating rate led to decrease in the amounts of resi-
tiles removal from the main structure. Another peak observed at dues. Accordingly, the final weights were obtained as 20.1%, 13.7%,
437 °C was caused by the plastic degradation and only small 11.3% and 9.1% of the initial weight as can be seen from Table 3.
weight losses recorded until 647 °C as in Fig. 3. At this tempera-
ture, the last peak was observed with weight loss rate of 0.36%/
4. Kinetic modelling
min. From this point to final temperature RDF lost additional 7%
of its initial weight. The peak divisions that represent the cellulose
Solid state kinetics can be studied with thermal methods by
and plastic decompositions were observed also in case of 10 °C/
measuring the sample property as it is heated or held at a constant
min shown in Fig. 4. After the moisture removal, two main peaks
temperature. In this study, reaction kinetics was applied to thermal
were observed at 298 °C and 441 °C with the weight loss rates of
data obtained under non-isothermal conditions with a constant
3.15%/min, 3.26%/min, respectively as in Table 3. However, as the
heating rate. The pyrolysis reaction of the solid material may be
heating rate increased, these shoulders were appeared to act as
given as below:
one main peak due to overlapping. Haykiri-Acma et al. (2006)
and Di Blasi (2008) explained the overlapping of peaks basing on Raw material ðsolidÞ ! Char ðsolidÞ þ Volatiles ðgasÞ ð1Þ
the fact that sufficiently low heating rates allow enough time for
Under isothermal conditions the rate equation for solid fuel
each individual component in the structure to decompose while
decomposition can be expressed as;
at high heating rates decomposition is almost simultaneous and
as such adjacent peaks representing hemicellulose and cellulose da
¼ kf ðaÞ ð2Þ
are merged to form broader peaks (Aboyadea et al., 2011). The dt

Fig. 4. DTG curves of RDF at different heating rates.

280 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284

where k is the rate constant of the reaction, f(a) is the function of a different integral functions proposed in the literature. Table 4 sum-
and a is the conversion or weight loss rate that can be calculated marizes the most common functions. It has been reported that
with the following equation, using nonlinear heating programs such as hyperbolic or parabolic
or non-Arrhenius temperature functions of the rate constant leads
W0
Wt
a¼ ð3Þ to exact analytical solutions of the temperature integral. However,
W0
Wf
this approach has not been widely implemented (Khawam, 2007).
In Eq. (3), W0 is the initial weight of the sample (mg), Wt is the To transform the above integral to a more general form, the integra-
weight of the sample at a given time (mg) and Wf is the final mass tion variable can be defined as replacing E/RT with x and integration
of the sample (mg). The temperature dependent reaction constant k limit is transformed as gives,
can be described with the Arrhenius law as given, Z 1

 AE e
x AE

E gðaÞ ¼ dx ¼ pðxÞ ð11Þ
k ¼ A exp ð4Þ bR x x2 bR
RT
where A is known as the pre-exponential or frequency factor Here, p(x) also represents the integral function. The solution from
(min
1), E is the activation energy (kJ/mol), R is the universal gas this point can be obtained by using different approaches. These
constant (8.3145 Jmol
1K
1) and T is the absolute temperature (K). approaches will be explained in the following sections. The sum-
By substituting Eq. (4), into Eq. (2) gives the following equation, mary of each method with their basic assumptions and plotting

 methods are given in Table 5.
da
E
¼ A exp f ðaÞ ð5Þ
dt RT
4.1. Model-fitting methods
f(a) can be proposed in the following form,
In this study, Coats-Redfern method, the most popular model-
f ðaÞ ¼ ð1
aÞn ð6Þ
fitting method first proposed in 1964 and utilizes Taylor series
In the non-isothermal TGA experiments, heating rate is also approach by limiting the numbers of terms in the series, was used
function of time as expressed in the following form, to apply the experimental data (Coats and Redfern, 1964). The Tay-
lor series expansion form can be given as,
da da dt
¼ x ð7Þ 

dT dt dT
AE AE e
x 2! 3! 4!
For non-isothermal measurements linear heating rate, b (K/ gðaÞ ¼ pðxÞ ffi 1
þ
þ   
bR bR x2 x x2 x3
min) may be defined as, 
x
 "
#
AE e 2 AE e
E=RT 2
dT ffi 1
¼ 1

