Process Safety and Environmental Protection 160 (2022) 130–138

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Process Safety and Environmental Protection

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Kinetics and thermodynamic study of Calligonum polygonoides pyrolysis

using model-free methods ]]
]]]]]]
]]

⁎ ⁎
Asma Nasrullah a,b,c, Amir Sada Khan c, , Shahan Zeb Khan c, Abrar Inayat d, ,
Taghreed M. Fagieh e, Esraa M. Bakhsh e, Kalsoom Akhtar e, Sher Bahadar Khan e,f, Israf Ud Din g
a
Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar, Perak, Malaysia
b
National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan
c
Department of Chemistry, University of Science & Technology, Bannu 28100, Khyber Pakhtunkhwa, Pakistan
d
Department of Sustainable & Renewable Energy Engineering, University of Sharjah, PO Box 27272, Sharjah, United Arab Emirates
e
Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia
f
Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia
g
Department of Chemistry, College of Science and Humanities, Prince Sattam Bin Abdulaziz University, P.O. Box 173, Al-Kharj, Saudi Arabia

a r t i cl e i nfo a bstr ac t

Article history: Pyrolysis kinetics was carried out for Calligonum polygonoides (C. Polygonoides) in an inert atmosphere at
Received 14 December 2021 three different heating temperatures such as 10, 15, and 20 °C/min using thermogravimetric analysis.
Received in revised form 18 January 2022 Physicochemical properties were studied using bomb calorimeter, elemental analyzer, and Fourier
Accepted 31 January 2022
Transform Infrared Spectroscopy. C. Polygonoides have a calorific value of 16.33 MJ/kg. Gas chromato­
Available online 8 February 2022
graphy–mass spectrometry was used to identify gases produced during pyrolysis. Thermogravimetric
analysis was used to investigate the pyrolysis characteristics of biomass. Activation energy for the three
Keywords:
Biomass zones of pyrolysis were determined using Kissinger and Ozawa model-free methods. Activation energy
Thermogravimetric analysis calculated for zone I, zone II and zone III using Ozawa and Kissinger model was 133.73, 164.50, 254 KJ/mol
Kinetics parameters and 135.61, 165.88, and 253.00 KJ/mol, respectively. Thermodynamic parameters such as enthalpy, entropy,
Pyrolysis and Gibbs free energy were calculated for the three different zones. Kinetic and thermodynamic study
Kinetics models confirmed that C. Polygonoides can be used as useful and potential bioenergy feedstock.
© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.

1. Introduction reused as a source of energy and chemicals. Biomass comprises

Energy resources are vital to the industrial revolution, because
existing natural conventional energy resources such as natural gas,
oil, and coal are limited. As a result, the need for the exploration of
alternative energy resources is essential for fulfilling our massive
energy requirements. Coal and oil, for example, are traditional en­
ergy sources that pollute our environment by producing toxic gases
during burning. Thermochemical conversion of biomass to fuel is
considered as a potential alternate source of energy (Khan et al.,
2018). Biomass-derived gas and oil can be used to replace the natural
gas and other fuels. Biofuels are ecologically friendly and a relatively
clean source of energy (they have minimal sulfur and nitrogen
content) (El-Sayed and Mostafa, 2014; Muñoz et al., 2011). Different
low biomass sources, such as forestry and agricultural waste, can be
⁎
Corresponding authors.
E-mail addresses: askhan@ustb.edu.pk (A.S. Khan),
ainayat@sharjah.ac.ae (A. Inayat).
cellulose and other high-energy organic molecules, and it is used as
a feedstock for the production of numerous chemicals and fuels (Ab
Rahim et al., 2020; Khan et al., 2018).
Wood is used for a variety of domestic and industrial applica­
tions, including construction materials (houses, furniture, transpor­
tation, and so on), telephone and electrical poles, and fuel.
Whenever these items reach the end of their useful lives, they are
discarded and considered waste materials. Cellulosic waste is also
created after cleaning gardens and woods, in addition to this major
source. Such residual wood produced by different ways can be re­
utilized if properly processed using suitable methods and technol­
ogies (Muhammad et al., 2015; Martinez et al., 2019). For the
conversion of biomass to high-energy fuels, a variety of efficient and
cleaner methods have been developed. Pyrolysis, torrefacation, fer­
mentation, combustion, and gasification are examples of these
technologies, among which torrefacation and pyrolysis being ther­
mochemical processes. Thermal breakdown of biomass occurs
during such processes. These technologies could be used to recover

