Applied Energy 327 (2022) 120040

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Conversion of mixed waste plastic into fuel for diesel engines through
pyrolysis process: A review
S.M.R. Mirkarimi a, S. Bensaid a, D. Chiaramonti b, *
a
Polytechnic University of Turin, Department of Applied Science and Technology (DISAT), Turin, Italy
b
Polytechnic University of Turin, Department of Energy (DENERG), Turin, Italy

G R A P H I C A L A B S T R A C T

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

Keywords: During the last decade, massive production of plastic materials causes a significant amount of waste. This
Waste to energy growing trend in waste plastic, and the related negative effect on environment raised many concerns leading to
Plastic pyrolysis oil propose different solutions for its disposal, recycle and re-use. Among different methods, landfilling, incineration
Value-added products
and mechanical recycling are more conventional, however due to their environmental problems or economic
Catalyst
issues, they would not be the best solutions for waste plastic management. The paper presents a review of a more
Combustion
Emission effective process to recover the energy contained in these materials, with a focus of their use for producing fuel
thorough the pyrolysis process. This conversion process does not only represent an environmentally friendly
solution for the management of waste plastics, but also allows producing a liquid product which can be used for
several energy-related applications. The focus of this review paper is to identify an optimum approach for
production of maximum waste plastic pyrolysis oil with the characteristic similar to diesel fuel through inves­
tigation on various previous studies in this area. To reach this target, a review of the recent studies related to
pyrolysis of waste plastics was carried out, and the main parameters affecting the liquid product yield were
investigated. Then, the quality of several waste plastic oil (WPO) was compared to the conventional diesel fuels,
based on the information reported about their physico-chemical properties, and their application in the diesel
engine based on the parameters such as combustion, performance, and emission have been studied.

* Corresponding author.
E-mail address: [email protected] (D. Chiaramonti).

https://doi.org/10.1016/j.apenergy.2022.120040
Received 31 March 2022; Received in revised form 14 September 2022; Accepted 22 September 2022
Available online 12 October 2022
0306-2619/© 2022 Published by Elsevier Ltd.
S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Nomenclature HRR Heat Release Rate

ID Ignition Delay
AC Air Cooled LDPE Low-Density Polyethylene
BSFC Brake Specific Fuel Consumption LPG Liquefied Petroleum Gas
BTE Brake Thermal Efficiency MWP Mixed Waste Plastic
CR Compression Ratio PCP Peak In-Cylinder Pressure
CSBR Conical Spouted Bed Reactor PET Polyethylene Terephthalate
DI Direct Ignition PILC Pillared Clays
DTG Derivative Thermo-Gravimetry PP Polypropylene
EGT Exhaust Gas Temperature PS Polystyrene
EMI Electro-Magnetic Induction PVC Polyvinyl Chloride
FCC Fluid Catalytic Cracking SA Silica-Alumina
FTIR Fourier-Transform Infrared St Stroke
GC–MS Gas Chromatography–Mass Spectrometry TG Thermo-Gravimetry
GHG Greenhouse Gases UHC Unburned Hydrocarbon
HCl Hydrogen Chloride WC Water Cooled
HDPE High-Density Polyethylene WPO Waste Plastic Oil

1. Introduction problems, landfilling in EU and several states of US like California has

been banned recently.
The unique properties of plastic such as light weight, corrosion and Mechanical recycling is an alternative approach to manage plastic
chemical resistance, mechanical strength, and durability make it a ver­ wastes, which can prevent disposal and reduce the consumption of
satile material, which can be used for wide range of applications. Plastic virgin materials. In this method, mixed plastic waste are sorted, washed,
products are consumed on large scale in different industries such as and melted into granulates, then formed into new products. However,
packaging, construction, automotive, electrical and electronic. Due to separating Mixed Waste Plastics (MWP) based on the resin compound,
the popularity of using plastic materials, the global production of plastic transparency and color is not cost-effective and would be labor-
had a significant growth during the last decade, and it has increased intensive, so chemical technologies are often preferred [1–2].
from 1.5 Mt in 1950 to 359 Mt in 2018 [1] and it is predicted this The most conventional chemical technology suggested for reducing
amount will be quadrupled by 2050 [2]. Also, it is estimated that around waste plastics is incineration, which is based on direct energy recovery
300 Mt of plastic wastes are generated annually which can create a from waste plastics via burning them as a source of energy. However, the
significant adverse effect on the environment [2]. One of the serious elimination of waste plastics by this method leads to releasing very
problems related to plastic is the irresponsible disposal of a large number harmful emissions to the environment and rising the amount of green­
of plastic wastes (4–12 Mt/y) in the oceans, which can have harmful house gases (GHG) [7]. Unlike incineration, the methods based on in­
impacts on marine life and even indirectly on human health [3]. direct energy recovery from waste plastics such as pyrolysis are
One of the basic solutions considered to address the environmental environmentally friendly solutions for the management of waste plastics
problems of waste plastics is to ban the consumption of certain plastic that compared to direct incineration has considerably lower carbon
products. Although this approach seems effective in short term for some footprint [8–9]. In the pyrolysis process, long-chain polymer molecules
non-essential items, it could not solve the challenges related to waste convert into smaller and less complex ones under intense heating, at
plastic produced in other sectors [1]. Thus, reducing unnecessary temperature around 500 ◦ C and in the absence of oxygen [2]. The major
packaging in order to reduce the volume of waste plastics should be products of waste plastic pyrolysis are gas, liquid oil, and char which are
followed along with end-of-life management to control the catastrophic valuable for different industries. Since liquid oil produced from waste
consequences of these wastes [1]. For this purpose, European Union sets plastic by this method can be used as fuel in diesel engines, boilers,
the basic concepts and definitions related to waste management, furnaces and turbines, the main focus of studies in this area is related to
including definitions of waste, recycling and recovery through Waste enhancement of the liquid yield. Hence, conversion of waste plastics into
Framework Directive. The Waste Framework Directive lays down some valuable products namely liquid oil through pyrolysis process not only
basic waste management principles. It requires that waste to be tackle the adverse environmental impacts of plastic wastes but also leads
managed, to saving fossil fuels as a source of energy for the next generations.
From the other point of view, the demand for diesel cut in the Eu­
• without endangering human health and harming the environment ropean countries and the United States is the main reason that waste
• without risk to water, air, soil, plants or animals plastics along with renewable biomass have attracted worldwide
• without causing a nuisance through noise or odors attention in recent years [10]. In some studies, it has been claimed that
• and without adversely affecting the countryside or places of special the crude liquid oil with dominant carbon range of C13–C20, which has
interest been obtained from pyrolysis of waste plastic can be used in a wide
range of diesel engines from light-duty (for passenger vehicle) to heavy-
Based on this, preparation for re-use and recycling of municipal duty (for marine and industrial equipment) applications.
waste shall be increased to a minimum of 55 %, 60 % and 65 % by Due to the important role of the pyrolysis process in eliminating
weight by 2025, 2030 and 2035 respectively [4]. waste plastic, this method has been experimentally investigated in many
Plastic waste disposal by landfilling was the most common way that research papers for various types of plastics at different operating con­
is recommended for management of waste plastics. For instance, more ditions. Also, many review papers have been published with a focus on
than 75 % of waste plastics in the US was sent to landfill for disposal in pyrolysis of an individual plastic, nevertheless, pyrolysis of plastic
2017 [1]. However, using this method causes severe environmental mixture for oil recovery has rarely been studied. Due to the few review
problems namely production of leachate which can pollute the soil and papers concerning pyrolysis of MWP and the importance of diesel cut,
groundwater, and spreading unpleasant odors [5–6]. Due to these the main focus of this paper has been to investigate the solutions to

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

maximize pyrolitic conversion of mixed plastic into fuel for diesel en­ Table 1
gines. In order to achieve this target, the impact of plastic-type, oper­ Plastic types and their SPI resin ID code, chemical structure, properties and
ating factors, type of reactor and catalyst on the liquid product has been applications [16,19].
studied. Also, in contrast with other reviews in this area, the quality of Plastic type and SPI Chemical structure Properties Applications
various WPOs has been evaluated through comparing their physico- resin identification
chemical properties with the standard characteristics of automotive code

and marine diesel fuels, as well as their combustion, performance, and • High chemical • Bottles
emission characteristics. and thermal • Food
stability packaging
Polyethylene • Transparency • Electrical
2. Pyrolysis of individual plastic Low gas and insulation
terephthalate
water vapor • Printing
Results of studies concerning pyrolysis of different types of plastics permeability sheets
reveal that in addition to the operating factors, yields and quality of • Gas barrier • X-ray
properties
liquid products are highly dependent on plastic type. Plastics are divided • Long polymer • Bottle caps
into two general groups of thermoplastics and thermoset. The primary chain • Chemical
difference between these two groups involves the fact that thermo­ • Highly storage
plastics can be reheated, remolded, and cooled back into a liquid High density crystalline containers
• High strength • Food storage
without causing any chemical changes, while, thermosets always remain polyethylene
containers
in a permanent solid state and strengthens when heated, so cannot be • Fuel tanks
remolded or heated after the initial forming. Thermoplastics are more for vehicles
favorable compared to thermosets in the perspective of their recycla­ • Resistant to • Wire and
bility, due to their susceptibility to change and molecular reformulation fire cable
insulation
with heat exposure (almost 80 % percent of plastics in Western Europe • Packaging
are thermoplastics). Polyvinylchloride
• Window
Thermoplastics themselves have been commercially-wise divided frames
into the following seven groups based on their chemical structure and • Food foil
Medical
applications: PET (Polyethylene Terephthalate), HDPE (High-Density
devices
Polyethylene), PVC (Polyvinyl Chloride), LDPE (Low-Density Poly­ Lower tensile • Wrapping
ethylene), PP (Polypropylene), PS (Polystyrene), and other (including strength and foils for
Polybutylene terephthalate (PBT), Polycarbonate (PC), Polylactide hardness but packaging
(PLA), Polyacrylic Acid (PAA), Acrylonitrile Butadiene Styrene (ABS), better ductility • Trash bags
Low density
compared to Plastic
and Polyamide (PA) or Nylon). Table 1 shows some information about polyethylene
HDPE bags
different types of plastics including SPI resin identification code,
• Good heat and • Medical and
chemical structure, properties and applications. chemical laboratory
As it is shown in Tables 1 and 2, PS and polyolefins (LDPE, HDPE and resistance devices
PP) are all hydrocarbons consisting entirely of carbon and hydrogen that • Low density • Piping
Polypropylene
has high calorific value, in the range of hydrocarbon fuels such as gas­ • High rigidity systems
• High hardness • Carpets
oline, diesel, and Liquefied Petroleum Gas (LPG). PET and PVC are lower
• Plastic pails
caloric value plastics that in addition to carbon and hydrogen, they have • Car batteries
also oxygen and chlorine in their hydrocarbon chains respectively. • Heat residence • Food
According to the Table 3, chemical properties of plastic compounds • Good packaging
are measured through proximate analysis based on the four particular durability • Construction
• High strength • Electronics
parameters including moisture content, fixed carbon, volatile matter, Polystyrene
• Lightness • Medical
and ash content. For instance, plastic with higher volatile matter such as devices
PS and LDPE shows higher potential for the production of liquid oil • Clothes
compared to PVC and PET [11]. hangers
• Plastic CDs
Ultimate analysis, also known as element analysis, is another char­ – –
and DVDs
acterization used to analyze the percent of CHNS (Carbon, Hydrogen, • Medical
Nitrogen, and Sulfur) in plastic. In some studies, besides the percent of storage
CHNS, the percent of Chlorine and Oxygen is also measured. The con­ Other containers
centrations of C, H, and O allow to estimate the heating value while the • Eyeglasses
• Baby bottles
amounts of N and S give an idea of the environmental impact [12–13].
Since PS and polyolefins make up a large portion of MWP, it is ex­
pected that a product with high content of liquid oil could be obtained which is produced by polymerization of ethylene terephthalate mono­
by pyrolysis of MWP. However, due to the chemical structure of PET and mers, with repeating (C10H8O4) units. Although conversion of PET
PVC, their presence in the MWP composition could be problematic. through pyrolysis helps to the recovery of this type of plastic, due to the
Hence, in order to be able to identify potential interactions between the technical and environmental problems related to thermo-chemical
different types of plastic during pyrolysis of MWP, it is required to have a conversion of PET, limited studies have been performed in this area.
comprehensive knowledge about thermo-chemical conversion of each Park et al. have studied the pyrolysis of PET over the carbon-
type of plastic separately. supported Pd catalysts and without any catalyst at the temperature
range of 400–800 ◦ C: based on their results, by thermal pyrolysis of PET
2.1. Impact of plastic type a product including 42 % liquid oil, 42 % gas, and 16 % char was ob­
tained at 800 ◦ C. They observed catalytic pyrolysis of PET over Pd
2.1.1. Polyethylene terephthalate (PET) catalyst with the ratio of 0.01 and 0.05 to the plastic led to a reduction in
Polyethylene terephthalate, commonly abbreviated PET or PETE, is liquid yield to 39 % and 33 % respectively [14]. The results of study
the most common thermoplastic resin belonging to the polyester family

