Bioresource Technology Reports 24 (2023) 101635

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Bioresource Technology Reports

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Improved bio-oil yield from thermo-catalytic pyrolysis of Citrus limetta

waste over pumice: Determination of kinetic parameters using
Kissinger method
Faisal Muhammad a, Jan Nisar a, *, Ghulam Ali a, *, Farooq Anwar b, c, Syed Tasleem Hussain d,
Sher Wali Khan e
a
National Center of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan
b
Department of Food Science, Faculty of Food Science and Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
c
Institute of Chemistry, University of Sargodha, Sargodha 40100, Pakistan
d
Department of Chemistry, Kohat University of Science and Technology (KUST), Kohat 26000, Pakistan
e
Department of Chemistry, Shaheed Benazir Bhutto University, Sheringal Dir (U), Pakistan

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

Keywords: The focus of this research is on thermo-catalytic conversion of Citrus limetta waste, with and without pumice,
Biomass waste using thermo gravimetric analysis and a pyrolysis chamber. TG/DTG results demonstrated weight reduction
Bio-valorization occurring in four stages i.e., evaporation of water, degradation of hemicellulose, decomposition of cellulose and
Pyrolysis
lignin. Activation energy (Ea) calculated using Kissinger method for non-catalytic decomposition of hemicellu­
Bioproducts
Bio-oil
lose, cellulose, and lignin was found as 99.76, 157.96 and 174.59 kJ mol− 1 and for catalyzed reactions as 83.14,
Kinetics 91.45 and 149.65 kJ mol− 1respectively. Thermal degradation of Citrus limetta waste produced 30 % oil in the
range of C2–C24, while catalytic pyrolysis produced more than 45 % pyrolysis oil with a wide range of com­
ponents from C4 to C32 which shows, that pumice has not only decreased the activation energy of the pyrolysis
reaction but improved the quality of bio-oil making it suitable for energy on upgradation.

1. Introduction emissions and environmental issues, fossil fuel energy poses sustain­
ability concerns (Pata et al., 2023). As a result, there is a global push to
The economy of a country is heavily dependent on energy, and the explore alternative sustainable and environmentally friendly fuel sour­
economic strength of any country directly affects its stability and pros­ ces (Nisar et al., 2023). International organizations have made consid­
perity (Demirbas, 2000). The provision of a reliable, inexpensive, and erable efforts to address this issue by adopting renewable and carbon-
eco-friendly energy source is essential for society, the ecosystem, and the neutral energy sources that can meet energy demands without causing
economy, and it will continue to be at the forefront of innovation in the harm to the environment (Najam, 2023). Hence, researchers and the
21st century (Sivalingam et al., 2023). Countries, as well as individuals, industry are exploring ways to develop cost-effective renewable energy
require a secure source of energy, and they need to be confident that sources (Praene et al., 2021; Raheem et al., 2016). These sources
they have enough and suitable energy resources under their own man­ comprise biomass, marine energies, solar, geothermal, wind, and hy­
agement (Jie et al., 2023). The exhaustion of traditional energy sources dropower (Afraz et al., 2024). Out of all renewable energy sources, there
like fossil fuels, which are the primary source of energy worldwide, is a greater interest in agro-industrial and agricultural wastes including
results in environmental adversities due to their excessive consumption citrus waste (Volpe et al., 2015; Yaashikaa et al., 2022).
and harmful effects on the environment. Furthermore, the fuel crisis Citrus is cultivated in diverse tropical and subtropical regions across
worldwide has highlighted the significance of renewable energy sources the globe (Zhong and Nicolosi, 2020). The United States, Brazil, China,
(Nathaniel et al., 2021). The greenhouse effect, which contributes to Spain, Mexico, Turkey, Iran, Egypt, India, Italy, Argentina, and Pakistan
global warming on earth, is caused by a rise in CO2 emissions and other are among the top global producers of Citrus limetta (Topi, 2020). Citrus
environmental pollutants (Kleidon et al., 2023). Apart from carbon limetta is a member of the Citrus genus, specifically the Limetta species,

* Corresponding authors.
E-mail addresses: jan_nisar@uop.edu.pk (J. Nisar), ghulamali@uop.edu.pk (G. Ali).

https://doi.org/10.1016/j.biteb.2023.101635
Received 18 August 2023; Received in revised form 18 September 2023; Accepted 19 September 2023
Available online 20 September 2023
2589-014X/© 2023 Elsevier Ltd. All rights reserved.
F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

