energies

Article
Production of Fuel Range Hydrocarbons from Pyrolysis of
Lignin over Zeolite Y, Hydrogen
Ghulam Ali 1 , Marrij Afraz 1 , Faisal Muhammad 1 , Jan Nisar 1, * , Afzal Shah 2, * , Shamsa Munir 3
and Syed Tasleem Hussain 4

1 National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan
2 Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan
3 School of Applied Sciences and Humanities, National University of Technology (NUTECH),
Islamabad 44000, Pakistan
4 Department of Chemistry, Kohat University of Science and Technology (KUST), Kohat 26000, Pakistan
* Correspondence: [email protected] or [email protected] (J.N.);
[email protected] or [email protected] (A.S.)

Abstract: In the current study, plain and lignin loaded with Zeolite Y, hydrogen was decomposed in
a pyrolysis chamber. The reaction parameters were optimized and 390 ◦ C, 3% catalyst with a reaction
time of 40 min were observed as the most suitable conditions for better oil yield. The bio-oil collected
from the catalyzed and non-catalyzed pyrolytic reactions was analyzed by gas chromatography
mass spectrometry (GCMS). Catalytic pyrolysis resulted in the production of bio-oil consisting of
15 components ranging from C3 to C18 with a high percentage of fuel range benzene derivatives.
Non-catalytic pyrolysis produced bio-oil that consists of 58 components ranging from C3 to C24 ;
however, the number and quantity of fuel range hydrocarbons were lower than in the catalyzed
products. The pyrolysis reaction was studied kinetically for both samples using thermogravimetry at
heating rates of 5, 10, 15 and 20 ◦ C/min in the temperature range 20–600 ◦ C. The activation energies
and pre-exponential factors were calculated using the Kissinger equation for both non-catalytic
and catalytic decomposition and found to be 157.96 kJ/mol, 141.33 kJ/mol, 2.66 × 1013 min−1 and
2.17 × 1010 min−1 , respectively. It was concluded that Zeolite Y, hydrogen worked well as a catalyst
Citation: Ali, G.; Afraz, M.;
to decrease activation energy and enhance the quality of the bio-oil generated.
Muhammad, F.; Nisar, J.; Shah, A.;
Munir, S.; Tasleem Hussain, S.
Keywords: lignin; zeolite Y; hydrogen; pyrolysis; GC/MS; kinetics; activation energy
Production of Fuel Range
Hydrocarbons from Pyrolysis of
Lignin over Zeolite Y, Hydrogen.
Energies 2023, 16, 215. https://
doi.org/10.3390/en16010215 1. Introduction
Non-renewable fossil resources are facing a serious challenge and their excessive
Academic Editors: Shie Jelueng
and Min-Hao Yuan
use and over consumption due to the increasing population growth is leading to their
depletion. Moreover, the global energy demand based on fossil fuels has a negative
Received: 13 November 2022 impact on the environment; therefore, there is an intense need for more efficient and
Revised: 13 December 2022 environmentally friendly alternative energy resources on large scale [1]. Climate change and
Accepted: 19 December 2022 other environmental issues are produced as a result of excessive use of fossil fuels as their
Published: 25 December 2022
combustion causes emissions of unburnt particles, carbon dioxide and other compounds
resulting in the greenhouse effect and global warming [2,3]. Moreover, fossil fuel such as
coal have some sulphur content and its burning causes emission of sulphur dioxide that
Copyright: © 2022 by the authors.
contributes to acid rain, which causes water pollution [4]. Therefore, we must use renewable
Licensee MDPI, Basel, Switzerland. energy sources to address all these issues, which is the preferable alternative for meeting
This article is an open access article growing energy demand. The use of renewable energy has greatly influenced human
distributed under the terms and activities and has a vast application in the energy sector. It is becoming the most valued
conditions of the Creative Commons alternative for fossil-based energy [5]. Biomass, sunlight, wind, hydro and geothermal are
Attribution (CC BY) license (https:// some important sources of renewable energy [6], and the focus of researchers on using
creativecommons.org/licenses/by/ renewable energy is increasing with increase in energy demand as it is a cheap and pollution
4.0/). free source [7].

Energies 2023, 16, 215. https://doi.org/10.3390/en16010215 https://www.mdpi.com/journal/energies