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Table 2
Calorific value of some plastics and fuels [12,122–123].
Material PET HDPE PVC LDPE PP PS Gasoline Diesel LPG

Calorific value (MJ/kg) 24.13 49.4 18.0 37.4–46.6 45.3–46.4 37.7–42.1 46.8 43 46.1

5 ◦ C/min. They claimed increasing pressure to 10 Mpa helps to achieve

Table 3
93 wt% liquid oil yield [20].
Proximate analysis of different types of plastics [8].
An experimental investigation performed by Sundararajan et al. on
Plastic-type Proximate analysis (wt.%) catalytic pyrolysis of HDPE in a batch type fixed-bed reactor at tem­
Moisture Fixed carbon Volatile Ash perature range 475–525 ◦ C and four different heating rates of 5, 10, 15,
PET <0.7 6–14 85–92 <0.1
and 20 ◦ C/min showed the highest liquid oil yield was achieved at the
HDPE <0.3 ~0 94–99.8 <1.5 heating rate of 10 ◦ C/min and 95 min of residence time. At this heating
PVC <0.8 5–7 58–94.8 <0.1 rate and with the ratio of 10 wt% activated bentonite to the plastic, a
LDPE <0.3 ~0 99–99.8 <0.4 product with 90.5 wt% liquid including 79.1 wt% liquid oil, and 11.4 wt
PP 95–99.6 1–4
% wax was obtained. Also, it was reported that rising heating rate from
<0.4 <1.2
PS <0.3 <0.2 99–99.8 <0.5
Other <0.2 <3 97–99.8 1 10 to 20 ◦ C/min led to a growth in the wax yield to 32.8 wt% and a
reduction in the liquid oil yield by 38.4 wt% [22]. There are also some
other studies which reported presence of wax in the liquid product at
performed by Singh et al. shows at heating rate of 20 ◦ C/min and high temperature [23–26].
pressure of 2 atm, increasing temperature from 400 to 600 ◦ C leads to a There are so many other studies that have been carried out on the
reduction in liquid oil from 32 to 25 wt% [15]. Based on the research thermal and catalytic pyrolysis of HDPE showing the high potential of
performed by Cepeliogullar and Putun on the pyrolysis of PET in a fixed- HDPE for achieving to the products with almost more than 80 wt%
bed reactor at 500 ◦ C, a product including 23.1 wt% liquid oil and 76.9 liquid oil [20,24,27–33]. Although generally high liquid yield was ob­
% gas was obtained. They also reported no solid was observed in the tained by pyrolysis of HDPE, pyrolysis of this type of plastic at tem­
final product [16]. Also, the results reported by FakhrHoseini and Das­ perature more than 450 ◦ C leads to increasing the possibility of wax
tanian indicate that the yield of pyrolytic liquid achieved from PET at (C21+) domination instead of liquid oil such as gasoline (C5–C12) and
500 ◦ C could not be more than 38.9 wt% which is almost half of LDPE diesel (C13–C20) in the liquid products [21–23,27].
and PP. Different degradation mechanism of PET has been reported as
the main reason for conversion of this plastic into less energy content 2.1.3. Polyvinylchloride (PVC)
products [17]. The low liquid yield of this plastic type also can be Polyvinylchloride (PVC) is an exceptional thermoplastic material
explained through the low volatile matter of PET. that, unlike the other thermoplastics such as polyethylene, poly­
The results of all the studies conducted on the pyrolysis of PET propylene, and polystyrene which are just produced from oil, is manu­
indicate the liquid oil obtained could not be higher than 42 wt%, factured from the mixture of 57 % chlorine (derived from industrial
whereas gas has been the dominant product in most of the studies and its grade salt) and 43 % carbon (derived from hydrocarbon feedstock such
content in the final product could even reach 77 wt% [14–17]. Due to as ethylene from oil or natural gas). Despite its various applications, the
this issue, for the conditions that the gas would be the desirable product, number of studies concerning the pyrolysis of PVC is limited and this is
pyrolysis of PET has been recommended. Only at higher pressure con­ due to the releasing hazardous chlorine gas (hydrogen chloride) during
ditions (10 MPa), the gas yield is not considerable (32 wt%) but even at heating PVC at high temperature [16,19].
this condition the liquid yield is low and the dominant product would be Miranda et al. studied the kinetics of PVC pyrolysis reactions and the
solid with 53 wt% [18]. products yields in a vacuum reactor (2 kPa) and heating rate of 10 ◦ C/
Pyrolysis of PET is one the best methods to recover this type of min at the temperature range of 200–520 ◦ C. They observed an increase
plastic; however, during this process, harmful materials such as poly­ in temperature from 200 to 520 ◦ C led to a growth in the yields of liquid
cyclic hydrocarbons and biphenyl derivatives are emitted having an oil and HCl from 0.45 to 12.79 wt% and 44.35 to 58.20 wt% respec­
adverse impact on human health and the environment. Analysis of liquid tively, however, the amount of solid residue obtained through its py­
oil produced from PET revealed almost half of the liquid composition is rolysis reduced considerably from 54.77 to 8.53 wt% [34]. Based on the
benzoic acid (benzoic acid can cause clogging of the pipes and heat other research performed on the pyrolysis of PVC in a fixed-bed reactor
exchanger). Due to these challenges, the number of studies concerning by Cepeliogullar and Putun, 12.3 wt% liquid oil was obtained at 500 ◦ C.
the conversion of PET into liquid oil by pyrolysis process is limited It is reported that at this temperature, the majority of the product was
[14,19]. gas with 87.7 wt% [16].
Based on the results, the amount of liquid oil obtained from pyrolysis
2.1.2. High density polyethylene (HDPE) of PVC is insignificant. Also, it was observed that HCl, as a toxic and
High density polyethylene (HDPE) is a thermoplastic polymer pro­ corrosive gas that not only has an adverse impact on the environment
duced from the monomer ethylene. Thermal degradation of HDPE but also can damage the process equipment, takes part the majority of
happens at a higher temperature compared to other types of plastic the products in PVC pyrolysis. Besides, presence of chlorinated com­
because of its molecular structure [20]. Due to the high potential of pound in the composition of pyrolytic oil produced from PVC was re­
HDPE for production of liquid oil, many studies have been performed ported, so other methods such as stepwise pyrolysis, catalytic pyrolysis,
concerning pyrolysis of this plastic. and pyrolysis with adsorbents are more preferable among the re­
Abbas-Abadi et al. claimed that they could obtain 92.8 wt% yields of searchers in order to reduce the chlorine content in liquid oil [35].
liquid product (including liquid oil and wax) through thermal pyrolysis
of HDPE in a semi-batch reactor at 450 ◦ C and 25 ◦ C/min. They also 2.1.4. Low density polyethylene (LDPE)
reported using Fluid Catalytic Cracking (FCC) catalyst with the ratio of Low density polyethylene (LDPE) is another member of the poly­
20 wt% to the plastic could help to achieve a product with 91.2 wt% ethylene group that unlike HDPE, is branched that results in weaker
liquid oil (without wax) [21]. Similar results also have been observed in intermolecular force and less crystalline. Similar to HPDE, pyrolysis of
a study performed by Williams and Slaney on pyrolysis of HDPE in a LDPE has received lots of attention due to its high potential to recover
batch reactor at the temperature of 500 ◦ C and the lower heating rate of energy through conversion to a product with high liquid yield.

