Beruflich Dokumente
Kultur Dokumente
Waste Management
journal homepage: www.elsevier.com/locate/wasman
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 predictions show that it will reach 31,500 tonnes per day by
2030. Final disposal methods in developing countries, including
Final disposal of the municipal solid wastes (MSW) has become Turkey, generally employ traditional methods due to their simplic-
one of the urgent challenges that the modern societies have been ity and low cost (Istanbul Metropolitan Municipality, 2015; Kanat,
encountered as a result of population growth and the increasing 2010). TurkStat data showed that 54% of the municipal waste is
trend of consumption. This situation not only creates landfill prob- sent to sanitary landfills and 44% is dumped into municipality
lems and hazardous contents but also forces countries to struggle dumpsites. 2% of the MSW was reported as composted or disposed
against this problem by developing serious policies (Gallardo of by other methods (ETC/SCP, 2013). Even though the waste man-
et al., 2014; Materazzi et al., 2015). European Environment Agency agement in Turkey is improving, there are still some points that the
(EEA) highlighted that a well-planned waste management may country should be strengthen especially about recycling by apply-
offer a way to cut greenhouse gas (GHG) emissions. In this respect, ing alternative technologies.
one of the important targets of EEA for the year of 2020 is to recy- From the environmental stand point, there are many alternative
cle 50% of the wastes (EEA, 2013a, 2013b). As a candidate country ways such as waste-to-energy/waste-to-products technologies
to EU, Turkey also has to take significant precautions in terms of (including pyrolysis and gasification), composting and anaerobic
waste management strategies. Istanbul as one of the crowded digestion instead of traditional disposal methods (Murphy and
metropolises in the world, amount of MSW accelerates drastically. McKeogh, 2004). Among these technologies, pyrolysis is known
In 2005, produced MSW amount was reported almost 13,000 as the common step of thermal processes that allows a detailed
tonnes per day. Today, this amount is 17,000 tonnes per day and 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-
Abbreviations: ASTM, American Society for Testing and Materials; DTG, Deriva- ysis products and valuable chemicals (Efika et al., 2015). In litera-
tive Thermogravimetry; FT-IR, Fourier Transform Infrared Spectroscopy; FWO,
ture, there are numerous studies about pyrolysis where MSW
Flylnn-Wall-Ozawa method; KAS, Kissinger-Akahira-Sunose method; RDF, refuse
derived fuel; SEM, Scanning Electron Microscope; TG, Thermogravimetry. derived from household wastes, plastic wastes, industrial or
⇑ Corresponding author. agricultural wastes were selected as feedstock (Tursunov, 2014;
E-mail addresses: cepeliogullar@itu.edu.tr (Ö. Çepelioğullar), hanzade@itu.edu.tr Zhou et al., 2014, 2015; Song et al., 2014). On the contrary to these
(H. Haykırı-Açma), yamans@itu.edu.tr (S. Yaman).
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
studies, a different form of MSW which is known as refuse derived aspects of thermal decomposition, since kinetic data may affect
fuel (RDF) was selected for this study. RDF is obtained as a result of the reactor selection, optimization of the reactor design and oper-
different operations such as composting, shredding, wind shifting ating conditions at the step of design and implementation (Saha
and screening, magnetic and eddy-current separation for more et al., 2008). For instance, Bosmans et al. (2014) used RDF pro-
manageable and storable form of wastes fuel. It contains pelletized cessed from excavated landfill waste in order to decompose in
or fluffy MSW that remains after the removal of noncombustible TGA. Experiments were carried out with a heating rate of 10 °C/
materials such as ferrous materials, glass, grit, and other min until 800 °C in N2 atmosphere. 1st order independent reaction
noncombustible materials (Sever Akdağ et al., 2016; Kara, 2012; model was applied to obtained data and the assumption of four
Kara et al., 2009). EU Directives such as Landfill Directive possible reactions was modelled by MATLABÒ. The authors claim
1999/31/EC; Waste Incineration Directive 2000/76/EC and The that they found a model that fits well to the measured data from
Renewable Energy Directive 2001/77/EC that came into force degradation of both the lignocellulosic and the plastics fractions
within the years increased the share of RDF in waste-to-energy in the waste material. In another study (Seo et al., 2010), sub-
technologies. In this respect, most of EU countries use RDF in co- bituminous coal, RDF and their blends were selected as feedstock.