Energies 2023, 16, 215 2 of 14

Zeolite is a solid material, and its use as catalyst is often preferred as the separation
of solid catalyst is comparatively easy after the reaction [8]. Due to its high activity and
durability, zeolite has been found to be a specialized catalyst for enhancing bio aromatic
production. Moreover, it is preferred over oxides, heteropoly acids, and various transition
metals due to its resistance to various catalytic poisons created during reactions. Zeolites
have unique structural and acidic qualities that lengthen their lifespan and improve their
selectivity for various gasoline hydrocarbons [9]. Zeolites have been extensively used for
the conversion of waste biomass to bio-oil; however, a few studies have reported on the
utilization of zeolite for decomposition of lignin. Decomposition kinetics of lignin has been
studied by a few research workers. Jiang et al. [10] studied the kinetic of decomposition of
four different types of lignin obtained from various sources using the Kissinger method
and observed that the activation energy is dependent on the plant from which the lignin
was obtained and the separation method used.
Sharma et al. [11] performed pyrolysis of lignin and char and characterized the py-
rolysates obtained under different conditions. The high yield of char was assigned to the
existence of inorganic components, and the removal of these components led to a decrease
in char yield. It was revealed from the experiment that lignin char has low reactivity in
comparison with the char obtained from other biomass components.
Kawamoto [12] presented a detailed review on lignin conversion into different compo-
nents via pyrolysis. However, there are still discrepancies in understanding the mechanism
of lignin pyrolysis and more experimental and theoretical work needs to be done to explain
the reaction mechanism.
Mu et al. [13] reviewed the pyrolysis of lignin and observed that the mechanism of
lignin pyrolysis is completely different to that of other biomass components, i.e., cellulose
and hemicellulose. The authors focused on recent advancements on the pyrolysis of lignin,
degradation mechanisms, catalytic and non-catalytic reactions, and upgradation of bio-oil.
Though the products obtained from lignin pyrolysis have been proved to be of commercial
importance, there are still many problems to be solved.
Liu et al. [14] used Van Soest’s method for extracting lignin from two different biomass
samples and studied the mechanism of pyrolysis. FTIR was used for characterization of the
products formed. The major volatile products were phenols along with alcohols, aldehydes
and some forms of acids. The gaseous fraction was found to compose of CO, CO2 and
methane. However, further research using advanced analytical techniques is necessary to
ascertain the exact mechanism of the pyrolysis reaction.
Lignin, with chemical formula C81 H92 O28 , is a stiff, aromatic, amorphous and hy-
drophobic biopolymer. One portion of lignin is found inside the cell wall, while the other
portion is found between the cells in the intermediate lamella [15]. Lignin is bonded with
the hemicellulose through covalent linkages and provide stiffness and strength to the plant
cell wall [16]. Wood contains 25–40% lignin [17]. Lignin sources are widely available all
around the world that include cotton, wood pulp, paper industries and different other
plant materials [18].
The large-scale production of lignin in pulp and paper industries has a great potential
to be converted into useful products such as bio-oils. This unnecessary waste lignin can be
utilized for conversions to biofuel which will encourage the proper use of waste lignin [19].
Moreover, it is cost effective, non-polluting and efficient energy source [20]. Therefore, the
major focus of present research is to analyze the kinetics of thermal and thermo-catalytic
decomposition of lignin. The pyrolysis process was performed in an in-house designed
furnace at a wide temperature range, and the liquid fuel collected with/without Zeolite Y,
hydrogen was analyzed by GC/MS. For kinetic study, lignin was subjected to thermal and
thermo-catalytic degradation using thermogravimetry. Kissinger equation was applied
to examine the kinetic parameters of the decomposition reaction. The data obtained from
these experiments will help in the utilization of lignin for production of useful products.
Energies 2023, 16, 215 3 of 14

2. Material and Methods

2.1. Materials
In the recent study, lignin used was an alkali lignin (CAS: 8068-05-1) with low
sulphonates content that was purchased from Aldrich Chemistry, USA. The Aldrich alkali
lignin was chosen for this investigation because it is commercially accessible and comes
in a highly purified form with a low moisture content (5%). It was in the form of brown
powder with a pH of 10.5 (3 wt.%) and is water soluble. The Zeolite Y, hydrogen (CAS:
1318-02-1) used in this study as a catalyst was purchased from Alfa Aesar GmbH & Co.
Karlsruhe, Germany. The compound was consisting of SiO2 :Al2 O3 with mole ratio of 80:1
and a surface area of 780 m2 /g.

2.2. Thermogravimetric Analysis and Kinetic Study

Thermogravimetric analysis of lignin was performed without/with catalyst at heating
rates of 15, 20, 25 and 30 ◦ C/min from room temperature up to 600 ◦ C using a thermogravi-
metric analyzer under N2 flow of 20mL/min. The kinetic parameters were calculated from
the resultant data using the following Kissinger equation [21,22]:
   
β A.R Ea
ln 2 = ln − (1)
Tm Ea RTm

where β, Ea, A, R and Tm stand for heating rate, activation energy, pre-exponential factor,
universal gas constant and temperature at the rate peak maximum.

