Fuel 341 (2023) 127663

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Exploration of the bioenergy potential of Dactyloctenium aegyptium through

pyrolysis, kinetics, and thermodynamic parameters to produce clean fuels
and biochemicals
Hesham Alhumade a, b, Omar S. Alayed c, Muhammad Waqas Iqbal d, Ayesha Shahid e,
Tanveer Iqbal d, Muhammad Sajjad Ahmad f, Ali Elkamel f, Yusuf Al-Turki b, g,
Muhammad Aamer Mehmood e, *, Ghulam Abbas Ashraf h, *
a
Department of Chemical and Materials Engineering, Faculty of Engineering, Center of Research Excellence in Renewable Energy and Power Systems, King Abdulaziz
University, Jeddah 21589, Saudi Arabia
b
K.A. CARE Energy Research and Innovation Center, King Abdulaziz University, Jeddah 21589, Saudi Arabia
c
Al-Balqa Applied University, Department of Chemical Engineering, Faculty of Engineering Technology, P. O. Box 15008, Marka 11134, Amman, Jordan
d
Chemical, Polymer and Composite Materials Engineering, University of Engineering & Technology, New Campus, Lahore, Pakistan
e
Bioenergy Research Center, Department of Bioinformatics and Biotechnology, Government College University, Faisalabad, Pakistan
f
Department of Chemical Engineering, University of Waterloo, N2L 3G1, ON, Canada
g
Department of Electrical and Computer Engineering, Faculty of Engineering, King Abdulaziz University, Jeddah 21589, Saudi Arabia
h
Key Laboratory of Integrated Regulation and Resources Development on Shallow Lake of Ministry of Education, College of Environment, Hohai University, Nanjing
210098, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The Egyptian grass (Dactyloctenium aegyptium) is a common low-cost coarse grass which is adapted to poor soils.
Low-cost biomass production The biomass of the Egyptian grass may be used to produce cleaner and sustainable fuels through pyrolysis
Pyrolysis without causing any contradictory impact on the land for food. It is profound to understand the thermochemical
Bioenergy
character of the Egyptian grass biomass for its efficient thermal conversion to clean fuels and chemicals. The
Reaction kinetics
Clean fuels
current study elucidated the pyrolysis process of this biomass for the very first time based on the pyrolysis data.
Heat-dried powdered biomass of Dactyloctenium aegyptium was pyrolyzed at 10 min− 1, 30 min− 1 and 50 ◦ C min− 1
in a simultaneous Thermogravimetry–Differential Scanning Calorimetry analyzer (TGA-DSC) under nitrogen
atmosphere. Isoconversional models of Kissenger-Akahira-Sunose (KSA), Flynn–Wall–Ozawa (FWO) and first and
second order reaction kinetics model were used to analyze the pyrolytic kinetic parameters. The pyrolysis of
D. aegyptium grass biomass was shown to be a three-stage pyrolysis process where around 50 % of the product
formation was happening within a narrow temperature range of 240–360 ◦ C with the Activation energies ranged
from 167 to 267 kJ mol− 1 and thermodynamic parameters including 18.25–18.63 MJ kg− 1 of high heating
values, 169–177 kJ mol− 1 of Gibb’s free energies, and 166–256 kJ mol− 1 of reaction enthalpy have shown the
outstanding pyrolysis and co-pyrolysis potential of Egyptian grass to produce clean fuels.

1. Introduction capacities with concomitant CO2 mitigation. Typically, biomass has

58–90 folds higher solar energy storage capacity via photosynthesis as
Escalating levels of toxic greenhouse gases (NOx, CO2, SOx) in the compared to lithium-ion batteries [1]. However, it is challenging to
environment driven by frequent fossil fuel combustion leads to serious reuse this energy. Direct combustion, biological fermentation, and
environmental concerns. Besides, fossil fuel consumption leads to their thermochemical transformation are the most often employed processes
depletion in near future. It demands for the eco-friendly, renewable, and for biomass conversion. Thermochemical conversion, specifically py­
sustainable energy alternatives. Biomass as cleanest energy source gain rolysis, are appealing approaches for extracting the plant-stored energy
popularity owing to its renewability, huge solar energy storage without producing byproducts [2]. Pyrolysis offers thermal biomass

* Corresponding authors.
E-mail addresses: [email protected] (M.A. Mehmood), [email protected] (G.A. Ashraf).

https://doi.org/10.1016/j.fuel.2023.127663
Received 28 November 2022; Received in revised form 9 January 2023; Accepted 30 January 2023
Available online 9 February 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
H. Alhumade et al. Fuel 341 (2023) 127663