b¼ ð8Þ bR x2 x bR ðE=RTÞ2 E=RT
dt 2

ART 2RT
E=RT
Finally, inserting linear heating rate (Eq. (8)) into Eq. (5) gives, ¼ 1
e ð12Þ
bE E




da A
E da da
E
¼ exp f ðaÞ or ¼b ¼ A exp f ðaÞ ð9Þ
dt b RT dt dT RT At this point g(a) can be written for different order of reaction val-
ues. For n = 1, it becomes g(a) =
ln (1-a) and for n–1 the function
This equation is known as the general equation of TGA curve. turns into in the following form,
Integration and recombination of Eq. (9) gives,
Z Z

a
da A T

E gðaÞ ¼ 1=n
1½ð1
aÞ1
n
1 ð13Þ
gðaÞ ¼ ¼ exp dT ð10Þ
0 f ðaÞ b 0 RT
If the g(a) functions were inserted into the Eq. (12) and recombined,
where g(a) is known the integrated reaction model, so called as the the below equations can be obtained,
‘‘integral function” or ‘‘temperature integral”. There are numbers of
  

lnð1
aÞ AR 2RT E
n ¼ 1; ln
¼ ln 1

ð14Þ
Table 4 T 2 bE E RT
Different integral functions proposed in the literature (Brems et al., 2011; Masnadi
et al., 2014; Gao et al., 2013; Chen and Wang, 2007). " # 

1
ð1
aÞ1
n AR 2RT E
Reaction mechanism g(a) n – 1; ln ¼ ln 1

ð15Þ
T 2 ð1
nÞ bE E RT
Chemical reaction models
1st order (Mampel)
ln(1
a) For the determination of the reaction order, plotting method is
Reaction order (n = 0.25, 1.5, 2, 3) [(1
a)(1
n)
1]/(n
1)
generally applied. By linear fitting of the left hand side of the equa-
Diffusion controlled models tions 14 and 15 versus 1/T, the order of the reaction can be
1D transport-plane a2
achieved. In addition, for the best fitted reaction order, the kinetic
2D transport a+(1
a)ln(1
a)
3D transport-spherical (Jander) 2 parameters A and E can be calculated. As a result of plotting, the
ð1
ð1
aÞ1=3 Þ
3D transport (Anti-Jander) [(1 + a)1/3
1]2
left hand side of the equations versus 1/T gives straight lines. The
highest R2 values among these straight lines represent the best
Phase boundary reaction models
2D, shrinking cylinder 1
(1
a)1/2
possible reaction order. By using the slope of these obtained
3D, contraction of sphere 1
(1
a)1/3 straight lines (
E/R), the activation energy (E) of the process can
Nucleation reaction models
be figured out. Also, by taking the temperature at which Wt =
n = 1, 1.5, 2, 3 (Avrami–Erofeev) [
ln(1
a)]1/n (W0 + Wf)/2 in the place of T in the intercept term of Eqs. (14)
Power law a and (15), the pre-exponential factor can be calculated (Brems
Power law a1/2 et al., 2011; Masnadi et al., 2014; Gao et al., 2013; Chen and
Power law a1/3
Wang, 2007; Khawam, 2007; Coats and Redfern, 1964).
 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284 281

Table 5
Summary of model free and model fitting kinetic methods (Coats and Redfern, 1964; White et al., 2011; Friedman, 1964; Ozawa, 1965; Flynn and Wall, 1966; Kissinger, 1956;
Doyle, 1961, 1962).

Model-free methods General forms and assumptions Plotting method

     da
Friedman Method (differential ln ddta ¼ ln b ddTa ¼ ln½Af ðaÞ
RT
E
ln dt
v sð1=TÞ Slope =
E/R
isoconversional) Assumes f(a) remains constant.
Degradation is independent of temperature and depends only on
the rate of mass loss.
Flynn–Wall–Ozawa Method (integral By an empirical formula proposed by Doyle: For different heating rates at fixed
isoconversional) log pðxÞ ffi
2:315
0:4567x, for 20 6 x 6 60 conversionðlog bÞv sð1=TÞSlope =
0.4567E/R
Taking natural logarithm and rearranging by using Doyle’s
approximation gives,


log b ¼ log A RgðEaÞ
2:315
0:4567 RT
E

Assumes apparent activation energy remains constant during

the degradation
(From t = 0 to ta where ta is the time at conversion is a).