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Das and Tiwari had an investigation on thermo-chemical conversion the others. However, the results of Gas Chromatography–Mass Spec­
of LDPE in a semi-batch tubular reactor at the temperature range of trometry (GC-MS) and Fourier-Transform Infrared (FTIR) show that the
350–400 ◦ C, the heating rate of 20 ◦ C/min, and long residence time of 8 oils from PS had mainly aromatic hydrocarbons in gasoline range
h. It was observed that almost 81.4 wt% of liquid oil was obtained from (C5–C9), while PP, LDPE and HDPE had longer aliphatic hydrocarbons
slow pyrolysis of LDPE and the optimum temperature was 400 ◦ C [27]. making them suitable for use in diesel engines [20].
Lee and Shin [28] as well as Uddin et al. [36] could achieve a similar In a study conducted by Park et al., continuous two-stage pyrolysis of
yield of liquid oil at a lower heating rate by catalytic pyrolysis of LDPE at polystyrene using an auger reactor and a fluidized bed reactor connected
400 and 430 ◦ C respectively. The liquid oil obtained from pyrolysis of in series has been experimentally investigated. Among the different
LDPE in a semi-batch reactor at the presence of FFC catalysts and the temperatures tested for the two reactors in this research, it was
heating rate of 7 ◦ C/min was reported 80.4 wt% by Lee and Shin [28]. concluded that maximum yield would be obtained at the temperature of
Uddin et al. could also produce a product with 80.2 wt% liquid yields by 15 ◦ C for the auger reactor and 505 ◦ C for the fluidized bed reactor. The
catalytic pyrolysis of LDPE at the heating rate of 3 ◦ C/min [36]. The distribution of oil and gas in the product was 98.71 and 1.17 wt%
results of the study carried out by Onwudili et al. indicates that the respectively, whereas the char produced from PS pyrolysis at this tem­
pyrolysis of LDPE in a batch pressurized autoclave reactor at the oper­ perature was only 0.12 wt% [43]. Adnan et al. could also obtain a
ating conditions of 1.6 MPa and 425 ◦ C, could promote the liquid oil product consist of almost 96.73 wt% liquid oil from catalytic pyrolysis of
yield up to 89.5 wt% [37]. PS at 450 ◦ C, 120 min heating time, and 1:0.2 feed to Zn catalyst ratio
High liquid yield in the range of 80–95 wt%, was also reported by [46]. The results of other studies support this fact that even at a lower
many other researchers through pyrolysis of LDPE at higher temperature temperature (around 430 ◦ C) but in a high-pressure reactor, it would be
of 500 ◦ C [17,32,38], however, similar to HDPE, pyrolysis of LDPE at possible to obtain more than 97 wt% liquid oil from pyrolysis of PS
temperature more than 550 ◦ C leads to the formation of wax in liquid [37,42]. However, Slaney and Williams observed using high pressure
product and rising the gas yield and reduction of liquid yield [33,36,39]. (10 MPa) at the temperature of 500 ◦ C would result in a high yield of
solid residue (27 wt%) while liquid yield dropped to 71 wt% in the
2.1.5. Polypropylene (PP) product [18]. High solid yield also has been reported as the result of
Polypropylene is a saturated polymer with a linear hydrocarbon zeolite catalyst [47].There are many studies that prove high liquid oil
chain produced by polymerization of the propylene monomers and be­ yield (above 85 wt%) would be obtained from pyrolysis of PS
longs to the group of polyolefins. Its characteristics are similar to poly­ [7,20,48–49], however the pyrolytic liquid product obtained from PS
ethylene, however, PP is slightly harder and more heat resistant has higher content of aromatic compared to the liquid oil produced from
compared to HDPE and LDPE. polyolefins which has highly aliphatic nature[20,37,42,48].
Das and Tiwari conducted the slow pyrolysis of PP at low tempera­
ture (325, 350, 375 ◦ C) and heating rate of 20 ◦ C/min in a semi-batch 2.1.7. Other plastics
reactor at residence time about 480 min. The percentages of liquid oil The remaining plastics including polybutylene terephthalate (PBT),
and solid residue in the product at 325 ◦ C were reported 54.02 ± 5.36 wt polycarbonate (PC), polylactide (PLA), polyacrylic acid (PAA), acrylo­
% and 16.19 ± 1.86 wt% respectively. It was reported increasing tem­ nitrile butadiene styrene (ABS), fiberglass, and polyamide (PA) or nylon
perature to 350 ◦ C caused a significant growth in the liquid oil to 81.31 are allocated to this group. Generally, the demand for each of these
± 1.81 wt% and a considerable reduction in the solid residue to 1.89 ± plastics compared to the previous six groups is insignificant.
0.36 wt%. The highest yield of pyrolytic oil (81.97 ± 2.47 wt%) was Fig. 1 indicates a brief summary of 36 studies [7] carried out on the
achieved at 375 ◦ C while the highest yield of gas was 29.79 ± 3.5 wt% at pyrolysis of six thermoplastics and their liquid yields. In these studies,
350 ◦ C [27]. 61 individual plastic (5 PET, 19 HDPE, 2 PVC, 11 LDPE, 13 PP, and 11
Similar liquid yield (80.1 wt%) was reported by Sakata et al. at PS) at different operating conditions and in presence of various catalysts
thermal pyrolysis of PP performed at 380 ◦ C, and lower heating rate of have been investigated that in total 154 cases have been evaluated. Each
3 ◦ C/min. They also observed using FSM as catalyst can improve liquid bar in this figure shows the average yield of liquid product reported in
yield up to 86.4 wt% [40]. This liquid yield was achieved through py­ the different studies and the error bars indicate the impact of operating
rolysis of PP at the presence of FCC catalyst and temperature of 400 ◦ C parameters and catalysts on the liquid yield. It would be observed in
by Lee and Shin. Compared to the research carried out by Sakata et al., Fig. 1 that PS has the maximum liquid yield compared to the other
the heating rate reported in this study was higher (7 ◦ C/min) and the gas plastics, with average of 84 wt%. After PS, the liquid yield obtained from
yield was double [28]. Abbas-Abadi et al. could obtain 92.3 wt% liquid PP, HDPE, and LDPE is almost equal and generally it would be in the
oil from catalytic pyrolysis of PP in a semi-batched reactor at the tem­ range of 78–81 wt% and PET and PVC by just 29 and 12.5 wt% yield of
perature of 450 ◦ C and the heating rate of 25 ◦ C/min [41]. Similar to liquid respectively, show the least potential for producing liquid. Fig. 1
pyrolysis of PE, liquid oil yield of higher than 90 wt% was also reported also shows different operating parameters such as temperature, pres­
in some studies through thermal pyrolysis of PP at high pressure sure, residence time, heating rate along with type of catalyst consumed
[18,42]. in this process can change the product distribution significantly. Due to
Some other studies reveal thermal pyrolysis of PP at temperature of this issue, the influence of each of these operating parameters as well as
around 500 ◦ C can lead to liquid oil with 80–90 wt% yield [17,31,43]. type of catalyst on product distribution should be studied. Table S1 in
Similar to PE, the temperature required for pyrolysis of this plastic is the appendix indicates a brief summary of studies carried out on the
high, and its thermal pyrolysis is so difficult. Also, it was reported that pyrolysis of different types of plastic and their product distribution.
catalytic pyrolysis of PP leads to the production of liquid oil with higher
aromatic compounds compared to PE [20,44]. 2.2. Pyrolysis of mixed plastic

2.1.6. Polystyrene (PS) Although many studies were performed related to the liquid oil
Polystyrene is a colorless thermoplastic that is produced from styrene production through pyrolysis process of an individual plastic, potential
monomers. This polymer is naturally transparent, however, it can be of this process for MWP needs an investigation on the conversion of
colored with colorants. Thermal degradation of polystyrene in the py­ plastics mixture. The advantage of thermo-chemical processes over
rolysis process occurs at lower temperatures compared to PP and PE, and mechanical recycling is that these technologies are less sensitive to
generally, the liquid oil obtained from this process has less viscosity than contaminants and do not require an intense sorting process. However,
the PE and PP [44–45]. PS has the highest liquid yield among the presence of PET and PVC in the composition of MWP could have an
different plastics because the volatile matter of this plastic is more than adverse impact on the yield and quality of desirable product. Thermal

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 1. Liquid yield of different plastics [7,14–18,20–24,27–34,36,38–43,46–49,62,85,92].

degradation of PVC produces chlorinated hydrocarbons and Hydrogen after PE had the largest share in the MWP. In some studies, the amount of
chloride (HCl) leading to corrosion in the reactor and production of PP reported in the composition MWP was even more than PE (Spain 3)
halogenated oil, PET also decomposes into phthalic acids which cause [60]. Also, analysis of MWP composition in different countries has
deterioration of oil quality in addition to clogging the pipes [2]. shown PET and PVC made up <10 and 5 wt% of MWP respectively in
Therefore, it is necessary to determine the MWP composition in order to most of these countries. Simulated Mixed Plastic (SMP) was prepared by
estimate the liquid yield in final product. Muhammad et al. based on the proportions of each plastic which have
As is shown in Fig. 2, MWP collected from different origins do not been reported for the composition municipal solid waste plastics in the
have similar composition [15,18,50–61] and this issue is the main previous studies [52].
reason that different MWP shows different product distribution. Based Fig. 3 shows the impact of mixed plastic composition, temperature,
on that, it could be concluded that the major part of MWP in most heating rate and residence time on the products distribution after
countries is allocated to PE, which is the mixture of LDPE and HDPE, and thermal pyrolysis process. This figure indicates that at similar operating
this type of plastic in some countries such as Thailand and Hungary can conditions how much liquid yield could be different due to the differ­
almost make up more than 60 percent of MWP generally. An investi­ ence in the proportion of resins in mixed plastic, e.g. (Singapore [55],
gation on the amount of PP in different MWP reveals this type of plastic Belgium [18], SMP [52]) or (Spain 1 [58], Spain 3 [60]) or (Belgium,

Fig. 2. Composition of MWP with different origins [15,18,50–52,54–61].

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 3. Influence of mixed plastic composition, temperature, heating rate, and residence time on the liquid yield in the thermal pyrolysis process
[15,18,50,52,54–55,57–61].