conversion to syngas, bio-oil, and biochar [3]. Therefore, the product

VM Ash FC
profile is contingent on reaction circumstances, particle size, and nature HHV = 19.2880 − 0.2135 − 1.9584 + 0.0234 (1)
FC VM Ash
of feedstock. Biochar production is influenced by its porosity, surface
area, oxygen content, and relative humidity during pyrolysis. For the Where VM (%) = Volatile matter and FC (%) = Fixed carbon.
creation of an efficient pyrolysis process, it is therefore essential to Average values obtained from three independent experiments were
comprehend the biomass-specific critical kinetic parameters. employed for HHV calculation in present model.
The cost of pyrolytic end-product significantly depends on the
selected biomass, biomass cost, and energy consumption during thermal
2.2. TGA-DSC experiment
conversion [4,5]. Nature of biomass and cultivation requirements are
the contributing factors towards biomass cost [6]. An attractive option
TGA is very effective to determine the degradation stages that occur
to reduce process cost is by using marginal lands that do not require
in a sample with an increase in temperature. TGA instrument monitors
supplementation of pesticides or fertilizers and provide the additional
the sample mass as relevance of time with the continuous temperature
benefit of converting infertile land into profitable landscape [7].
rise, according to the provided conditions of temperature, heating rate,
Although reaction conditions like pressure, heating rate, and resi­
and the environment. Almost 10 mg of Egyptian grass was heated from
dence time are the major influencing factors of the pyrolysis process yet
ambient temperature to 800 ◦ C in Alumina crucibles. It reflects the
the reaction chemistry also depends on biomass composition [8]. Hence,
sample degradation and weight loss with point-to-point increase in
detailed understanding of the pyrolytic conditions and kinetics of re­
temperature. The results were simulated on the software side by side
action chemistry is mandatory for efficient pyrolysis of any biomass [9].
that makes peak by keeping the temperature on X-axis and mass per­
Aiming at this, previously many studies have been conducted on plant
centage on Y-axis. In the present study, biomass was pyrolyzed at 10, 30
biomasses and their wastes including Para grass, Camel grass [7], red
and 50 ◦ C min− 1 of heating rates. The pyrolytic characteristics were
pepper waste [9], sawdust [10], elephant grass, rice husk [11], tobacco
determined by thermal analyzer. All samples were placed in aluminum
waste [12], blends of low-rank coal with microalgae [13], blends of coal
crucibles with lids and investigated the accuracy of the crucibles by
with rice husk [14], hemp hurds [15], and liquor industry waste [16].
keeping observation throughout the experiment when heated in TG
The current study was aimed to estimate the kinetic parameters and
analyzer from ambient temperature to 1000 ◦ C at rates described before
pyrolytic behavior of Egyptian grass (Dactyloctenium aegyptium) to
in the furnace under 100 mL min− 1 of nitrogen flow rate to maintain an
evaluate its bioenergy potential. The Egyptian grass is a common grass
inert environment.
which is widespread in several Asian and African countries including
It also provided the first derivative of the mass percentage with the
India, China, Pakistan, Malaysia, Japan, Morocco, Egypt, Sudan, Tunisia
rise in temperature and drew the peaks on different heating rates as
and Libya [17]. It could be a low-cost and abundant biological resource
provided. The data were saved in a notepad file that was further trans­
that is acclimatized to poor soils. Owing to these properties, Egyptian
ferred to MS-Excel for observing the clear picture of the experimental
grass may be an attractive source to be explored for bioenergy produc­
data.
tion. The current study was aimed to characterize the pyrolytic behavior
of Egyptian grass for the first time. For this purpose, the biomass was
pyrolyzed under inert environment using TGA-DSC analyzer. The data 2.3. Kinetic modeling
showed the considerable bioenergy potential of Egyptian grass via
pyrolysis. The basic standard general equation used by researchers is of the
form that is amenable to mathematical manipulations is employed in the
2. Materials and methods present research work.
( )
dα E
2.1. Proximate and elemental composition analyses = Aexp − (1 − α)n (2)
dt RT
After randomly selecting locations in the field, the grass being pro­ Where, α is conversion function, n is the reaction order which is
duced on marginal land was harvested from one-meter square area. assumed to take values 1 & 2 to indicate first and second order chemical
Analyses were performed on freshly harvested and air-dried biomass. reactions.
Collected grass was cleaned by tap water and then left for air drying. Eq. (2) is modified to fit the desired manipulations to calculate the
Afterwards, biomass was crushed by manual crusher into 150–200 µm activation energy E, and the frequency factor, A, of the Arrhenius
particle size and dried for 48 h in oven. Proximate analysis of sun-dried Equation for rate temperature dependency term. The modifications are
biomass was performed in terms of moisture content (%), volatile matter ( )
dα dT dα dT dα E
(VM, %), and alkali content (%) by adopting standard ASTM protocols = = β = Aexp − (1 − α)n (3)
dt dT dT dt dT RT
(E871-82 2006, E872-82 2006, and E1755-01 2007). equationFC(%) =
100 − (ashcontent + VM + moisture) was used to determine the fixed Where β is the heating rate degree Kelvin per minute. The final form
carbon (FC %). All experiments were performed in triplicates. Mass of Eq. (3) used in the analysis is written as indicated in Eq. (4);
difference between pre-dried and post-dried (105 ◦ C for 16–24 h)
dα A E
biomass provided information of moisture content. Similarly, mass loss = exp(− )(1 − α)n (4)
dT β RT
of Muffle furnace treated (550 ◦ C for 3–4 h) biomass indicates VM
content, while the residual indicates ash content. The composition of (C, To calculate the activation energy and the corresponding frequency
H, S, N and O) in Egyptian grass was assessed by elemental analyzer factor, the order of reaction must be assumed before further analysis.
(Vario EL Cube, Germany) using Argon (Ar) as carrier gas.
High heating value (HHV) is a crucial parameter that reflect the 2.3.1. First order kinetics analysis
potential energy released upon the pyrolytic combustion of the biomass. This research work employed calculations of activation energy and
Conventional HHV (MJ kg− 1) determining approaches are prone to error the corresponding frequency factor based on certain assumptions. The
bias [18], but availability of multiple mathematical models allow for the analysis was conducted assuming a first order and a second reaction
reliable and effective calculation. Presently, HHV has been calculated by order. The second assumption is that the activation energy and the
using the most authentic correlation model developed to date [18] as frequency factor are constant for a reaction temperature interval greater
given below; than 10◦ to enable solving the kinetic equation directly by elimination as
follows:

2
H. Alhumade et al. Fuel 341 (2023) 127663

( ) ( )
dα A E
= exp − (1 − α1 ) (5) lnA = aEα + b (15)
dT 1 β RT1
( ) ( ) ΔH = E − RT (16)
dα A E
= exp − (1 − α2 ) (6)
dT 2 β RT2 ΔG = E + RTm ln(KB Tm /hA) (17)
Taking the natural logarithm for both sides of Eqs. (5) and (6), and
subtracting for constant activation and frequency factor assumption ΔS = ΔH − ΔG/Tm (18)
would results in Eq. (7) as follows:
( ) ( ) [ ( )] 3. Results and discussion
dα dα E 1 1
ln /(1 − α2 ) − ln /(1 − α1 ) = exp − − (7)
dT 2 dT 1 R T2 T1 3.1. Phyiscochemical properties of the grass
Or in more compact form
⎡ ⎤ Proximate analyses of Egyptian grass (EG) showed that it contained
( dα ) [ ( )] 71.04 % volatile matter, 6.99 % moisture content, 17.75 % fixed carbon,
⎢ dT /(1 − α2 ) 2 ⎥
ln⎢ ⎥ E 1 1
(8) and 4.22 % ash (Table 1). The 69–71 % of VM content is closer to
⎣( dα/(1 − α ) ) ⎦ = exp − R T2 − T1
dT 1 1 common bioenergy crops [20]. The presence of < 10.0 % of mositure
content in the biomass indicates the promising potential of Egyptina
grass for pyrolysis. Higher Fixed carbon (FC) of Egyptian grass as
Solving Eq. (8) using experimental data, two adjacent data points in
compared to other bioenergy grasses indicated its suitability to produce
which the assumption of 10 degrees of reaction temperature or more is
biochar and bioenergy gases because FC improves the biochar properties
valid and where the activation energy was assumed to be constant, were
[21] and facilitates the biofuel production by effecting the nature and
culminated in activation energy calculations.
quality of the evolved gases [22].
Elemental analysis of Egyptian grass represented the C, H, O, N, and
2.3.2. Second order kinetics analysis
S composition as 45.23 %, 5.33 %, 48.18 %, 0.97 %, and 0.29 %
For second order kinetics, Eq. (4) becomes
( ) ( ) repectively. Low content of toxic elements such as N and S in the
dα A E biomass would reduce the production emission s of toxic NOx and SOx
= exp − (1 − α1 )2 (9)
dT 1 β RT1 gases upon oxidative pyrolysis of Egyptian grass. The 18.09 MJ kg− 1
( ) ( ) HHV of Egyptian grass was higher than 15–17.80 MJ kg− 1of HHV re­
dα A E ported for A. donax, Salix spp., Camel grass, M. gigantus, Para grass, and
= exp − (1 − α2 )2 (10)
dT 2 β RT2 Phalaris arundinacea [3,20,25,26]. It indicates substantial energy po­
tential of the Egyptian grass in comparison to popular bioenergy crops.
In similar manipulations, these Eqs. (9) and (10) were subtracted
from each other for the foresaid assumption of constant activation en­
ergy over a reaction temperature range greater than 10◦ . The direct 3.2. Analyses of thermal degradation pattern
substitution of experimental data into Eq. (8) leads to activation energy
calculations: Thermogravimetric analysis of Egyptian grass was performed in
⎡ ⎤ reponse to heating rates of 10, 30, and 50 ◦ C min− 1. Thermal decom­
( dα
⎢ dT
)
/(1 − α2 )2 2 ⎥
[ ( )] position trend was observed by mass loss curves (Fig. 1) which indicated
ln⎢( ) ⎥ = exp − E 1 − 1 (11) simpler relationship between temprature rise and mass at all heating
⎣ dα/(1 − α )2 ⎦ R T2 T1
dT 1 1 rate when temprate rose from ambient to 270 ◦ C but after that huge mass
loss was observed till 360 ◦ C. It is due to degradation of pectin, cellulose,
Using either first order or second reaction order to model the reac­ and hemicellulose. A tilt in degradation pattern was observed from
tion kinetics would result in modelling experimental TGA/DTGA data. If 360 ◦ C to 490 ◦ C which was preceeded by straight line upto 1000 ◦ C, it is
the activation energy is determined in the constant reaction temperature an indicative of lignin degradation and biochar formation. The differ­
range, the frequency factor is calculated by back substitution in the main ence in degradation pattern may be due to the difference in chemical
Eqs. (5) or (6). As this method of calculations has direct access to composition of the selected biomasses. Moreover, variation in pyrolytic
experimental data and is based on real mass of reaction rather than behavior is an indicative of biomass suitability to produce multiple
assuming different models as indicated by DAEM, and other distribution products.
functions of activation energies. Egyptian grass showed linear curves parallel to temperature axis
from ambient temperature to 155 ◦ C to 226 ◦ C maximum, however,
2.3.3. Other kinetic models there was a sudden drop of major mass loss from minimum 155 ◦ C to
504 ◦ C. This trend was found similar when compared with cherry stones,
β AEa Ea
ln( ) = ln − (KAS) (12) cedar wood [27,28], sugarcane mill waste [29], sewage sludge [30],
T2 Rg(α) RT
bamboo and fibre of coconut fruit [31], Columbian agriculture residue
[32], spoxy composts [33], tomato peels [34], silane wood [35], date
AEa Ea
lnβ = ln − (FWO) (13) palm residue [36]. Tables 2 and 3 represent the mass losss assciated
Rg(α) RT
characteristic temperature, obtained from TG-DTG data. The results
β AEa Ea showed a direct relation between mass loss tempeature, reaction rate,
ln( ) = ln − (Starink) (14) pyrolysis tempearature, and heating rate during themral conversion of
T 1.92 Rg(α) RT
Egyptian grass. However, thermal conversion of this biomass was shown
Left hand side of Eqs. (12), (13), and (14) were plotted on Y-axis to be compromised at all stages as depicted by DTG curves.
against the inverse pyrolytic temperature, and each conversion rate α At heating rates of 10 ◦ C min− 1 and 30 ◦ C min− 1, First stage mass loss
was applied to calculate kinetic and thermodynamic parameters by occurred between ambient to 151 ◦ C temperature which correspond to
using standard Eqs. (15)–(18) as recommended by ICTAC kinetics 7.67 % and 7.79 % of mass loss, respectively. Whereas, at 50 ◦ C min− 1,
committee [19]. first stage mass loss was 8.22 % which occurred from 25 ◦ C to 169 ◦ C. In
all instances, major mass loss occurred during second stage which was

3
H. Alhumade et al. Fuel 341 (2023) 127663

Table 1
Comparative summary of Proximate and elemental composition analyses of the Egyptian grass with other bioenergy lignocellulosic sources.
Grass species Proximate analyses Elemental composition (%) Reference
VM (%) Moisture Ash FC (%) HHV C H O N S
(%) (%) (MJ
kg− 1)

