Fuel 323 (2022) 124416

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Fuel
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Full Length Article

Extraction of transportation grade fuels from waste LDPE packaging

polymers using catalytic pyrolysis
A. Pakiya Pradeep , S. Gowthaman *
Department of Automobile Engineering, Kalasalingam Academy of Research and Education, Tamil Nadu, India

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

Keywords: The recovery of liquid fuel from waste polymers through pyrolysis is an intelligent approach to minimize
LDPE polymers environmental impact and reduce fossil fuel demand in the future. Pyrolysis is an effective method to extract
Catalytic Pyrolysis pyrolysis oil (PO) from waste polymers. The addition of catalysts during the pyrolysis process further improves
Plastic fuel
the molecule cracking rate, oil yield and reduce the processing duration. This study investigates, the effect of
Fuel Composition
magnesium bentonite catalysts on pyrolysis of low-density polyethylene (LDPE) with different percentages such
Percentage of Yield
as 1, 2, 3, and 4 by weight and analyse the quality and yield percentage of extracted liquid. During the exper­
imentation, the pyrolysis is performed under different catalyst levels at a constant temperature of 340˚C. From the
result, it is noted that the pyrolysis process with 1% and 2% of catalysts increased PO extraction rate with better
fuel properties. The pyrolysis process with 1% of catalysts resulted with 77.97% of PO, 14.23% of residue and
7.79% of gas with average fuel properties which has higher PO extraction rate compared to other catalyst
concentrations. The pyrolysis process with 2% of catalysis has resulted 69.6 % of PO, 24.01% of residue and
6.12% of gas with better fuel properties than other catalysts percentages and possess similar properties of pe­
troleum diesel. It has high cetane number, heating value and low viscosity of 51.6, 43.421 MJ kg− 1 and 2.73 m2
s− 1 respectively compared to other catalysts percentage.

1. Introduction environment. Hence recycling the plastic wastes is considered as a

Generally, polymer materials are in high demand due to their char­
acteristic lightweight and high mechanical strength which led to their
increased commercial application every year. The higher consumption
of polymer in many sectors resulted in the ever-increasing amount of
plastic waste in solid waste streams. A survey reported that the global
production of plastics in the year 2015 is estimated at 381 million metric
tonnes (MMT), which is 75 % higher than the plastic production during
the early millennium [1]. In another study, the global consumption of
plastic per capita is 28 kg/year and for India it is around 11 kg/year [2].
The central pollution control board (CPPB) of India has estimated that
the polymer waste increased by 9.47 MMT during 2017 wherein 70 % of
the waste is from the packaging polymer. With the higher utilization of
HDPE and LDPE polymer in the packaging sector, both the polymers
took 66 % more stock than other polymer materials in plastic waste
generation.
Some solid waste management practices like incineration and land­
filling methods are unsatisfactory since it has a direct impact on the
promising strategy to reduce the waste generation and it will cater the
increased demand of commercially viable plastic materials. For this
purpose, the polymer needs to be procured from both raw polymer and
recycled polymer sources. India has recycled around 60 % of waste
polymer from the total waste generation and the remaining 40 % of the
waste is transported for incineration or landfilling [3]. Increase in the
generation of plastic wastes coupled with the depletion of crude oil re­
serves (2.1 %) has led the researchers to find a solution by means of
pyrolysis of plastic wastes which will also fulfil the need for petroleum
products. Thermolysis is the process of breaking the reinforced polymer
framework present in the waste plastics into smaller hydrocarbon (HC)
fragments. The addition of catalysts with the polymer during thermol­
ysis can improve the reaction rate when compared to the pyrolysis of the
polymer. Moreover, the presence of catalysts in polymer thermolysis can
improve the properties of the obtained fluid products. Researchers used
various catalysts such as spent FCC (Fluid catalyst cracking) [4],
different varieties of zeolites [5] such as Y-zeolite [6], natural zeolite
[6], ZSM [7], ZSM-5 [8], HZSM-5 [9], HUSY [10], HY [11], Hβ [11], the

* Corresponding author.
E-mail address: gowthammech@hotmail.com (S. Gowthaman).