https://doi.org/10.1016/j.psep.2022.01.084
0957-5820/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
A. Nasrullah, A.S. Khan, S.Z. Khan et al.
energy from waste biomass in a cost-effective way. Among the
aforementioned thermal processes, biomass pyrolysis is the most
important source of energy and chemicals, as it occurs in an inert
atmosphere and lowers our dependence on fossil fuels (Hoang et al.,
2021; Zadeh et al., 2020). In pyrolysis, biomass is converted into li­
quids, gases, and char. This phenomenon is complex, involving a
series of reactions influenced by various factors, such as tempera­
ture, heating rate, residence time, pressure, particle size, particle
moisture, and composition of biomass. The process of pyrolysis
(673–873 K) occurs at low temperature compared with gasification.
Low temperature and elongated residence time lead to the forma­
tion of char, whereas long residence time and high temperature
promotes formation of gas (Singh et al., 2019). Thermal behavior and
thermal decomposition of biomass can be studied by use of ther­
mogravimetric analysis (TGA), which is a very useful and effective
technique that provides rapid quantitative methods for the study of
thermal processes under isothermal and non-isothermal conditions.
Thus, TGA can provide a means of calculating the effective kinetics
parameters for biomass pyrolysis. These kinetic parameters include
energy of activation, order of reaction, and the pre-exponential
factor. Among these parameters, activation energy provides in­
formation about the reactivity of the wood materials (He et al.,
2019). Kinetic parameter can be determined globally by TGA, based
on Kissinger (Kissinger, 1957), Ozawa (Ozawa, 1965), Flynn–Wall
(Flynn and Wall, 1966), and Friedman’ methods (Friedman, 1964),
which are models of ‘‘free kinetics’’ giving straight lines with slopes
-Ea/R. The most important application of model-free methods is
simplicity and low chances of errors.
Lignocellulosic biomass contains three different components
such as hemicellulose, cellulose and lignin which are bound with
each other by covalent and non-covalent bond (Khan et al., 2016). At
lower temperature, the biomass degradation is due to hemicellulose.
Main degradation of biomass can taking place above 300 °C, called
active pyrolysis zone. This main degradation is due to cellulose de­
gradation. The slow degradation of lignocellulosic biomass after
active zone can be dedicated to lignin pyrolysis. These three com­
ponents have different structures and different thermal behaviors
(Khan et al., 2016). Until now, the kinetic study for lignocellulosic
biomass using TGA analysis has been performed together for all
three zones. To the best of our knowledge, there is no kinetic and
thermodynamic study for pyrolysis of C. Polygonoides using TGA ki­
netics performed for three different zones. Therefore, it is required
to perform the pyrolysis kinetics and thermodynamic study for three
zone of C. Polygonoides using TGA data.
The genus Calligonum, which belongs to the Polygonaceae family,
has roughly 80 species which found in southern Europe, northern
Africa, and western Asia. This plant is abundantly available in district
Lakki Marwat, KPK, Pakistan, and its proper utilization will solve
future energy problems (Nasrullah et al., 2016). In the present work,
GC-MS analysis, elemental analysis and calorific value were de­
termined to check its feasibility towards pyrolysis process. Kinetics
and thermal behavior for C. Polygonoides under pyrolytic conditions
were determined. TGA in an inert N2 atmosphere was utilized in
these studies, and thermal curves were obtained at various heating
rates under non-isothermal conditions. Different non-isothermal
kinetics free models were used for the three different zones of C.
Polygonoides to determine kinetics parameters. Apart from kinetic
parameters, various thermodynamics functions such as Gibbs free
energy, entropy and enthalpy were calculated for the three different
zones.
2. Experimental method
C. Polygonoides was selected from local agricultural former land
of Lakki Marwat, Khyber Pakhtunkhwa Pakistan. C. Polygonoides
biomass is abundantly available in this area and famous for its
131
Process Safety and Environmental Protection 160 (2022) 130–138
smooth burning and therefore is used for domestic cooking purpose.
The sample was washed with water to remove sand and dust at­
tached to its surface, cut into small pieces with sharp knife and then
dried in sun light in an open atmosphere. The biomass sample was
placed in an oven at 105 °C to become dry and then grinded into fine
powder with grinding machine. The thermal behavior and kinetics
parameters of C. Polygonoides powder having size 250 µm were de­
termined using TGA (Perkin Elmer, STA 6000) in temperatures ran­
ging from 50° to 850°C at three different heating rates such 5, 10, and
20 °C/min in an inert atmosphere having flow rate of 20 mL/min of
nitrogen. The biomass TGA was divided into three different zone
such as zone I (190–415 °C), zone II (415–555 °C) and zone III
(555–800 °C). Pyrolysis kinetics and thermodynamics were per­
formed for each zone. The CV of C. Polygonoides was determined
using a bomb calorimeter (IKA-WERKE of GMBH & CO., KG).
Pyrolysis gas chromatography–mass spectrometry (Py/GC–MS)
analysis was applied for the determination of the type and amount
of compounds liberated during pyrolysis of Calligonum polygonoides.
FTIR (PerkinElmer spectrum one 2000 Explorer) spectroscopy was
used to determine functional groups present in biomass sample. FT-
IR spectra were recorded in the range of 4000–400 cm−1 with five
scanning. The elemental composition of biomass was determined
using a CHNOS elemental analyzer (varion EL III).
2.1. Kinetic theory and modeling
The process of devolatilization is considered as a single-step re­
action according to the one-step global model.
k
Cellulose Glucose + Char (1)
Or
Biomass Volatiles + Char (2)
Here, “volatiles” mean char and all gases evolved during pyr­
olysis. k is the rate constant of reaction when biomass is converted
into char and volatiles. The thermal degradation of lignocellulosic
biomass is not simple and contains large numbers of series and
parallels reaction, which make a kinetic study very complicated. In
the present study, Kissinger and Ozawa methods were used for
biomass pyrolysis. The merits of these two non-isothermal methods
are their simplicity, fast calculation, and non-requirement of ap­
parent activation energy calculation for each conversion value. These
two methods are frequently used for the thermal degradation study
of lignocellulosic biomass to calculate various kinetic parameters
using multiple heating rates.
In the non-isothermal decomposition of biomass, the relation­
ship between k and temperature is given by the following form of
Arrhenius equation:
k = Ae( )
Ea
RT (3)
d /dt = (T ) f ( ) (4)
= Ae( )f (
d Ea
RT )
dt (5)
Where k represents the rate constant, A (min−1) denotes the pre-
exponential factors, Ea denotes the activation energy (kJ mol−1), R is
the gas constant (8.314 J.K−1.mol−1), T is the absolute temperature
(K), α is the degree of biomass conversion, t is time, k(T) is the rate
constant of biomass conversion, and f(α) is the conversion factor
denoting the reaction model. The degree of conversion α is mathe­
matically defined as
mo m
=
m mf (6)
A. Nasrullah, A.S. Khan, S.Z. Khan et al. Process Safety and Environmental Protection 160 (2022) 130–138