Egyptian grass 71.04 ± 6.99 ± 4.22 ± 17.75 ± 18.09 45.23 ± 5.33 ± 48.18 ± 0.97 ± 0.29 ± This study
0.67 0.18 0.14 0.11 0.53 0.13 0.64 0.05 0.02
Switch grass 83.24 – 2.60 14.16 17.94 48 6.9 43.68 0.53 – [22]
Miscanthus 78.2 5.79 3.89 12.14 17.52 41.8 5.59 52.07 0.2 0.35 [23]
grass
Bamboo 75.94 5.41 2.24 16.32 18.39 46.7 6.06 43.1 0.47 0.06 [16]
Camel grass 82.67 – 6.31 – 15.0 44.96 6.64 45.08 0.93 0.23 [24]
Para grass 79.4 7.23 9.32 – 15.04 44.73 6.88 46.84 0.98 0.24 [7]

stage ranged from 369 ◦ C to 1000 ◦ C for 10 ◦ C min− 1 heating rate,

120 0 380 ◦ C to 1000 ◦ C for 30 ◦ Cmin− 1 heating rate, and 372 ◦ C to 1000 ◦ C for
-5 50 ◦ C min− 1 heating rate where 17.85 %, 17 %, and 17.82 % of biomass
100
Heating Rate ( C min-1) -10 decomposition occurred respectively. In response to 10 ◦ C min− 1, 30 ◦ C
-15 min− 1, and 50 ◦ C min− 1 of heating rates 23.69 %, 24.29 %, and 24.82 %

DTG/(% min-1)
80
Mass (%)

-20 of residual biomass was obtained that referred as biochar (Tables 1 and
60 -25
2). Biochar production was comparable with Typha and rice straw
-30
40 -35 which respectively produced 23.7–24.6 % and 23.68 % of biochar [3].
-40 The reported biochar production is also higher than bamboo biochar
20
-45 which accounts for 16.5 % [16]. The results are indicative of suitability
0 -50 of Egyptian grass for the biochar production.
0 200 400 600 800 1000 In all instances, <8.0 % of mass was lost during first stage which
Temperature ( C) reflect removal of entrapped moisture. It indicate biomass suitablity for
combustion and pyrolysis as < 10 % moisture is recommended for
Fig. 1. TG-DTG curves indicating percent mass loss of Egyptian Grass in pryolysis process [11]. The second stage (divided in zone-I and zone-II)
response to three heating rates of during pyrolysis. mass loss is associated with thermal conversion of biochemical compo­
nents of the biomass. Where smaller sugars are converted in zone-I and
polysaccharides are converted in zone-II to gaseous products (Tables 1
Table 2 and 2).
Temperature characteristics associated with pyrolysis of the Egyptian grass.
Heating rate (◦ C min¡1) Temperature (◦ C) 3.3. Heat flow measurement via DSC analyses
T1 T2 T3 T4 T5

Egyptian Grass Temperature dependent heat-flow directional analysis of Egyptian

10 151 268 297 331 369 grass during pyrolysis was performed by Differential scanning calorim­
30 157 279 309 346 380
etry (DSC) technique. The sample is maintained at a nearly same tem­
50 169 282 318 340 372
perature in comparison with a reference. Generally, the temperature of
sample holder increases linearly with time. It can be used to measure a
few characteristic properties of a sample such as fusion, crystallization,
Table 3 oxidation, and other thermochemical conversions.
Mass loss of Egyptian grass during different stages of decomposition under
Three different heating rates were used to obtain DSC curves of each
heating rate of 10, 30, and 50 ◦ C min− 1.
sample. The DSC curves obtained for Para grass showed a variation of
Stages Heating rate (◦ C min¡1) heat flow (Fig. 2). An increase in heat flow in response to all heating
10 30 50
rates was observed. Endothermic peaks observed up to 100 ◦ C indicates
Egyptian Grass the heat absorbed in the dehydration of the moisture from the Egyptian
Stage-I, Mass Loss (%) 7.67 7.79 8.22
Stage-II, Mass Loss (%) Zone-I 23.76 23.18 24.07

Zone-II 27.03 27.74 25.07

Stage-III, Mass loss (%) 17.85 16.99 17.82
Residual Mass loss (%) at 1000 ◦ C 23.69 24.30 24.82

consisted of two zones (namely zone-I and zone-II). In the case of lowest
heating rate, 23.76 % of mass was lost during zone-I at 151 ◦ C to 297 ◦ C
followed by 27.03 % of mass loss from temperature 297 ◦ C to 369 ◦ C.
Overall, 50.79 % of mass was lost from 151 ◦ C to 369 ◦ C at 10 ◦ Cmin− 1 of
heating rate. Similarly, at 30 ◦ C min− 1 of heating rate, 23.18 % of
biomass was lost during zone-I (157 ◦ C to 309 ◦ C) followed by 27.74 %
during zone-II (309 ◦ C to 380 ◦ C) which accumulatively correspond to
50.92 % of biomass loss during second stage of thermal degradation. It
was observed that with the highest heating rate of 50 ◦ C min− 1, second
stage mass loss was 49.14 % where 24.07 % mass was lost during zone-I
(169 ◦ C to 318 ◦ C) and 25.07 % during zone-II (318 ◦ C to 372 ◦ C). Third Fig. 2. DSC curves indicating heat flow across the biomass the Egyptian Grass
at three different heating rates.