and belongs to the Rutaceae family and it is generally known as sweet using Scherer’s equation.
lemon in various parts of the world (Federici et al., 1998; Gautam,
2018). Citrus limetta fruit comprises of only 40–50 % citrus juice, with a
2.3. Pyrolysis and GCMS
considerable amount of its byproducts, such as pulp, peel, and seeds,
accounting for approximately half of the fruit’s total weight (Sharma
The pyrolysis was performed in a salt furnace. A comprehensive
et al., 2019). Tons of waste is created during the processing of the fruit
explanation of the system has previously been provided in our former
products in the form of fruit seeds, peel, and pulp. The majority of solid
articles (Ali et al., 2023; Nisar et al., 2022b). Yet, a brief description is
waste is discarded without being reused, which otherwise is a valuable
presented here. The salt bath (Fig. 1) consists of a circular steel can fitted
resource for producing value-added products through chemical or bio­
in another rectangular steel can and the space between the two vessels is
logical conversion processes due to their affordability, active ingredient
filled in with insulated materials. The salt mixture in the bath was
content, and suitability for enzymatic fermentation (Singhi et al., 2023).
heated by an electric heater to the desired temperature and the pyrolysis
Earlier investigations have reported polyphenols in abundance in peels,
of the sample was conducted in a glass flask hanging inside the bath and
and tocopherol and hesperidin in seeds of Citrus limetta, both of which
joined with a condenser that had provision for collection of oil. The
exhibit robust antioxidant properties (Damián-Reyna et al., 2017;
pyrolytic oil obtained was weighed, filtered, and its composition was
Padilla-Camberos et al., 2014). Moreover, it is a rich source of several
analyzed using a Shimadzu QP2010 Ultra GC/MS, Japan.
phytochemicals, polyphenols and flavonoids that are highly valued in
the pharmaceutical industry for their use in producing drugs and dietary
supplements. These compounds are known for their numerous health 2.4. Thermogravimetry
benefits, making Citrus limetta a popular choice for use in various
healthcare products (Khan et al., 2016; Mahato et al., 2018; Safaeian A Simultaneous Thermogravimetric Analyzer (TGA Q500, TA, USA)
Laein et al., 2021). Conversely, dumping of citrus waste causes an un­ was used to conduct Thermogravimetric analysis of Citrus limetta waste
pleasant odor and pollutes the land, air, water and spreads diseases by from 25 to 600 ◦ C at various programme rates (15, 20, 25, and
many means, which is a significant concern, particularly in developing 30 ◦ C⋅min− 1). The data collected was utilized to calculate kinetic pa­
countries. Moreover, the management of citrus waste is also associated rameters, employing Kissinger model (Eq. (1)).
with high costs, both economically and environmentally (Anticona [ ] ( )
β AR E
et al., 2020). ln 2 = ln − (1)
Tm E RTm
Hence, the motive behind the current research work is thermo-
catalytic degradation of Citrus limetta waste using pumice as a catalyst; where R (JK− 1 mol− 1) stands for general gas constant, Ea (kJ⋅mol− 1)
therefore, we utilized thermogravimetry to assess the kinetics of the activation energy, A (min− 1) pre-exponential factor, β (◦ C⋅min− 1)
reaction applying Kissinger equation. Moreover, we conducted pyrolysis heating rate, and Tm (◦ C) represents the maximum degradation tem­
experiments with the same catalyst over a temperature range of perature. Ea and A values were evaluated from the intercept and slope of
300–400 ◦ C and employed pyrolysis GC–MS to identify the resulting [ ]
products and comprehend the degradation mechanism. Although the the plot ln Tβ2 versus 1000
Tm using the Kissinger method (Blaine and Kis­
m

components found in the resulting bio-oil were not found completely singer, 2012).
analogous to those of commercial fuel oil, however, the oil if upgraded
properly will make it useful for energy use. If this project is implemented 3. Results and discussion
on a commercial scale, it would have promising prospects as a source of
energy and could have positive implications for the environment. 3.1. Characterization of catalyst

2. Experimental Fig. 2(a and b) displays the SEM images obtained of pumice at
different magnifications. Careful observation reveals that the sample has
2.1. Materials a rough surface with wide cavities and micro pores. The image also re­
veals the presence of various microstructures distributed irregularly in
Central and southern Punjab is known for their large production of the pumice, with granular and homogenous features. Some of these
Citrus limetta. For the purpose of this study, Citrus limetta waste was microstructures are agglomerated masses, and they vary in size, with
procured from a local juice shop in Sargodha. The collected waste were some being small and others being larger. The average size of these
then dried completely for a period of three to four weeks, following micro-structures was determined to be 0.506 μm in diameter using
which they were finely ground into a mesh size of 35. ImageJ software. Additionally, the scanning electron microscope image
To select the most suitable catalyst, pumice was chosen from various showed the porous nature of the catalyst’s surface, which is consistent
natural wastes, based on its anticipated properties. The pumice was with previous research.
ground into powder using a laboratory disc mill/disc crusher and stored Ersoy et al. (2010) conducted SEM analysis of pumice and observed
for further study. To maintain proper cleanliness of the equipment used irregular (oval-shaped cavities) with a fibrous structure with no aggre­
in the pyrolysis experiment, including the condenser, connecting glass gation. They found pore diameter of these cavities ranging from 0.5 μm
tubes, and other glassware were regularly washed with acetone after to 2 nm. Rakhman et al. (2023) studied morphology and particle size of
each use. pumice particles and observed an average size of 30 ± 16 nm. Çifçi and
Meriç (2016) examined SEM images of pumice and observed a highly
2.2. Characterization of catalyst porous and rough surface with irregularly arranged grain size particles
with varying edges.
The structural features and elemental composition of pumice was The data presented in Fig. 3 displays EDX of pumice, showing the
studied using scanning electron microscopy (JSM-IT-100 JEOL, Japan) atomic percentages of various elements. These include oxygen (52.90
and Energy-dispersive spectroscopy (INCA 200, Oxford Instrument, UK). %), sodium (4.35 %), magnesium (3.02 %), aluminum (7.64 %), silicon
The existence of various compounds in the sample was determined (19.64 %), phosphorus (0.41 %), sulfur (0.29 %), chlorine (0.19 %),
using X-rays fluorescence spectrometer (model EDX 7000, Japan). potassium (1.78 %), calcium (6.57 %), titanium (0.51 %), and iron (2.71
Additionally, the sample’s crystalline phase was identified with X-rays %). The findings are somewhat consistent with prior research. Çifçi and
diffractometer (JDX-3532, JEOL, Japan) using Match software. The in­ Meriç (2017) performed EDX analysis of pumice. They found that oxy­
tensities versus 2θ were plotted, and the crystal size was determined gen and silicon are the major elements. Further, they noticed that

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Fig. 1. Schematic sketch of pyrolysis assembly.

