Received: 26 March 2020 

|  Revised: 23 May 2020 

|
  Accepted: 12 June 2020

DOI: 10.1002/ese3.778

RESEARCH ARTICLE

Isoconversional nonisothermal kinetic analysis of municipal solid

waste, refuse-derived fuel, and coal

Mudassar Azam1,2   | Asma Ashraf2,3  | Saman Setoodeh Jahromy1  | Waseem Raza4  |

Hassan Khalid2  | Nadeem Raza5  | Franz Winter1

1
Institute of Chemical, Environmental
and Bio Science Engineering, TU WIEN,
Abstract
Vienna, Austria The thermal characteristics and kinetic behavior of various solid wastes, including
2
Institute of Chemical Engineering & refuse-derived fuel (RDF) and municipal solid waste (MSW), were investigated as
Technology (ICET), University of the
a potential renewable energy source, in comparison with low-rank coal. The exper-
Punjab, Lahore, Pakistan
3 imental data were obtained in nonisothermal conditions through TGA analysis at
Sharif College of Engineering &
Technology, Affiliated with UET, Lahore, specific heating rates. In addition to thermal characteristics of solid fuels, four iso-
Pakistan conversional (model-free) kinetic methods: a: Kissinger-Akahira-Sunose (KAS), b:
4
State Key Laboratory of Fine Chemicals, Flynn-Wall-Ozawa (FWO), c: Friedman, and d: Vyazovkin were applied to calculate
Dalian University of Technology, Dalian,
China activation energies. In case of solid wastes, it is possible to say that the trend of ac-
5
Govt. Emerson College Affiliated with tivation energies of all isoconversional methods remains almost same in the selected
Bahauddin Zakaryia University, Multan, region of conversion (0.1-0.6 and 0.7-0.9). Whereas in case of coal, Friedman model
Pakistan
exhibits lower and inconsistent values of activation energy than others selected iso-
Correspondence conversional methods. The experimental and modeling results revealed that that solid
Mudassar Azam, Institute of Chemical, wastes (RDF and MSW) can be promising alternative energy sources to encounter
Environmental and Bio Science
Engineering, TU WIEN, Vienna, Austria.
energy crisis and uncontrolled waste disposal issues.
Email: mudassar.azam@tuwien.ac.at
KEYWORDS
coal, isoconversional, model free, MSW, waste

1  |   IN TRO D U C T ION globally still do not have even basic energy infrastructure.4 At
present, Pakistan is a developing country and facing serious
The secure supply of energy sources is a key indicator for the energy crisis with total energy demand and supply of 93.91,
sustainable development of societies. Normally, various types 70.94 Mtoe, respectively.5 Considering, the huge energy sup-
of fossil energy reserves (natural gas, coal, and gasoline) are ply and demand gap, it is highly recommended to explore
the major sources of conventional energy demand. The use sustainable energy alternatives to address the issue of current
of fossil fuel for energy production is posing many problems energy crisis.
including global warming, reduction in fossil energy sources, Coal is one of the abundantly and evenly distributed fossil
and other related environmental issues.1,2 On the other hand, fuel (~65% of the total fossil fuels) around the globe, unlike
the population rise, economics, and rapid industrialization oil and gas reserves which are only present in a fewer regions
have also posed energy and environmental concerns in var- of the world.6 At present, coal is the major source of energy
ious countries.3 It is estimated that about 1.2 billion people and continues to dominate as a main contributor for energy

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original
work is properly cited.
© 2020 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.