Kissinger-Akahira-Sunose method This method also employs another derived approximation by ln b
Tm2
v sð1=TmÞSlope = E
(integral isoconversional) Doyle:
exp
x
log pðxÞ ffi x2
for 20 6 x 6 50
,
Rearranging by using Doyle’s approximation gives,
  h  R i
b a da
2 Þ ¼
R Tm
ln
E 1 E
lnðTm AR 0 f ðaÞ , Tm: temp. @max reaction rate
Assumes a has a fixed value.
Model fitting Methods
h i h  i E
Coats-Redfern method (integral based non- n = 1, ln
lnð1
aÞ
¼ ln AR ln½gðaÞ=T 2 v sð1=TÞ
bE 1
E
RT
2RT
T2
isothermal method) h i h  i E Slope =
E/R
1
ð1
aÞ1
n
n – 1, ln T 2 ð1
nÞ ¼ ln bE 1
E
AR 2RT

RT Intercept = lnðAR=bEÞ
Uses Taylor series expansion and makes assumption regarding
the value of the reaction order.

Table 6
Calculated E (kJ/mol) and A (min
1) values obtained from Coats-Redfern model.

n Reaction 1 190–340 °C Reaction 2 350–460 °C Reaction 3 470–680 °C Reaction 4 690–890 °C

R2 E A R2 E A R2 E A R2 E A
6 6
0 0.9321 75.1 1.27  10 0.9084 91.0 1.01  10 n/a – – 0.9051 86.19 9.2  102
0.5 0.9569 82.1 7.52  106 0.9472 106.2 2.1  107 n/a – – 0.9522 107.78 1.5  104
1 0.9748 90.5 6.3  107 0.9709 125.1 8.4  108 0.9366 77.8 8.2  103 0.9737 135.7 5.7  105
1.5 0.9809 100.1 7.87  108 0.9750 147.8 7.0  1010 0.9595 97.7 2.27  105 0.9659 170.1 4.94  107
2 0.9740 112.1 1.39  1010 0.9622 174.2 1.15  1013 0.9578 121.2 1.01  107 0.9403 211.9 8.99  109

n/a: non-linear correlation.

4.2. Model-free methods loss rate. In order to calculate the activation energy, the slope of
ln [db/dt] vs 1/T plot which gives a straight line is generally
Some researchers pointed that even the model-fitting methods employed.
were satisfactorily predict reaction kinetics in solid state form, On the other hand, FWO method assumes the change in the
simplifications while applying the model may not describe the apparent activation energy constant during the thermal process
complex processes such as biomass decomposition during which and employs Doyle’s (Doyle, 1961, 1962) approximation (Eq.
numbers of reactions involve simultaneously (Masnadi et al., (17)) in order to approach to a solution for temperature integral.
2014). Therefore, innovative methods so-called ‘‘model-free”
lnðpðxÞÞ ¼
2:315
0:4567x; for 20  x  60 ð17Þ
methods were proposed on an isoconversional basis where the
degree of the conversion assumed to be constant and the reaction Taking logarithm and rearranging by using Doyle’s approxima-
rate (k) depends on the reaction temperature. In this study, three tion yields,
different approaches which are Friedman (1964), FWO (Ozawa,

1965; Flynn and Wall, 1966) and KAS (Kissinger, 1956) were E E
log b ¼ log A
2:315
0:4567 ð18Þ
employed. RgðaÞ RT
Friedman method, as one of the first proposed isoconversional
Obtained data at different heating rates are used for plotting log
methods, can be expressed by taking the natural logarithm of each
b vs 1/T to produce linear lines. The apparent activation energy can
side from Eq. (9) gives:
be calculated by using the slope of these lines (
0.4567E/R).