where mo is the starting mass of sample, m is the mass of pyrolyzed 2.2.3. Invariant kinetic parameter (IKP) method
sample at a given time, and mf is the mass of final residual after The kinetic analysis of some non-isothermal data performed by
thermal decomposition. The combination of Eqs. (2) and (3) give a the IKP method (Purnomo et al., 2020). This effect is confirmed from
key and fundamental expression shown by Eq. (5) to calculate ki­ the straight line plot of ln A vs. Ea using the following equation:
netic parameters based on TGA results. V +b*
ln A= a* V ·Ea (14).

d Ea
= f ( ). A. e RT 2.2.4. Thermodynamics study
dt (7)
The following equation was used for the calculation of pre-ex­
The unknown terms (A, Ea, and f ( )) in Eq. (7) are important ponential factor (Vlaev et al., 2008):
terms used to characterize biomass pyrolysis reactions.
d
For non-isothermal reactions where the heating rate ( = dt ) is ex . kB . Tmax S0
A= . exp
constant, the above equation is expressed as h R (15)

d d Ea Changes in various thermodynamic parameters such as entropy

= = f ( ). A. e RT
dt dt (8) (∆S°), enthalpy (∆H°), and Gibbs free energy (∆G°) were calculated
using Eqs. (16–18), respectively (Janković et al., 2014):
Expressions of the function f (α) and its derivative f (α) are used
to describe a solid-state first-order reaction; thus, many authors A. h
S o = R. ln
restrict f (α) to the following expression: e. x. KB. Tmax (16)
f ( ) = (1 )n (9) Ho = Ea R. Tmax (17)
where n is the reaction order. Substituting expression (6) into Eq. (5) Go = Ho Tmax So (18)
gives the expression of reaction rate in the form
where A is the pre-exponential factor, e is 2.7183), x is the transition
d Ea factor, kB is the Boltzmann factor (kB = 1.38065 × 10−23) J/K, h is
= A. (1 )n . e RT
dt (10) Planck’s constant (h = 6.62607 × 10−34 J/s), R is the ideal gas constant
(R = 8.314 J/K.mol), Ea is activation energy, and Tmax is the peak
For non-isothermal TGA experiments at linear heating rate β = dT/
temperature obtained from the DTG curve.
dt, Eq. (7) can be written as

d Ea 3. Results and discussion

= A/ . (1 )n . e RT
dt (11)
3.1. CV
Ea for biomass are determined applying non-isothermal TGA
analysis. Based on this method, kinetic parameters are obtained
CV is the most important property for determining the quantity
from a set of experimental data obtained using various heating rates.
of energy content of biomass. Fig. 1 shows the CVs of C. Polygonoides
and other biomass. C. Polygonoides has a considerable CV, in agree­
2.2. Model-free methods ment with a previously reported CV (Núñez-Regueira et al; Sajdak
et al., 2014). The considerable CV of C. Polygonoides make it an at­
2.2.1. Kissinger method tractive, alternative source of energy and fuel (Natarajan, 2009).
This model was developed by Kissinger for the determination of
the kinetic parameters of solid-state reaction without determining 3.2. Chemical composition
the reaction mechanism (Kissinger, 1957). This model-free non-iso­
thermal method used to determine kinetic parameters does not The elemental composition (carbon, hydrogen, nitrogen, and
require calculation of Ea for all conversion values. Instead, Ea is ob­ sulfur contents) and elemental ratios (H:C and O:C) of Calligonum
tained from a plot of ln (β/T2max ) against 1000/Tmax, where Tmax is the
peak temperature in the derivative thermogravimetric (DTG) curve.
Kissinger method is based on the following equation:

AR E
ln 2
= ln
Tmax E RTmax (12)
Ea
Ea can be determined from the slope (– R
) of linear plot when

ln is plotted versus 1000/Tmax for various heating rate.