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3728    
wileyonlinelibrary.com/journal/ese3 Energy Sci Eng. 2020;8:3728–3739.
AZAM et al.
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     3729

generation in developing countries.7 Pakistan has huge coal steps involved during combustion. Conversely, isoconver-
reserves that nearly approach to 185 billion tons in its dif- sional models address this issue and estimate value of activa-
ferent provinces, especially in Sindh. It is estimated that the tion energy as function of fractional conversion (𝛼) that varies
recoverable coal reserves in Pakistan are about 1.45 thousand continuously till the end of complete combustion.25,26
Mtoe with total production capacity of 2.33 Mtoe per year.8 In this work, the thermogravimetric analysis is carried
The continuous consumption of coal as an energy source can out, following by application of model-free methods to pro-
pose severe environmental concerns due to large amount of pose a set of the kinetic parameters for combustion of coal,
CO2 emission in atmosphere.9 Due to growing concerns of MSW, and RDF, to provide fundamental information for op-
climate change and its associated environmental problems, timization of combustion process. The novel objective was to
authorities related to environmental protection are forcing investigate the variance in thermal decomposition and kinetic
to shift conventional energy sources to renewable energy parameters of locally available sustainable fuels. The thermal
sources to minimize carbon foot print.2,10 behavior and kinetic data of MSW and RDF in comparison
The generation, disposal, and treatment MSW are major with coal with application of isoconversional are rare, it will
concerns in every country. Currently, Pakistan is one of the help researchers and policymakers in great deal regarding
developing countries, experiencing severe environmental is- planning of combustion and cocombustion of these fuels. The
sues that are mostly linked to mismanagement of MSW dis- characteristics and thermogravimetric results of these sam-
posal. The continuous release of greenhouse gases (GHG) ples used for evaluation of kinetics parameters are presented
into the atmosphere due to inadequate landfills facilities ulti- in our previous work.27
mately results in serious environmental issues.11 In Pakistan,
the estimated release of methane into the atmosphere due to
these unusual landfilling practices is about 14.18 Gg per year 2  |  M ATERIAL S AND M ETHOD S
which contributes almost 22 times greater greenhouse effect
than CO2.12 In light of these concerns, energy from waste The preparation of experimental samples (MSW and RDF)
sources is getting much attraction worldwide. Currently, the was based on representative components of MSW collected
most common and adopted strategies of waste disposals are from city Lahore, Punjab, Pakistan, as described in our previ-
landfilling, incineration, sea dumping, and composting.13 ous paper,28 whereas low-rank coal sample was taken from
In the past few years, waste to energy concept in respec- Chiragh reserves located in province of Punjab, Pakistan.
tive technology has gained great attention.14,15 Incineration of Thermogravimetric analysis was performed with the sam-
waste is one of the simplest strategy to convert waste into its ple size of 20  mg in Mettler Toledo (TGA/DSC 1 STAR,
corresponding energy.16 In this regard, a good understanding USA) System. Initially, samples were heated from room tem-
of the combustion process will be of great help in designing perature to 105°C. Four specific heating rates (10, 20, 30,
the incinerators with improved efficiency. The combustion and 40°C/min) were adopted to reach final temperature of
process can be understood carefully by knowing the Kinetic 1000°C. A holding time of 10 minutes and 30 minutes was
parameters. The most popular and simple technique to study insured at temperature of 105°C and 1000°C, respectively.
the combustion kinetic is thermogravimetric analysis (TGA). Synthetic air with constant flow rate of 80 mL/min was pro-
Many researchers have utilized the TGA analysis to evaluate vided for all complete runs of experiments.
kinetics of combustion process in incineration by developing
various kinetic models.17-22 Typically, two kinds of kinetic
models are employed such as model-free (isoconversional) 3  |  KINETIC M ODELING
and model-fitting. In this paper, isoconversional methods were
adopted, as these methods are reflected as more reliable and Generally, for solid particles the rate of reaction is given as
accurate compared to complex data fitting methods that are follows:
generally dependent to type of reaction mechanism and lead to
imprecise data estimation over wide experimental range.17,23,24 d𝛼
= f (T) × f (𝛼) (1)
However, model-free strategy does not depend on a reaction dt
mechanism for fitting of respective thermodynamic data that
ultimately results in precise error-free modeling. Another Here
significant issue is variation of activation energy during the E
f (T) = Ae− RT (2)
combustion process, as combustion process consists of more
than one steps with different activation energies. In model-fit- And α can be ascribed to fractional conversion and de-
ting methods, whole combustion process is characterized by noted as
a single value of activation energy. Thus, value of activation m − mi
𝛼= O
energy obtained is an average value and cannot depict all the mO − m∞ (3)
 |
3730      AZAM et al.