2.3. Pyrolysis Experiments and Products Characterization

Thermal and thermo-catalytic reactions were carried out at a wide temperature range
in a furnace constructed locally. A detailed description of the pyrolysis assembly has already
been given in our previous articles [23,24]; however, a schematic diagram of the same is
reproduced here in Figure 1. A precisely weighed 5 g sample was taken in a reaction flask,
put inside the furnace and heated at desired temperature by a coiled heater.The temperature
of the furnace was monitored by a temperature controller. The flask was connected to a
condenser, and the oil was collected in a vessel put inside the cold water. The pyrolysates,
i.e., bio-oil, biochar and gas, were collected separately. The bio-oil was analyzed through
GCMS (Shimadzu QP 2010 Plus). Helium at 2.0 mL/min was used as a carrier gas and split
ratio of 1:18. A sample of about 1 µL was injected at an initial temperature of 60 ◦ C with a
holding time of 1 min, after which the temperature was increased at the rate of 4 ◦ C/min to
265 ◦ C with a holding time of 5 min. The column used for analysis was HP-5 Agilent. The
peaks obtained from GC-MS chromatograph were then interpreted and identified using the
NIST05 library of GC-MS. A scanning electron microscope (SEM) (JSM-5910, JEOL, Tokyo,
Japan) and a transmission electron microscope (TEM) (JEM-2100 TEM, Japan) were used
to characterize the biochar obtained from the pyrolysis in the presence and absence of the
catalyst. For the SEM analysis, the biochar sample was mounted on the stub through a
conducting carbon tape and sputtered with a gold layer by a coater. The SEM was fully
evacuated and the sample was shifted to the machine for examining the morphology of the
sample at 15 kV. A distance of 10 mm was maintained between the tip of the electron gun
and biochar sample. For TEM analysis, the biochar was dissolved in acetone and sonicated
for 10 min and then put one drop of sonicated colloidal solution on the formvar coated
grid and air dried and then it was moved to the analysis chamber for examination at an
accelerating voltage of 120 kV.
Energies 2023, 16, x FOR PEER REVIEW 4 of 14

Energies 2023, 16, 215 4 of 14

Figure 1. Experimental assembly for thermo-catalytic decomposition of lignin. 1. Nitrogen cylinder;

Figure 1. Experimental
2. Insulation; 3. Display;assembly
4. Powerfor thermo‐catalytic
supply; decomposition
5. Thermocouple; 6. Coiledof lignin.
heater; 7. 1. Nitrogen
Salt bath; 8.cylin‐
Reaction
der; 2. Insulation; 3. Display; 4. Power supply; 5. Thermocouple; 6. Coiled heater; 7. Salt bath; 8.
vessel; 9. Oil collection vessel; 10. Condenser; 11. Water outflow; 12. Water inflow; 13. Gas collection bag.
Reaction vessel; 9. Oil collection vessel; 10. Condenser; 11. Water outflow; 12. Water inflow; 13. Gas
collection
3. Results bag.
and Discussion
3.1. Thermogravimetric Analysis and Kinetic Study
3. Results and Discussion
Thermogravimetric analysis of lignin was done without/with catalyst and the re-
3.1. Thermogravimetric
sultant Analysis plots
data from TG/DTG and Kinetic Studyfor finding out kinetic parameters using
was used
Thermogravimetric
Equation (1). The plotsanalysis
obtainedofare lignin was done
depicted without/with
in Figure 2, and thecatalyst
kineticand the re‐
parameters
sultant dataare
calculated from TG/DTG
presented plots 1.was
in Table Theused forshow
results finding
thatout kinetic
Zeolite parameters
Y, hydrogen using
decreased
Equation (1). The
the activation plots
energy obtained
from 157.96 are depicted
to 141.33 in Figure
kJ/mol. These 2, and the kinetic
observations are in parameters
accord with
reported results.
calculated Wang etinal.,
are presented [25] studied
Table the pyrolysis
1. The results show that of Douglas
Zeolite Fir with/without
Y, hydrogen ZSM-5.
decreased
Coats–Redfern
the
Energies 2023, 16, x FOR PEER REVIEW activation approach
energy from was
157.96 used
to for
141.33finding
kJ/mol. out kinetic
These parameters
observations are of
inthe pyrolysis
accord 5with
of 14
reaction. results.
reported AuthorsWang
observed that[25]
et al., ZSM-5 speeded
studied the up the reaction
pyrolysis and decreased
of Douglas the energy
Fir with/without
neededCoats–Redfern
ZSM‐5. for the breakdown process.
approach was used for finding out kinetic parameters of the py‐
rolysis reaction. Authors observed that ZSM‐5 speeded up the reaction and decreased the
energy needed for the breakdown process.
Shrestha et al. [26] analyzed thermogravimetric analysis of lignin. The optimum
temperature of mass decomposition was observed to be 345 °C and the char yield was
32% at 900 °C at heating rate of 5 K/min. When the rate was increased to 20 K/min, the
optimum decomposition temperature was 341 °C, and the yield of biochar at 800 °C was
37.7%. Therefore, by increasing the heating rate, the optimum degradation temperature
was decreased and the char yield was increased from 32 to 38%.
Nisar et al. [27] investigated the decomposition of peanut shells with/without ter‐
mite hill at heating rates of 3, 12, 20, and 30 °C/min using Kissinger approach. The acti‐
vation energies for hemicellulose, cellulose, and lignin were found 108.08, 116.4, and
182.91 kJ/mol for non‐catalytic reaction and 66.512, 74.826 and 133.024 kJ/mol for catalytic
reaction, respectively.

Figure 2. Kissinger
Figure 2. Kissingerplots
plotsconstructed
constructedfrom (a)(a)
from thermal and
thermal (b)(b)
and thermo-catalytic decomposition
thermo‐catalytic of lignin.
decomposition of
lignin.