Germany, Europe [18]). Unfortunately, there is not adequate data in the chemical processes and it controls the conversion of plastics into the
literature review to extrapolate any trend between mixed plastic products. The Van der Waals force helps the molecules of polymers to be
composition and product distribution, and even no data was reported attracted to each other and prevents the collapse of the polymer chain.
regarding the composition of MWP in Germany and Belgium. Never­ But in the high temperature, the vibration of molecules rises and when
theless, based on the results of most of the studies concerning thermal these vibrations dominate over the Van der Waals force, the carbon
pyrolysis of mixed plastics, it could be concluded that working at proper chain would be collapse [53]. Thermo-Gravimetry analysis (TG) and
operating conditions, guaranteed the yield of more than 50 wt% for derivative Thermo-Gravimetry Analysis (DTG) curves help to analyze
liquid oil if PET and PVC content in the mixture would be with <10 and the thermal degradation behavior of the different plastics. The weight
5 wt% respectively. Besides, the results of studies reveals presence of change of plastic as a function of temperature and time is measured by
foreign materials in the waste plastic can cause an increase in the yield of the TG plot and the temperatures of the maximum degradation rates
gas and solid that results in reducing liquid product [15]. The detailed could be determined from the DTG plot [19,53]. The TG and DTG studies
information regarding mixed plastic composition and operating pa­ conducted in the past reveal good information about the degradation
rameters are reported in Tables S2 and S3 in the appendix. temperature range of different plastics. Therefore, a review concerning
the previous researches regarding TG and DTG analysis of different types
3. Impact of process parameters of plastic and their mixture was performed in the next part.
The results of the study carried out on the PET and PVC pyrolysis by
In addition to the type of plastic, many other parameters can directly the Cepeliogullar and Putun, show thermal degradation of PET mainly
affect the products distribution. Conversion of waste plastic into a started at 400 ◦ C and the maximum weight loss is at the temperature of
product including high liquid oil through pyrolysis process is not 427.7 ◦ C [16]. Also, in this study, very small weight changes were
possible unless optimum operating conditions consider for these sys­ observed at the temperature range of 200–400 ◦ C. Hence, it was
tems. Besides, proper understanding concerning the performance of concluded that thermal degradation of PET occurred at the temperature
different types of reactors and catalysts helps to achieve liquid oil with range of 350–520 ◦ C. The thermal behavior of PVC is different compared
higher yield and quality. to the other types of plastics. Its major weight loss occurred at two
different temperature ranges, the first weight loss was 62.25 % and
3.1. Operating factors happened at the temperature range of 260–385 ◦ C, and the second
weight loss was 21.74 % and occurred at the temperature range of
According to the studies performed on the pyrolysis of plastic waste, 385–520 ◦ C. Also, it was reported that at temperatures above 470 ◦ C, the
it was concluded that temperature, heating rate, pressure, and residence degradation was insignificant.
time are the key operating parameter in this process. In the following The thermal degradation of HDPE, LDPE, and PP at the heating rate
subsections, the influence of each one on achieving the maximum liquid of 10 ◦ C/min has been investigated in the study carried out by Das and
oil has been investigated. Tiwari. Based on the TG analysis, it was observed that degradation of PP
started at lower onset temperature (300 ◦ C) and was almost completed
3.1.1. Temperature at 480 ◦ C while degradation of HDPE and LDPE started at 370 and
Temperature is the most important operating factor in thermo- 335 ◦ C respectively and both completed at 500 ◦ C. Also, the TGA curves

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

indicate that the major weight loss for PP, LDPE, and HDPE happens at 600 ◦ C, during thermal pyrolysis of Indian mixed plastic, had insignifi­
440, 472, and 475 ◦ C respectively [27]. Furthermore, the studies per­ cant effect on the yield of liquid oil in the final product [15]. Colantonio
formed on the pyrolysis of PS show that this plastic decomposes at lower et al. observed similar results for increasing temperature from 450 to
temperatures compared to PP and PE. The temperature range reported 650 ◦ C during thermal pyrolysis of Italian mixed plastic, however they
for thermal degradation of PS is between 250 and 480 ◦ C [20,62]. reported that this temperature rise led to increase of solid wax in liquid
Furthermore, at the conditions of the flash pyrolysis (heating rate of product [57]. Formation of wax at high temperature (700 ◦ C) was also
100 ◦ C/min), it was reported that 50 % weight loss for PS, PET, PP, and proved in another study performed by A. Williams and T. Williams [61].
PE has happened at temperatures of 457, 470, 487, and 505 ◦ C respec­ The results of study carried out on the pyrolysis of Spanish mixed plastic
tively [50]. 1 by López et al., has shown the highest liquid oil has been obtained at
Similar trend was observed in a study carried out by Singh et al., and 440 ◦ C [53,58,60]. However, Ates et al. observed a significant growth in
they reported that individual plastic waste the degradation order follows the liquid yield from 19.2 wt% to 49.9 wt% by changing temperature
as HDPE > LDPE > PP > PET > PS [63]. In the other study performed by from 500 to 600 ◦ C during thermal pyrolysis of Hungarian mixed plastic.
this group, degradation of plastics such as HDPE, PP, PS, and PET Low liquid yield at 500 ◦ C could be due to the other operating conditions
individually and in mixed forms was investigated. It was observed the [65] (See Fig. 3). Thus, it could be concluded optimum temperature of
peak degradation rate of these plastics follows the order PS > HDPE > thermal pyrolysis of mixed plastic is in the range of 450–500 ◦ C.
PET > PP. Also, it was reported mixing PS with HDPE, PP and PET,
decreases the degradation of all these plastics, whereas mixing HDPE 3.1.2. Heating rate
with the other plastics leads to a delay in their degradations. Further­ Heating rate is another important operating factor in pyrolysis that
more, the interaction of PP and PET in a mixture caused PET degrada­ influences the thermal degradation of plastics. The impact of heating
tion temperature to be delayed. Although the DTG analysis showed four rate on the product distribution varies in different studies, because of the
separated peaks for the degradation of each plastic, during the degra­ differences in the type of reactor and other operation conditions (tem­
dation of their blend the reaction peaks decreased to two. It was perature and pressure) [66]. Nevertheless, the results of various studies
explained that in the mixed sample a synergistic effect was observed that have shown that higher heating rate leads to higher reaction rate
represented via combined peaks of PS, PET, HDPE, and PP. Convolution through speeding up the weight loss [67–68]. Based on the analysis of
of the individual peaks was observed in the mixture of two and three the TG curve for LDPE, HDPE, PP, and PLA (polylactic acid) at seven
plastics [64]. The TG and DTG for each plastic and their mixture are heating rates from 5 to 50 ◦ C/min, Das and Tiwari concluded that by
shown in Fig. 4. rising the heating rate, the thermal degradation range shifts right which
Fig. 5 (a–f) gives summary regarding the temperatures considered for leads to a delay in thermal degradation at higher heating rate. Also, the
each type of plastic and the impact of that on the liquid yield. Based on DTG analysis showed that increasing heating rate leads to a growth in
that, regardless of the plastic type, temperature range of 425–500 ◦ C was maximum degradation rate [68]. The TG and DTG curves reported at
selected for the pyrolysis, however for HDPE higher temperatures (up to this study, are depicted in Fig. 6. It could be concluded that heating rate
550 ◦ C) have been preferable. Considering this temperature range, the and temperature are highly connected, to achieve the optimum product,
liquid yield of PVC and PET cannot be more 13 and 42 wt% respectively, their impacts should be evaluated simultaneously.
whereas the liquid yield above 60 wt% was reported for other four types The lower heating rate during the slow conversion of plastic allows
of plastic. Pyrolysis at temperatures more than 600 ◦ C leads to a sig­ the volatiles to remain in the heating zone for an extended period
nificant reduction in liquid yield and rising gas products instead. Also, at compared to the higher heating rate. This issue leads to the formation of
temperatures <350 ◦ C, the conversion of plastics has not been more hydrocarbon with low carbon range in the liquid product at lower
completed, so the liquid yield is low in these temperatures. Besides, it heating rate, whereas at higher heating rate, long-range hydrocarbon
should be noticed that due to the influence of other operating parame­ oils is observed which caused increasing the density of liquid product.
ters such as heating rate and residence time, the liquid yield for each Furthermore, pyrolysis at higher heating rate increases the chance of
type of plastic, at a specific temperature, has been varied. formation wax in the final product.
According to the Fig. 5 (g), it could be concluded that wide tem­ Fig. 7 (a–f), which is about the impact of heating rate on the liquid
perature range (450–600 ◦ C) have been selected to study on thermal yield for each type of plastic at temperature range of 470–500 ◦ C and
pyrolysis of mixed plastic. Comparing the liquid yield obtained from atmospheric pressure, shows that the heating rate of 5–20 ◦ C/min
mixed plastic with the single type of plastic reveals the composition of generally has been opted for pyrolysis of plastics. Variation of other
mixed plastic has considerable effect on the liquid yield at a specific process parameters such as residence time is the main reason of differ­
temperature. Regarding temperature above 500 ◦ C, although high liquid ence in the liquid yield at a specific heating rate for each type of plastic.
yield has been observed, pyrolysis at these temperatures has not been Generally, it can be seen that at this specific range of temperature,
recommended. Singh et al. claimed increasing temperature from 500 to increasing heating rate leads to reduction in liquid yield of PET, LDPE

Fig. 4. (a) TG, (b) DTG curves of individual plastic waste and Mixed Plastic at a heating rate of 10 ◦ C/min [63].

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 5. Impact of temperature on the liquid yield of different types of plastic (a) PET, (b) HDPE, (c) PVC, (d) LDPE, (e) PP, (f) PS, and (g) mixed plastic
[14–18,20–24,27,29–30,32–34,36,38–43,46–49,62,92].

and to some extent PP, however its impact on other types of plastic is 3.1.3. Residence time and pressure
unclear and requires more experimental data. Fig. 7 (g) shows that the The definition of residence time is different for batch and continuous
variations of liquid yield at a specific heating rate have been even higher systems. In the batch process, it refers to the time when feedstock plastic
for the mixed plastics, due to impact of waste plastic composition on the starts to be heated until the time the products are removed. Conversely,
yield of liquid product, but it seems that pyrolysis of MWP at 10 ◦ C/min for the continuous pyrolysis, the residence time is equal to the contact
yields higher liquid product compared to the others. time of the plastic on the hot surface throughout the reactor [66]. Longer

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 6. Thermal degradation profile for (a) TG, (b) DTG of (1) LDPE, (2) HDPE, (3) PP, (4) PLA at heating rates of 5–50 ◦ C/min [68].