Fig. 2. SEM images of pumice at (a) ×15,000 (b) ×10,000.

pumice mainly contains 27.8 % Si, 60.9 % O, 6.6 % Al, 1.3 % K, 0.3 % Fe alumina (19.7 %) and potassium oxide (10.2 %), while calcium oxide,
and 3.2 % Na. Ismail et al. (2013) conducted an EDX analysis of pumice ferric oxide, magnesium oxide and sodium oxide were observed in
and discovered that the sample contained oxygen, silicon, aluminum, smaller amounts. Kitis et al. (2005) utilized X-ray fluorescence to
potassium, calcium, and iron. analyze the composition of pumice and found SiO2 (59.0 %), Al2O3
XRF analysis was also conducted on the pumice. Table 1 shows the (16.6 %), TiO2 (0.6 %), CaO (4.6 %), Fe2O3 (4.8 %), MgO (1.8 %), K2O
results obtained from XRF analysis of the pumice, which indicated high (5.4 %), SO3 (0.4 %), and Na2O (5.2 %).
levels of silica (44.18 %), alumina (18.18 %), calcium oxide (17.47 %), The degree of crystallinity of the pumice was assessed through XRD.
ferric oxide (13.28 %), potassium oxide (3.09 %), titanium oxide (2.57 The XRD of the natural catalyst pumice displayed broad lines, indicating
%), sulfur oxide (0.52 %), strontium oxide (0.27 %), manganese oxide its crystalline form. Alongside the prominent peak at 28◦ , several weaker
(0.22 %), vanadium oxide (0.10 %), zirconium dioxide (0.039 %), signals were also observed at 35◦ , 33◦ , and 40◦ , as illustrated in Fig. 4.
chromium oxide (0.024 %), copper oxide (0.023 %), zinc oxide (0.020 The results are in line with earlier work. Ersoy et al. (2010) used XRD
%), nickel oxide (0.015 %), niobium monoxide (0.008 %) and yttrium analysis to assess the crystallinity of pumice, which revealed two peaks
oxide (0.005 %), respectively. The XRF data is consistent with the results at 23◦ and 28◦ . These peaks were attributed to the existence of natural
obtained from EDX analysis and with relevant literature. Sepehr et al. zeolite. The remaining peaks were wider, indicating the amorphous
(2014) studied the chemical components of natural pumice. They found nature of the pumice. Chuan et al. (2004) examined the original
that the pumice contains alumina, silica, calcium oxide, titanium oxide, composition and properties of pumice using XRD. The data showed
ferric oxide, strontium oxide, potassium oxide, and sulfur oxide with presence of a broad band for amorphous phase around 24◦ in 2θ, and
percentage 17.24, 63.45, 3.22, 0.37, 2.86, 0.09, 2.16, and 0.16 respec­ sharp peaks for crystalline feldspar. The researchers also found that
tively. Alvarez-Galvan et al., (Álvarez-Galván et al., 2008) examined the impurities, such as feldspar, were not evenly distributed among pumice
XRF of pumice and found silica in abundance (52.5 %), followed by particles and were absent in some cases. Ismail et al. (2013) conducted

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Fig. 3. EDX of natural catalyst pumice.

XRD analysis on pumice and authors identified that the sample was
Table 1
primarily comprised of small crystals of quartz and cristobalite (SiO2).
XRF analysis demonstrating different compounds and their percentages in
pumice.
S. no. Compounds %age 3.2. Pyrolysis of Citrus limetta waste and characterization of bio-oil
1. SiO2 44.18
2. Al2O3 18.18 Experiments involving pyrolysis of Citrus limetta waste were con­
3. CaO 17.47
ducted using a homemade furnace at different temperatures and dura­
4. Fe2O3 13.28
5. K2O 3.09 tion. Each experiment involved taking 3 g of the sample in reaction flask
6. TiO2 2.57 and inserted into the bath. The experiments were done at temperature
7. SO3 0.52 intervals of 10◦ , ranging from 300 ◦ C to 380 ◦ C. Fig. 5a demonstrates the
8. SrO 0.27 results of non-catalytic pyrolysis experiments conducted on Citrus limetta
9. MnO 0.22
waste, showing a gradual increase in oil content that peaks at 340 ◦ C.
10. V2O5 0.10
11. ZrO2 0.039 Beyond this temperature, the amount of oil decreases. The study
12. Cr2O3 0.024 determined that the optimal temperature for achieving maximum oil
13. CuO 0.023 recovery was 340 ◦ C. At elevated temperature, the gaseous fraction
14. ZnO 0.020
increased, which is because of the secondary breakdown of the liquid
15. NiO 0.015
16. NbO 0.008
fraction that was formed during the process. Moreover, the increased gas
17. Y2O3 0.005 production is also due to the breakdown of secondary pyrolysis of solid
products which resulted in decrease in amount of solid product (Demi­
rbas, 2007; Nisar et al., 2022b; Nisar et al., 2022c; Williams and Besler,
1996).
Miranda et al. (2009) conducted a study to explore the pyrolysis
process of dry sweet orange peels. This investigation yielded three main
fractions: biochar, bio-oil, and gases. The percentage yield of bio-oil was
53.1 %, while the yields of biochar and gaseous were found as 21.1 %
and 25.8 %, respectively.
Fig. 5b illustrates the results of catalytic degradation on Citrus limetta
waste at different temperatures. The graph indicates that the maximum
liquid product is obtained at 320 ◦ C with %yield of 45 %, after which it
decreases. This implies that the utilization of pumice catalyst resulted in
the highest possible oil yield while also decreasing the optimum tem­
perature to 320 ◦ C. These results align with those of Nisar et al. (2022d)
on degradation of Karanja seed press cake. The study demonstrated
lowering of temperature for maximum oil production from Karanja seed
waste with anthill. Poddar et al. (2022) investigated the non-catalytic
and catalytic pyrolysis of orange peel using a semi-batch reactor at
temperatures ranging from 573 to 1173 K. They discovered that the
addition of catalysts resulted in a higher yield of pyro-oil, ranging from
30.79 to 49.45 wt%, with the ZnO nano-catalyst proving to be the most
efficient among the catalysts tested. Aho et al. (2008) investigated
degradation of woody biomass loaded with zeolite, and achieved a
Fig. 4. XRD analysis of natural catalyst pumice. noteworthy enhancement in bio-oil yield. These outcomes are in har­
mony with our research findings.
The study was also aimed to optimize the time at optimum