https://doi.org/10.1016/j.fuel.2022.124416
Received 21 February 2022; Received in revised form 15 April 2022; Accepted 26 April 2022
Available online 6 May 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
A.P. Pradeep and S. Gowthaman
composite catalyst such as Si-Al [12], Al-Zn [13], mesoporous Al-silica-
MCM41[11], mixture of MCM-41/HZSM-5 and SAHA/HZSM-5 [14],
photoionized HZSM-5 zeolite [15], ZSM-11 and β-zeolite [16], Ni(SiO2)
[17], MgCO3 [18], MgO [19], CuCO3 [20], bentonite/clinoptilolite [21],
red mud [22] and metal based catalysts [23] for thermolysis of waste
plastic to obtain liquid hydrocarbon (HC) fuels.
Other than that, the ZSM-5 catalyst can be effective in aromatization
reactions of polymer molecules. It is proved that the addition of 1 wt% of
ZSM-5 catalyst is sufficient to obtain a fuel with low viscosity and
density by thermolysis of waste high-density polyethylene (HDPE) [24].
The blending of coal with pyrolysis feedstock can increase the concen­
tration of C–H bonds in the plastic oil [25]. Mixed waste plastics con­
sisting of polyethylene terephthalate (PET), HDPE, LDPE, polyvinyl
chloride (PVC), and polystyrene (PS) were blended with coal (10 %)
while ZSM-5 (1%) is employed as catalyst for the catalytic cracking
process. The obtained oil from thermolysis is about 75 % by weight with
its fuel properties similar to diesel [26,27]. The mixed waste plastic oil
possessed a lower cetane number than diesel fuel, however, the viscosity
value satisfies the EN 590 standard [28]. The GC/MS analysis of WPO
(waste plastic oil) from mixed waste polymer contains 39 wt% of aro­
matic content and oxygenated rich components, which is useful in
minimizing CO2 and HC emissions, where it was used as a fuel in the
combustion process.
Rajasekaran et al 2020 and Kulanthaivel et al 2020 used the same
catalyst ratio with the addition of different feed materials like LDPE and
HDPE, however, the GC/MS studied were shows that the different
compositions of the chemical component present in the fluid oil. It was
observed that the chemical composition of LDPE oil contains a large
amount of 9-Octadecen-12-ynic acid, methyl ester, and 10,13-Octadeca­
dienoic acid while the HDPE oil has a high amount of hexadecane, 3-
heptadecene, and methyl z-11-tetradecenoate. The variation in chemi­
cal composition of thermolysis oil obtained from waste LDPE and HDPE
may be the reason for the variation of fuel property. Aguado et al 2008
concluded that catalytic cracking of polymer with various catalysts such
as HZSM-zeolite, HY, Al-MCM-41, and silica-alumina are the favourable
materials to improve the yield of quality plastic oil. The use of HZSM-5
zeolite indicated that the strong acid sites primarily lead to the forma­
tion of olefins (C3 – C5) while Al-MCM-41 and SiO2-Al2O3 being the
weak acid catalysts resulted in plastic fuel with middle-range carbon
distribution due to the presence of accessible acid sites of the catalyst.
Therefore, the rate of conversions of plastic wastes into oil is greatly
enhanced by using nanocrystalline and hierarchical mesoporous-
microporous zeolites when compared to conventional zeolites. Fekhar
et al 2018 investigated the effect of catalysts on pyrolysis of mixed
polymer with different catalyst mixtures in the various ratio: Ni/ZSM-5,
red mud, Ca(OH)2, and Ni/SAPO-11. Increasing the amount of Ni/ZSM-
5 and Ni/SAPO-11 in the catalyst mixture can improve the yield of oil
and increase the concentration of hydrogen in the gas product. More­
over, adding more red mud with other catalysts can further maximize
the hydrogen concentration [29]. The use of calcium bentonite catalyst
in thermolysis of individual polymer such as HDPE, LDPE, PP and
mixture of all the three plastics at a reaction temperature of 500˚C and
1:4 feed ratio yielded plastic oil with heating value greater than 42 MJ
and lower kinematic viscosity when compared to diesel. However, the
pyrolysis oil obtained from PP has an analogous value with kerosine
properties, due to the high Bronsted acidity of calcium bentonite catalyst
leading to the carbenium mechanism by the addition of a proton to the
C–C bonds of the polymer molecule resulting in the formation of plastic
oil with mixture of olefins and aromatic compounds [30].
Aisien et al 2021 have studied the influence of temperature on py­
rolysis of WPP (waste polypropylene) with FCC catalyst. The pyrolysis
oil consisted of a wider range of HCs with number of C atoms ranging
between C4-C17. The extracted plastic oil consists of paraffin (30.83%),
olefin (44.6%), naphthalene (19.44%), and aromatic compounds
(5.13%). Hence, the properties of pyrolysis oil are similar to petrol and
diesel. Moreover, increasing the reactor temperature from 300 to 375˚C,
2
Fuel 323 (2022) 124416
affected the fuel properties such as heating value, carbon residue, flash
point, kinematic viscosity, and density. The FCC catalyst did not have
sufficient active catalytic sites to break the long-chain molecules of the