Table 1. Determination of Kinetic parameters applying Kissinger equation.

Thermal Thermo‐Catalytic
Component
Ea (kJmol−1) A (min−1) Ea (kJmol−1) A (min−1)

Lignin 157.96 2.66 × 1013 141.33 2.17 × 1010

Energies 2023, 16, 215 5 of 14

Table 1. Determination of Kinetic parameters applying Kissinger equation.

Thermal Thermo-Catalytic
Component
Ea (kJmol−1 ) A (min−1 ) Ea (kJmol−1 ) A (min−1 )
Lignin 157.96 2.66 × 1013 141.33 2.17 × 1010

Shrestha et al. [26] analyzed thermogravimetric analysis of lignin. The optimum

temperature of mass decomposition was observed to be 345 ◦ C and the char yield was
32% at 900 ◦ C at heating rate of 5 K/min. When the rate was increased to 20 K/min, the
optimum decomposition temperature was 341 ◦ C, and the yield of biochar at 800 ◦ C was
37.7%. Therefore, by increasing the heating rate, the optimum degradation temperature
was decreased and the char yield was increased from 32 to 38%.
Nisar et al. [27] investigated the decomposition of peanut shells with/without termite hill
at heating rates of 3, 12, 20, and 30 ◦ C/min using Kissinger approach. The activation energies
for hemicellulose, cellulose, and lignin were found 108.08, 116.4, and 182.91 kJ/mol for
non-catalytic reaction and 66.512, 74.826 and 133.024 kJ/mol for catalytic reaction, respectively.

3.2. Characterization of Biochar

3.2.1. SEM Analysis
The surface features of biochar obtained from thermal and thermo-catalytic reactions
were evaluated using a scanning electron microscope and transmission electron microscope.
The SEM images are shown in Figure 3a,b. SEM analysis of non-catalyzed biochar reflects a
smooth surface with a disc-like texture, while on the other hand the catalytic biochar was
found to have a rough and uneven surface with multiple pores and irregular morphology.
The application of biochar in energy storage supercapacitors requires a highly porous
and larger surface area that could be produced by catalytic pyrolysis of lignin [28]. The
interaction between lignin and the catalyst produced lump-like structures with a larger
surface area and bigger diameter in the catalytic biochar. The use of the catalyst produced
a strong morphological change that deformed the surface with a highly developed pore
structure. Using textural examination, the lignin particles in biochar were further revealed
to have been softened and merged into a mass of matrix and vesicles. These results agree
with reported studies. Wang et al. [29] analyzed the textural properties of biochar produced
Energies 2023, 16, x FOR PEER REVIEW 6 of 14
from the exposure of alkali lignin to pyrolysis which showed the presence of irregularly
fragmented surface pores that appeared to be broken and collapsed.

(a) (b)
Figure 3.
Figure 3. SEM
SEM images
images of
of biochar
biochar obtained
obtained from
from (a)
(a) non-catalytic
non‐catalytic and
and (b)
(b) catalytic
catalytic reactions.
reactions.

3.2.2. TEM Analysis

The microstructure of lignin biochar was also analyzed using TEM. The TEM images
(Figure 4a,b) obtained for non‐catalytic biochar reflected a small surface area and an as‐
sembled structure due to the carbonization leading towards the fusion of the carbon
skeleton. Biochar was observed to contain nanosized carbon particles with irregularly
arranged fragments having submicron size and even surface area. The particle size was
Energies 2023, 16, 215
(a) (b) 6 of 14
Figure 3. SEM images of biochar obtained from (a) non‐catalytic and (b) catalytic reactions.

3.2.2. TEM
3.2.2. TEM Analysis
Analysis
The microstructure
The microstructure ofof lignin
lignin biochar
biochar waswas also
also analyzed
analyzed using
using TEM.
TEM. The
The TEM
TEM images
images
(Figure 4a,b) obtained for non‐catalytic biochar reflected a small surface
(Figure 4a,b) obtained for non-catalytic biochar reflected a small surface area and area and an as‐
an
sembled structure due to the carbonization leading towards the fusion
assembled structure due to the carbonization leading towards the fusion of the carbon of the carbon
skeleton. Biochar
skeleton. Biochar was
was observed
observed to to contain nanosized carbon
contain nanosized carbon particles
particles with
with irregularly
irregularly
arranged fragments having submicron size and even surface area.
arranged fragments having submicron size and even surface area. The particle size The particle size was
was
small and
small and exhibited
exhibitedaahighly
highlyrigid
rigidstructure,
structure, while thethe
while catalytic biochar
catalytic (Figure
biochar 4c,d)4c,d)
(Figure ob‐
tained showed
obtained showed different morphology
different morphologydue duetotothe
thedispersion
dispersionofofthe
thecatalyst
catalystand,
and,ultimately,
ultimately,
an increased
an increased surface
surface pore
pore size
size due
due toto agglomeration
agglomeration of of nanosized
nanosized carbon
carbon particles.
particles. The
The
results agree well with reported literature. A TEM analysis of lignin biochar by
results agree well with reported literature. A TEM analysis of lignin biochar by Li et al. [30] Li et al.
[30] showed similar agglomeration of carbon particles and the particles were
showed similar agglomeration of carbon particles and the particles were evenly distributed evenly dis‐
tributed
in in thematrix.
the carbon carbon matrix.