T2
max

2.2.2. Ozawa method

This method also describes the thermal decomposition of bio­
mass and allows the calculation of Ea by plotting lnβ against 1000/Tα,
which shows a linear relation with a given value of conversion at
different heating rates. Ozawa method is based on the following
equation (Ozawa, 1965):

AE Ea
ln ( ) = ln 5.331 1.052
R g( ) RT (13)

Values of Ea can be determined from the slope (−1.052 Ea/R) of a Fig. 1. Comparison of calorific values of C. Polygonoides with other biomass (Lim
linear plot between ln( ) against 1000/Tm at different heating rates. et al., 2017).

132
A. Nasrullah, A.S. Khan, S.Z. Khan et al.
Table 1
Result from ultimate and elemental composition.
Parameters Unit Magnitude
C % 42.82
H % 4.934
N % 1.754
O % 50.49
S % 0.336
polygonoides, obtained using a CHNOS analyzer (Table 1). The con­
tents of C, H, N, and S were directly measured by the elemental
analyzer and oxygen content was obtained from the difference. To
correlate the high heating value of biomass materials, their H:C and
O:C ratios were also calculated. The energy content value of lig­
nocellulosic biomass is largely influenced by its chemical composi­
tion (carbon, hydrogen, and oxygen) and is negatively affected by its
moisture and inorganic contents (El-Sayed and Mostafa, 2014;
Ceylan et al., 2014).
3.3. FTIR analysis
FTIR spectra of C. Polygonoides were performed to find out the
functional groups. Fig. 2 shows the FT-IR spectra of C. Polygonoides
and its ash content measured from 4000 to 400 cm−1. The broad
peak appeared at 3400 cm −1, attributed to the stretching vibration
of O-H and N-H groups. The broadness of this peak is due to in­
volvement of O-H group in inter- and intra-molecular hydrogen
bonding which demonstrate the presence of hydroxyl group and
chemisorbed water (Daifullah et al., 2003; Lim et al., 2017). The
signal observed at 2910 cm−1 assigned to C-H stretching vibration of
both symmetric and asymmetric, showing the presence of methyl/
methylene groups in samples (Said et al., 2010; Nasrullah et al.;
Natarajan, 2009; Singh, 2013). Peak located at 1380 cm−1 is dedicated
to –CH3 group. A sharp intense peak appeared in FT-IR spectra at
1637 cm−1 assigned to O-H bending vibration of secondary adsorbed
water molecules. The presence of C]C bond of alkene and aromatic
ring was confirmed from the peak appeared at 1528 and 1445 cm−1
(Pattiya et al., 2008). The cellulose/hemicellulose and aryl-OH group
in lignin vibrate at 1035 cm−1 and observed in the same region. The
existence of Si–H was confirmed by presence of a peak at
793 cm−1(Nasrullah et al.; Singh, 2013), while the presence of car­
bonyl component of carboxylic acid, alcohols, and esters was con­
firmed from the signal located at 1300 cm−1 to 900 cm−1(Gong et al.,
2006; Zhang et al., 2014). The peak at 900 cm−1 corresponds to O–H
Fig. 2. TG of weight loss curves of C. polygonoides recorded at 10, 15 and 20 °C/min.
133
Process Safety and Environmental Protection 160 (2022) 130–138
stretching vibrations, which was absent in the ash of C. polygonoides
due to thermal treatment. The C. Polygonoides ash give a signal in FT-
IR spectra at 3700 cm−1 assigned to the stretching of free O–H (Rosa
et al., 2010; Roy et al., 2013). The disappearance of most peaks in ash
was observed.
3.4. Py/GC-MS analysis
Py-GC/MS analysis was used for the determination of the type and
amount of compounds liberated from the pyrolysis of C polygonoides.
Based on the chromatogram of pyrolysis C polygonoides, the nature and