residence time leads to further conversion of the primary products and influence of particle size for samples with higher fixed carbon and ash
as a result higher yield of more thermal stable products such as light contents, such as kitchen garbage is much more significant, compared to
molecular weight hydrocarbons and non-condensable petroleum gases the sample with higher volatile content, plastic in the test.
[66]. Also, based on an experimental investigation on thermo-catalytic Maqsood et al. [73] also reported that particle size should be
pyrolysis of HDPE, it was reported that residence time should decrease determined based on the other operating parameters such as tempera­
with a rise in heating rate because it might lead to changes in reaction ture and heating rate. Particle size between 5 and 50 mm could be
kinetics [22]. In conclusion, residence time is highly dependent on the appropriate for slow/conventional pyrolysis however for fast and flash
temperate and heating rate in order to achieve the highest liquid yield. pyrolysis which occurs at higher temperature and heating rate, and re­
Pressure is another operating factor that can be effective significantly quires less residence time, the particles size of the feedstock should be as
on the products. Increasing pressure in the pyrolysis of HDPE, LDPE and small as possible (<1 mm for fast pyrolysis and<0.2 mm for flash
PP leads to increasing liquid products, however influence of that on PS pyrolysis).
and PET was different [16,67,69]. Although at lower temperature
(<450 ◦ C) high liquid obtained through pyrolysis of PS, at higher tem­
3.2. Type of reactors
perature (more than 500 ◦ C) increasing of solid product along with
reduction of liquid yield for PS and PET has been reported [16,67,69].
Assessments of the results regarding using different types of reactors
Regarding pyrolysis under vacuum conditions also several studies
for plastics conversion reveals the importance of reactor type on
were carried out. In vacuum pyrolysis, plastic is heated in vacuum
achieving maximum desired product. In general, the following param­
conditions in order to reduce its boiling point and prevention of adverse
eters can influence the efficiency of reactors in the pyrolysis processes.
chemical reactions. Parku et al. had an investigation on the influence of
vacuum conditions on the yield and composition of liquid products and
• Type and particle size of input plastic
based on the results, they concluded that complete conversion of PP at
• Moisture content of plastic
lower temperatures has happened under vacuum conditions. Also, it was
• Reaction temperature
reported vacuum suction limited the concentration of gasoline range
• Residence time
compounds in the liquid product that results in Diesel/Gasoline ratio
• Catalyst type and concentration
reaches to higher than 30 [70]. An increase in diesel fraction of the
• Mixing intensity (stirring)
liquid product under vacuum conditions was also reported by Lopez
• Type and flow rate of carrier gas [74]
et al. when the composition of liquid products obtained from continuous
pyrolysis of waste tires under vacuum (25 and 50 kPa) and under at­
High flexibility for treating waste plastics with a large size distri­
mospheric pressure compared with each other [71]. Although vacuum
bution, providing good heat and mass transfer, rendering rapid heating
pyrolysis was recommended for the production of diesel range com­
rates, low energy consumption, feasibility for precise temperature con­
pounds, this process has also proved to enhance wax production [70].
trol, obtaining higher interaction between feedstock and catalyst, and
Furthermore, the complexity and high investment and maintenance
low investment and operating costs are some of the characteristics of a
costs, as well as poor heat transfer, are the main drawbacks of using
proper reactor. In the following section, different reactor types selected
vacuum reactors [2].
for thermo-chemical conversion of plastic were introduced and the
strengths and limitations of each one were discussed.
3.1.4. Particle size
Particle size is also another effective parameter that can change the
3.2.1. Batch and Semi-batch reactor
product distribution. Luo et al. [72] had an experimental investigation
A batch reactor is a closed system with no possibility of adding or
on pyrolysis of municipal solid waste with three different size fractions
removing materials during the operation. This reactor is the best option
(0–5 mm, 5–10 mm and 10–20 mm) at the temperature of 800 ◦ C, in
for pyrolysis in laboratory scale, due to its simplicity in design and
order to evaluate the influence of particle size on pyrolysis performance.
ability to control different operational parameters. Also, using this
They observed that higher gas yield with less tar and char would be the
reactor helps to achieve high conversion when plastic remains in this
result of using smaller particle sizes. Also, it was reported that reduction
reactor for an extended time. However, thermo-chemical conversion of
of particle size causes growth of H2 and CO contents of gas, as well as the
plastic using the batch-scale reactors leads to variability of products
ash and carbon element contents in the char. Based on their results, the
from batch to batch. Furthermore, limited production capacity in batch-

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 7. Impact of heating rate on the liquid yield of different types of plastic (a) PET, (b) HDPE, (c) PVC, (d) LDPE, (e) PP, (f) PS, (g) mixed plastic at temperature near
to 500 ◦ C [16–17,20,22–23,32,38,48].

scale process results in higher incidence of the labor costs and mainte­ scale [75]. Besides, low thermal conductivity and high viscosity of
nance on the final product. Therefore, batch reactors are not recom­ plastic wastes cause batch and semi-batch reactors to suffer from tem­
mended for large-scale productions [75–76]. perature gradients [53]. However, using a stirrer with appropriate
Unlike the batch reactor, in the semi-batch reactor, adding plastic design and speed can help to control the temperature homogeneity and
and removing product is possible while the reaction is carrying out. Due improve the mixing of catalysts and plastics leading to an increase in the
to the high labor costs in large-scale production, the semi-batch reactor yield and quality of the liquid product [7,21,41]. The other limitation of
similar to the batch type is more suitable to be utilized for the laboratory these reactors is related to coke formation on the surface of catalysts that

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

disturb the conversion process. Hence, these reactors are more prefer­ flow, have the responsibility of proving to heat for the reaction. These
able for thermal pyrolysis in order to obtain high liquid oil [75–76]. reactors similar to the CSBR has high flexibility for treating mixed waste
plastic with a wide range of shape and size distribution whereas their
3.2.2. Fixed-bed reactor design and operation are simple [2]. Low capital cost is the other benefit
The fixed-bed reactor is a cylindrical tube filled with catalysts of using this type of reactor [2,82–83]. Unlike the fluidized bed reactors
generally in palletize form and packed in the static bed. In this reactor, that residence times are only a few seconds, rotary kiln reactor requires
plastic flows through the bed and convert into products. Although the long residence times (more than 20 min) for pyrolysis of plastics [79].
design and operation of these reactors are easy, their constraints in The screw kiln reactors (Auger reactors) are a subgroup of the rotary
handling plastics with irregular particle size, and disability in providing kiln reactors taking advantage of a screw or an auger. This equipment is
a large accessible surface area of catalyst for the reaction are their main placed coaxially in a fixed kiln and helps feedstock movement through
problems [12]. In some cases, fixed-bed rectors were selected for sec­ the heated reactor. This form of feedstock transfer allows better control
ondary pyrolysis reactions in the two-step process. In this type of pro­ over the residence time in the reactor and as a result easier handling of
cess, at first step, plastic is introduced in a batch thermal process and at complex plastic [2].
second step the gaseous products from the first step are brought In addition to the mentioned reactors, some other technologies are in
immediately into contact with catalysts in a fixed bed reactor [77–78]. the incipient stage of their development such as Microwave-assisted and
This design avoids the direct contact of the catalysts with the melted Electromagnetic technologies. In the next section, these technologies
plastic which leads to challenges for catalyst recovery, rapid deactiva­ and their potential to use for pyrolysis were investigated.
tion of catalyst after contacting with melted plastic and the impurities
that are present [76]. However, it should be noticed using two reactors 3.2.6. Microwave-assisted technology
would not be cost-effective [19]. Conventional pyrolysis involves surface heating of plastics using
fuels like coal, whereas microwave electromagnetic radiation has the
3.2.3. Fluidized-bed reactor potential for volumetric heating which is faster than surface heating. In
Unlike the fixed-bed reactor, the catalyst in the fluidized-bed reactor microwave-assisted technology, the required heating for conversion of
is not packed in the static bed and sits on a distributor plate where feedstock into the desired product is generally provided by microwave-
fluidizing gas pass throw. This structure allows the catalyst particles to absorbent materials. These materials can absorb microwave energy and
be in a fluid state and move freely when the fluidizing gas flows through release this energy when mixing with the plastics in order to provide the
the bed. In comparison with fixed-bed reactors, the fluidized-bed reactor heat required for the pyrolysis process. The absorber should be selected
provides better access to the catalyst and consequently a larger surface based on the dielectric properties of feedstock in order to accelerate the
area for the reaction, due to the fluid state of catalyst particles. Also, step of converting absorbed energy to heat. For this purpose, metals (as
product variation is negligible due to the good heat and mass transfer wire or powder), or carbon (in almost any form) are suitable materials to
provided in this reactor type [11,79]. Since frequent feedstock charging convert microwave radiation into heat at a frequency of 2.45 or 0.972
is not required, this type of reactor is more flexible than batch one. The GHz. [84]. Besides the general parameters mentioned for all reactors,
fluidized-bed reactor is the best option for catalytic pyrolysis of plastics other factors such as microwave output power, microwave type
because the catalyst can be consumed many times without requiring (multimode or single-mode), microwave receptor characteristics (type,
discharge. Besides, from the economic viewpoint, this type of reactor is size, and amount/concentration), and reactor design/type can influence
the most suitable one to be utilized in large-scale operations and pilot the efficiency of microwave-assisted pyrolysis processes [74].
plants [12,19]. Despite all the advantages of fluidized-bed reactors, this The superiorities of this technology over conventional pyrolysis
type of reactor has a severe problem in handling feedstock with large methods are higher production speed, rapid energy-efficient heating and
size distribution. Moreover, high investment cost especially on the small lower production cost. For instance, the results of studies performed on
scale could be considered as the other constraint of this type of reactor the pyrolysis of LDPE using or at the operating conditions of 1.6 MPa and
[2,76]. 425 ◦ C, could promote the liquid oil yield up to 89.5 wt% [85]. Process
flexibility and equipment portability are the other advantages of this
3.2.4. Conical spouted bed reactor (CSBR) technique. One of the biggest limitation of this technology is the lack of
The conical spouted bed reactor is a form of fluidized bed reactor sufficient data to quantify the dielectric properties of the treated waste
taking advantage of the characteristic of spouting behaviors. This stream [19,74]. This issue is the main reason that only few studies
reactor has a small inlet that is connected to a fixed-diameter column performed on the microwave-assisted pyrolysis [84,86–87]. Also due to
filled with static spouting media, through a conical section. Unlike the the high price of electricity, this technology has not been developed.
fluidized-bed reactor, this type can handle large particle size distribution
even with different densities. The CSBR has low bed segregation and 3.2.7. Electro-magnetic induction technology
lower attritions and pressure drop compared to the fluidized bed re­ In this method, an altering magnetic flux induces an eddy current in
actors. This type of reactor provides high heat transfer between phases the body of reactor that this current can create Joule heat and conse­
and minor defluidization problems when handling sticky solids [80]. quently rising the temperature of the reactor. Generally, low frequency
According to the studies, CSBR is suitable for wax production at low- (20–40 kHz) used for heating this type of reactor in order to decrease the
temperature pyrolysis [81]. But complicated design and technical radiation risk. Due to the rapid heating in this system, formation of side
challenges such as catalyst feeding, catalyst entrainment, and product products such as dioxin during reaching to opt temperature would be
(solid and liquid) collection made this type of reactor less favorable. avoided [88]. Furthermore, controlling temperature is precise and
Furthermore, due to using lots of pumps to provide sufficient pressure flexible in EMI reactors and the reactors taking advantage of this tech­
for spouting behaviors, the operating cost of these reactors is generally nology are more energy efficient compared the conventional ones. Given
high [12,19]. the fact that heating in this method is contactless, it has a pollution free
nature [88–89]. Furthermore, it was reported that the energy consumed
3.2.5. Rotary kiln and screw kiln reactors in this method is less than the conventional electrical resistance furnace
The rotary kiln reactor is a rotating drum that is inclined slightly to [90]. All these characteristics made this technology very effective and
the horizontal. The feedstock is fed into the upper end of the cylinder environment-friendly. This technology similar to the microwave-
and due to the kiln rotation, material converts to products during assisted technology, due to the high price of electricity, is not as
gradually moving toward the lower end. The hot gases passing along the economical as the conventional ones. However, it is predicted due to
kiln, co-current or counter-current with the direction of the feedstock development of new methods for electricity production such as nuclear,