Energies 2023, 16, x FOR PEER REVIEW 7 of 14

from (a,b)
Figure 4. TEM images of biochar obtained from (a,b) non-catalytic
non‐catalytic and
and (c,d)
(c,d) catalytic
catalytic pyrolysis.
pyrolysis.

3.3.
3.3. Pyrolysis
Pyrolysis Experiments
Experiments and
and GC/MS
GC/MS of of Bio-Oil
Bio‐Oil
In
In order to investigate the effect of temperature,
order to investigate the effect of temperature, pyrolysis
pyrolysis experiments
experiments were were carried
carried
out over wide range of temperature and the results are presented in
out over wide range of temperature and the results are presented in Figure 5a,b. Figure 5a,b. Pyrolysis
Pyroly‐
carried outout
in the absence of of
catalyst produced ◦ C (Figure 5a),
sis carried in the absence catalyst producedmaximum
maximumbio-oil
bio‐oilatat410
410 °C (Figure 5a),
whereas ◦
whereas catalytic
catalytic pyrolysis
pyrolysis yielded
yielded maximum
maximum bio-oil
bio‐oil at
at 390
390 °CC (Figure
(Figure 5b).
5b). This
This shows
shows
that the catalyst has dropped the maximum degradation temperature
that the catalyst has dropped the maximum degradation temperature for maximum for maximum bio-
oil yield.
bio‐oil TheThe
yield. subsequent
subsequentbreakdown
breakdown caused a drop
caused a dropininthe
thebio-oil
bio‐oilbeyond
beyondthe the optimal
optimal
temperature
temperature and an increase in gases [31,32]. Additionally, a reduction in biochar was
and an increase in gases [31,32]. Additionally, a reduction in biochar was
seen along with an increase in temperature. The trend is in consonance with earlier work.
seen along with an increase in temperature. The trend is in consonance with earlier work.
Nizamuddin et al. [33] studied the degradation of corn stalk and observed an increase in
Nizamuddin et al. [33] studied the degradation of corn stalk and observed an increase in
yield of oil with rise in temperature and then a decline was observed, a trend similar to
yield of oil with rise in temperature and then a decline was observed, a trend similar to
our results. A similar pattern was also noted by Kalogiannis et al. [34]. They studied
our results. A similar pattern was also noted by Kalogiannis et al. [34]. They studied
temperature effects on catalytic and thermal pyrolysis of lignin and observed an increase in
temperature effects on catalytic and thermal pyrolysis of lignin and observed an increase
in bio‐oil with rise in temperature up to certain level and then a decrease in bio‐oil was
noted with increase in temperature. Jung et al. [35] investigated the influence of temper‐
ature on the formation of oil from the pyrolysis of lignin and observed maximum bio‐oil
of 31% at 670 °C. In another study, Jiang et al. [36] studied the influence of temperature
 Energies 2023, 16, 215 7 of 14

bio-oil with rise in temperature up to certain level and then a decrease in bio-oil was noted
with increase in temperature. Jung et al. [35] investigated the influence of temperature on
the formation of oil from the pyrolysis of lignin and observed maximum bio-oil of 31%
at 670 ◦ C. In another study, Jiang et al. [36] studied the influence of temperature on the
pyrolytic products obtained from pyrolysis of lignin and recovered 18 wt% bio-oil at an
optimized temperature of 600 ◦ C having phenolic compounds in abundance. The influence
of catalyst concentration on bio-oil yield is depicted in Figure 5c. As evident from the figure,
nergies 2023, 16, x FOR PEER REVIEW 8 of 14
with rise in catalyst loading from 1 to 3%, the bio-oil yield was observed to increase and
then decline. This shows that rise in catalyst concentration favours bio-oil yield; however,
it has adverse effects beyond 3% due to catalyst poisoning.

Figure 5. Cont.
Energies 2023, 16, 215 8 of 14

Figure
Figure 5. 5. Product
Product distribution
distribution fromfrom pyrolysis
pyrolysis ofof lignin:(a)
lignin: (a)non‐catalytic
non-catalytic reaction;
reaction;(b)(b)
catalytic reaction;
catalytic reac‐
and (c) effect of catalyst concentration.
tion; and (c) effect of catalyst concentration.