polymer backbone which resulted in the formation of plastic oil with
considerably higher viscosity and density than the petroleum diesel
[31]. From the previous studies, it is noted that pyrolysis is an effective
technique to extract liquid fuels from various plastic wastes with higher
conversion efficiency. Particularly, LDPE has delivered more PO with
better fuel properties compared to other plastic wastes obtained from
HDPE and PP. The addition of catalysts in the pyrolysis process has
accelerated the cracking of strong HC bonds present in the polymer
matrices into lighter hydrocarbon molecules, which resulted more yield
with better fuel properties at shorter processing duration. The present
study investigates the effect of magnesium bentonite catalysts on py­
rolysis process with different percentages such as 1, 2, 3, and 4 by weight
and the best ratio is optimized based on the yield and quality of
extracted pyrolysis oil.
2. Materials and methods
2.1. Materials
This study investigates with LDPE as a feed material for pyrolysis
process, which is collected and separated with the help of an identifi­
cation code. The LDPE is transparent and has low GSM (gram per square
meter). The LDPE is procured from the packaging and printing industries
from Sivakasi district, Tamil Nādu. The collected LDPE polymer based
waste materials are pre-treated before feeding into the pyrolysis cham­
ber. Initially, it is washed with clean water to remove the dust particle
from it and dried in sun light for 20 h. The dried waste LDPE is ground
into fine pieces with an area of less than 3–8 mm2.
2.2. Methods
The systematic pyrolysis plant diagram is shown in Fig. 1. The dried
waste LDPE plastic is fed into a 2000 cm3 round shaped borosil com­
mercial glass reactor with wall thickness of 2 mm. The glass reactor has
three sections: the largemouth is used as a feeder, the smallmouth has a
thermometer pocket and adapter. The glass reactor is placed in the
thermally insulated silica wool chamber. An electrical furnace has a 500-
watt capacity and attains a maximum temperature of 500 C̊, which is
connected with a partially integrated and differential (PID) temperature
controller. The pyrolysis reactor started at room temperature of 29˚C,
which is reaching the highest temperature within 35 min. The whole
process started in atmospheric air. A glass reactor is used to degrade the
LDPE waste polymer at the reaction temperature of 340˚C and convert
the solid waste sample into vapor form, and further, it passed through
the bulb condenser (400 mm length) to convert into the liquid product
which is collected in a 500 ml flask. Non-Condensable gases flowed
through the atmosphere; whereas the non-volatile residue products were
collected after the glass reactor was cool down to room temperature. The
yields of liquid, residue, and gases are calculated by the following
equation Fig. 2.
Yield of Liquid oil(wt.%) = (ML /Mwaste LDPE ) × 100 (1)
Yield of Residue(wt.%) = (MR /Mwaste LDPE ) × 100 (2)
Yield of Gases(wt.%) = (MG /Mwaste LDPE ) × 100 (3)
Mass of Gases(wt.%) = Mwaste LDPE –(ML + MR ) × 100 (4)
Where, ML - Mass of liquid (g), MR - Mass of Residue (g) and Mwaste LDPE -
Mass of gases (g).
A.P. Pradeep and S. Gowthaman
Fig. 1. Catalytic Pyrolysis Plant.
Fig. 2. FTIR spectrum of waste LDPE polymer.
2.3. Characterization techniques
The FTIR analysis of the membranes is carried out in a IRTracer-100
spectrometer in the range of 400–4000 cm− 1. The SEM images of the
sample materials is taken using a Carl Zeiss EVO 18 SEM instrument at
an operating voltage of 10 kV and the EDAX is acquired from a Bruker
Nano XFlash energy dispersive X-ray spectrometer. The thermal analysis
of the samples are carried out in a Perkin-Elmer TGA-DSC instrument in
the temperature range of 50–1300 ˚C with a heating rate of 5 ˚C per
minute.
3. Pre-analysis of LDPE
3.1. FTIR analysis of LDPE
The FTIR spectra of LDPE is shown in Fig. 3 and the peak descriptions
3
Fuel 323 (2022) 124416
Fig. 3. TGA analysis on waste LDPE.
are listed in Table 1. The absorption band at 3745.76 cm− 1 is due to the
O–H stretching, which proves the presence of alcohol. Alkene (C = C)
linked with methyl group is confirmed from the absorption band present
at 2914.44 cm− 1. The peak at 2846.38 cm− 1 is associated with the
stretching vibration of O-CH3 and C–H group. The absorption band at
1649.14 cm− 1 is attributed to the presence of conjugated ketone moi­
eties (νC = O). The peak at 1462.04 cm− 1 is associated with the meth­
ylene (δC-H) group. The presence of sulfonic acid group is confirmed
from the peak at 1332.81 cm− 1 which is attributed to the stretching
mode of S-O bonds (νS = O). The presence of alkyl aryl ether (Me-O-Ph)
and aliphatic ether (C-O-C) groups are confirmed from the absorption
bands present at 1151.50 and 1029.99 cm− 1. The alkene C = C group is
in the functional frequency range of 721.38 cm− 1 Fig. 4.
A.P. Pradeep and S. Gowthaman Fuel 323 (2022) 124416