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Fig. 5. Optimization study of Citrus limetta waste (a) temperature effect without pumice (b) temperature effect with pumice (c) time effect (d) effect of pumice
concentration.

temperature for catalytic pyrolysis of Citrus limetta waste. This was done formulas, molecular weights, and percent area of the components traced
by varying the time at optimum temperature while measuring the bio-oil in the oil. The oil from non-catalytic decomposition contains hydro­
in each experiment to determine the optimal time for maximum oil. The carbons ranging from C2–C24. The prominent group of compounds
optimal time for highest oil yield was determined to be 25 min. In identified were derivatives of benzenes, phenols, naphthalenes, ketones
addition, increasing the time resulted in rise in gaseous contents and a and alcohols. The major compounds traced were 2-naphthalenemetha­
decline in solid residue. Graphical presentation of the percentages of nol, Catechol (1,2-Benzenediol), 4-isobenzofurancarboxylic acid,
pyrolytic products obtained through catalytic pyrolysis for time opti­ (+)-4-Carene, 1H-Cyclopropa[a]naphthalene, 2-methoxy-phenol, and
mization is given in Fig. 5c. These outcomes are in line with literature. naphthalene, decahydro-4a-methyl-1-methylene.
Nisar et al. (2022b) investigated pyrolysis of almond shell and maximum In contrast the oil from catalytic reaction resulted in a distinct
bio-oil was achieved at 40 min at an optimum temperature of 420 ◦ C. chemical composition and nature of the oil. Hydrocarbons ranging from
The effect of catalyst on oil production was studied by varying the C3 to C32 were traced. The prominent group of compounds identified
concentration of catalyst under optimal time and temperature condi­ were derivatives of furan, benzenes, phenols, naphthalenes, aldehydes,
tions. The results showed catalyst concentration of 3 % as the optimum ketones, carboxylic acids, and alcohols. The major hydrocarbons iden­
amount for maximum bio-oil yield. The results are depicted in Fig. 5d. tified were 2-Furanmethanol, 2-Furancarboxaldehyde, 4H-Pyran-4-one,
The figure clearly illustrates that the oil yield undergoes improvement as 2,3-dihydro-3,5-dihydroxy-6-methyl, 5-Hydroxymethylfurfural, 6-
the catalyst loading is increased from 1 to 3 %. However, beyond this Amino-1,3,5-triazine-2,4(1H,3H)-dione, 1,2-Cyclopentanedione, 3-
optimal level, the bio-oil yield starts to decline. This suggests that methyl 2-Furancarboxaldehyde, Benzene-D6, 2-Methoxy-4-vinylphenol,
increasing the catalyst promotes liquefaction, but has a detrimental 2-Pentene, 1-ethoxy-4,4-dimethyl, and 2-methoxy Phenol. The presence
impact beyond the optimal threshold of 3 %. This decline is attributed to of phenolic compounds is a result of lignin decomposition, while furan is
the bio-oil molecules being readily adsorbed onto the catalyst’s high produced by hemicelluloses breakdown. Acidic components were
specific surface area, resulting in catalyst poisoning (Nisar et al., 2022a). formed by the partial decomposition of lignin, cellulose, and hemicel­
Nisar et al. (2022a) performed pyrolysis experiments on peanut shells, lulose (Uçar and Karagöz, 2009). The GC–MS analysis further highlights
employing termite hill as the catalyst. Their findings revealed that in­ the presence of valuable compounds within the bio-oil, including
crease in bio-oil yield was observed when a catalyst loading of 5 % was furfural, phenols, maltol and benzene derivatives. These components
utilized. contribute significantly to enhancing the overall quality of the oil,
thereby indicating its potential value and desirability in various appli­
cations. Therefore, the results suggest that the use of pumice as a catalyst
3.3. GCMS of bio-oil
was effective in refining the oil. These findings are consistent with
earlier work. Nisar et al. (2022b) studied pyrolysis of almond shells and
Both the pyrolytic oils were analyzed through GC–MS. Fig. 6(a, b)
it was observed that zinc oxide increased the quality of bio-oil. A similar
displays the chromatograms obtained from the GC–MS analysis, while
trend was also observed during the decomposition of Karanja seeds press
Tables 2 and 3 present the retention times, compound names, chemical

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Fig. 6. Chromatograms of oil obtained from pyrolysis of Citrus limetta waste (a) without pumice (b) with loaded pumice.

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Table 2
Compounds detected in Citrus limetta waste oil obtained from pyrolysis without pumice.
S. no. RT Compound Chemical Molecular Area
formula weight %