Further, f(α) can be denoted as a function of fractional As for isoconversional models, g(α) is not dependent on
conversion (α). The equation can be simplified in derivative heating rate so,
form using Equation (2) at respective ramping rates for tem-
perature increase. A𝛼 ( ) A ( ) A ( )
I E𝛼 , T𝛼,1 = 𝛼 I E𝛼 , T𝛼,2 = … = 𝛼 I E𝛼 , T𝛼,n (8)
𝛽1 𝛽2 𝛽n
d𝛼 A − RTE
= e f (𝛼) (4)
dT 𝛽 The above equation can be rewritten as follows:

3.1  |  Isoconversional methods n n

( ( ) ( ))
∑ ∑ I E𝛼 , T𝛼,i I E𝛼 , T𝛼,j
∕ = n (n − 1) (9)
i=a j≠i
𝛽i 𝛽j
Many researchers have pointed that the prediction of reaction
kinetics with model-fitting approach always poses inaccu- ( ( ) ( ) )|
rate estimation due to reaction mechanism involvement.29-31
| n n
| ∑ ∑ I E𝛼 , T𝛼,i I E𝛼 , T𝛼,j |
|n (n − 1) − ∕ | = minimum
Conversely, isoconversional approach does not follow any
≠
| 𝛽i 𝛽j |
| i = a j i |
preassumption for reaction mechanism that ultimately re- | |
(10)
duces the possibility of errors for homogenous and hetero-
geneous combustion kinetic data. This model-free approach The integral value of I(Eα, Tα,i) can be evaluated by re-
can play an effective role to estimate activation energies in solving a complex integration or by using Senum-Yang poly-
wide range of experimental temperatures and conversions. nomial 4th-degree approximation44 as described below.
The isoconversional methods applied in this study are Flynn-
Wall-Ozawa (FWO), Friedman, Kissinger-Akahira-Sunose (
−x
)
x3 + 18x2 + 86x + 96
p (x) = exp × 4 (11)
(KAS), and Vyazovkin. x x + 20x3 + 120x2 + 240x + 120

x can be taken as equivalent to α in the previous equa-

3.1.1  |  Friedman differential model tion. The activation energies can be calculated by substitu-
tion of experimental values (Tα and β) in Equation (10) with
Taking natural logarithm on Equation (4) will result in fol- condition of changing Eα to approach a minimum value. The
lowing form of equation minimum value was achieved for each value of α to estimate
[ ( ) ] activation energy dependency on conversion. This strategy
d𝛼 [ ] E
ln 𝛽 i = ln A𝛼 × f (𝛼) − 𝛼 (5) has also been reported reliable and consistent in various stud-
dT 𝛼,i RT𝛼,i
ies reported in the literature.25,31,32,36,40,45-47

Equation  (5) present differential isoconversional model

and is known as Friedman model. Many researchers have em- 3.1.3  |  Flynn-Wall-Ozawa method
ployed this approach for approximation of reaction kinetics in
solid particles.20,32-43 This method was proposed by cumulative contribution of
Eα (apparent activation energy) can be calculated for re- Flynn, Ozawa and Wall by the modification of Doyle contri-
spective conversion value (α) by estimating resultant slope of bution as described in Equation (12).
Equation (5) and 1/Tα,i. [ ]
( ) A𝛼 E𝛼 E
ln 𝛽 i = ln − 5.331 − 1.0516 𝛼 (12)
Rg (𝛼) RT𝛼i
3.1.2  |  Vyazovkin integral model
The resultant straight lines by plotting Equation  (12) vs
This model-free approach is also known as nonlinear integral 1/Tαi will give the estimation of activation energy at different
method that is outcome of revised expression of temperature conversion levels.35,37,38,45,48
integral from Equation (6).