 
 In addition to these models, KAS method is also very common
da da E method for the determination of the kinetic data. KAS method
ln ¼ ln b ¼ ln½Af ðaÞ
ð16Þ
dt dT RT assumes a has a fixed value and applies another approximation
of Doyle’s for 20 6 x 6 50 interval and can be given as:
According to Friedman’s kinetic model, conversion function f(a)
is assumed to be constant that means thermal degradation process exp
x
log pðxÞ ffi ð19Þ
is independent from temperature and only depends on the mass x2
282 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284

Table 7
Calculated kinetic parameters, R2 values and fitted equations from Friedman, FWO and KAS models (E, kJ/mol).

a Friedman FWO KAS

2 2
Fitted equation R E Fitted equation R E Fitted equation R2 E
0.1 y =
18056x + 30.328 0.9834 150.1 y =
17397x + 34.728 0.9741 137.4 y =
16305x + 20.121 0.9705 135.6
0.2 y =
19516x + 32.213 0.9682 162.2 y =
19165x + 36.696 0.9630 151.4 y =
18033x + 22.019 0.9584 149.9
0.3 y =
20102x + 32.65 0.9589 167.1 y =
19661x + 36.717 0.9636 155.4 y =
18500x + 21.989 0.9591 153.8
0.4 y =
20073x + 32.097 0.9481 166.8 y =
20042x + 36.743 0.9231 158.4 y =
18860x + 21.979 0.9141 156.8
0.5 y =
19494x + 30.067 0.9581 162.1 y =
20841x + 37.465 0.9458 164.7 y =
19639x + 22.668 0.9394 163.3
0.6 y =
19105x + 28.764 0.9719 158.8 y =
20426x + 36.122 0.9680 161.4 y =
19204x + 21.29 0.9640 159.6
0.7 y =
19567x + 28.457 0.9556 162.6 y =
17343x + 30.406 0.9434 137.1 y =
16097x + 15.534 0.9351 133.8
0.8 y =
12962 + 17.237 0.9610 107.7 y =
12682x + 22.299 0.9606 100.2 y =
11395x + 7.3631 0.9523 94.7
0.9 y =
9633.9x + 10.954 0.9305 80.1 y =
9369.2x + 16.62 0.9429 74.1 y =
8032x + 1.6074 0.9251 66.7

Substituting Eq. (19) into temperature integral (Eq. (11))

provides the general equation of KAS method as below:


 
 Z a 
b E 1 E da
ln ¼

ln ð20Þ
T2m R Tm AR 0 f ðaÞ
where Tm is the temperature at maximum reaction rate. The appar-


b
ent activation energy can be obtained by plotting ln
T2m
vs 1/Tm.
The slope of the obtained straight lines gives the activation energy.