1 3.785 2-Methoxyphenol C7H8O2 124.14 3.89

2 4.215 3-Acetoxy-2-methyl-pyran-4-one C8H8O4 168.15 1.68
3 4.524 3,5-Dihydroxy-6-methyl-2,3-dihydro-4H-pyran-4-one C6H8O4 144.12 2.29
4 5.193 alpha-TERPINEOL C10H18O 154.25 2.01
5 5.347 Catechol (1, 2-Benzenediol) C6H6O2 110.11 6.13
6 5.748 2-Fluorobenzyl alcohol C7H7FO 126.13 0.94
7 6.355 1-(2,3-Dihydroxyphenyl)ethenone C8H8O3 152.15 1.65
8 6.629 Hydroquinone (1,4-Benzenediol) C6H6O2 110.11 3.15
9 6.824 3,7,7-Trimethyl-8-(2-methyl-propenyl)-bicyclo[4.2.0]oct-2-ene C15H24 204.35 0.76
10 6.875 2-Methoxy-4-vinylphenol C9H10O2 150.17 1.39
11 7.270 (4S,5S)-(− )-2-Methyl-5-phenyl-2-oxazoline-4-methanol C11H13NO2 191.23 0.86
12 7.367 (+)-4-Carene C10H16 136.23 4.35
13 7.711 Azulene, 1,2,3,3a,4,5,6,7-octahydro-1,4-dimethyl-7-(1-methylethenyl)-,[1R(1.alpha.,3a.beta.,4.alpha. C15H24 204.3511 0.66
14 7.882 2-Acetamido-4-methylphenyl acetate C11H13NO3 207.23 0.92
15 8.037 Cyclohexene, 1-methyl-4-(1-methyle C10H18 138.25 0.55
1H-Cyclopropa[a]naphthalene, 1a,2,3,3a,4,5,6,7b-octahydro-1,1,3a,7-tetramethyl,[1Ar(1a.alpha.,3a.
16 8.180 C15H24 204.35 0.54
alpha.,7b.alpha.)]-
17 8.386 gamma.-Elemene C15H24 204.35 1.11
18 8.409 2-(4a,8-Dimethyl-2,3,4,5,6,8a-hexahydro-1H-naphthalen-2-yl)propan-2-ol C15H26O 222.3663 0.70
19 8.552 Aromandendrene C15H24 204.3511 4.38
20 8.666 2-(4a,8-Dimethyl-2,3,4,5,6,8a-hexahydro-1H-naphthalen-2-yl)propan-2-ol C15H26O 222.3663 0.79
21 8.712 Isolongifolene, 9,10-dehydro- C15H22 202.3352 2.30
22 8.821 Alloaromadendrene C15H24 204.3511 2.51
23 9.004 4a,8-Dimethyl-2-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,7-octahydronaphthalene C15H24 204.3511 1.67
24 9.158 Naphthalene,decahydro-4a-methyl-1-methylene-7-(1-methylethenyl)-,[4Ar-(4a.alpha.,7.alpha.,8a.beta.) C15H24 204.3511 3.58
1H-Cyclopropa[a]naphthalene,1a,2, 3,3a,4,5,6,7b-octahydro-1,1,3a,7-tetramethyl-, [1Ar-(1a.alpha.,3a.
25 9.261 C15H24 204.3511 4.23
alpha.,7b.alpha.)]-
26 9.416 Aromandendrene C15H24 204.35 1.63
Azulene, 1,2,3,3a,4,5,6,7-octahydro-1,4-dimethyl-7-(1-methylethenyl)-, [1R-(1.alpha.,3a.beta.,4.alpha.,7.
27 9.542 C15H24 204.3511 1.67
beta.)]-
28 10.057 Aromandendrene C15H24 204.3511 1.04
Naphthalene, 1,2,3,5,6,7,8,8a-octahydro-1,8a-dimethyl-7-(1-methylethenyl)-, [1S-(1.alpha.,7.alpha.,8a.
29 10.102 C15H24 204.3511 0.60
alpha.)]-
Naphthalene, 1,2,3,5,6,7,8,8a-octaHydro-1,8a-dimethyl-7-(1-methylethenyl)-, [1S-(1.alpha.,7.alpha.,8a.
30 10.148 C15H24 204.3511 1.03
alpha.)]-
1H-Cycloprop[e]azulen-7-ol, decahydro-1,1,7-trimethyl-4-methylene-,[1ar-(1a.alpha.,4a.alpha.,7.beta.,7a.
31 10.268 C15H24O 220.3505 2.20
beta.,7b.alpha.)]-
32 10.349 (− )-Globulol C15H26O 222.3663 2.31
33 10.503 Longifolene C15H24 204.3511 1.81
34 10.566 1H-Indene,1-ethylideneoctahydro-7a-methyl-,(1E,3a.alpha.,7a.beta.) C12H22 166.30 0.69
Naphthalene, 1,2,3,5,6,7,8,8a-octahydro-1,8a-dimethyl-7-(1-methylethenyl)-, [1S-(1.alpha.,7.alpha.,8a.
35 10.720 C15H24 204.3511 1.45
alpha.)]-
Azulene, 1,2,3,3a,4,5,6,7-octahydro-1,4-dimethyl-7-(1-methylethenyl)-, [1R-(1.alpha.,3a.beta.,4.alpha.,7.
36 10.806 C15H24 204.3511 2.20
beta.)]-
37 10.835 2-Naphthalenemethanol, 1,2,3,4,4a,5,6,7-octahydro-.alpha.,.alpha.,4a,8-tetramethyl-, (2R-cis)- C15H26O 222.3663 2.49
38 10.898 2-Naphthalenemethanol, 1,2,3,4,4a,5,6,7-octahydro-.alpha.,.alpha.,4a,8-tetramethyl-, (2R-cis)- C15H26O 222.3663 2.06
39 10.978 4-Isobenzofurancarboxylic acid, 1,3-dihydro-1-oxo- C9H6O4 178.14 4.79
2-Naphthalenemethanol, decahydro-.alpha.,.alpha.,4a-trimethyl-8-methylene-, [2R-(2.alpha.,4a.alpha.,8a.
40 11.121 C15H26O 222.3663 10.02
beta.)]-
2-Naphthalenemethanol,1,2,3,4,4a,5,6,8a-octahydro-.alpha.,.alpha.,4a,8-tetramethyl-, [2R-(2.alpha.,4a.
41 11.144 C15H26O 222.37 1.93
alpha.,8a.beta.)]-
42 11.848 Pregn-5-en-20-one, 3,21-bis(acetyloxy)-, (3.beta.)- C24H40O2Si 388.7 1.29
43 12.071 Ylangenal C15H22O 218.3346 2.22
44 12.311 (1S,4R,5S)-1-Methyl-4-(prop-1-en-2-yl)spiro[4.5]dec-7-ene-8-carbaldeHyde C15H22O 218.3346 0.46
45 12.391 1,3-Benzodioxole, 4-methoxy-6-(2-propenyl)- C12H14O4 222.24 0.73
46 13.095 1,1,2,2-Tetramethyl-5-methylidene-octahydrocyclopropa[e]azulene C15H24 C15H24 0.27
47 14.159 Phenol, 2,6-bis(1,1-dimethylethyl)-4-ethyl- C16H26O 234.3770 2.02
48 17.335 Ethanol, 2-bromo- C2H5BrO 124.964 0.35
49 21.901 13-Docosenamide, (Z)- C22H43NO 337.5829 1.69