Table 1 4. Pre-analysis of catalyst

FTIR characterization of LDPE.
Sl. Waste Appearance Vibration Assignment Compound 4.1. FTIR analysis of magnesium catalyst
No LDPE peak type class
(cm− 1) Fig. 5 shows the IR spectra of the commercial magnesium bentonite
1 721.38 Strong Bending C=C Alkene catalyst sample. Table 3 lists the absorption peaks and their description
2 1029.99 Strong Stretching C-O Alkyl aryl of Mg containing clay sample. The broad absorption band at 3695.60
ether cm− 1 is due to stretching vibration of O–H groups which is characteristic
3 1151.50 Strong Stretching C-O Aliphatic ether
4 1332.81 Strong Stretching S=O Sulfonic acid
to all the clay materials. The appearance of a band position at 790.81
5 1462.04 Medium Bending C–H Alkene and 914.26 cm− 1 is due to Al-Mg-OH as well as the Al-Al-OH stretching
(Methylene vibrations respectively. The presence of absorption peaks at 696.30
group) cm− 1, 534.28 cm− 1 and 468.70 cm− 1 are due to the stretching vibrations
6 1649.14 Strong Stretching C=O Conjugated
associated with the Si-O, Al-O-Si, and Si-O-Si groups respectively.
Ketone
7 2846.93 Medium Stretching C–H alkene
8 2914.44 Medium Stretching C–H alkene 4.2. SEM and EDX analysis of magnesium bentonite catalyst
9 3745.76 Medium Stretching O–H alcohol
sharp
Fig. 6 shows the SEM images of the raw magnesium bentonite clay
material displaying less than 2 µm clay flakes. The chemical composition
of the magnesium bentonite catalyst is investigated using EDX analysis
(Fig. 7 and Table 4). From the EDX analysis, it is found that the per­
centage of oxygen is higher than the amounts of Si and Al. Heavy metals
such as Ti and Fe are found in trace quantities while the amount of Mg is
calculated to be 1.6 %. The Si/Al ratio of the magnesium bentonite clay
is found to be 2.06. The presence of MgO has maximized the gas and
char weight percentage and simultaneously increased the quality of
liquid bio-oil (Ersan pudin 2010). Increasing the amount of MgO in Na-
bentonite is an important approach to carry out the pyrolysis reaction
with improved reaction rate as well as plastic oil yieldTable 5.
From this study, the presence of magnesium bentonite with waste
LDPE polymer during pyrolysis increased the hydroxyl group of com­
ponents in the PO due to the oxygenation of metal. High selectivity of
aromatic (light and heavy fraction HC) content in the liquid oil can be
attained by the presence of Ti and Fe metals.