abundance (obtained from percentage peak area) of released com­
pounds were determined. Table 2 shows the molecules obtained on
biomass pyrolysis. About 66 various types of pyrolytic compounds
were identified using Py-GC/MS of biomass sample. As already ex­
plained that biomass have complex nature and release various com­
pounds on pyrolysis. Various types of volatile compounds such as
alkanes, CO2, alkenes, furan, aromatic hydrocarbon, benzene, phenol,
butylamine, ketone, and acetic acid were observed from the pyrolysis
of lignocellulose biomass pyrolysis. Aldehyde is generated by from
secondary decomposition of dehydrated sugar. Phenol and hetero­
cyclic compounds produced from pyrolysis of lignin. Acetic acid from
aliphatic side chain of lignin basic units. Hemicellulose can produced
ketones and acids. Cellulose is more dedicated to the products of
furans and small molecule aldehydes (Lv and Wu, 2012). Result shows
the large amount of carbohydrate in C polygonoides compared with
lignin. Similar compounds have been found to be released and de­
tected from pyrolysis processes of biomass by other researchers
(Muhammad et al., 2012; Lu et al., 2010; Pattiya et al., 2008).
3.5. Pyrolysis and combustion characteristics
TGA and DTG analyses of C. polygonoides biomass were per­
formed in inert nitrogen atmosphere in temperature range from 50
to 800 °C at heating rate 10, 15, and 20 °C/min. Fig. 3 shows the
percentage weight loss thermogram of C polygonoides as a function
of T using three different heating rate. The percentage mass loss
thermogram of C. polygonoides shows that the decomposition of
sample gradually increases with increased temperature, as expected.
Three main thermal degradation peaks were observed in the TGA
thermogram for biomass. The first weight loss below 120 °C is due to
evaporation of water and thermal degradation of lower weight or­
ganic compounds(Khan et al., 2016). Biomass pyrolysis were divided
into three major regions: (i) removal of water and volatile compo­
nents (˂120 °C), (ii) hemicellulose-cellulose degradation
(200–350 °C), and (iii) degradation of cellulose and lignin (350 °C to
410–550 °C) and decomposition of lignin (˃450 °C). The predominant
weight loss from 200 °C to 440 °C is mainly due to cellulose thermal
degradation. The thermal degradation of lignin has a wide tem­
perature range, i.e., 180–900 °C. At < 220 °C, the small weight loss is
assigned to the loss of water attached to surface of biomass
(El-Sayed and Mostafa, 2014; Li et al., 2019).
The TGA curve of C polygonoides sample represented that the
thermal decomposition of C polygonoides starts at 225 °C, and one
predominant weight loss corresponding with the major degradation
occurs at 225–350 °C. This degradation is due to the active pyrolysis
degradation of biomass sample (Özsin and Pütün, 2019). Apart from
this main peak (peak II), a shoulder peak (peak I) appears at around
270 °C, the appearance of this shoulder peak is due to the hemi­
cellulose pyrolysis. With increased heating rate from 10 °C/min to
20 °C/min, a decrease in peak intensity was observed. C polygonoides
sample contains three major components: hemicellulos, cellulose,
and lignin. The thermal degradation of hemicellulose in C. Poly­
gonoides sample starts from 225 °C, and that of cellulose decom­
position occurs at 325–380 °C (Ceylan and Topçu, 2014). This region
is important because it presents the maximum weight loss and
A. Nasrullah, A.S. Khan, S.Z. Khan et al. Process Safety and Environmental Protection 160 (2022) 130–138