The chromatogram of bio-oil collected from non-catalytic decomposition of lignin

at optimized conditions as analyzed by GCMS is shown in Figure 6, and the identified
components with their %area along with retention time are given in Table 2. The ta-
ble indicates the presence of 58 components. Major components in the oil were Ben-
zene, 1,10 -(1,3-propanediyl)bis, Phenol, 2-methoxy-, Naphthalene, 2-phenyl-, Benzene,
1,10 -(1,4-butanediyl)bis-, Benzene, 1,10 -(1-methyl-1,3-propan ediyl)bis, Benzene, 1,10 -(1,4-
butanediyl)bis-, Vanillin, beta.-Phenyl propiophenone, and Diethanolamine with %area
of 14.13, 8.47, 6.22, 3.66, 3.61, 3.60, 3.27 and 3.1%, respectively, which were produced as a
result of lignin decomposition. These observations are in agreement with reported investi-
gations [37]. Sharma et al., [11] pyrolyzed lignin between 150 and 550 ◦ C and observed the
relationship of lignin reactivity with the production of polycyclic aromatic hydrocarbons.
Ateş et al. [37] examined the decomposition of sesame biomass to find out the influence
of different parameters on the fuel production and their product distribution. Reaction
temperature within the range of 400 to 700 ◦ C was used for analysis under nitrogen-flow.
The maximum bio-oil yield was noted to be 37.20 wt% of total weight at 550 ◦ C and the
bio-oil was found to comprise of branching hydrocarbons, alkenes, and alkanes.
GC/MS of the bio-oil collected from the catalyzed reaction of lignin was also per-
formed and the results indicated that the zeolite has considerably reduced the oxygen-
containing chemicals in the oil. The chromatogram is presented in Figure 7, and the different
constituents present in the oil with their percent composition are presented in Table 3. The
major constituents in the oil were observed as Benzene, 1,10 -(1,3-propanediyl)bis-, Phenol,
2-methoxy, Thiirane, methyl-, Naphthalene, 2-phenyl-, Naphthalene, 2-phenyl-, Vanillin,
Apocynin, Benzene, 1,10 -(1-methyl-1,3-propane ediyl)bis-, Benzene, 1,10 -(1,4-butanediyl)bis-,
m-Terphenyl, 1,2-Diphenylcyclopropane with % area of 33.3, 13.37, 12.18, 7.18, 4.47, 3.66,
3.62, 3.39, 3.35 and 3.14%, respectively. Besides these components, some other minor com-
ponents were Butanoic acid, 2-methyl-, I-Stilbene, Benzene, (3-nitropropyl)-, Naphthalene,
2-(phenylmethyl)- and p-Terphenyl. GC/MS analysis also revealed that the presence of
some value-added products has enhanced the quality of bio-oil. A comparative study of
catalytic and non-catalytic decomposition shows that catalytic breakdown produced more
benzene and phenol-like substances, which not only augmented the amount of bio-oil
produced but also enhanced the value of oil. These observations agree well with some
 Energies 2023, 16, 215 9 of 14

reported work. Jeon et al. [38] studied catalytic degradation of biomass and observed
an improvement in the quality of bio-oil as compared with oil recovered from an un-
catalyzed pyrolysis process. Poplar wood catalytic cracking at 465 ◦ C was explored by
Mante et al. [39]. Their findings showed that the amount of Zeolite Y affected oil output
and quality. The catalyst was also found efficient in refining the oil through elimination
of some undesirable components. Ohra-aho and Linnekoski [40] studied Kraft lignin and
Scots pine wood via pyrolysis using a variety of catalysts, including Zeolite Y, HZSM-5,
and Pd/C. When compared with non-catalytic pyrolysis, both acid zeolite produced more
aromatic hydrocarbons.
Hernando et al., [41] studied the decomposition of eucalyptus woodchips with ZSM-5
and Beta zeolites. Due to coke deposition on the catalyst and increased gas generation,
the use of zeolite reduced the amount of bio-oil, however, the catalysts were able to lower
the bio-oxygen in the oil’s level and, therefore, improved the quality of the oil produced.
Nisar et al., [42] carried out pyrolysis of sesame biomass in a salt bath in the presence of
cobalt oxide. The GC/MS analysis indicated the oil consisting of 2-propanone, 2-pentanon-
Energies 2023, 16, x FOR PEER REVIEW
1-heptene, methanol, 2-propanone-1-hydroxy, 1-heptanol-2, 4-diethyl, 1-hexadecanesulfonyl 10 of 14
chloride, 5-eicosene, 1-dodecanol-2-hexyl, 1-dodecanol-2-hexyl and nonadecyl trifluoroac-
etate, making the bio-oil a potential source of compounds with additional benefits.

Figure
Figure 6. GCMSofofoil
6. GCMS oilcollected
collected from
fromthe
thepyrolytic
pyrolyticdecomposition of lignin
decomposition in thein
of lignin absence of catalyst.
the absence of cata‐
lyst.

Table 2. Composition of bio‐oil collected from lignin pyrolysis in the absence of catalyst

Retention Chemical
S No Compound Name Mol.wt (g) Area %
Time Formula
1 3.34 Phenol, 2‐methyl‐ C7H6N2O5 198.13 0.7
2 3.60 Phenol, 3‐methyl‐ C7H8O 108.14 0.89
3 3.82 Phenol, 2‐methoxy‐ C10H12O2 170.16 8.47
4 4.27 Pentanoic acid, 2‐methyl‐, methyl ester C7H14O2 130.18 0.32
5 4.55 Benzene, 1,2‐dimethoxy‐ C8H10O2 138.16 2.01
6 4.84 Phenol, 3‐ethyl C8H10O 122.16 0.52
7 5.19 Creosol C8H10O2 138.16 0.96
Energies 2023, 16, 215 10 of 14

Table 2. Composition of bio-oil collected from lignin pyrolysis in the absence of catalyst.