4
H. Alhumade et al. Fuel 341 (2023) 127663

grass. After this point, the exothermic reactions were predominant -1.65 x1021 s− 1) and Para grass (1.42 x1007 s− 1–2.26 x1019 s− 1) [40,43].
during pyrolysis. Gibbs free energy (ΔG) indicates the thermodynamic potential of
biomass during pyrolysis. Here, the ΔG values of Egyptian grass were
3.4. Kinetic analyses and thermodynamic parameters ranged from 173 to 177 kJ mol− 1 that were higher than 139.4 kJ mol− 1
for red pepper waste, 167.17 kJ mol− 1 for rice barn, and 164.59 kJ
Activation energy of Egyptian grass was determined by linear plots mol− 1 for rice husk [9] but were in accordance with ΔG values of Para
(Fig. 3) devised by KSA and FWO methods. Whereas, compensation ef­ grass and Camel grass [3,7].
fect between values of activation energy (R2 ≥ 0.99) and exponential
factors was determined by linear fit plots of Fig. 4. Activation energies 3.5. Comparison of reaction kinetics first order and second order with
(E) and the pre-exponential factors (A) were calculated from the slopes isoconversional models KAS and FWO
and dervied equations (Figs. 3 and 4). It was observed that calculated E-
values (Table 4) for biomass vary according to the conversion points and The activation energy values obtained through first order and second
shown to be decreased with further increase in conversion rate up to order reaction kinetics through Eqs. (6b) and (7) are shown in Fig. 4 and
conversion point 0.5–0.6 followed by decrease in E-values at higher Table 4. Three different peaks of activation energy were observed when
conversion points. In response to all heating rates, conversion rate (α) compared with conversion (α) at all heating rates. First peak was ranging
and pyrolysis temperature represent linear relationship (Fig. 5). The E- from 0.1 to 0.3 that purely resides in the area where moisture contents
values of Egyptian grass were observed to be withing the range of were evaporated. This is clear understanding of release of moisture
157.45–177.99 kJ mol− 1 which were in accordance with the E-valuee of contents because energy needs to release the moisture from the
bamboo (151.90–160.19 kJ mol− 1) and sorghum grass (167.7–189.5 kJ boundaries of intracellular space. The activation energy ranges from
mol− 1) [16,37]. The lower E-value of Egptian grass as compared to coal 89.7 kJ mol− 1 to 34.55 kJ mol− 1 and 70.06 kJ mol− 1 to 15.57 kJ mol− 1
(338 kJ mol− 1) [38] indicates its kinetic suitability as compared to non- at this region. Second peak is associated with cellulose, hemicellulose,
renewable fuel sources. and fraction of lignin degradation and is observed from 0.3 to 0.75. The
The relationship of E, T and α is described in Table 5. According to temperature was observed ranging from 280C – 350 ◦ C that is pure
KAS and FWO methods, average E-values of Egyptian grass were pyrolysis temperature to obtain maximum bioenergy in the form of
166–167 kJ mol− 1 while it ranged from 91 to 193 kJ mol− 1 with biooil for Egyptian grass. There are also latest studied of several biomass
reference to the conversion (0.1–1.0). The observed values were higher sample like pearl millet, Sida cordifolia L. and Rhus typhina [3,44,45]
as compared to 118–257 kJ mol− 1 of E-value for tobacco waste [39]. which strengthen Egyptian grass as a potential candidate for bioenergy
Moreover, average E-values of Egyptian grass were lower as compared to production on large scale. The activation energy values ranged from
the average activation energies of 191 kJ mol− 1 for cellulose, 221–229 34.55 kJ mol− 1 – 77.72 kJ mol− 1 for first order reaction and 15.57 kJ
kJ mol− 1 for rice husk, and 218–227 kJ mol− 1 for elephant grass but mol− 1 – 64.33 kJ mol− 1 for second order reaction in this peak region
higher than switchgrass and Para grass [40]. The results showed the from 0.3 to 0.75. The last peak was increased continuously, and its
suitability of Egyptian grass for co-pyrolysis in an energy efficient activation energy values were ignored due to non-degradation of ma­
manner as compared to other biomasses. terial at very high temperature. The average activation energy was
Difference between enthalpy change (ΔH) and activation energy (E) 90–101 kJ mol− 1 and 66–69 kJ mol− 1 for first and second reaction order.
represent biomass disintegration for product formation. Egyptian grass The more interesting thing is the sum of first and second reaction order
has ~ 5 kJ mol− 1 of difference between E and ΔH values. Lower dif­ activation energy values were ranging from 95.37 kJ mol− 1 to 177 kJ
ference between these parameters indicate easier product formation in mol− 1 that is also approximately equal to average activation energy
energy efficient manner [41] which is in agreement with the prior values obtained from KAS and FWO models. It also validates the cor­
studies [3,9]. relation of proposed model with the already established kinetic models,
Pre-exponential factor (A) is significant to comprehend the reaction because activation energy values were seeming to be same as deter­
chemistry for pyrolysis optimization. A-values < 109 s− 1 indicate surface mined from KAS and FWO models. Moreover, Fig. 5 showed the linear fit
reaction, but in case of surface area independent reaction it implies plots for the compensation effects between the pre-exponential factors
closed complex. Whereas A-values higher than 109 s− 1 indicate simple and the activation energy of Egyptian Grass by KAS and FWO methods
complex [42]. The A-values for Egyptian grasses ranged from 6.80 x1004 while Fig. 6 reflects the relationship between the conversion and py­
s− 1 –6.46 x1014 s− 1 (Table 4) which indicated a complex reaction. rolysis temperature (◦ C) of Egyptian Grass which is obvious that heating
Comparatively, A-values of Egyptian grass were higher as compared to rate has negligible effect (Table 6).
A-values of rice bran (1.00 x1007 s− 1 and 1.58 x1010 s− 1), red pepper
waste (3.80 × 100 s− 1 to 2.80 x1012 s− 1), and rice straw (1.70 x1007 s− 1
to 9.35 x1012 s− 1) but similar to A-values of switchgrass (3.70 x1003 s− 1

Fig. 3. Linear fit plots for determining activation energy of Egyptian Grass Where, ln (β/T 2 ) and ln (β) were plotted against inverse of pyrolysis temperature (K− 1)
using KAS and FWO methods, respectively.