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

solar and wind power, the price of electricity would be reduced in near Table 4
future. Advantages and disadvantages of different reactors for pyrolysis of plastic.
Since selecting proper reactor type leads to improve the yield and Reactor type Advantages Disadvantages Note
quality of desirable products, a brief summary concerning different
Batch reactor, • The best reactors • Variability of Using a stirrer
types of reactor used for pyrolysis of waste plastic along with their ad­ Semi-batch in thermal product from can lead to
vantages and constrains are presented in Table 4. reactor pyrolysis (higher batch to batch rising liquid oil
liquid yield) (Batch reactor) yield
• Simplicity in • High labor costs
3.3. Catalysts
design and especially in
controlling the large scale
Due to the endothermic nature of pyrolysis, this technology is operating • Not suitable for
considered as an energy-intensive process, so using the catalyst for this parameters catalytic
system would reduce the energy requirement for thermal degradation pyrolysis
• Not suitable for
and as a result decreases temperature and reaction time required for the
large scale
pyrolysis of plastics. However, catalyst lifetime and regeneration in the production
process are the limitation of catalytic process, hence their efficiency on Fixed-bed reactor Easy to design and • Not suitable for Merely used as
the production of maximum liquid oil with characteristic similar to the operate feedstock with the secondary
irregular pyrolysis
diesel fuel should be investigated.
particles size reactor in the
Catalysts are classified into two groups of homogeneous and het­ and shape two-step process
erogeneous, based on their phase and the reaction phase. Homogeneous • Providing
catalysts occupy the same phase of the reaction mixture (mostly liquid limited surface
solution), whereas heterogeneous catalysts have different phases from area of the
catalyst for the
the reaction phase (solid). The most common homogeneous catalyst
reaction
which is used for the plastic pyrolysis is aluminum chloride [59]. Fluidized bed • The best reactor • Not suitable
Nevertheless, the heterogeneous catalyst is more favorable compared to reactor for catalytic when particle
the other one because this type can tolerate severe reaction conditions plastic pyrolysis size is irregular
• Higher flexibility • High
(up to 1300 ◦ C and 35 MPa), also its separation from the final product is
compared to the investment
much easier [45]. The most conventional heterogeneous catalysts are as batch reactors costs especially
follows: nanocrystalline Zeolites (such as HZSM-5, HUSY, HY, Y, and β), • Providing a in small scale
conventional acid solid, mesostructured catalyst, metal supported on larger surface
carbon and basic oxides [45]. Many studies carried out on the catalytic area of the
catalyst for the
pyrolysis of plastics and the performance of various types of heteroge­
reaction
neous catalysts on the product yield and quality. However, among them, compared to the
Silica-Alumina (SA), Zeolites, and FCC catalysts have been received fixed-bed
more attention. Hence, these three catalysts along with bentonite clay reactors
would be investigated in detail in the next subsections. • Constant process
conditions with
good heat and
3.3.1. Silica-alumina catalyst mass transfer
Silica-Alumina combination has been utilized as a catalyst that • The most
contains Lewis acid electron-accepting sites and Bronsted acid sites with economic reactor
for large scale
ionizable hydrogen atoms as electron sharing sites. The acid concen­
operation and
tration of silica-alumina is determined by the molar ratio of SiO2/Al2O3, pilot plant
in a way that the silica-alumina catalysts having higher molar ratio of Conical spouted • Providing good • Less favorable Suitable for wax
SiO2/Al2O3 show higher strength of acidity. Based on the catalyst bed reactor mixing with the because of production at
acidity, silica-alumina is divided into two groups of SA-1 and SA-2 with ability to handle technical low-
large particle size challenges temperature
the order of catalyst acidity of SA-2 ˃ SA-1. distribution and • Complicated pyrolysis
Although the analysis of pyrolysis products obtained through ther­ different particle design
mal and catalytic degradation of HDPE indicates using silica-alumina densities • High operating
catalyst decreased the coke formation [29], as it is shown in Fig. 8, • Having low bed cost
segregation and
using this catalysts in any type and any form (powder or pellet) have not
lower attritions
changed the liquid yield significantly (almost ±5 wt%). Based on the than the bubbling
studies performed concerning catalytic pyrolysis of HDPE, LDPE, and fluidized bed
PP, it could be concluded that generally using silica-alumina leads to a reactor
growth in the gas yield and a reduction in the liquid and solid products • Providing high
heat transfer
[29,36,40]. between phases
and minor
3.3.2. Zeolite catalyst defluidization
Zeolites catalysts are the crystalline alumina-silicates sieves having a problems when
handling sticky
three-dimensional framework with an oxygen atom link the tetrahedral
solids
sides. The ion exchange capabilities and open pores are two main • Having lower
characteristics of these catalysts [44]. Different types of zeolite catalysts pressure drop
are built by different ratio of SiO2/Al2O3 that determine their reactivity than fluidized
and finally results in the product fraction yield of pyrolysis. Although bed reactors
• Rotary kiln • Simplicity in Controlling
similar to silica-alumina, the acid concentration of zeolite is determined reactor, design and residence time
by the molar ratio of SiO2/Al2O3, in contrast with silica-alumina, zeolite operation and handling
catalysts with low ratio of SiO2/Al2O3 show higher acidity [91]. Most of (continued on next page)
zeolites show an excellent catalytic efficiency on cracking, isomerization

13
S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Table 4 (continued ) and aromatization due to their strongly acidic properties and their
Reactor type Advantages Disadvantages Note micropore crystalline structures. ZSM-5, HZSM-5, HUSY, Y-zeolite, and
β-zeolite are some of the most favorable zeolites utilized for catalytic
• Screw kiln • Low capital cost complex plastic
reactor (Rotary kiln waste are much
pyrolysis of plastics.
(Auger reactor) reactor) easier in screw As, it is shown in Fig. 9, similar to the silica-alumina, the liquid yield
• The capability of kiln reactor obtained from plastics at presence of zeolite catalyst is generally less
producing wide compared to than thermal pyrolysis [29,33,38,40,47,52,57–59].
variation of rotary kiln
Only at low temperature (370 ◦ C) [57] or low catalyst/plastic ratio
products because reactor
of the large (3 wt%) [30] a growth has been observed in the liquid yield. Also the
temperature liquid yield for Hungarian MWP has been improved through using
gradient in the zeolite catalyst, it could be due the specific composition of this MWP
system that requires higher temperature for pyrolysis (see Fig. 3), and thus,
• High flexibility
for treating MWP
zeolite catalysts can help to enhance the low liquid yield obtained at
with very 500 ◦ C [61].
different shape Among zeolite catalysts, ZSM-5 and HZSM-5 have smaller pore
and size diameter and more micropores that leads to yield more gas fraction and
Microwave- • Rapid energy- • The absence of Several
as a consequence lower liquid product [29,33,57,61]. Comparing the
assisted efficient heating sufficient data parameters
technology • Higher to quantify the influence the liquid obtained from HDPE over the powder catalysts of silica-alumina
production speed dielectric microwave and zeolite indicates that ZSM-5 and Y-zeolite yields less liquid prod­
and lower properties of the heating uct compared to SA [29]. Similar results were also observed about ZSM-
production costs treated waste performance in 5 and SA-1 for catalytic pyrolysis of PP [40].
than stream plastic pyrolysis
conventional • High operating
pyrolysis cost due to the 3.3.3. FCC (fluid catalytic cracking) catalyst
methods price of FCC catalysts are known as silica-alumina with the binder comprised
• Process flexibility electricity of zeolites crystal and non-zeolites matrix [44]. This catalyst is widely
and equipment
consumed in the petroleum refining industry for cracking heavy oil
portability
Electromagnetic • Low energy High operating The features fractions into lighter products such as gasoline and LPG fractions.
induction consumption cost due to the such as Although the FCC catalyst used in the petroleum refineries is contami­
reactor • Rapid energy- price of electricity contactless nated, this spent FCC catalyst has the potential to be reused in the py­
efficient heating heating, energy- rolysis process. Similar to zeolite catalyst, this catalyst have been used in
• Providing saving, and
many studies for liquid oil production from plastic through pyrolysis.
uniform pollution-free
temperature nature EMI Based on the results shown in Fig. 10, the liquid product obtained from
profile heating is very HDPE and PP would be reduced with increasing the FCC/plastic ratio
• Precise effective and (more than 10 wt%) [21,41]. However, it has been reported that at
temperature eco-friendly
lower ratio of catalyst to the plastic (<5 wt%) [30,92], an improvement
control
• High process has been observed in the liquid yield. Regarding mixed plastic, Hun­
efficiency garian MWP has been investigated and similar to zeolite at presence of
FCC, liquid yield enhanced compared to thermal pyrolysis [61].

Fig. 8. Catalytic cracking of plastics using Silica-Alumina [29,36,40].

14
S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 9. Catalytic cracking of plastics using Zeolites [29–30,33,38,40,47,52,57–59,61].

Fig. 10. Catalytic cracking of plastics using FCC catalysts [21,30,41,61,92].

3.3.4. Bentonite clay plastics slightly [20]. In another study, high liquid yield (almost 90 wt
Bentonite clay is another inexpensive catalyst which has been uti­ %) was obtained at proper operating conditions through catalytic py­
lized in powder and pellet form for pyrolysis of waste plastic. Although rolysis of waste HDPE by activated bentonite [22]. Based on Fig. 11,
this material has been used in a limited number of studies and in general using Fe-, Ti-, Zr- and Al-pillared clays (PILC) for catalytic pyrolysis of
form has not enhanced the liquid yield and quality significantly, when it MWP shows pyrolysis of MWP over Fe-PILC led to an enhancement in
has been used as a raw material for the synthesis of pillared clayed the yield of liquid oil from 67.6 to 79 wt%, however, catalytic pyrolysis
catalyst of Fe-PILC, it has shown acceptable performance for production through using Ti-PILC and Zr-PILC catalysts caused a reduction in liquid
of liquid oil with high yield and quality. oil and a growth in the gas product [55]. Also, it has been also reported
The results of investigation carried out by Budsaereechai et al. con­ in this study that catalytic pyrolysis of MWP over Al-PILC had no sig­
cerning thermal and catalytic pyrolysis of different waste plastics nificant impact on the product distribution.
including PS, PP, LDPE and HDPE, in a bench scale reactor indicates According to Fig. 12, catalytic pyrolysis of plastics using silica-
using bentonite catalysts can enhance the liquid yield of all these waste alumina, zeolites, and FCC catalyst leads to a growth in gasoline

15
S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 11. Catalytic cracking of plastics using Bentonite clay [20,55].