Retention Chemical
S No Compound Name Mol.wt (g) Area %
Time Formula
1 3.34 Phenol, 2-methyl- C7 H6 N2 O5 198.13 0.7
2 3.60 Phenol, 3-methyl- C7 H8 O 108.14 0.89
3 3.82 Phenol, 2-methoxy- C10 H12 O2 170.16 8.47
4 4.27 Pentanoic acid, 2-methyl-, methyl ester C7 H14 O2 130.18 0.32
5 4.55 Benzene, 1,2-dimethoxy- C8 H10 O2 138.16 2.01
6 4.84 Phenol, 3-ethyl C8 H10 O 122.16 0.52
7 5.19 Creosol C8 H10 O2 138.16 0.96
8 5.29 Catechol C6 H6 O2 110.10 0.68
9 5.55 Mequinol C7 H10 O2 124.13 0.28
10 5.64 Butanoic acid, 2-octyl ester C12 H24 O2 200.38 0.32
11 5.83 3,4-Dimethoxytoluene C9 H12 O2 152.19 0.29
Tricyclo [6.3.0.0(4,7)]undec-2-en-5-one,
12 5.92 C16 H24 O4 280.36 0.31
9-[(2methoxyethoxy)methoxy]-8methyl-
13 6.14 1,2-Benzenediol, 3-methyl- C7 H8 O2 124.13 0.53
14 6.21 1-Propanol, 2-methyl- C4 H10 O 74.12 0.14
15 6.38 Phenol, 4-ethyl-2-methoxy- C9 H12 O2 152.19 2.7
16 6.60 Propanoic acid C3 H6 O2 74.08 2.01
17 6.66 Diethylhydroxylamine C4 H11 NO 89.14 0.99
18 6.86 Butanoic acid, 2-methyl- C5 H10 O2 102.13 2.08
19 7.07 N,N-Dimethylformamide diisopropyl acetal C9 H21 NO2 175.27 2.32
20 7.24 Diethanolamine C4 H11 NO2 105.13 3.02
21 7.39 Phenol, 2,6-dimethoxy- C8 H10 O3 154.16 0.57
22 7.45 Phenol, 2-methoxy-3-(2propenyl)- C8 H10 O3 154.26 0.27
23 7.58 Benzenemethanol,.alpha.ethyl-4-methoxy- C10 H14 O2 166.21 0.12
24 7.85 Pentanedioic acid, 2-methyl- C7 H12 O4 160.17 0.35
25 8.06 Vanillin C8 H8 O3 152.15 3.27
26 8.12 trans-Isoeugenol C10 H12 O 164.20 0.21
27 8.39 1-(1-(Methylthio)propyl)-2propyldisulfane- C7 H16 S3 196.39 0.99
28 8.41 Diphenylmethane C13 H12 168.23 0.25
29 9.26 Butanoic acid, 3,3-dimethyl-, methyl ester C10 H20 O2 172.26 2.13
30 9.72 2-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- C10 H12 O4 196.20 0.57
31 9.95 Butyrovanillone C11 H14 O 194.22 0.13
32 10.12 Ethanone, 1-(3,4dimethoxyphenyl)- C10 H12 O3 180.20 0.5
33 10.17 1,10 -Biphenyl, 2-ethyl- C14 H14 182.26 0.11
34 10.32 1-Propanone, 1-(4-hydroxy-3-methoxyphenyl)- C10 H12 O4 196.19 0.85
35 10.38 4-Ethylbiphenyl C14 H14 182.26 0.87
36 10.51 Benzene, 4-butyl-1,2dimethoxy- C12 H18 O2 194.27 0.9
37 11.17 Benzenepropanol, 4hydroxy-3-methoxy- C10 H14 O 182.21 0.93
38 11.27 1,2-Diphenylcyclopropane C15 H14 194.27 0.87
Energies 2023, 16, 215 11 of 14

Table 2. Cont.