Table 2 Table 2 (continued)

Analysis of various gases by GC-MS evolved from C. polygonoides.
Peak no RT (min) Area Compounds
Peak no RT (min) Area Compounds
64 65.910 3.21 7-Chloroquinoline-2,4-dicarboxylic acid
1 1.278 11.51 Carbon dioxide
Anthracene
2 1.301 9.72 N-Methyl-7-azabicyclo(2,2,1)hept-2 -ene
65 66.719 2.39 2-Amino-4-hydroxy-6,8-dimethyl-7(H)-
Cyclopropanecarboxaldehyde Propene
pteridinone Benzo[h]quinoline, 2,4-dimethyl-
3 1.419 1.26 1,2-Butadiene
Methyl 3-bromo-1-adamantaneacetate
4 2.929 2.08 Toluene
66 67.505 4.73 Ethyl 3-cyano-2-((diethoxyphosphorothioyl)
5 3.041 1.14 2-Butenal
oxy)-6-Methylisonicotinate
6 3.109 1.60 1,3-Pentadiene
7 3.170 0.85 Nitro-L-arginine
8 3.215 1.33 1-Nonanol
9 3.288 0.96 Diisopropylamine
10 3.361 1.94 Ethyl 2-(bromomethyl) acrylate
11 3.513 0.59 1-Buten-3-yne
12 3.580 0.99 Water
13 3.637 2.02 Cyclotrisiloxane,
14 3.754 0.75 N-Acrylonitrylaziridine
15 3.878 0.70 3-(5-Bromo-3-nitro-1H-1,2,4-triazo l-1-yl)-
6,8-dioxabicyclo[3.2.1] oct an-4-one
16 3.929 0.64 Propanamide, 3-(3,4-dimethylphenyl
sulfonyl)-
17 4.046 0.58 Piperazine
18 4.153 0.75 1,2-Ethanediamine
19 4.226 0.98 cis-1,2-Cyclohexanedimethanol 3H-Naphth
[1,8a-b]oxiren-2(1aH)-one
20 4.271 0.56 Furan
21 4.344 0.55 Bicyclo[2.2.1]hept-2-ene, 2-methyl
22 4.400 0.59 Benzaldehyde
23 4.501 0.53 1H-Pyrrole, 3-methyl-
24 4.647 1.18 Ethyl benzene
25 4.821 0.74 Benzo[h]quinoline, 2,4-dimethyl-
Cyclotrisiloxane, ethyl ester
26 4.878 1.52 Benzene
27 5.243 0.77 Acetic acid
28 5.349 0.71 1-Decanol Fig. 3. DTG curves of C. polygonoides recorded in nitrogen at 10, 15 and 20 °C/min.
29 5.433 1.14 Styrene
30 5.574 0.50 Ethene hence the combustibility of sample. The largest weight loss in bio­
31 5.995 0.63 2-Cyclopenten-1-one mass sample was observed at 250–550 °C. The weight loss from
32 6.259 0.98 Formamide
33 7.219 0.46 Imidazo[1,2-a]pyridin-2(3H)-one,1H-
225 °C to 350 °C is assigned to the decomposition of all three com­
Pyrazole ponents of biomass: hemicellulose, cellulose, and lignin. This sharp
34 7.399 0.50 1,2,3-trimethyl- 1,3-Cyclopentadiene weight decrease is due to the release of large amount of various gas
35 9.106 1.08 Phenol species, such CO, CO2, and CH4 (Gu et al., 2014).
36 9.594 0.48 Limonene, Cyclohexene
The third region of thermogram shows very minor weight loss
37 28.091 0.97 Diethyl Phthalate, Dodecanoic acid
38 33.297 0.74 Tetradecanoic acid and low amount of gas species compared with the first and second
39 33.381 0.50 1-Tridecene regions. This region corresponds with the end of decomposition of
40 37.648 0.77 7-Pentadecyne cellulose and volatile compounds of biomass. As a result of the de­
41 38.188 2.68 n-Hexadecanoic acid composition of C–C bond, char formation occurs. However, some
42 38.305 0.93 2,3-dicarboxylic acid, dimethyl ester
43 38.440 0.56 Benzene propanol
researchers have reported that the decomposition of lignin is also
44 42.180 0.95 9-Octadecenoic acid continued in this region. Most woody plants with 4–35% lignin
45 42.320 0.84 1-Nitro-2,4,6-trimethoxybenzene, component has a wide thermal degradation temperature range of
Carboxamide 180–900 °C. Lignin decomposition occurs in both active and passive
46 42.680 0.51 Thiazolo[4,5-d]pyrimidin-7(4H)-one
regions. The thermal decomposition of C. Polygonoides at high tem­
47 42.904 1.25 Hexadecanamide
48 43.606 0.50 1,3,5-Triazine-2,4-diamine perature decreases because of the presence of remaining lignin or
49 44.095 0.53 Dibenzofuran, char (El-Sayed and Mostafa, 2014; Kumar et al., 2008).
50 44.230 0.53 Lycorine
51 44.516 0.58 1,2-Benzenedicarboxylic acid, phenyl methyl
ester 3.6. Effect of heating rate
52 45.79 0.60 Phenol, 4,4′-(1-methylethylidene)
53 46.038 0.81 Chloroxine
54 46.633 0.47 2,11-Dimethyl-2,11-dodecanediol-9-
Fig. 5 shows the DTG curve of biomass sample recorded at three
Octadecenamide different heating rates. The temperature at which maximum weight
55 55.000 0.54 2,6,10-Dodecatrien-1-ol loss occurred (Tmax) is found to depend on heating rates (Table 3).
56 55.926 0.88 Cholesta-3,5-diene Tmax of sample is important because it provides information about
57 59.464 0.76 Benzamide
58 60.093 0.56 1H-Indole-2-carboxylic acid
59 61.199 1.00 5-(p-Aminophenyl)-4-(p-tolyl)-2- Table 3
thiazolamine The maximum decomposition temperature (Tmax) of biomass at
60 62.687 4.42 Stannane various heating rates.
61 63.855 4.92 4-Dehydroxy-N-(4,5-methylenedioxy-2- Heating rate Tmax1 Tmax2 Tmax3
nitrobenzylidene)tyramine Silicic acid, (°C/min)
62 64.102 0.63 2-dimethyl ester
63 65.057 7.96 5,5′-Di(ethoxycarbonyl)-3,3′-dimethyl-4,4′- 10 533.86 596.54 729.53
dipropyl-2,2′-dipyrrylmethane 15 539.54 602.87 735.25
20 543.76 609.05 742.04