5
H. Alhumade et al. Fuel 341 (2023) 127663

1.
Fig. 4. First and second order reaction kinetics at Heating rates 10, 30, 50 ◦ C min−

Table 4
Activation energy values obtained through first order and second order reaction kinetics.
First Order Reaction Second Order Reaction Sum of Reaction Order 1 and 2
A Activation Energy Values Activation Energy Values E = kJ/mol
E = kJ/mol E = kJ/mol
10 30 50 10 30 50 10 30 50

0.1 90.43 103.39 75.28 80.47 74.41 55.3 170.9 177.8 146.65
0.15 65.59 54.39 74.05 51.79 50.2 71.37 117.38 104.59 191.73
0.2 40.92 100.46 129.79 23.86 90.98 117.68 64.78 191.44 224.98
0.25 22.47 86.23 110.15 4.4 71.93 95.19 26.87 158.16 143.66
0.3 24.58 26.73 52.36 5.58 7.63 33.51 30.16 34.36 60.11
0.35 44.92 19.51 12.15 24.62 5.32 7.75 69.54 24.83 25.4
0.4 104.88 43.95 34.19 80.28 22.96 13.25 185.16 66.91 82.65
0.45 174.87 129.32 73.2 136.31 100.92 48.46 311.18 230.24 227.72
0.5 167.92 152.38 192.02 98.96 116.4 154.52 266.88 268.78 333.46
0.55 117.76 178.45 231.06 38.23 135 141.44 155.99 313.45 250.87
0.6 33.49 210.26 68.64 61.46 133.7 19.81 94.95 343.96 114.86
0.65 182.86 164.99 142.37 220.23 73.39 46.22 403.09 238.38 294.5
0.7 70.33 90.44 75.63 29.29 97.53 152.13 99.62 187.97 90.95
0.75 126.11 54.94 52.13 81.66 96.01 15.32 207.77 150.95 121.555
Avg. 90.51 101.10 94.50 66.94 76.88 69.43 157.45 177.99 164.94

4. Conclusion investigation. Kinetic and thermodynamic investigations demonstrated

that the pyrolysis of Egyptian grass proceeded in three stages, with most
Egyptian grass is a low-cost, coarse, and adapted to poor soil, which of the pyrolytic reactions occurring from 151◦ C to 380 ◦ C. According to
makes its bioenergy potential through pyrolysis an intriguing topic of the degradation pattern, gaseous products might be derived from the

6
H. Alhumade et al. Fuel 341 (2023) 127663

Fig. 5. Linear fit plots for the compensation effects between the LnA and the activation energy (kJ/mol).

Table 5
Kinetic and thermodynamics parameters of Egyptian grass calculated by KAS and FWO methods.
А Ea R2 ΔH A ΔG ΔS Ea R2 ΔH A ΔG ΔS
kJmol¡1 kJmol¡1 s¡1 kJmol¡1 Jmol¡1 kJmol¡1 kJmol¡1 s¡1 kJmol¡1 Jmol¡1

KAS method FWO method

0.1 91.16 0.99 86.02 7.06 x1005 177.22 − 147.3 79.80 0.99 74.66 6.80 x1004 177.90 − 166.7
0.2 143.59 0.99 138.44 2.95 x1010 174.88 − 58.86 144.87 0.99 139.72 3.82 x1010 174.83 − 56.72
0.3 191.06 0.99 185.92 3.99 x1014 173.41 20.21 190.35 0.99 185.21 3.46 x1014 173.43 19.03
0.4 172.86 0.99 167.72 1.05 x1013 173.92 − 10.02 173.49 0.99 168.34 1.19 x1013 173.90 − 8.99
0.5 174.63 0.99 169.48 1.49 x1013 173.87 − 7.09 185.66 0.99 180.51 1.35 x1014 173.56 11.24
0.6 183.74 0.98 178.59 9.24 x1013 173.61 8.05 184.37 0.98 179.22 1.05 x1014 173.59 9.10
0.7 193.08 0.98 187.93 5.96 x1014 173.35 23.55 193.48 0.98 188.34 6.46 x1014 173.34 24.22
0.8 168.82 0.99 163.68 4.68 x1012 174.05 − 16.75 171.38 0.99 166.23 7.80 x1012 173.97 − 12.50
0.9 182.12 0.99 176.97 6.68 x1013 173.66 5.36 185.90 0.99 180.76 1.42 x1014 173.55 11.64
Avg. 166.79 – 161.64 – – – 167.70 – 162.55 – – –

Table 6
Relationship between conversion (α), pyrolytic temperature (T) and activation
energies (E) of Egyptian grass.
Conversion Temperature Reactions Activation energy
range (α) range (◦ C) (E)

Egyptian grass
α ≤ 0.1 0–153 Removal of entrapped Enhanced from
moisture and thermal starting point to 91
conversion of simple kJ mol− 1
sugars
0.1 ≤ α ≤ 0.4 153–208 Thermal degradation Escalate from 91 to
of biochemical 172 kJ mol− 1, and
content then declined from
202 to 163 kJ mol− 1
0.4 ≤ α ≤ 0.7 208–357 Conversion of lignin Enhanced from 172
to 193 kJ mol− 1
0.7 ≤ α ≤ 1.0 357–418 Decomposition of Decreased from 193
Fig. 6. Relationship between the Conversion and Pyrolysis Temperature (◦ C) of
residual lignin along to 168 kJ mol− 1, and
Egyptian Grass.
with biochar then escalate from
formation 168 to 182 kJ mol− 1
biomass primarily within this temperature range. Whereas, 23.7–24.82 for final conversion
% of biochar could be achieved. Lower N (0.97 %) and S content (0.29
%) in Egyptian grass imply reduced emission of toxic gases during
reaction have indicated that Egyptian grass is feasible for direct energy
oxidative pyrolysis which showed eco-friendly thermal conversion na­
production. It may be possible to convert into bio-oil, biochar, and other
ture of the biomass. Moreover, 18.09 MJ kg− 1 of HHV and 174.23 kJ
gaseous products through pyrolysis in cost-efficient manner. It is also
mol− 1 of ΔG values were determined by KAS and FWO models that show
suggested that this feedstock can be utilized in lab-scale pyrolysis and
the energy efficient thermal conversion potential of Egyptian grass for
gasification reactors in order to examine pyrolysis products that could
bioenergy production. Additionally, 71.04 ± 0.67 % of volatile content,
be enhanced using process optimization techniques employing
34.55 kJmol− 1–77.72 kJmol− 1 of first order reaction activation energy,
advanced machine learning techniques.
and 15.57 kJmol− 1–64.33 kJmol− 1 of activation energy for second order