Retention Chemical
S No Compound Name Mol.wt (g) Area %
Time Formula
39 11.84 3-(Benzylthio)acrylic acid, methyl ester C11 H12 O2 S 208.28 2.75
40 11.12 Benzene, 1,10 -(1,3-propanediyl) bis C15 H16 196.28 14.13
41 11.42 Benzene, 1,10 -(1-methyl-1,3-propan ediyl) bis- C16 H18 210.31 3.61
42 11.98 1,2-Diphenylcyclopropane C15 H14 194.27 3.66
43 12.21 Benzene, 1,10 -(1,4-butanediyl) bis- C16 H18 210.31 3.6
44 13.25 Beta.-Phenyl propiophenone C16 H13 NO 235.28 3.1
45 13.30 Naphthalene, 1-phenyl- C16 H12 204.27 0.92
46 14.44 Naphthalene, 2-phenyl- C16 H12 204.27 6.22
47 14.94 1,4-Diphenyl-1,3-butadiene benzene C16 H14 206.20 0.11
48 15.65 Naphthalene, 2-(phenylmethyl)- C17 H14 218.29 2.18
49 16.09 m-Terphenyl C18 H14 230.3 2.61
50 17.33 1-Methyl-2,4,5-trioxoimidazolidine C4 H4 N2 O3 128.09 0.96
51 17.43 n-Butanol, 2-[3chlorophenoxy]- C10 H13 ClO2 200.66 0.48
L-Ornithine,N,N0 -bis(methoxycarbo nyl)-,
52 17.50 C5 H12 N2 O2 132.26 0.95
methyl ester
53 18.27 Cyclononasiloxane, octadecamethyl- C18 H54 O9 Si9 667.4 2.59
54 19.41 Cyclooctasiloxane, hexadecamethyl- C16 H48 O8 Si8 593.2 2.87
55 19.01 2-Aminophenol,N,O-bis(pentafluoropropionyl)- C6 H7 NO 109.13 2.16
56 20.88 Tetracosamethyl-cyclododecasiloxan C24 H72 O12 Si12 889.8 2.41
Benzamide,4-methoxy-N-[4-(1-
57 22.29 C10 H13 NO2 179.22 0.73
methylcyclopropyl)phenyl]-
Energies 2023, 16, x FOR PEER REVIEW 12 of 14
58 25.25 Tetracosamethylcyclododecasiloxan C24 H72 O12 889.84 0.53

Figure
Figure 7. 7. GCMS
GCMS of of
oiloil collected
collected from
from the the pyrolytic
pyrolytic decomposition
decomposition of lignin
of lignin in theinpresence
the presence
of catalyst.
of catalyst.

Table 3. Composition of bio‐oil collected from lignin pyrolysis in the presence of catalyst.

Chemical For‐
S.No Retention Time Compound Name Mol. Wt. (g) % Area
mula
Energies 2023, 16, 215 12 of 14

Table 3. Composition of bio-oil collected from lignin pyrolysis in the presence of catalyst.

Retention Chemical
S.No Compound Name Mol. Wt. (g) % Area
Time Formula
1 3.768 Phenol, 2-methoxy C7 H8 O2 124.13 13.37s
2 6.165 Thiirane, methyl- C3 H6 S 74.14 12.18
3 7.991 Vanillin C8 H8 O3 152.15 4.47
4 9.107 Apocynin C9 H10 O3 166.17 3.66
5 10.468 Butanoic acid, 2-methyl- C5 H10 O2 102.13 2.40
6 11.063 Benzene, 1,10 -(1,3-propanediyl) bis- C18 H22 238.40 33.30
7 11.40 Benzene, 1,10 -(1-methyl-1,3-propane ediyl)bis- C16 H18 210.31 3.62
8 11.69 (E)-Stilbene C14 H12 180.25 2.75
9 11.81 Benzene, (3-nitropropyl)- C9 H11 NO2 165.19 2.92
10 11.96 1,2-Diphenylcyclopropane C15 H14 194.27 3.14
11 12.20 Benzene,1,10 -(1,4 butanediyl)bis- C16 H18 210.31 3.39
12 14.41 Naphthalene, 2-phenyl- C16 H12 204.27 7.18
13 15.64 Naphthalene, 2-(phenylmethyl)- C17 H14 210.29 2.52
14 16.07 m-Terphenyl C18 H14 230.30 3.35
15 16.43 p-Terphenyl C18 H14 230.30 1.75

4. Conclusions
Thermo-catalytic decomposition of lignin was performed in a locally made pyrolysis
chamber. The bio-oils collected as a result of catalyzed and non-catalyzed pyrolytic reactions
were studied using gas chromatography mass spectrometry. The bio-oil recovered from
catalytic pyrolysis was found to be superior in quality due to the presence of fuel range
hydrocarbons as compared to the bio-oil formed from non-catalytic pyrolysis. For the
kinetic study, both the samples were subjected to thermogravimetric analysis at various
heating rates and activation energy was calculated using Kissinger equation for both
catalytic and non-catalytic decomposition reactions and found to be 141.33 kJ/mol and
157.96 kJ/mol, respectively. From the results, it has been concluded that Zeolite Y, hydrogen
demonstrated to be an efficient catalyst as it has not only decreased the activation energy
of the pyrolysis reaction but also enhanced the quality of bio-oil. The presence of some
fuel range hydrocarbons in the bio-oil produced from the catalyzed reaction has bright
prospects for use as commercial fuel if upgraded properly.

Author Contributions: G.A., writing, results and analysis. M.A. and F.M., investigation, methodol-
ogy, writing—original draft. J.N., conceptualization, funding acquisition, resources, project adminis-
tration. A.S., visualization, writing—review and editing. S.M., review and editing. S.T.H., review and
editing. All authors have read and agreed to the published version of the manuscript.
Funding: Jan Nisar acknowledges the support of the Higher Education Commission of Pakistan
through grant No. 20-1491.
Conflicts of Interest: The authors have no conflict of interest.

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