cake over anthill (Nisar et al., 2022d). 3.4. Kinetic study

Shah et al. (2016) conducted analysis of bio-oils derived from
different biomass sources, employing GCMS. The results revealed mul­ In order to calculate kinetic parameters from TG data for catalytic
tiple components in the oil, including phenols, aromatics, alcohols and and non-catalytic reactions, Kissinger equation was used and the plots
ketones. Decomposition of pomegranate peel was studied by Rehman constructed are presented in Fig. 7(a, b). Kinetic parameters were
et al. (2023) using sulphonated tea waste as catalyst and derived bio-oil calculated from the plots for the degradation of hemicellulose, cellulose
was characterized by GC/MS. Hydrocarbons ranging between C5-C13 and lignin (Table 4). The results show that pumice has reduced Ea of
were traced in non-catalytic liquid whereas the catalyst enhanced the hemicellulose, cellulose and lignin degradation from 99.76, 157.96,
hydrocarbons range from C5-C23. 174.59 to 83.14, 91.45 and 149.65 respectively. These outcomes are in
line with earlier work. Nisar et al. (2022c) studied catalyzed/non-
catalyzed reactions of grape fruit waste using NiO as catalyst. The Ea

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Table 3
Compounds detected in Citrus limetta waste oil obtained from pyrolysis with loaded pumice.
S. no. RT Compound Chemical formula Molecular weight Area %