3.1.4  |  Kissinger-Akahira-Sunnose method

T

𝛽∫
A E
(6)
g (𝛼) = e− RT dT
0

[ ]
A ( ) 𝛽i A𝛼 R E
g (𝛼) = I E𝛼 , T𝛼,i (7) ln = ln − 𝛼
𝛽i T2𝛼i E𝛼 g (𝛼) RT𝛼i (13)
AZAM et al.
|
     3731

The resultant plot of Equation (13) vs 1/Tαi yields slope these samples has dissimilar degradation profiles, as shown
equal to −Eα/R. The application of this model has been re- in Figure  2. The physical composition of simulated solid
ported satisfactory by many researchers.41,49-52 wastes is presented in Table 1. The proximate and ultimate
analysis presented in Table 2 showed that all the fuels were
low in content of moisture and fixed carbon, as a result, first
4  |  R E S U LTS A N D D IS C U S S ION and third region showing less prominent weight loss. As ex-
pected, apart from the heating rate, the decomposition pro-
4.1  |  TG and DTG profiles cess of MSW and RDF shows a very high weight loss due to
high reactivity, whereas coal TG behavior is slower, which is
TG and DTG curves for coal, MSW, and RDF were observed characterized by a low volatile content and high ash content.
individually, as function of time and temperature range of The mass percent of ash content of coal is ~32.1% that is
25°C to 1000°C. Figures 1 and 2 present TG and DTG trends much higher than that of MSW (~11.1%) and RDF (~12.9%).
of the sample fuels at specific heating rates (10, 20, 30, and The decomposition pattern of solid wastes showed that a
40°C/min). It is important to define the extent of conversion number of individual shoulders or peaks appeared at lower
through an observable adequate physical property. According heating rate, which disappear or overlap as the heating rate
to different thermal decomposition studies, among all physi- is increased. The thermal decomposition of coal results in
cal properties, mass loss is the most suitable physical prop- one major peak, due to release of carbon-containing vola-
erty to describe the dependency of the overall rate constant tile matter,58 whereas existence of different peaks in case of
on the temperature. The is mainly due to fact that the mass solid wastes is credited to the heterogeneous nature of these
loss during the combustion process does not depend upon the wastes fuels. The solid wastes show prominent weight loss
heating rate.53-56 between 180°C and 550°C, whereas the coal weight loss is
It is broadly accepted that fuel decomposition process mainly between 400°C and 770°C at heating rate of 20°C/
mainly contains three stages over complete range of tempera- min. The solid wastes exhibit multicomponents sharp weight
ture, which are (a) moisture drying, (b) major loss of weight, loss peaks in the fast devolatilization stage. The weight loss
due to release of volatile organic matter, and (c) consecutive of first peak of MSW (~43.1%) and RDF (~39.8%) is mainly
slow combustion of fixed carbon.57 Last two steps, certainly, contributed by the highly volatile and easily decomposable
are linked with chemical composition (homogeneous/het- components in solid wastes such as biodegradables (cellulose
erogeneous nature) of these samples, as main constituent of and hemicellulose), textile, and paper with temperature range

F I G U R E 1   TG curves of coal, MSW, and RDF samples at different heating rates

3732     
| AZAM et al.