Fig. 12. Carbon number distribution in liquid fraction [20,29–30,36,40,55].

content with carbon range of C5–C12 and reduction of wax product with would be less than thermal pyrolysis [29,36,40]. However, in another
typically more than 21 carbon atoms. Regarding diesel range hydro­ study reported that using HZSM-5 and FCC catalyst with lower ratio (3
carbon (C13–C20), it could be observed that at high ratio of these cat­ wt%) has not changed the diesel range hydrocarbon [30].
alysts to the plastics (more than 10 wt%), this range of carbon atom In the study performed on bentonite clay, it has been reported that

16
S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

using this catalyst results in higher concentration of product in carbon with the characteristics of these diesel fuels Figs. 14 (a-e).
range of gasoline and less content of C13+ compared to the thermal Since the standard for automotive diesel is stricter compared to the
pyrolysis [20]. However, using PILC catalysts regardless of the type marine diesel, it would be predictable that many of WPO which could be
could enhance the diesel range hydrocarbon in the liquid oil. Maximum used as the marine diesel, cannot meet the requirements of EN590
diesel range hydrocarbon was observed in the liquid oil produced over (Figs. 14 (a-e)). Fig. 14 (a) indicates that just 7 from 19 WPO reported in
Fe-PILC with 80.5 wt% and for the other types was of the order of Al- studies has the density in the range of standard automotive diesel,
PILC ˃ Zr-PILC ˃ Ti-PILC [55]. whereas except one of them all the reported WPO has similar density
Fig. 13 shows the content of paraffinic, olefinic and aromatic com­ with marine diesel. Based on Fig. 14 (b), almost all the WPO has kinetic
pounds in the liquid product and based on that, using zeolites, FCC and viscosity at range of 2–4.5 cSt. Fig. 14 (c) shows just two of them can
PILC (except Ti-PILC) catalysts increases the aromatics concentration in meet the standards of EN590 and ISO 8217 regarding to the standard
the liquid product. The concentration of aromatics in the liquid product flash point for automotive and marine diesel. Concerning cetane index
obtained at presence of HZSM-5, ZSM-5, HUSY and Fe-PILC is significant (Fig. 14 (d)), it could be observed that almost all the WPO can meet this
and can make environmental problems after consumption in the diesel requirement for both automotive and marine diesel. Among 10 WPO
engines. No considerable changes has been observed in aromatic content reported based on cetane number, just 6 of them have cetane number
after catalytic cracking of HDPE using silica-alumina, however it has more than 51 (Fig. 14 (e)). In addition to these properties, some data
been observed that production of liquid oil at presence of this catalyst about other properties such as ash, sulfur, and aromatic content as well
reduces the paraffin content and increases the olefinic compounds to as calorific value also reported in Table S4 in appendix.
more 90 wt%. Increase of olefin concentration in the liquid product has Although some studies claimed that diesel engines can run on neat
been also reported at presence of FCC and Y-zeolite catalysts. PILC WPO [96,106,108,110,113], among 19 different WPO, just a few of
catalysts are the only ones that leads to an increase in paraffinic com­ them meet most of the requirements of EN590 standard. Almost all of
pounds of liquid oil and since the liquid oil with high content of paraffin them could be used as a fuel for marine diesel engine if some modifi­
is more favorable to consume as a fuel, using PILC catalysts especially cation performed on their flash point.
Al-PILC and Ti-PILC are highly recommended for degradation of In order to evaluate the quality of WPO in the diesel engine, the
plastics. parameters such as combustion, performance, and emission character­
As an overview concerning catalysts, it could be concluded that using istics of engine when it works with WPO should be analyzed and
silica-alumina, zeolite and FCC catalysts leads to a reduction in liquid compared with the time using diesel fuel.
yield and a growth in gas product compared to the thermal pyrolysis.
Using these three types of catalyst also more favorable for production of 4.1. Combustion characteristics
a liquid oil with low hydrocarbon chain (C5–C12) with high aromatic
content (FCC and zeolite catalysts) or high concentration of olefinic Combustion characteristics of fuel are determined based on factors
compounds (silica-alumina). Regarding bentonite clay, it has been including Ignition Delay (ID), Peak in-Cylinder Pressure (PCP), and Heat
observed although in the raw form, it cannot change the liquid yield and Release Rate (HRR). Thus, comparing these parameters for the diesel
hydrocarbon distribution in the liquid fraction, using Fe-, Ti-, Zr- and Al- engines using WPO with the ones using diesel would help to have better
pillared clays improve the yield or quality of liquid product. Fe- and Al- understanding regarding the combustion characteristics of WPO.
pillared clays enhanced the liquid yield and diesel range hydrocarbons,
and the order of Ti-PILC ˃ Al-PILC ˃ Zr-PILC ˃ Fe-PILC ˃ thermal, has 4.1.1. Ignition delay (ID)
been observed for the paraffin content. In addition to the mentioned It is defined as the delay period between the start of injection and
catalysts, the impact of other types catalyst including Activated Carbon start of combustion. Based on the studies, it can be observed that the
[14], Mordenite, Alumina [29], NCM1 [30], Silicate, Silica-gel, FSM2 ignition delay of WPO is significantly longer than diesel fuel
[40], Zn, ZNO, ZnCl2 [46], Red Mud [58], AlCl3 [59], MnO3, Ni-Mo, Al [96–97,105,113–116]. Mani et al. believed the high viscosity (impacts
(OH)3 [61] on the liquid yield has been reported in the Tables S1 and S3. on the spray characteristics) and lower cetane number of WPO resulting
in higher ID for the combustion process in the engine [96]. These two
4. Using waste plastic oil as a fuel parameters were also mentioned by Kaimal and Vijayabalan, as the main
reasons for higher ID in the neat WPO operation [105].
The growth of demand for diesel cut in the European countries and
the United States is the main reason that waste plastics along with 4.1.2. Heat release rate (HRR)
renewable biomass have attracted worldwide attention [10]. The crude HRR is influenced by two parameters, ID and premixed combustion
liquid oil obtained from pyrolysis of waste plastic has the potential to be phase. These parameters themselves are affected by the chemical
replaced instead of conventional fossil-based gasoline and diesel fuels. composition of fuel and mixing of fuel with air [108]. Researches con­
Although most of the studies carried out in this area were engaged in cerning using WPO in diesel engines show this oil has higher heat release
generating gasoline range liquid fuels, during recent years more atten­ rate comparing with diesel fuel during the initial stage and longer
tion allocated to the production of diesel fuel through thermal-chemical combustion duration at full load [96–98,105,108,112,114–119]. Kaimal
conversion of waste plastics. Waste plastic oil with dominant carbon and Vijayabalan claimed that higher calorific value and more oxygen
range of C13–C20, can be used in a wide range of diesel engines from content are the reasons for higher HRR of engines using WPO instead of
light-duty (for passenger vehicle) to heavy-duty (for marine and indus­ diesel fuel [105]. In the other study carried out by them, in addition to
trial equipment) applications. However, the physico-chemical proper­ the high calorific value of WPO, its high viscosity as the parameter
ties of WPO should be in the standard range presented for mentioned causes higher ID was mentioned as the reason for higher HRR in the neat
fuels (EN590 [93] for the Automotive diesel and ISO 8217 [94] for the WPO [115].
Marine diesel). The standard physico-chemical properties of automotive
and marine diesel fuels as well as standards for measuring each of these 4.1.3. Peak in-cylinder pressure (PCP)
properties are shown in Table 5. For this purpose, the physico-chemical Cylinder pressure is a pivotal parameter indicating the power
properties of WPO presented in different studies [95–113] compared developed by the cylinder. In many studies, it is observed that WPO
produces a higher peak cylinder pressure compared to diesel fuel at full
load [96,98,105,108,112–113,118–119]. Mani et al. concluded that
1
Clinoptilolite containing rhyolite tuff. longer ID and higher heat release in the premixed combustion phase are
2
Non-acidic mesoporous silica catalysts. the main reasons for higher peak pressure in neat WPO operation at full

17
S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 13. Paraffin, olefin and aromatic content of liquid product [29,33,55,92].

load [96]. In a study carried out by Kaimal and Vijayabalan, higher

Table 5
viscosity of WPO which causes higher ID was considered as the reason
Characteristics of diesel fuel [93–94].
for higher PCP [105].
Properties Standard Automotive Marine
Diesel Diesel
4.2. Engine performance
ISO ASTM EN EN590 ISO 8217

Density @ 15 ◦ C 3675 D1298 820–845 <900

The performance of a compression ignition engine is highly influ­
(kg/m3) 12185 D4052
Ash Content (wt. 6245 D482 <0.01 <0.01 enced by the parameters such as Brake Thermal Efficiency (BTE), Brake
%) Specific Fuel Consumption (BSFC), and Exhaust Gas Temperature (EGT).
Kinematic 3104 D445 2–4.5 2–11
Viscosity @ 4.2.1. Brake thermal efficiency (BTE)
40 ◦ C (cSt)
Brake thermal efficiency reveals how efficiently a combustion system
Cetane Number 5165 D613 15195 >51
16144 can convert the fuel into mechanical energy. The results of studies
16715 regarding consumption of WPO in diesel engines reveal that substitution
Cetane Index 4264 D976 >46 >35 of diesel with WPO resulting in a reduction in the BTE of the engine
D4737
[97–98,105–106,108,112,114–118,120–121]. The main reasons
Flash Point (◦ C) 2719 D93 >55 >60
Pour point (upper) 3016 <0 (winter)
mentioned in the studies are related to the higher density and viscosity
(◦ C) <6 of plastic oil compared to diesel fuel [106,119]. Also, due to the pres­
(summer) ence of high aromatic content [106,119] and heavy hydrocarbon chains
Carbon residue 10370 D189 <0.3 [99,105] in the WPO, more energy is required to break the aromatic
(wt.%) D4530
bonds of these heavy hydrocarbon chains, so the thermal efficiency of
Sulfur Content (wt. 20846 D129 <0.001 <1.5
%) 20884 D5453 the engine would be decreased.
13032 D2622
Water Content 12937 D6304 <0.02 (wt.%) <0.3 (vol. 4.2.2. Brake specific fuel consumption (BSFC)
%)
The BSEC is defined based on the amount of energy consumed by the
Aromatic Content D5186 12916 <8 (wt.%)
Total 12662 <0.0024
engine to produce one kW power in one hour [106]. This parameter is
contamination generally used for comparing two fuels with different heating values and
(wt.%) physical properties. It is reported that using WPO instead of diesel in
FAME content (vol. 14078 <7 <7 engines leads to higher BSEC [97–98,106,108,112,114,120–121]. The
%)
reason presented for this trend is the higher density and viscosity of
Oxidation stability 12205 <25 (g/m3) <25 (g/m3)
WPO compared to diesel fuel [106]. Also, this can be partly attributed to
the lower heating value of WPO [99,112]. The higher BSFC of WPO

18
S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Fig. 14. Comparison between characteristics of different WPO and standard range for automotive and marine diesel (a) density, (b) viscosity, (c) flash point, (d)
cetane index, (e) cetane number [95–113].