134
A. Nasrullah, A.S. Khan, S.Z. Khan et al.
the temperature where the maximum weight loss occurs due to the
fast and rapid volatilization, leading to the formation of carbonac­
eous residue (Sharara et al., 2014; Yuan et al., 2019). This tempera­
ture conveys information about the combustibility of sample, lower
Tmax means better ignition of sample. Generally, with increased
heating rate from 10 °C/min to 20 °C/min, value for Tm also increases,
this finding may be related to heat transfer limitation. Higher
heating rate provides shorter time for biomass pyrolysis and non-
uniform heating, thus the temperature required for thermal de­
composition of sample is higher. This reason mainly explains the
shift of DTG curves from lower to high temperatures region in DTG
thermogram (Gu et al., 2014). This shift of Tmax from lower to higher
temperature with the increase of heating rate is very common and
documented elsewhere in literature (Khan et al., 2016). The other
reason that at lower heating rate, the particles of C. Polygonoides
have enough time to become uniformly heated due to large time of
contact with heat (Zhou et al., 2014; Brand et al., 2014). At high
heating rate, too much heat exists to initiate and induce a large
number of parallel and series reactions for the evolution of hydro­
carbons from biomass and hence leads to the formation of a large
amount of char (Gu et al., 2014). The intensity of DTG peaks in all
three regions (peaks I–III) decrease with the increased of heating
rate, whereas peaks become broader with increased heating rate.
This finding may be due to the delayed degradation that diffuses
more heat in C. Polygonoides for a short time (Khan et al., 2016). DTG
peaks show a high decomposition rate (weight loss per unit time) of
C. Polygonoides sample in the second region, which is the active
pyrolytic zone and is very important for kinetic studies of biomass.
3.7. Kinetic study of three regions of Calligonum polygonoides
Kissinger and Ozawa methods were used to determine Ea, thermo­
dynamics parameters, and pre-exponential factor for three different
zones of biomass sample. Kinetic parameters of C. Polygonoides sample
were calculated by Kissinger and Ozawa methods using Eqs. (12) and
(13), respectively. The regression lines obtained for the first zone using
Kissinger and Ozawa methods are shown in Fig. 4. The values of Ea cal­
culated by Kissinger and Ozawa methods for the first zone are about
133.73 and 135.61 kJ/mol respectively (Tables 4 and 5). The fitted equa­
tion’s correlation coefficient (R2) is higher than 0.999 for both Kissinger
and Ozawa methods. The close agreement among the values of Ea con­
firmed that both model-free methods are equally applicable and reliable
for the calculation of Ea for biomass. A lower Ea for this zone is due to the
fast degradation of hemicellulose, which has an amorphous structure and
therefore have high degradation rate and a lower Ea value.
The regression lines obtained for the second zone using Kissinger
and Ozawa methods are shown in Fig. 5. The values of Ea calculated for
Fig. 4. Kissinger and Ozawa plot for the first zone of pyrolysis.
135
Process Safety and Environmental Protection 160 (2022) 130–138
the second zone using Kissinger and Ozawa methods are about 164.50
and 165.88 kJ/mol, respectively. The fitted equation’s correlation coef­
ficient (R2) values are higher than 0.999 for both Kissinger and Ozawa
methods. The higher value of Ea for the second zone in comparison to
first zone is due to cellulose degradation. Cellulose has a three di­
mensional crystalline structure and have lower degradation than that
of hemicellulose. This second zone of pyrolysis is kinetically important
because maximum thermal degradation of biomass taking place in this
region. In this region, major degradation of cellulose occurs because of
the unzipping of cellulose molecules at such high temperatures. As a
result of this fast unzipping of cellulose molecules, the original struc­
ture of cellulose molecules disappears (Khan et al., 2016). The regres­
sion lines obtained for the third zone using Kissinger and Ozawa
methods are shown in Fig. 6. The values of Ea calculated for the third
zone using Kissinger and Ozawa methods are 253.99 and 253.06 kJ/
mol, respectively. The fitted equation’s correlation coefficient (R2) va­
lues are higher than 0.999 for both Kissinger and Ozawa methods. The
high value of Ea for this zone reveals the slow pyrolysis of biomass
because of the formation of char after the removal of volatile matter
and slow rate of thermal degradation of lignin in this zone (Du et al.,
1990; Zhang et al., 2006; Guerrero et al., 2014).
The values of pre-exponential factor (A) calculated by Kissinger and
Ozawa methods for three different zones are listed in Tables 4 and 5,
respectively. The values of A are increasing when switch from first to
third zone of biomass pyrolysis. The values of A calculated for three
zone of biomass pyrolysis are in line with already reported values of A
reported for various biomass pyrolysis. Result shows that the values of
lnA and Ea increase when moved from zone I to zone III. The values of
Ea and lnA for all the three zones is shown in Fig. S3. The result in­
dicated that the value of Ea and lnA for all three zones are different
from each other’s and increasing when shift from first zone to third
zone. Based on the results of Ozawa and Kissinger methods, the value
of Ea differ for all three zones, values of Ea increases when moved from
the first to the third zones. The different values of Ea for different zones
of biomass clearly show that the thermal decomposition of C. Poly­
gonoides is a complex phenomenon and the mechanism of reaction is
not the same throughout the entire decomposition process. The values
of Ea obtained from the Kissinger and Ozawa methods well agree with
one another for all three zones, but the value of Ea increases when
moved from the first to the third zones (Mamleev et al., 2006) (Fig. 7).
3.8. Estimation of IKPs for investigated decomposition process
IKP method was used for both Ozawa and Kissinger methods to
examine compensational effect, and a graph of lnA against Ea was
plotted. Fig. S4 shows the best fitted plot (R2 = 0.999) for both Kissinger
and Ozawa methods. Therefore, the values of activation energy
A. Nasrullah, A.S. Khan, S.Z. Khan et al. Process Safety and Environmental Protection 160 (2022) 130–138

Table 4
Kinetic parameters obtained using Kissinger method.

Degradation zone Equation R2 Ea ln A (min−1)

First zone y = −16.019 X + 19.905 0.999 133.73 KJ/mol 25.5 = 1.87 × 1011
Second zone y = −19.787 X + 22.662 0.999 164.50 KJ/mol 28.5 = 2.38 × 1012
Third zone y = −30.551 X + 31.007 0.999 254.00 KJ/mol 37.2 = 1.87 × 1016

Table 5
Kinetics parameters obtained using Ozawa method.