Coal β = 10 °C/min MSW β = 10 °C/min

β = 20 °C/min 0.40 β = 20 °C/min
0.25
β = 30 °C/min β = 30 °C/min
dw/dt (%S–1 )

0.20 0.30

dw/dt (% S-1)
β = 40 °C/min β = 40 °C/min
0.15
0.20
0.10
0.10
0.05

0.00 0.00
0 1000 0 200 400 600 800 1000
Temperature (°C) Temperature (°C)

RDF β = 10 °C/min
β = 20 °C/min
0.60
β = 30 °C/min
dw/dt (% S–1 )

β = 40 °C/min
0.40

0.20

0.00
0 200 400 600 800 1000
Temperature (°C)

F I G U R E 2   DTG curves of coal, MSW, and RDF at different heating rates

T A B L E 1   Physical percentage
Simulated Simulated
(average) of MSW, simulated MSW, and
Order Material True MSW (%) MSW (%) RDF (%)
simulated RDF27
1 Biodegradable 56 69 -
2 Nylon plastic bags 11 14.5 47.3
3 Textile 9.1 11.5 37.6
4 Paper 2.8 4.1 13
5 Noncombustible 6.3 - -
6 PET 0.7 0.9 1.8
7 Tetrapak 1.1 - -
8 Combustibles 6.2 - -
9 Diaper 5.3 - -
10 Hazardous 1.3 - -
11 Glass 0.7 - -

of 180-390°C and 216-376°C, respectively. The second vol- maximum weight loss obtained from TG and DTG curves for
atile release peak from solid wastes mainly corresponds to combustion of the studied samples at different heating rates
combustion of mixed plastic (LDPE, HDPE, and PVC) with are summarized in Table  3. Thermal behavior and charac-
almost same temperature range 388-550°C for MSW and terization studies at specific heating rates are an imperative
RDF. In the carbonization stage, tiny weight loss in MSW criterion for kinetics studies. It is noticed that the heating
and coal is attributed to thermal decomposition of lignin and rate affects the TG and DTG curves.62 At specific heating
char present in samples. This result is in agreement with the rates, contact of fuel particles varies, which change the curve
findings of researchers using MSW and RDF as fuel samples shape and combustion characteristics considerably, as indi-
in TGA.16,17,59-61 cated in Figures  1 and 2. It is evident from analysis, with
The combustion characteristic parameters such as the the increasing heating rates, TGA curves are shifted toward
initial temperature, burnout temperature, and temperature at the right and DTG curves are slightly shifted toward higher
AZAM et al.
|
     3733

T A B L E 2   Proximate & ultimate analysis of samples27

Proximate analysisa  Ultimate analysisb 

H2O VM Ash F.Cc  HHV

Order Samples (%) (%) (%) (%) C (%) H (%) Oc  (%) N (%) S (%) (kJ/kg)
1 Biodegradeable 4.1 77.5 10 8.4 62.5 8.0 28.8 0.4 0.1 10 338
2 Textile 2.94 81.23 5.01 10.82 58.4 4.98 35.7 0.6 0.16 20 392
3 Nylon plastic bags 0.02 93.71 5.52 0.741 78.7 12.4 8.7 0.12 0.02 40 416
4 Paper 3.44 75.85 18.82 1.89 50.5 6.41 42.3 0.22 0.55 16 239
5 PET bottles ND 92.26 0.19 7.55 62.0 4.04 33.9 0.05 0.01 23 060
6 MSW 3.3 79.7 9.1 7.2 63.6 8.1 27.1 0.4 0.11 15 978
7 RDF 1.6 86.2 7.07 4.7 66.9 8.7 23.8 0.32 0.14 29 429
8 Coal 1.84 38.8 31.7 27.53 80.7 3.6 9.6 1.02 5.04 30 362
a
Air-dried basis.
b
Dried ash-free basis.
c
Calculated by difference.