5. Result and discussion

5.1. Products of catalytic pyrolysis

Fig. 4. DSC analysis on waste LDPE. The catalytic pyrolysis delivered three different components such as
HC liquid, solid carbon residues and gas products. The percentage of
3.2. TGA-DSC analysis of LDPE yielded produces are varied based on the following parameters such as
processing temperature, feed stroke material, type of catalysts and
Thermogravimetric analysis (TGA) is a thermal analysis technique processing duration. The pyrolysis of LDPE with absents of catalyst has
that measures the weight loss of a material as a function of temperature resulted 59.25 % of PO, 35.25 % of residue, and 5.5 % of gases product
and time under externally controlled atmosphere. This can be useful to by weight ratio. The addition of catalysts in the pyrolysis made drastic
investigate the stability of materials at elevated temperatures. The
experimental results from TGA/DSC of waste LDPE polymer analysed
under air atmosphere (19.8 ml min− 1) are shown in the Fig. 3. From the
thermogram of waste LDPE, it is found that at 508˚C, the material started
to degrade, and no residue remains at 700˚C indicates that the plastic
waste is devoid of any metal traces. The DSC thermogram of the polymer
material showed two distinct exothermic peaks at ~ 130˚C and 482˚C
respectively. The first exothermic peak is due to the cleavage of olefinic
bonds while the second peak is attributed to the breakage of saturated
bonds of the HCs. Table 2 presents the onset temperature, Tmax values
obtained from TGA and DSC analysis.

Table 2
TGA analysis of waste LDPE: Degradation temperature range, onset, end, and
maximum degradation temperatures at 5 ◦ C/min.
Material Initial Temperature TGA DSC
Mass (g) range (oC) Tonset Tend Tmax T (qmax)
(oC) (oC) (oC) o
C

Waste 7.71 50–700 442 500 508 482

LDPE
Fig. 5. FTIR spectrum of magnesium bentonite.

4
A.P. Pradeep and S. Gowthaman Fuel 323 (2022) 124416

Table 3 liquid oil under the operating temperature at 340 ◦ C and 3.3 h residence
FTIR characterization of magnesium bentonite. time.
Sl. No Magnesium Appearance Vibration type Assignment
bentonite peak 5.2. FTIR analysis of catalytic pyrolysis oil
(cm− 1)