Degradation zone Equation R2 Ea ln A (min−1)

First zone y = −17.16 X + 34.486 0. 999 135.61 KJ/mol 23.7 = 1.96 × 1010
Second zone y = −20.992 X + 37.466 0.999 165.88 KJ/mol 26.5 = 3.23 × 1011
Third zone y = −32.021 X + 46.207 0.999 253.00 KJ/mol 34.8 = 1.29 × 1015

Fig. 5. Kissinger and Ozawa plots for the second zone of pyrolysis.

Fig. 6. Kissinger and Ozawa plots for the third zone of pyrolysis.

calculated for three different zones of biomass pyrolysis by Kissinger
and Ozawa methods is valid. Results also indicated a linear relationship
between A and Ea for all three zones. The value of b* V was calculated
from the slope of line and a*V was calculated from the intercept of the
same line (Purnomo et al., 2020; Kumagai et al., 2017) (Fig. 8).
3.9. Thermodynamics study
Based on the values of activation energy Ea and pre-exponential
factor A, changes in the values of ∆H°, ∆S°, and ∆G° were calculated
for biomass using Kissinger and Ozawa methods based on the
maximum degradation temperature of DTG curves. The values of
∆H°, ∆S°, and ∆G° obtained for three zones using Kissinger and
Ozawa methods are listed in Tables 6 and 7. Tables 6 and 7 show that
the value of ∆S° is negative for the first and second zones, meaning
that biomass degradation has a high degree of arrangement (low
entropy), and vice versa for the third zone. In terms of the theory of
activated complex (transition state theory), the third stage of
thermal decomposition of biomass may be interpreted as fast stages,
whereas the first and second stages are slow stages (indicated by a

136
A. Nasrullah, A.S. Khan, S.Z. Khan et al. Process Safety and Environmental Protection 160 (2022) 130–138

Fig. 7. Comparison of (a) Ea and (b) lnA obtained for three zone using Kissinger and Ozawa methods.

Fig. 8. Relationship between lnA and Ea using (a) Kissinger and (b) Ozawa methods.

Table 6 Polygonoides using Kissinger and Ozawa methods are in close

Values of ∆H°, ∆S° and ∆G° obtained for three zones using Kissinger method. agreement with each other. The positive values of ∆H and ∆G for all
Degradation zone ∆Ho (kJ/mol) ∆So (J/mol.K) ∆Go (kJ/mol) three zones indicate that the thermal degradation of biomass is non-
First zone 128.7 -46.1 153.0
spontaneous (Khan et al., 2016; Vlaev et al., 2008).
Second zone 159.5 -22.4 173.0
Third zone 248.8 48.9 212.0
4. Conclusion

Kinetic and thermodynamic parameters for C. Polygonoides were

Table 7 successfully determined based on TGA data performed at different
Value of ∆H°, ∆S° and ∆G° obtained for three zones using Ozawa method. heating rates. Three different distinct zones were observed for the
Degradation zone ∆Ho (kJ/mol) ∆So (J/mol.K) ∆Go (kJ/mol) pyrolytic decomposition of C. Polygonoides and therefore kinetic and
First zone 131.0 -61.1 165.0
thermodynamic parameters were determined for each zone in­
Second zone 160.92 -22.4 184.0 dividually using Kissinger and Ozawa methods. Heating rate sig­
Third zone 246.99 28.9 226.0 nificantly affects pyrolysis, and both TGA and DTG curve shifts
toward higher temperature with increase of heating rate from 5 °C/
min to 20 °C/min. The average Ea calculated for zone I, zone II and
zone III of C. Polygonoides using Kissinger method were 133.73,
negative value). The values of ∆H° is used to decide about the pro­ 164.50, and 253.99 kJ/mol, while 135.61, 165.88, and 253.06 kJ/mol
cess endothermic and exothermic nature. The positive values of ∆H° using Ozawa method. Ea calculated by Kissinger and Ozawa methods
for the first, second, and third zones calculated by Kissinger method were in close agreement for all three zones having a regression
are 128.7, 159.5, and 248.8 kJ/mol, respectively. While the values of coefficient (R2) of 0.999. The high ratio of C:H indicates high energy
∆H° for the first, second and third zone calculated by Ozawa content value of biomass. GC-MS analysis shows the release of 66
method.are 131.0, 160.92, and 246.99 kJ/mol, respectively. Similarly, various types of volatile compounds from biomass pyrolysis. Based
∆G° values are positive for the first, second, and third zones and are on the values of change in entropy, enthalpy, and Gibbs free, certain
153.0, 173.0, and 212.0 kJ/mol calculated by Kissinger method, as conclusions have been derived for the thermal analysis of biomass,
well as and 165.0, 184.0 and 226.0 kJ/mol calculated by Ozawa which is useful for theoretical and can be useful in designing pyr­
method. The values of thermodynamic parameters calculated for C. olysis reactor for Calligonum polygonoides.

137
A. Nasrullah, A.S. Khan, S.Z. Khan et al.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The Deanship of Scientific Research (DSR) at King Abdulaziz
University, Jeddah, Saudi Arabia has funded this project, under grant
no. (KEP-8-130-42).
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.psep.2022.01.084.
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