7
H. Alhumade et al. Fuel 341 (2023) 127663

CRediT authorship contribution statement [16] Liu Z, Asghar A, Hou C, Ali I, Naqvi SR, Wang N, et al. Co-pyrolysis of the Chinese
liquor industry waste and bamboo waste, elucidation of the pyrolysis reaction
chemistry, and TG-FTIR-MS based study of the evolved gases. Fuel 2022;326:
Hesham Alhumade: Writing – original draft. Omar S. Alayed: 124976.
Conceptualization, Data curation. Muhammad Waqas Iqbal: Method­ [17] Sreedhar Naik B, Dangi NB, Sapkota HP, Wagle N, Nagarjuna S, Sankaranand R,
ology. Ayesha Shahid: Writing – review & editing. Tanveer Iqbal: et al. Phytochemical screening and evaluation of anti-fertility activity of
Dactyloctenium aegyptium in male albino rats. Asian Pac J Reprod 2016;5(1):51–7.
Writing – review & editing. Muhammad Sajjad Ahmad: Conceptuali­ [18] Nhuchhen DR, Salam PA. Estimation of higher heating value of biomass from
zation, Writing – original draft. Ali Elkamel: Writing – review & editing. proximate analysis: A new approach. Fuel 2012;99:55–63.
Yusuf Al-Turki: Writing – review & editing. Muhammad Aamer [19] Vyazovkin S, Chrissafis K, Di Lorenzo ML, Koga N, Pijolat M, Roduit B, et al. ICTAC
Kinetics Committee recommendations for collecting experimental thermal analysis
Mehmood: Writing – review & editing. Ghulam Abbas Ashraf: Writing data for kinetic computations. Thermochim Acta 2014;590:1–23.
– review & editing. [20] Jeguirim M, Dorge S, Trouve G. Thermogravimetric analysis and emission
characteristics of two energy crops in air atmosphere: Arundo donax and Miscanthus
giganthus. Bioresour Technol 2010;101(2):788–93.
Declaration of Competing Interest [21] Qiu J, Fernandes de Souza M, Robles-Aguilar AA, Ghysels S, Ok YS, Ronsse F, et al.
Improving biochar properties by co-pyrolysis of pig manure with bio-invasive weed
The authors declare that they have no known competing financial for use as the soil amendment. Chemosphere 2023;312:137229.
[22] Nie N, Wang Y, Yellezuome D, Liu X, Wang P, Wang X, et al. Exploring kinetic and
interests or personal relationships that could have appeared to influence thermodynamic mechanisms of switchgrass pyrolysis using iterative linear integral
the work reported in this paper. isoconversional method and master plots approach. Fuel 2023;338:127266.
[23] Kumar A, Monika, Mishra RK, jaglan S. Pyrolysis of low-value waste miscanthus
grass: Physicochemical characterization, pyrolysis kinetics, and characterization of
Data availability
pyrolytic end products. Process Saf Environ Prot 2022;163:68–81.
[24] Mehmood MA, Ye G, Luo H, Liu C, Malik S, Afzal I, et al. Pyrolysis and kinetic
Data will be made available on request. analyses of Camel grass (Cymbopogon schoenanthus) for bioenergy. Bioresour
Technol 2017;228:18–24.
[25] Howaniec N, Smolinski A. Steam gasification of energy crops of high cultivation
Acknowledgements potential in Poland to hydrogen-rich gas. Int J Hydrogen Energy 2011;36(3):
2038–43.
This project was funded by the Deanship of Scientific Research (DSR) [26] Paulrud S, Nilsson C. Briquetting and combustion of spring-harvested reed canary-
grass: effect of fuel composition. Biomass Bioenergy 2001;20(1):25–35.
at King Abdulaziz University, Jeddah, Saudi Arabia, under grant no. RG- [27] Özsin G, Pütün AE. Kinetics and evolved gas analysis for pyrolysis of food
39-135-42. The authors, therefore, acknowledge the technical and processing wastes using TGA/MS/FT-IR. Waste Manage 2017;64:315–26.
financial support provided by the DSR. The authors also acknowledge [28] Tuly S, Parveen M, Islam M, Rahman M, Haniu H. Pyrolysis kinetics study of three
biomass solid wastes for thermochemical conversion into liquid fuels. AIP Conf
the support provided by King Abdullah City for Atomic and Renewable Proceed. 1851. AIP Publishing; 2017:020083.
Energy (K.A. CARE) under K.A. CARE-King Abdulaziz University [29] Martelli-Tosi M, Masson MM, Silva NC, Esposto BS, Barros TT, Assis OBG, et al.
Collaboration Program. Soybean straw nanocellulose produced by enzymatic or acid treatment as a
reinforcing filler in soy protein isolate films. Carbohydr Polym 2018;198:61–8.
[30] Nozela WC, Braz CEM, Almeida S, Ribeiro CA, Crespi MS. Mixture of biomass to
References energy reuse. J Therm Anal Calorim 2018;131(1):765–9.
[31] Rocha EPA, Sermyagina E, Vakkilainen E, Colodette JL, de Oliveira IM, Cardoso M.
[1] Saqib A, Tabbssum MR, Rashid U, Ibrahim M, Gill SS, Mehmood MA. Marine macro Kinetics of pyrolysis of some biomasses widely available in Brazil. J Therm Anal
algae Ulva: A Potential feed-stock for bio-ethanol and biogas production. Asian J Calorim 2017;130(3):1445–54.
Agri Biol 2013;1(3):155–63. [32] Romero Millán LM, Sierra Vargas FE, Nzihou A. Kinetic analysis of tropical
[2] khan M, Raza Naqvi S, Ullah Z, Ali Ammar Taqvi S, Nouman Aslam Khan M, lignocellulosic agrowaste pyrolysis. BioEnergy Res 2017;10(3):832–45.