1. 3.186 2-Furanmethanol C5H6O2 98.0999 5.38

2. 3.270 Pyrazole, 1,4-dimethyl- C5H8N2 96.1304 1.38
3. 3.500 Benzene-D6 C6D6 84.1488 2.77
4. 3.529 Methyl methacrylate C5H8O2 100.1158 0.56
5. 3.624 4,4-Dimethyl-2-cyclopenten-1-one C7H10O 110.1537 0.08
6. 3.681 Pentane, 1-(ethenyloxy)- C7H14O 114.19 0.69
7. 3.726 2(5H)-Furanone, 5-methyl- C5H6O2 98.0999 0.35
8. 3.806 1,2-Cyclopentanedione C5H6O2 98.0999 2.15
9. 3.891 2-Furancarboxaldehyde, 5-methyl- C6H6O2 110.1106 2.86
10. 3.943 2-Furancarboxaldehyde, 5-methyl- C6H6O2 110.1106 2.99
11. 4.092 2-Butanone, 3,3-dimethyl- C6H12O 100.1589 1.00
12. 4.155 2-Furancarboxaldehyde, 5-methyl- C6H6O2 110.1106 2.27
13. 4.367 2-Butenoic acid, 4-oxo- C14H25NO3 255.35 1.04
14. 4.450 2,4-Dihydroxy-2,5-dimethyl-3(2H) C6H8O4 144.12 1.42
15. 4.487 4(1H)-Pyrimidinone, 6-hydroxy- C4H4N2O2 112.0868 0.55
16. 4.519 2-Methyliminoperhydro-1,3-oxazine C5H10N2O 114.15 0.34
17. 4.576 Phenol C6H6O 94.11 1.99
18. 4.622 Pyridine, 3-methoxy- C6H7NO 109.1259 0.74
19. 4.682 Tetrahydrofuran, 2-propyl- C7H14O 114.1855 0.30
20. 4.771 2-Mercaptopyrimidine C4H4N2S 112.153 0.28
21. 4.852 1H-Pyrrole-2-carboxaldehyde C5H5NO 95.0993 0.66
22. 4.914 Methacrylic anhydride C8H10O3 154.1632 0.35
23. 5.053 1,2-Cyclopentanedione, 3-methyl- C6H8O2 112.1265 3.06
24. 5.096 2,5-Norbornanediol C7H8 92.14 0.82
25. 5.269 1-Methyl-pyrrolidine-2-carboxyli… C6H11NO2 129.16 0.49
26. 5.338 Menthyl acetate C12H22O2 198.30 0.44
27. 5.444 Ethanone, 1-(1H-pyrrol-2-yl)- C6H7NO 109.1259 0.98
28. 5.523 2-Cyclopenten-1-one, 3-ethyl- C7H10O 110.1537 0.29
29. 5.616 Cyclohexanamine, N-3-butenyl-N-m… C11H21N 167.29 1.79
30. 5.699 6-Amino-1,3,5-triazine-2,4(1H,3H)-dione C3H4N4O2 128.0895 4.95
31. 5.838 Phenol, 2-methoxy- C7H8O2 124.1372 2.50
32. 5.888 Spiro[3.4]octan-5-one C8H12O 124.18 0.68
33. 6.103 Maltol C6H6O3 126.1100 1.97
34. 6.270 2-Cyclopenten-1-one, 3-ethyl-2-h… C7H10O2 126.1531 1.49
35. 6.317 3-Methyl-2-furoic acid C6H6O3 126.1100 0.34
36. 6.350 sec-Butyl (E)-2-methylbut-2-enoate C9H16O2 156.2221 0.27
37. 6.728 4H-Pyran-4-one, 2,3-dihydro-3,5-dihydroxy-6-methyl C6H8O4 144.12 5.51
38. 6.822 2-Furoic acid, anhydride with ac… C7H6O4 154.1201 0.55
39. 6.852 3-Hydroxypyridine monoacetate C7H7NO2 137.1360 0.45
40. 6.911 Diisopropylaminoacrylonitryl C9H16N2 152.24 0.65
41. 6.991 3-Pyridinol C5H5NO 95.0993 1.67
42. 7.264 Benzoic acid C7H6O2 122.1213 1.71
43. 7.416 2-Pentene, 1-ethoxy-4,4-dimethyl- C9H18O 142.24 2.58
44. 7.478 2-Hydroxy-3-propyl-2-cyclopenten… C8H12O2 140.1797 1.12
45. 7.766 5-Hydroxymethylfurfural C6H6O3 126.1100 9.19
46. 7.980 Propanedioic acid, 2-propenyl-, C10H16O4 200.23 0.67
47. 8.276 1H-Inden-1-one, 2,3-dihydro- C9H8O 132.1592 0.28
48. 8.359 4-Hydroxy-2,4,5-trimethyl-2,5 C9H12O2 152.19 1.88
49. 8.452 Pyrazine, 2-methoxy-3-(1-methyle… C8H12N2O 152.1937 0.34
50. 8.523 3-Cyclohexen-1-carboxaldehyde C7H10O 110.15 0.32
51. 8.566 5-Acetoxymethyl-2-furaldehyde C8H8O4 168.1467 0.23
52. 8.752 1,4-Ethanonaphthalene-5,8-dione, … C12H10O2 186.21 1.94
53. 8.888 2-Methoxy-4-vinylphenol C9H10O2 150.1745 2.70
54. 9.066 4-Hydroxy-3-methylacetophenone C9H10O2 150.1745 0.21
55. 9.148 2-Penten-4-yn-1-ol, 5-(methylthi… C6H8OS 128.19 0.24
56. 9.260 Phenol, 2,6-dimethoxy- C8H10O3 154.1632 0.47
57. 9.476 1,4-Benzenediol, 2-methyl- C7H8O2 124.1372 0.19
58. 9.532 1,4-Benzenediol, 2-methyl- C7H8O2 124.1372 0.70
59. 9.707 cis,trans-2-Ethylbicyclo[4.4.0]d… C12H22 166.3031 0.25
60. 10.048 3-Acetyl-2,5-dimethyl furan C8H10O2 138.1638 0.53
61. 10.152 1-Butanol, 4-bromo-, acetate C6H11Br2 195.054 0.27
62. 10.514 Isocyclocitral C10H16O 152.2334 0.21
63. 11.037 2-Butanone, 4-(4-hydroxyphenyl)- C10H12O2 164.2011 0.17
64. 11.306 Phenol, 2,4-dimethyl-, acetate C10H12O2 164.2011 0.25
65. 11.356 Benzoic acid, 2-(methylthio)-, m… C8H8O2S 168.21 0.44
66. 11.503 5-tert-Butylpyrogallol C10H14O3 182.22 0.72
67. 11.582 D-Allose C6H12O6 180.16 0.23
68. 11.943 2,3,5,6-Tetrafluoroanisole C7H4F4O 180.0997 0.51
69. 12.082 5,6-Dimethoxy-1-indanone C11H12O3 192.2112 0.09
70. 12.143 Ethyl N-(2-methylphenyl)carbamate C10H13N2 179.2157 0.14
71. 12.645 2,4-Diamino-7(8H)-pteridinone C6H6N6O 178.15 1.58
72. 12.797 2(1H)-Naphthalenone C13H20O 192.30 0.27
73. 12.834 Furan, 2,3-dihydro-2,2-dimethyl-… C10H12O 148.20 0.21
74. 13.200 2-Methyl-2-phenylthiophane C11H10S 174.26 0.90
(continued on next page)

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Table 3 (continued )
S. no. RT Compound Chemical formula Molecular weight Area %

75. 14.014 cis-anti-cis-Tricyclooctane C12H18O 178.27 0.22

76. 14.317 4-Methyldaphnetin C10H8O4 192.17 0.38
77. 15.639 Pyrrolidine, 2.alpha.-[1-pyrroli… C4H7NO 85.10 0.17
78. 18.018 cis-13-Octadecenoic acid C18H34O2 282.4614 0.15
79. 18.721 Cyclopentane, 1-pentyl-2-propyl- C13H26 182.35 0.12
80. 18.924 Cyclopentane, 1-pentyl-2-propyl- C13H26 182.35 0.16
81. 19.330 11,13-Dimethyl-12-tetradecen-1-o… C18H34O2 282.5 0.37
82. 19.459 Cyclopentane, 1,2-dibutyl- C13H26 182.3455 0.10
83. 19.957 Bicyclo[3.1.1]heptan-3-one, 2-(2… C10H16O 152.2334 2.03
84. 20.081 Cyclohexane, 1-ethyl-2-propyl- C11H22 154.2924 0.27
85. 20.140 Cyclopentane, 1,2-dibutyl- C13H26 182.3455 0.10
86. 20.221 Octacosyl heptafluorobutyrate C32H57F72 606.7826 0.61
87. 20.577 1,1′:3′,1″-Terphenyl, 5′-phenyl- C24H18 306.3997 1.93
88. 20.705 1,1′:3′,1″-Terphenyl, 5′-phenyl- C24H18 306.3997 0.60
89. 23.130 11,13-Dimethyl-12-tetradecen-1-o C18H34O2 282.5 2.16

for catalytic reaction was found less as compared to non-catalyzed re­

action. Poddar et al. (2022) conducted experiments on citrus waste
(orange peel) using non-catalytic and catalytic pyrolysis methods to
determine the kinetics of the reactions through both isothermal and non-
isothermal techniques. The ZnO nano-catalyst had a significant impact
on the overall pyrolysis process, as evidenced by the activation energy
values of 51.91 kJ mol− 1 and 83.71 kJ mol− 1 for catalytic and non-
catalytic pyrolysis, respectively. Kinetics of zinc oxide loaded almond
shell was studied by Nisar et al. (2022b) and activation energy was noted
to decrease with the use of catalyst as compared to without catalyst.