4.3. Kinetic analysis of RDF decomposition

There are two main stages of applying the model-fitting meth-

ods which are: (i) determination of the model that fits the data best
and (ii) calculation of the kinetic parameters such as the activation
energy (E) and frequency factor (A) using the Arrhenius equation
(Eq. (4)) (Khawam and Flanagan, 2005). Therefore, at the first step,
Coats-Redfern model was used to predict the best fitted reaction
order for RDF pyrolysis and at the further step, kinetic parameters
were calculated. To do this, Coats-Redfern application to RDF
decomposition was progressed not only for the first order assump-
tion but also for changing reaction orders from 0 to 2 with the
increments of 0.5. The calculated activation energies together with
pre-exponential factors were given in Table 6. Calculations were
achieved for 5 °C/min, since the kinetic modelling generally
applied to slower heating rates. By the help of the TG and DTG
curves, it was observed that RDF decomposition involved four main
reactions between 190–890 °C. In this temperature range, the reac-
tion orders were varied and kinetic parameters were recalculated
for each reaction mechanism and each order. As can be seen from
Table 6, the highest regression coefficients were achieved for the
reaction order of 1.5th (R2 values: 0.9810, 0.9750, 0.9596) for the
first three reactions while 1st order for the fourth reaction
(R2:0.9737). According to Coats-Redfern model, the relationship
between the reaction order and activation energy were found pro-
portional to some point. As the reaction order increased, the calcu-
lated activation energy also increased as in Table 6. The apparent
activation energies for the best fitted reaction orders were found
as 100.1, 147.8, 97.7, and 135.7 kJ/mol for each reaction mecha-
nism, respectively. Activation energy is defined as the minimum
energy requirement that must be overcome before molecules can
get close enough to react and form products (White et al., 2011).
In this respect, the reaction with high activation energy needs a
high temperature or a long reaction time. On the other hand,
pre-exponential factors were calculated as 7.87  108, 7.0  1010,
2.27  105 and 5.7  105 min
1, respectively.
There have been ongoing debates about the use of isoconver- Fig. 5. Plots for kinetic models. 1Friedman, 2FWO, 3KAS.
sional methods for the solid state decomposition since the activa-
tion energy (E) varies on the reaction progress, a, although it was
assumed to be constant in most of the studies. Vyazovkin revealed complexity of a process and specifies the reaction scheme
that this dependency should be used as kinetic information rather (Vyazovkin, 1996). At this point, model-free approaches play an
than as a difficulty to be overcome since it helps to disclose the important role for the investigation of the change in activation
 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284
Fig. 6. Varying activation energies according to conversion.
energy according to varying conversion. The fitted equations of lin-
ear lines among isoconversional techniques and their regression
coefficients together with calculated activation energies were sum-
marized in Table 7. Fig. 5 shows the plotted lines of Friedman, FWO
and KAS models respectively. The models were applied to main
decomposition region between 200–500 °C where cellulose and
plastic decompositions involved. It can be seen that each line had
good correlation with the selected models and high R2 values were
achieved. In the literature, the parallelism of these lines is attribu-
ted to the similar kinetic behavior probably the same reaction
mechanism is achieved (Alvarenga et al., 2012). In this respect,
the trend of the lines in this study can be investigated in three
groups which are a = 0.1, 0.2–0.7 and 0.8–0.9 since they followed
the same parallelism. Fig. 6 shows the activation energy change
according to changing conversions for each model and the average
activation energies. The apparent activation energy was found as
150.1, 137.4 and 135.6 kJ/mol at a = 0.1 for each model in the given
order. For the interval of a = 0.2–0.7, the calculated activation ener-
gies were close to each other and determined between 162–
167 kJ/mol, 151–164 kJ/mol and 149–153 kJ/mol as given in
Table 7. In the last reaction progress (a = 0.8–0.9), the apparent
activation energies decreased which means that the energy
requirement for the final stages of the pyrolysis was lower than
the previous parts. Comparison of obtained activation energies
showed that Friedman and FWO methods provided closer results
than KAS for a = 0.8–0.9. On the other hand, calculated activation
energies from overall models were found 137 and 134 kJ/mol for
FWO and KAS and 146 kJ/mol for Friedman. From the average acti-
vation energy point of view, it is possible to say that FWO and KAS
models produced closer results to the average activation energies
compared to Friedman model as shown in Fig. 6. In addition, at
a = 0.5 and 0.6, calculated activation energies from the all three
models were almost the same with the average activation energies.
5. Conclusions
According to TG and DTG curves, it was observed that thermal
decomposition of RDF involved multiple stages that were
comprised of decomposition of cellulose and plastics in the struc-
ture. Pyrolysis process of RDF was modelled by four reaction steps
(190–340, 350–460, 470–680 and 690–890 °C) with the best possi-
ble reaction orders as 1.5th for the first three and 1st for the fourth
reaction. In addition, Friedman, KAS and FWO as model-free
methods were used to investigate the RDF decomposition. Results
showed that the pyrolysis behaviors of RDF can be investigated in
three groups according to the reaction progress as a = 0.1, 0.2–0.7
and 0.8–0.9.The activation energies were found as 150.1, 137.4 and
135.6 kJ/mol for a = 0.1, 162–167 kJ/mol, 151–164 kJ/mol and
283
149–153 kJ/mol for a = 0.2–0.7 for each model in the given order.
For the final step, decrease in the activation energy was observed.
RDF is a quite complex fuel due to its heterogeneous nature, and
the number of the studies on the kinetic modelling of RDF is very
rare compared to other fuels. That’s why this study is crucial since
RDF pyrolysis kinetics were investigated comparatively in terms of
different approaches. Even though each model has its own
assumption and these assumptions bring limitations, experimental
results showed that RDF kinetics were in good agreement and it
could be a promising and sustainable feedstock for alternative
methods.
Acknowledgments
The authors would like to thank The Scientific and Technologi-
cal Research Council of Turkey for their financial support (TUBITAK
214M403). In addition, the assistance of ISTAÇ Co. Compost and
Recovery Plant for the provision of RDF as raw material is also
acknowledged gratefully by the authors.
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