T A B L E 3   The combustion characteristics parameters for Coal, zone/ thermal lag is observed for burnout temperature values.
MSW, and RDF from TG and DTG curves The higher burnout temperature of coal is attributed to higher
ash content, which again is main factor for further character-
Heating rate Ti Tf T1 T2
Sample (°C/min) (°C) (°C) (°C) (°C) ization of burnout process. It is evident that the heating rate
had a significant effect on the weight loss rate during com-
Coal 10 443 713 562 -
bustion process. In combustion process of these samples, the
20 444 727 578 -
higher heating rates result in lower weight loss (conversion)
30 451 743 599 - and high reactivity. The reactivity during combustion process
40 460 778 610 - is proportional to the height of DTG peak. In case of coal,
MSW 10 219 560 301 455 as heating rate increased, the weight loss rate at same tem-
20 223 573 313 461 perature is increased. As revealed in Figure 2, as heating rate
30 225 586 325 470 increased from 10 to 40°C/min, the weight loss rate increased
40 230 598 329 479 from to 0.1 to 0.19%  S−1. Even though, similar trend was
RDF 10 238 556 316 465
observed in case of MSW and RDF, as greater weight loss
rate was recorded in both peaks with increasing heating rate.
20 242 559 334 473
However, in solid wastes overlapping of peaks was prominent
30 245 563 342 481
at higher heating rates. This may be explained on the basis of
40 255 570 367 495 residence time during the combustion process. At low heat-
Note: Ti: the ignition temperature, Tf: burnout temperature, T1, T2: temperature at ing rate, more residence time results in efficient and effective
maximum weight loss rate of first peak and second peak. heat transfer compared to higher heating rate. Similar results
of combustion process are reported by researcher using dif-
peak temperatures without changing the thermal profile. This ferent heating rate such as MSW,16,61 RDF,17 and coal.20 The
shows that the overall reaction rate in decomposition process reactivity of these fuels was investigated at peak tempera-
is a function of temperature only.55 Consequently, all the tures, resulting an order of RDF > MSW > coal.
combustion characteristic parameters were shifted to higher
values, showing thermal lag at increasing heating rate. This
might be credited to heat and mass transfer limitations due to 4.1.1  |  Kinetic analysis
poor thermal conductivity of materials present in samples.59
Among the selected fuel samples, coal has highest ignition In order to describe the dependence of the activation energy
and burnout temperature, while MSW and RDF have con- (E𝛼 ) on the conversion degree, four models from model-free
siderably low and slight close range of these temperatures. kinetic methods were tested. The isoconversional plots of
The coal ignition temperature at four heating rates (10, 20, KAS, FWO, and Friedman for conversion (𝛼) range of 0.1-
30, and 40°C/min) varies from 443°C to 460°C. For MSW 0.9 are shown in Figure 3. According to reported studies, the
and RDF, this thermal lag varies from 219°C to 230°C and parallelism of these lines is accredited to the same reaction
238°C to 255°C, respectively. Similar shift of temperature mechanism and kinetic behavior.63 For considered range of
 |
3734      AZAM et al.

F I G U R E 3   Plots for kinetic model. Friedman, FWO, KAS

conversion (𝛼), the activation energy (E𝛼) values were ob- for estimation of kinetics. The average values of obtained E𝛼
tained from individual slopes based upon linear model equa- from isoconversional methods are summarized in Figure 4.
tions. The obtained E𝛼 and correlation coefficient (R2) values Many researchers have presented such findings about iso-
together with the values from nonlinear Vyazovkin proce- conversional models.17,25,29,32,64 Activation energy means the
dure are summarized in Tables  4-6. The correlation coeffi- minimum energy requirement that must be acquired to start a
cient of obtained E𝛼 is close to unity, which indicates that reaction. This indicates, the reaction with high activation en-
these models had capability for better fit of experimental data ergy needs a high temperature or an extended reaction time.