1 468.70 Medium sharp Stretching Si-O-Si The comparative analysis of liquid oil obtained from thermolysis and
2 534.28 Strong Broad stretching Si-O Al-O-Si catalytic cracking of waste LDPE polymer with commercial diesel fuel by
3 696.30 Broad Stretching Bending Si-O Si-O-Si
FTIR spectroscopy to study their chemical composition. The FTIR results
4 790.81 Weak Broad Stretching Al-Mg-OH
5 914.26 Strong Broad stretching Al-Al-OH are displayed in the table.1 and the figure. Catalytic pyro-oil has a
6 1035.77 Strong Stretching Si-O-Si similar chemical composition to diesel fuel. The FTIR spectrum of the
7 1641.42 Medium Bending H-O–H thermally derived liquid oil from waste LDPE (PO1) was provided in
8 3421.72 Strong, broad Stretching H-O–H Fig. 9. Several major and minor transmittance peak with different in­
9 3624.25 sharp Stretching H-O–H
10 3695.61 sharp Stretching O–H Si-O–H
tensities in the wave-number range from 4000 cm− 1 to 400 cm− 1 was
observed. Several strong peaks are observed in the range of 2920.23
cm− 1 2854.65 cm− 1 1458.18 1377.17 cm− 1 and 721.38 cm1 corre­
sponding to the alkane, methylene, methyl, phenol, and benzene
derivatives.
The FTIR spectrum of the catalytic pyro-oil (CPO) addition of 1,2 and
3 wt% of catalyst (CPO1, CPO2, CPO3) is displayed in Fig. 9. Several
peaks are observed at 3743.83 cm− 1, 2920.23 cm− 1, 2852.72 cm− 1,
1460.11 cm− 1, 1375.25 cm− 1, and 721.38 cm− 1 corresponding to me­
dium sharp O–H stretching (alcohol), medium C–H stretching (alkane),
medium C–H bending (methylene and methyl group), medium O–H
bending (phenol) and strong C–H bending (benzene derivatives). This
indicated that all peaks are similar to diesel fuel and produced the same
chemical composition as pyrolysis oil except the peak value of 3743.83
cm− 1 corresponding to O–H stretching vibration, due to the presence of
oxygen content in the catalyst were improved the oxygenated fraction in
the catalytic liquid oil.
From this detailed study, it was confirmed that the presence of O–H
C-CH3, CH3, and C–C (ring) groups in all of the catalytic liquid oils. It
was concluded that the liquid oils from catalytic cracking contain more
amount of alcohol, paraffin, olefin, and naphthenic hydrocarbons (HC).
the thermolysis of waste LDPE with the addition of catalyst facilitated
Fig. 6. SEM micrograph of raw magnesium bentonite catalyst. the oxygenated component present in the liquid oil, which is useful for
more complete combustion and less emission.
changes in the products, it is shown in the Fig. 8. The addition of 1 wt%
of a catalyst extracted 77.97% of PO, 14.23% and 7.29% of residue and 5.3. Properties of catalytic pyrolysis oil
gases respectively. The addition of 2 wt% catalysts resulted with 69.6%
of PO, 24.01% of residue, and 6.12% of gases by weight. From the Fig. 8, The plastic oil samples obtained from the catalytic cracking of waste
it is noted that the 2 wt% of catalysts improved the rate of PO extraction LDPE at various wt % of catalyst have similar attributes to the existing
compared to 1 wt% of catalytic pyrolysis. The presence of 3 wt% of Mg-
bentonite catalyst attained the lowest yield of liquid oil about 50.24 wt
Table 4
%, the highest amount of residue and gases products are delivered, Composition of magnesium bentonite samples based EDX (weight %).
which is about 40.77 wt% and 8.98 wt%. The high viscus and the
Chemical O Na Mg Al Si K Ca Ti Fe
average yield of liquid can be obtained at 4 % of catalyst addition with
content
waste LDPE polymer. From this deep discussion, it was optimized that
Weight % 50.3 1.9 1.6 11.5 23.7 1.0 0.8 1.4 7.9
the 1 wt% of Mg-Bentonite catalyst has resulted in the highest yield of

Fig. 7. EDX analysis on magnesium bentonite.

5
A.P. Pradeep and S. Gowthaman Fuel 323 (2022) 124416

Table 5
List of components in pyrolysis oil.
S.No Peak (cm− 1) Appearance Vibration Assignment Compound
Diesel PO2 CPO1 CPO2 CPO3 type class

1 3674.39 – 3743.83 3747.69 3745.76 Medium sharp Stretching O–H Alcohol (free)
2 2954.95 – – – Medium Stretching C–H alkane
3 2922.16 2920.23 2920.23 2920.23 2920.23
4 2854.16 2854.65 2852.72 2852.72 2852.72
6 – 2357.01 – – – Strong Stretching O≡C≡C Carbon dioxide
7 – 2225.85 – – – Weak Stretching C≡C Nitrile
8 – 2162.20 – – – Strong Stretching S≡C≡N Thiocyanate
9 – 2112.05 – Weak Stretching C≡C alkyne
11 2059.98 2069.62 2048.40 – 205.61 Strong Stretching N≡C≡S isothiocyanate
12 2002.26 2009.83 –
13 1965.46 – – – – Medium Stretching C≡C≡C allene
14 – 1643.35 – – – Strong Stretching C=C alkene
15 1460.11 1458.18 1460.11 1460.11 1460.11 Medium Bending C–H Methylene (or) methyl group
16 1375.25 1377.17 1375.25 1375.25 1375.25 Medium Bending O–H Phenol
17 – 993.34 – – – Strong Bending C=C alkene
18 723.31 721.38 721.38 721.38 723.31 Strong Bending C–H Benzene derivatives