incineration process or industrial applications (coal or cement The pyrolysis characteristics of the raw materials and their blends
plants) as alternative fuel. Use of RDF in industrial processes offers were investigated under isothermal and non-isothermal condi-
more flexibility than incineration and provides a large number of tions. During isothermal experiments, the reactor was heated to
ecological advantages. Therefore, some EU countries view RDF as a desired temperature (500–800 °C) under N2 flow while non-
part of their strategy to help them fulfil the requirements and com- isothermal experiments were carried out until 900 °C with a heat-
mitments of Kyoto protocol (Gendebien et al., 2003). As a candi- ing rate of 15 °C/min. The kinetic modelling of the materials was
date country to EU, although the legislation process is still on employed for both isothermal and non-isothermal data. The first
progress, RDF use is very welcomed especially in cement industry order reaction assumption resulted in high correlation coefficient
as an alternative fuel. RDF compositions may show differences and four first order reactions at different temperature ranges well
according to different regions since it is derived from MSW. Table 1 represented the data of RDF. These authors determined that the
summarizes some of the studies in the literature that employed activation energy obtained from isothermal experiments was
RDF as solid fuel together with its varying fractions. On the other lower than that from the non-isothermal experiments. In addition,
hand, its high calorific value and more predictable features are it was concluded that the increase of RDF ratio in the blend caused
some of the superiorities of RDF compared to other solid fuels such a linear decrease in the activation energy. Grammelis et al. (2009)
as waste biomass species (Gendebien et al., 2003). Even though, also investigated pyrolysis and combustion behaviors of tetrapack,
there are some studies about the pyrolysis of RDF in literature RDF and fractions of each waste for a detailed comparison.
(Hwang et al., 2014; Blanco et al., 2013, 2014; Zhou and Yang, Devolatilization experiments were conducted with a heating rate
2015; Singh et al., 2012; Seo et al., 2010), the fewness in the studies of 20 °C/min until 1000 °C in He atmosphere and first order inde-
about detailed thermal and kinetic investigations are remarkable. pendent reaction model was applied to pyrolysis data. Pyrolysis
Especially, kinetic modelling constitutes as one of the significant 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) 275–284 277
reactions with first order. Singh et al. (2012) pyrolyzed waste extractive-free sample. For lignin analysis, 1 g of extractive-free
materials, woody waste biomass, scrap tire, RDF and waste plastic sample was treated with sulfuric acid solution and washed with
in two different thermal analyzers which are TGA-FTIR and hot distilled water, dried and weighted. The lignin content was cal-
TGA-MS. Decomposition experiments were carried out from room culated in accordance with the ‘‘van Soest’s Method” (van Soest,
temperature to 900 °C with a heating rate of 25 °C/min in N2 atmo- 1963). For the holocellulose isolation 2–5 g of extractive-free sam-
sphere. Coats-Redfern integral method with first order reaction ple was treated with the mixture of NaClO2, acetic acid and water
assumption was employed. The pyrolysis mechanism was according to ‘‘Wise’s Chlorite Method” (Wise et al., 1946). Ultimate
modelled for two stages which were between 240–380 °C and analysis was also performed in order to determine the elemental
410–500 °C with high R2 values as 0.998 and 0.999, respectively. composition of the fuels using Leco TruSpecÒ CHN model with S
In this respect, additional added value of this study is based on module an elemental analyzer. On the other hand, gross calorific
the selection of the fuel in terms of local availability and its future value of the fuel was determined by IKA2000 model calorimeter.
sustainability. Therefore in this study, RDF was selected as feed- Results are given in Table 2. In addition to these, surface morphol-
stock for pyrolysis process. After the pretreatment and characteri- ogy was investigated using a SEM FEI Quanta Feg 250 model
zation steps, RDF was pyrolyzed in a thermal analyzer at different equipment. Determination of the functional groups in the structure
heating rates (5, 10, 20, 50 °C/min.) until 900 °C in the nitrogen was completed by FT-IR analysis using a Perkin Elmer Spectrum
atmosphere. The obtained data was used to characterize the ther- equipment. FT-IR and SEM results are given in Figs. 1 and 2.
mal behaviors of RDF at high temperature regions. In addition, both
model-free and model-fitting kinetic approaches (Lu et al., 2009;
2.3. Pyrolysis experiments in thermal analyzer
Brems et al., 2011; Oyedun et al., 2014; Özveren and Özdoğan,
2013) were applied to thermal data in order to determine the
Pyrolysis experiments were conducted using a TA Instruments
kinetic parameters such as activation energy and pre-exponential
SDTQ600 model thermal analyzer equipment. The fuel was pyrol-
factor.