T A B L E 4   Dependency of activation energy (E𝛼, kJ/mol) of coal T A B L E 5   Dependency of activation energy (E𝛼, kJ/mol) of MSW
on conversion degree from model-free methods on conversion degree from model-free methods

Coal MSW

KAS FWO FM VK KAS FWO FM VK

𝜶 R2 E𝜶 R2 E𝜶 R2 E𝜶 E𝜶 𝜶 R2 E𝜶 R2 E𝜶 R2 E𝜶 E𝜶

0.1 0.999 151.3 0.999 155.8 0.997 124 151 0.1 0.954 239.9 0.957 236.5 0.968 232.1 240
0.2 0.999 121.3 0.999 127.9 0.994 90.7 121 0.2 0.980 210.3 0.981 208.8 0.992 186.1 210
0.3 0.997 102.6 0.997 110.6 0.988 74.1 103 0.3 0.997 186.5 0.997 186.5 0.996 184.1 186
0.4 0.995 90.6 0.997 99.5 0.984 57.7 91 0.4 0.991 172.9 0.992 173.9 0.969 168.2 173
0.5 0.994 81.1 0.996 90.7 0.978 46.4 82 0.5 0.952 179.1 0.957 180.2 0.941 175.1 179
0.6 0.991 72.9 0.994 83.2 0.976 39.4 73 0.6 0.873 376.2 0.879 368.5 0.822 379.9 205
0.7 0.988 65.7 0.993 76.6 0.919 63.9 66 0.7 0.973 243.2 0.976 242.8 0.980 245.2 243
0.8 0.984 59.9 0.991 71.5 0.975 59.8 61 0.8 0.998 134.4 0.999 139.8 0.986 134.1 134
0.9 0.980 56.8 0.989 68.9 0.954 56.7 58 0.9 0.993 108.4 0.995 115.6 0.933 108.5 109
Average 89.2 98.3 68.1 89.5 Average 205.6 205.8 201.4 186.5
AZAM et al.
|
     3735

T A B L E 6   Dependency of activation energy (E𝛼, kJ/mol) of RDF trend of E𝛼 value obtained by these isoconversional methods
on conversion degree from model-free methods is very consistent. The E𝛼 values of solid wastes reported in
RDF the literature show great variation due to nonuniform compo-
sition of such kind of fuels. In case of solid wastes with the
KAS FWO FM VK
conversion rates increased from 0.1 to 0.9, two obvious peaks
𝜶 R2 E𝜶 R2 E𝜶 R2 E𝜶 E𝜶 were observed at 𝛼: 0.1 and 0.6, respectively. As it can be
0.1 0.973 115.5 0.977 118.7 0.977 123.7 115
observed from first peak of MSW, between 0.1 ≤ 𝛼 ≤ 0.5 for
temperature range between 180 and 365°C shows a progres-
0.2 0.977 138.4 0.979 141.1 0.984 156.7 138
sive decrease in the activation energy from 239 to 180  kJ/
0.3 0.981 154.8 0.983 156.9 0.986 163.4 155
mol, whereas first peak in case of RDF shows a progressive
0.4 0.982 156.5 0.984 158.7 0.976 152.1 156
increase in the activation energy (118-165 kJ/mol) for same
0.5 0.996 166.1 0.997 167.9 0.937 160.2 150 conversion degree with shorter temperature range between
0.6 0.877 289.3 0.885 285.8 0.950 291.5 339 226 and 356°C. This behavior is credited to complex mul-
0.7 0.999 194.6 0.999 196.5 0.714 203.2 195 tistep reaction during biomass decomposition of MSW. As
0.8 0.923 127.1 0.935 132.3 0.817 129.6 127 mentioned earlier, the first peak is attributed to combustion
0.9 0.995 268.1 0.995 266.8 0.982 268.6 268 of volatile matter and second peak corresponds to combus-
Average 178.9 180.5 183.2 182.5 tion of different organic compounds which offer greater
energy barrier. Finally, both MSW and RDF at conversion
degree 0.6 observed a maximum increase in activation en-
Figures  5-7 show dependence of activation energy on the ergy values, ~365 kJ/mol and ~290 kJ/mol at corresponding
extent of selected fuel conversion. Comparison of obtained temperature of 445°C and 405°C, respectively. This interval
E𝛼 showed that Vyazovkin, FWO, and KAS methods formed 0.6 ≤ 𝛼 ≤ 0.9 is attributed to components of solid wastes with
closer results than Friedman. The coal E𝛼 at 𝛼 0.1 was found lower activity (biochar) and complex decomposition phase of
as 151.3, 155.8, 124, and 151 kJ/mol for each model as per PVC, which dictate the rate of reaction and need more energy
given order in Table 4. For interval of 𝛼 0.2-0.9, the activation under high temperature.65,66 For solid wastes at conversion
energies were close to each other with decreasing trend. This range (𝛼  =  0.1-0.5), smaller fluctuations in E𝛼 values with
thermal event at temperature ~400°C and conversion degree increasing trend were observed, whereas at conversion range
~0.1 is characterized by slow reaction rate with highest en- (𝛼 = 0.6-0.9), higher fluctuations with decreasing trend were
ergy barrier ~155 kJ/mol, which means that in case of coal observed throughout the process. This fluctuation in the E𝛼
the energy requirement for the main mass combustion was value is generally attributed to heterogeneous nature of solid
less after initializing the reaction. It is noticeable that the coal wastes, which leads to complex reaction system including
activation energy values obtained from Friedman differen- parallel, competitive, and complex reaction scheme.57
tial method are slightly lower than integral methods. In case It is possible to say that the average activation energy of
of MSW and RDF, activation energy analysis shows tedious solid wastes obtained from all considered isoconversional
dependency on conversion and specifies the typical behavior methods is very close, compared to average activation en-
of complex parallel reaction, involving multiple and consec- ergy of coal, as illustrated in Figure 7. It is important to note
utive degradation steps. For solid waste fuel, the changing that the MSW E𝛼 by the all isoconversional methods were