Farooq W, et al. Applications of machine learning in thermochemical conversion of [33] Ferdosian F, Yuan Z, Anderson M, Xu CC. Thermal performance and thermal
biomass-A review. Fuel 2023;332:126055. decomposition kinetics of lignin-based epoxy resins. J Anal Appl Pyrolysis 2016;
[3] Ahmad MS, Mehmood MA, Taqvi STH, Elkamel A, Liu C-G, Xu J, et al. Pyrolysis, 119:124–32.
kinetics analysis, thermodynamics parameters and reaction mechanism of Typha [34] Brachi P, Miccio F, Miccio M, Ruoppolo G. Pseudo-component thermal
latifolia to evaluate its bioenergy potential. Bioresour Technol 2017;245:491–501. decomposition kinetics of tomato peels via isoconversional methods. Fuel Process
[4] Mercado JP, Ubando AT, Gonzaga JA, Naqvi SR. Life cycle assessment of a biomass Technol 2016;154:243–50.
based chemical looping combustion. Environ Res 2023;217:114876. [35] Mishra S, Verma J. Thermal decomposition kinetics of silane treated wood: PVC
[5] Patel M, Zhang X, Kumar A. Techno-economic and life cycle assessment on microcellular composites. Int J Plast Technol 2016;20(1):93–105.
lignocellulosic biomass thermochemical conversion technologies: A review. Renew [36] Elmay Y, Jeguirim M, Trouvé G, Said R. Kinetic analysis of thermal decomposition
Sust Energ Rev 2016;53:1486–99. of date palm residues using Coats-Redfern method. Energy Sour, Part A: Recover
[6] Rogers J, Brammer J. Estimation of the production cost of fast pyrolysis bio-oil. Util Environ Effec 2016;38(8):1117–24.
Biomass Bioenergy 2012;36:208–17. [37] Iqbal A, Badshah SL, Alves JLF, da Silva JCG, Di Domenico M. An insight into the
[7] Ahmad MS, Mehmood MA, Al Ayed OS, Ye G, Luo H, Ibrahim M, et al. Kinetic thermokinetics of the pyrolysis of invasive grass Sorghum halepense towards its
analyses and pyrolytic behavior of Para grass (Urochloa mutica) for its bioenergy bioenergy potential. Biomass Convers Bior 2022.
potential. Bioresour Technol 2017;224:708–13. [38] Bhagavatula A, Shah N, Honaker R. Estimating the pyrolysis kinetic parameters of
[8] Slopiecka K, Bartocci P, Fantozzi F. Thermogravimetric analysis and kinetic study coal, biomass, and their blends: a comparative study. Energy Fuels 2016;30(12):
of poplar wood pyrolysis. Appl Energy 2012;97:491–7. 10045–54.
[9] Maia AAD, de Morais LC. Kinetic parameters of red pepper waste as biomass to [39] Hameed S, Sharma A, Pareek V, Wu H, Yu Y. A review on biomass pyrolysis
solid biofuel. Bioresour Technol 2016;204:157–63. models: Kinetic, network and mechanistic models. Biomass Bioenergy 2019;123:
[10] Heo HS, Park HJ, Park Y-K, Ryu C, Suh DJ, Suh Y-W, et al. Bio-oil production from 104–22.
fast pyrolysis of waste furniture sawdust in a fluidized bed. Bioresour Technol [40] Biney PO, Gyamerah M, Shen J, Menezes B. Kinetics of the pyrolysis of arundo,
2010;101(1):S91–6. sawdust, corn stover and switch grass biomass by thermogravimetric analysis using
[11] Braga RM, Melo DMA, Aquino FM, Freitas JCO, Melo MAF, Barros JMF, et al. a multi-stage model. Bioresour Technol 2015;179:113–22.
Characterization and comparative study of pyrolysis kinetics of the rice husk and [41] Vlaev L, Georgieva V, Genieva S. Products and kinetics of non-isothermal
the elephant grass. J Therm Anal Calorim 2014;115(2):1915–20. decomposition of vanadium (IV) oxide compounds. J Therm Anal Calorim 2007;88
[12] Mei Y, Liu R, Wu W, Zhang L. Effect of hot vapor filter temperature on mass yield, (3):805–12.
energy balance, and properties of products of the fast pyrolysis of pine sawdust. [42] Turmanova SC, Genieva S, Dimitrova A, Vlaev L. Non-isothermal degradation
Energy Fuels 2016;30(12):10458–69. kinetics of filled with rise husk ash polypropene composites. Express Polym Lett
[13] Khan WUH, Khoja AH, Gohar H, Naqvi SR, Din IU, Lumbers B, et al. In depth 2008;2(2):133–46.
thermokinetic investigation on Co-pyrolysis of low-rank coal and algae consortium [43] Ren S, Lei H, Wang L, Bu Q, Chen S, Wu J. Hydrocarbon and hydrogen-rich syngas
blends over CeO2 loaded hydrotalcite (MgNiAl) catalyst. J Environ Chem Eng production by biomass catalytic pyrolysis and bio-oil upgrading over biochar
2022;10(5):108293. catalysts. RSC Adv 2014;4(21):10731–7.
[14] Tauseef M, Ansari AA, Khoja AH, Naqvi SR, Liaquat R, Nimmo W, et al. [44] Boubacar Laougé Z, Merdun H. Kinetic analysis of Pearl Millet (Penissetum
Thermokinetics synergistic effects on co-pyrolysis of coal and rice husk blends for glaucum (L.) R. Br.) under pyrolysis and combustion to investigate its bioenergy
bioenergy production. Fuel 2022;318:123685. potential. Fuel 2020;267:117172.
[15] Mankeed P, Onsree T, Naqvi SR, Shimpalee S, Tippayawong N. Kinetic and [45] Boubacar Laougé Z, Merdun H. Pyrolysis and combustion kinetics of Sida cordifolia
thermodynamic analyses for pyrolysis of hemp hurds using discrete distributed L. using thermogravimetric analysis. Bioresour Technol 2020;299:122602.
activation energy model. Case Stud Therm Eng 2022;31:101870.