compared to diesel fuel shows that more WPO is required in the engine carbon dioxide (CO2), and smoke opacity. Thus, for comparing the
for combustion in order to generate the same power output as diesel fuel. emission characteristics of WPO and diesel fuel, it is necessary to mea­
sure and analyze the exhaust gases released.
4.2.3. Exhaust gas temperature (EGT)
The EGT indicates the amount of heat that is wasted with the exhaust 4.3.1. Nitrogen oxides (NOx)
gases. The results of studies that compared this parameter for engines The assessment of NOx released engine working by WPO and diesel
using WPO and diesel reveals the EGT for WPO was higher at all loads fuel shows that the NOx emitted in the WPO operation is higher in the
[96–97,108,112,114,117]. This trend was explained by higher ID [112] entire load range compared to diesel fuel operation
and higher HRR of neat WPO operation in comparison with diesel fuel [96–98,106,108,112,114,117–119]. High aromatic content [96,106]
operation [96]. Another reason reported for this trend is due to the and long-chain carbon compounds [99] in the WPO cause higher HRR
oxygen content of the WPO which promotes more complete combustion and ID resulting in an increase in NOx in the neat WPO operation.
resulting in higher EGT [96,108].
4.3.2. Unburned hydrocarbon (UHC)
Unburned hydrocarbon emissions are due to the incomplete com­
4.3. Emissions characteristics bustion of the fuel–air mixture. Based on the studies performed on the
UHC emission of WPO and diesel fuel operations, it can observe the
Incomplete combustion of fuel causes when fuel burnt inside the concentration of UHC released by burning WPO is marginally higher
combustion chamber of the engine releases emissions such as nitrogen than diesel fuel [96–98,106,108,110,112–114,116–121]. Kaimal and
oxides (NOx), Unburned HydroCarbon (UHC), carbon monoxide (CO),

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

Vijayabalan concluded the higher UHC emission of WPO in the exhaust Although it is not a harmful gas like CO, it is strongly required to reduce
is due to its high density and viscosity which reduces the combustion CO2 emissions due to being greenhouse gas. The results of studies
efficiency [106]. The aromatic nature of WPO is the other reason re­ regarding the comparison of CO2 emitted in the WPO operation and
ported for high UHC in WPO operation [106,108,112]. diesel operation shows two different trends. The results of studies car­
ried out by Kalargaris et al. [112] and Devaraj et al. [113] an increase in
4.3.3. Carbon monoxide (CO) CO2 emission is observed when diesel engine were fuelled with WPO.
Carbon monoxide is produced because of incomplete combustion This trend was explained by the higher carbon to hydrogen ratio of WPO
due to the lack of oxygen. Similar trend reported for the NOx and UHC, than that of diesel, resulting in the same amount of energy released from
CO emission is higher for the engine using WPO combustion, more carbon oxidized and more CO2 will be produced by
[96–98,106,110,112,114,118–120]. Several reasons were reported for the WPO [112–113,118]. However, other researchers reported a
this increase of CO emission in neat WPO operation. Kaimal and different trend and they observed that the amount of CO2 produced in
Vijayabalan claimed because of the low volatility and high viscosity and neat WPO operation is lower than diesel fuel [96,98,110]. It could be
aromatic content of WPO, the amount of CO in the exhaust for WPO due to the late burning of fuel that leads to incomplete combustion and
increased [106]. Kumar et al. believed in their study, the lower calorific production of more CO instead of CO2 [96,98].
value of WPO leading to higher quantity of fuel injection which resulted
in caused production of higher quantity of CO emission [110]. Wathakit 4.3.5. Smoke opacity
et al. explained the higher emission of CO in neat WPO operation by the Smoke is nothing the solid soot particles that are suspended in the
presence of lower cetane index and a higher amount of long-chain car­ exhaust gas [96]. It was observed that the smoke for WPO was higher
bon compounds (C12–C20) in the WPO [99]. than diesel fuel [96–98,106,108,114,116–117,119–121]. Various rea­
sons were presented for this increase of smoke when WPO was used
4.3.4. Carbon dioxide (CO2) instead of diesel fuel. Kaimal and Vijayabalan reported the low volatility
Carbon dioxide emission is a result of complete combustion where and high viscosity and aromatic content of WPO caused an increase in
the carbon atoms contained in the fuel are completely oxidized. the amount of smoke in the exhaust [106]. Wathakit et al. also claimed

Table 6
Combustion, performance and emission characteristics of engines using neat WPO compared to diesel fuel.
Diesel Engine Specifications Combustion Performance Emission Ref.

ID HRR PCP BTE BSFC EGT NOx UHC CO CO2 Smoke

Kirloskar, 1-cylinder, 4St, 4.4 kW@1500 rpm, a – [96]

CR: 17.5:1, AC, DI
1-cylinder, 4S, 3.7 kW@1500 rpm, – – – – – [106]

CR: 16.5:1, WC, DI

Kirloskar, 1-cylinder, 7.5 kW@1500–3000 rpm, – [108]
CR: 17.5:1, AC, DI
Kirloskar, 1-cylinder, 4St, 5hp@1500 rpm, – – – [110]

CR: 17.5:1, WC, DI

AKSA, 4-cylinder, 68 kW@1500 rpm, – [112]
CR: 17:1, WC, DI
Kirloskar, 1-cylinder, 4St, 3.7 kW@1500 rpm, – [113]

CR: 16.5:1, WC, DI

Kirloskar, 1-cylinder, 4.4 kW@1500 rpm, – – [97]
CR: 17.5:1, AC
CVCR, 1-cylinder, 2.237–3.728 kW@1450–1550 rpm, – – [98]
CR: 6:1–20:1, AC, DI
1-cylinder, 4St, 3.7 kW@1500 rpm, – – – [119]

CR: 16.5:1, WC, DI

Kirloskar, 1-cylinder, 4.4 kW@1500 rpm, – – – – [117]
CR: 17.5:1, AC
Kirloskar, 1-cylinder, 4.4 kW@1500 rpm, – – – – – [120]
CR: 17.5:1, AC, DI
Kirloskar, 1-cylinder, 4St, 3.5 kW@1500 rpm, – – – [103]

CR: 12–18, WC, DI

Kirloskar, 1-cylinder, 4St, 5.2 kW@1500 rpm, – – [116]
CR: 17.5:1, AC, DI
Kirloskar, 1-cylinder, 4St, 5.2 kW@1500 rpm, – [114]
CR: 17.5:1, AC, DI
AKSA, 4-cylinder, 68 kW@1500 rpm, – – – – [118]
CR: 17:1, WC, DI
1-cylinder, 4St, 3.7 kW@1500 rpm, – – – – – – – [105,115]

CR: 16.5:1, WC, DI

Kirloskar, 1-cylinder, 4St, 5.2 kW@1500 rpm, – – – – – [121]
CR: 17.5:1, AC, DI

: More than diesel, : Less than diesel, : Varied during different loads, : Equal.
St: Stroke; CR: Compression ratio; AC: Air cooled; DI: Direct ignition.
a
Except full load.

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S.M.R. Mirkarimi et al. Applied Energy 327 (2022) 120040

higher viscosity and higher distillation temperature of WPO were the products in different studies have been compared to the standards
reason for higher smoke emission [99]. Senthilkumar and Sankaranar­ related to diesel fuel. It was observed among 19 different WPO, just a
ayanan believed longer ID and combustion duration may be the reasons few of them meet most of the requirements of EN590 standard, while by
for higher smoke in neat WPO operation. Also, it was mentioned due to just modification of the flash point almost all of them could be used as a
heavier molecules of WPO compared to diesel fuel, its smoke opacity is fuel for marine diesel engine. Comparing diesel engine using neat WPO
higher [97]. with the ones working with diesel has shown lower performance and
In conclusion, although diesel engine using neat WPO has shown combustion characteristics as well as higher emissions for the first
lower performance and combustion characteristics as well as higher category. Hence, upgrading WPO should be done by means of blending
emissions compared to diesel, upgrading WPO could be carried out by with diesel, employing oxygenated components during combustion, and
the methods namely blending with diesel, employing oxygenated com­ hydrogenation.
ponents during combustion, and hydrogenation. A summary of previous Although lots of studies have been performed on the pyrolysis of
studies regards to the effect of using WPO on the combustion, perfor­ waste plastic at different operating conditions and in the various types of
mance, and emission characteristics of diesel engines is presented in reactor, there is still a research gap due to the insufficient data in the
Table 6. following subjects.

5. Conclusion • Influence of waste plastic composition on the product distribution

and quality of WPO
The pyrolytic conversion of different types of waste plastic and their • Impact of heating rate on the liquid yield of PVC, HDPE, and PS
mixture (MWP) into fuel for a diesel engine was extensively reviewed in • Investigation on methods for upgrading WPO
this paper. Based on the studies conducted on pyrolysis of plastics with • Investigation on co-pyrolysis and comparing quality of liquid prod­
different resin type including PET, HDPE, PVC, LDPE, PP, and PS, it was uct with blend of WPO and biofuel
concluded that type of plastic impacts significantly on the product dis­
tribution. At optimum operating condition, PS produces the highest
liquid yield compared to the other types of plastic (≥95 wt%), and PET Declaration of Competing Interest
and PVC show the least liquid oil with less 42 wt% and 32 wt%,
respectively and the liquid product obtained from HDPE, LDPE and PP is The authors declare that they have no known competing financial
in the range of 80–90 wt%. Also, MWP could yield more than 50 wt% interests or personal relationships that could have appeared to influence
liquid oil, if PET and PVC content in the mixture would be with<10 and the work reported in this paper.
5 wt% respectively.
Analysis of operating factors such as temperature, heating rate, Data availability
residence time, pressure and particle size indicates that based on the
type of plastic, the optimum range for achieving the highest yield of Data and information are reported in the Appendix
liquid oil would be changed. It has been observed thermal degradation
order of plastic with different resin follows as HDPE ˃ LDPE ˃ PP ˃ PET Acknowledgements
˃ PS. This issue results in MWP that has higher content of plastic with
lower thermal deration such as PS, requires less energy to convert into This research did not receive any specific grant from funding
the fuel. Concerning optimum temperature for yielding highest liquid agencies in the public, commercial, or not-for-profit sectors.
oil, it was observed the optimum temperature for thermal pyrolysis of all
the plastics, regardless of their types, would be in the range of Appendix A. Supplementary material
425–500 ◦ C, whereas for MWP this temperature range would be
450–500 ◦ C. Evaluation of experimental data near to 500 ◦ C, it is Supplementary data to this article can be found online at https://doi.
concluded that rising heating rate from 5 to 20 ◦ C/min leads to yielding org/10.1016/j.apenergy.2022.120040.
higher liquid oil for PET, LDPE, and PP, however a higher liquid yield
was observed at 10 ◦ C/min for the mixed plastics. Furthermore, it is
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