Coal MSW RDF

250

200
E (kJ/moL)

150

100

50

0
F I G U R E 4   Average activation energy KAS FWO FM VK
from model-free method Model-free methods
3736     
| AZAM et al.

205.6, 205.8, 201.4, and 186.5 kJ/mol with the given order, less volatile content in MSW than RDF.67 Conferring to ki-
which was 26.7, 25.3, 18.2, and 4.0 kJ/mol higher than that netic analysis by all four isoconversional models, the selected
of RDF. This means, on average, more energy is required in fuels could be set in subsequent order of activation energy
the combustion process of MSW. It might be the result of MSW > RDF > coal.

Coal F I G U R E 5   Activation energies based

on coal conversion
180
160
140
120
E (kJ/moL)

100
80
60
40
20
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

KAS FWO FM VK

MSW F I G U R E 6   Activation energies based

on MSW conversion
400
350
300
250
E (kJ/moL)

200
150
100
50
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

KAS FWO FM VK

RDF
400
350
300
250
E (kJ/moL)

200
150
100
50
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

F I G U R E 7   Activation energies based

KAS FWO FM VK on RDF conversion
AZAM et al.
|
     3737

5  |   CO NC LU S ION g (𝛼) Integral Form of Reaction Model

R2 Correlation Coefficient
According to TG and DTG analysis, it was observed that n order of reaction
thermal decomposition of coal sample comprised single
stage, whereas thermal decomposition of MSW and RDF CONFLICT OF INTEREST
involved complex set of multiple and simultaneous steps re- The authors have no potential conflicts of interest to declare.
lated to decomposition of biowaste (ie, food waste, textile,
and paper) and plastic. The rate of thermal decomposition ORCID
of all solid fuels was found increasing with the increase in Mudassar Azam  https://orcid.org/0000-0002-4557-2817
heating rates. The dependency of the apparent activation en- Franz Winter  https://orcid.org/0000-0001-9854-3836
ergy (E𝛼 ) on conversion (𝛼) was estimated through isoconver-
sional approaches using three integral methods (Vyazovkin, R E F E R E NC E S
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