catalytic pyro-oil sample have lower than the value of diesel. high heat
values (greater than43 MJ/kg) can attain with the presence of a catalyst
when compared to pyrolysis oil. Increasing the concentration of cata­
lysts to more than 3 wt% were increase the viscosity of catalytic pyro-oil.
This is because of the abundant presence of long-chain hydrocarbons in
the liquid product obtained by increasing the amount of catalyst. The
sample of oil without and with the addition of 1–3 wt% catalyst was
found low viscosity, high octane number, low flash point than refinery
diesel fuel.
The commercial diesel has a density range from 0.8323 kg/m3, a
flash point of 53 ◦ C, and cetane number 51.2. It was confirmed that the
characteristic of liquid oil from both pyrolysis and catalytic cracking
with the addition of 1 and 2 wt% of the catalyst is equivalent to diesel
fuel. The ultimate analysis resulted that the pyrolysis and catalytic py­
rolysis oil has lower carbon content and high hydrogen content than the
commercial diesel. The addition of a catalyst can increases the hydrogen
and oxygen content in catalytic pyro-oil due to the presence of a catalyst
can improve the reaction against the polymer molecule chain and pro­
duced the O–H hydroxyl group of components, which is indicated in the
FTIR table. The high amount of oxygen content in the plastic oil sample
improved the oxidation of fuel particles during combustion of CI engine
operation and also minimize emission.
Fig. 8. Percentage of yield at 340 ◦ C operating temperature.
Conclusion

The pyrolysis of LDPE in a glass reactor with the presence of mag­

nesium bentonite at 340˚C with 3.3 h processing duration resulted higher
oil yield with better fuel properties. The quality and yield percentage of
pyrolysis oil is varied based on the addition of catalysts in the process.
The following observations are made from this experimentation,

• A high yield of oil 77.97 wt% could be attained at 1 wt% catalyst

Fig. 9. Comparison of FTIR spectrum LDPE oil and diesel fuel.
commercial diesel fuel. The fuel characteristic (evaluated using ASTM
standards) of all the liquid oil samples is summarized in Table 6. The
addition of catalysts was greatly affecting the fuel properties of the
liquid sample. The density and specific gravity of the pyrolytic and
presence, due to the presence of magnesium accelerating the rate of
reaction.
• Increasing the weight percentage of catalysts improved the reaction
rate, which resulted in increased viscosity of the fuel.
• From the FTIR analysis of the liquid product, the addition of catalyst
produced a hydroxyl OH (alcohol) group of compounds, which is not
present in the pyrolytic oil sample. This because the presence of Ti
and Fe metal were released the light fraction of aromatic hydrocar­
bons like benzene and naphthalene.
• The properties study of catalytic pyrolysis oil with the addition of 1
wt% of catalyst has a high heat value of 43.224 MJ/kg, low kine­
matic viscosity is about 2.86 cSt, and high cetane index value of 51.4.

6
A.P. Pradeep and S. Gowthaman Fuel 323 (2022) 124416

Table 6
Influence of catalysts on properties of liquid oil from catalytic cracking of waste LDPE.
Proximate Analysis
Test Commercial
Method diesel fuel

Mg-bentonite 0% 1% 2% 3% 4%
Density @ 15 (oC) (g/cc) ASTM D 1298 0.7793 0.7459 0.7433 0.7452 0.7497 0.8323
Specific Gravity @ 15◦ deg C (g/cc) 0.7468 0.7444 0.7461 0.7508 0.8332
Flash point (oC) ASTM D 93 22 27 30 31 38 53
Fire Point (oC) 24 29 33 34 42 59
Kinematic Viscosity @ 40 ◦ C (cSt) ASTM D 445 2.02 2.86 2.73 2.76 3.76 3.14
Calorific value (MJ/Kg) ASTM D 240 41.989 43.224 43.421 43.162 43.053 44.698
Pour Point (oC) ASTM D 97 − 20 23 18 16 25 − 17
Cetane Number 50.8 51.4 51.6 51.2 50.9 51.2
Ultimate Analysis
Carbon (%) 83.81 83.82 83.91 84.03 83.71 88.53
Hydrogen (%) 14.06 14.13 14.2 14.09 14.16 11.27
Nitrogen (%) 0.42 0.21 0.19 0.17 0.2 0.012
Sulphur (%) 0.29 0.18 0.2 0.16 0.19 0.038
Oxygen by difference (%) 1.42 1.66 1.5 1.55 1.74 0.15

• It was confirmed that the addition of catalysts in the thermolysis of
waste LDPE increased the yield of liquid oil and improved the fuel
properties when compared to the pyrolysis process.
CRediT authorship contribution statement
A. Pakiya Pradeep: Investigation, Formal analysis, Validation. S.
Gowthaman: Conceptualization, SupAervision, Writing – original draft.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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