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
2. Experimental 100 mL/min. This nitrogen flow ensured an inert atmosphere on
the sample during the run, while the small amount of sample
2.1. Preparation of RDF and the slow heating rate ensured that the heat transfer limitations
can be ignored.
RDF used in this study was provided from ISTAÇ Co. Compost
and Recovery Plant in Istanbul-Turkey and the main fractions were 3. Results and discussion
identified as textile (66%), paper (17.1%) and plastic derivatives
(13.3%). 3.1. Characterization of the raw material
The feedstock was first dried in open containers under labora-
tory conditions and then in an oven at 60 °C to prevent some struc- One of the important parameters that affect the yield of the
tural changes at micro-level. After drying process, raw material thermal system is the moisture content of the chosen fuel. As
was grinded, sieved to the particle size less than 250 lm and par- can be seen from Table 2, the moisture content of RDF was deter-
ticles were shaken very well to make a more uniform distribution mined as 7.1% which seems appropriate for the system. Addition-
of the particles. After the preparation step, characterization tests ally, ash yield is another point, since it has negative impact on
were carried out. the systems. The ash content of RDF was determined as 15.6%
which seemed considerably higher compared to other solid fuels
2.2. Characterization of RDF such as biomass. However, this was an expected outcome, since
RDF is the residual organic part along with some inorganics of
Characterization studies of RDF were carried out by applying municipal solid wastes and known with its high calorific
proximate, ultimate and component analyses as well as determina- value despite the fact that high ash content. Even though the
tion of the calorific value. The proximate analysis was carried out
in TA Instruments SDTQ600 model thermal analyzer equipment.
Table 2
This equipment has 0.1 lg balance sensitivity, a temperature range Proximate, ultimate and component analysis results (%wt, dry basis).
of up to 1500 °C platinum/platinum–rhodium thermocouples, and
temperature sensitivity of 0.001 °C. The reference material used as Proximate analysis
the benchmark in this equipment is thermally inactive alumina. Moisture (as received) 7.1
About 10 mg of fuel was placed in platinum pans and then the Volatiles 71.5
Ash 15.6
heating was programmed according to ASTM standards. In spite
Fixed C* 12.9
of the fact that it is highly difficult to take a representative sample
Component analysis
of 10 mg from a bulk, the limitations of the thermal analyzer
Extractives 10.2
necessitated this and to check the repeatability of the results the Lignin 27.4
experiments were repeated three times. Component analysis of Holocellulose 62.3
RDF was carried out analytically. Elimination of extractives to get Ultimate analysis (dry ash free)
the extractive-free bulk was performed in accordance with ASTM C 58.0
D1105 (2013). At the beginning, 10 g of sample (<0.250 mm) was H 7.3
N 1.2
extracted with benzene-ethanol (1:2, v/v) mixture for 4 h in soxh-
S 0.7
let extractor according to TAPPI, T264 om-97 (TAPPI, 1997). In the Oa 32.8
following step, sample was extracted with ethanol (95%) for 4 h in H/Cb 1.50
order to remove benzene. Then, the extracted bulk was washed O/Cb 0.42
with ethanol, hot and cold distilled water, respectively. The yield Calorific value (MJ/kg) 17.7
of extractives was calculated from the loss in the mass. The deter- a
Calculated by difference.
b
mination of holocellulose and lignin was carried out using this Atomic molar ratio.
278 Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284
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 cm1. The peak at around 870 cm1 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 cm1 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 cm1 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 cm1. 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 cm1 and this was followed by CAH stretch at 1317 cm1.
The region of the infrared spectrum from 1200 to 700 cm1 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 cm1 can be Fig. 3. TG curves of RDF at different heating rates.
Ö. Çepelioğullar et al. / Waste Management 48 (2016) 275–284 279
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 ex 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
(min1), 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 Jmol1K1) 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 ex 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 eE=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 aÞ1n 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 aÞ1n 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)(1n) 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).
Table 6
Calculated E (kJ/mol) and A (min1) values obtained from Coats-Redfern model.
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 expx
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).
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
Fig. 6. Varying activation energies according to conversion.
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