4. Conclusions

Citrus limetta waste was pyrolyzed using thermogravimetry and an

indigenous furnace operated within the range of 300–400 ◦ C. Natural
catalyst (pumice) was used to see the effects on activation energy and
quality and quantity of oil produced. Kissinger model was used to
1000/T (k )
-1 determine the kinetic parameters from TG data. For non-catalyzed re­
action, the values of Ea for decomposition of hemicellulose, cellulose
and lignin were calculated as 99.76, 157.96, and 174.59 kJ⋅mol− 1
whereas for pumice loaded sample, the activation energy were reduced
to 83.14, 91.45, and 149.65 kJ⋅mol− 1, respectively. The effect of catalyst
on quantity and quality of bio-oil was studied and the results indicated
that thermal degradation of Citrus limetta waste produced 30 % oil in the
range of C2–C24, while catalytic pyrolysis produced more than 45 %
pyrolysis oil with a wide range of components from C4 to C32, which is
indicative of the fact, that pumice has not only altered the composition
of the resulting bio-oil but also decreased the activation energy of the
pyrolysis reaction. Though the components found in the bio-oil were less
analogous to commercial fuel oil, however, it can be made suitable for
energy purposes if upgraded properly.

CRediT authorship contribution statement

Faisal Muhammad., Investigation, Methodology, Writing - original

draft. Jan Nisar., Conceptualization, Funding acquisition, Resources,
Project administration. Ghulam Ali., Writing, Results and analysis.
-1
1000/T (k )
Farooq Anwar., Editing and visualization. Syed Tasleem Hussain and
Fig. 7. Plots constructed from decomposition of citrus waste applying Kissinger Sher Wali Khan., Review and editing.
method (a) without pumice (b) with loaded pumice.

Table 4
Kinetic parameters computed applying Kissinger method.
Component Catalytic reaction Non-catalytic reaction

Ea(kJ⋅mol− 1) A(min− 1) R2 Ea(kJ⋅mol− 1) A(min− 1) R2

Hemicellulose 83.14 3.98 × 108 0.979 99.76 3.87 × 1012 0.884

Cellulose 91.45 5.17 × 109 0.939 157.96 1.07 × 1016 0.949
Lignin 149.65 1.8 × 1012 0.951 174.59 9.29 × 1017 0.910

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F. Muhammad et al. Bioresource Technology Reports 24 (2023) 101635

Funding Mahato, N., Sharma, K., Sinha, M., Cho, M.H., 2018. Citrus waste derived nutra-/
pharmaceuticals for health benefits: current trends and future perspectives. J. Funct.
Foods 40, 307–316.
Higher Education Commission, Pakistan. Miranda, R., Bustos-Martinez, D., Blanco, C.S., Villarreal, M.G., Cantu, M.R., 2009.
Pyrolysis of sweet orange (Citrus sinensis) dry peel. J. Anal. Appl. Pyrolysis 86 (2),
245–251.
Najam, H., 2023. Optimization of renewable energy supply for a carbon neutral society:
Declaration of competing interest role of environmental regulations, sustainable finance, and financial innovation
through the lens of game theory. Geol. J. 58, 3466–3475.
Nathaniel, S.P., Alam, M., Murshed, M., Mahmood, H., Ahmad, P., 2021. The roles of
The authors declare that they have no known competing financial
nuclear energy, renewable energy, and economic growth in the abatement of carbon
interests or personal relationships that could have appeared to influence dioxide emissions in the G7 countries. Environ. Sci. Pollut. Res. 28 (35),
the work reported in this paper. 47957–47972.
Nisar, J., Ahmad, A., Ali, G., Rehman, N.U., Shah, A., Shah, I., 2022a. Enhanced bio-oil
yield from thermal decomposition of peanut shells using termite hill as the catalyst.
Data availability Energies 15 (5), 1891.
Nisar, J., Rahman, A., Ali, G., Shah, A., Farooqi, Z.H., Bhatti, I.A., Iqbal, M., Ur
Data will be made available on request. Rehman, N., 2022b. Pyrolysis of almond shells waste: effect of zinc oxide on kinetics
and product distribution. Biomass Convers. Biorefinery 12 (7), 2583–2595. https://
doi.org/10.1007/s13399-020-00762-6.
Acknowledgements Nisar, J., Sharaf, M., Ali, G., Farooqi, Z., Iqbal, M., Khan, S., 2022c. Pyrolysis of juice-
squeezed grapefruit waste: effect of nickel oxide on kinetics and bio-oil yield. Int. J.
Environ. Sci. Technol. 19 (10), 10211–10222.
Higher Education Commission, Pakistan is acknowledged for Grant Nisar, J., Waris, S., Shah, A., Anwar, F., Ali, G., Ahmad, A., Muhammad, F., 2022d.
No. 20-1491. Production of bio-oil from de-oiled Karanja (Pongamia pinnata L.) seed press cake
via pyrolysis: kinetics and evaluation of anthill as the catalyst. Sustain. Chem. 3 (3),
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