Fuel 337 (2023) 126890

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

A critical review on pyrolysis method as sustainable conversion of waste

plastics into fuels
K. Radhakrishnan a, b, P. Senthil Kumar a, b, e, *, Gayathri Rangasamy c, e, *, L. Praveen Perumal d,
S. Sanaulla d, S. Nilavendhan d, V. Manivasagan d, K. Saranya d
a
Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam 603 110, Tamil Nadu, India
b
Centre of Excellence in Water Research (CEWAR), Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam 603 110, Tamil Nadu, India
c
Department of Sustainable Engineering, Institute of Biotechnology, Saveetha School of Engineering, SIMATS, Chennai 602105, India
d
Adhiyamaan College of Engineering (Autonomous), Dr. M. G. R. Nagar, Hosur, Tamilnadu 635 109, India
e
School of Engineering, Lebanese American University, Byblos, Lebanon

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

Keywords: Plastic production has increased globally, and many of these plastic items are no longer in use. The plastic wastes
Plastic waste end up as garbage, disposed of in landfills, or scattered, posing major health and environmental risks. In terms of
Fuel sustainability, converting plastic trash into fuels or any other better option, individual monomers, is a far more
Pyrolysis
environmentally friendly waste management option than landfill dumping. Nearly 1.3 billion metric tonnes of
Waste management
Catalyst
plastic are produced annually as businesses strive to meet the demands of consumers. Plastic is made through a
process called polymerization, in which hydrocarbons are rearranged into new molecules. These hydrocarbons
often have a high molecular mass, and they may also contain other chemicals to boost their performance. Plastic
is a useful material because, among other things, it is durable, lasts a long time, is inexpensive, and has many
other benefits. Because plastic can take decades to degrade if left alone, effective waste plastic disposal should be
a top priority for every-one. Yet, growing industrialization and urbanization have contributed to a discernible
rise in fuel demand. Finding renewable energy sources to replace fossil fuels is now a critical global priority.
Plastics-to-gasoline conversion provides a means to solve both of these problems. By applying intense heat (more
than 370 ◦ C) and an oxygen-free environment, pyrolysis thermochemically decomposes organic materials. The
byproducts of pyrolysis are carbon black, hydrocarbons, and pyrolysis oil. This review focuses on pyrolysis as it is
the most popular and efficient method for turning polymers into fuels in comparison with other methods. This
review comprises the knowledge of different types of plastics and their properties. The major discussion was
focused on pyrolysis methods for recycling plastics. To have better knowledge competitive recycling method
were discussed. The optimization parameter for recycling process, by-products of plastics, advantages and dis­
advantages of pyrolysis process are discussed to identify the drawbacks and research gaps. The pyrolysis method
are potential for addressing waste plastic management and highlights the need for a reliable alternative fuel
source.

1. Introduction that result in a rapid growth in the solid wastes generated around 1.5
billion tons per year. Today, more than 250 million ton in a single year
The world population growth led to the increase in usage of plastic are either scattered in the environment or dumped in the landfills and

Abbreviations: FCC, fluid catalytic cracking; PVC, Polyvinyl Chloride; HDPE, High-Density Poly Ethylene; PET, Poly Ethylene Terephthalate; PP, Poly Propylene;
LDPE, Low-Density Poly Ethylene; HZSM, H-Zeolite Socony Mobil–5; MCM, Mobil Composition of Matter; PSW, Public Solid Waste; PE, polyethylene; PS, poly­
styrene; MSW, Municipal Solid Waste; ZMS, Zeolite Socony Mobil-5; GC–MS, Gas Chromatography, Mass Spectrometry; MW, Molecular Weight; TG, Thermog­
ravimetry; DTG, Derived Termogravimetry; CSBR, Conical Spouted Bed Reactors; SA, silica-alumina; EU, European Union; SAC, Single Atom Catalyst; TPD, Thermal
Desorption; AC, Activated Carbon.
* Corresponding authors at: Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam 603 110, Tamil Nadu, India (P.
Senthil Kumar); School of Engineering, Lebanese American University, Byblos, Lebanon (Gayathri Rangasamy).
E-mail addresses: [email protected] (P. Senthil Kumar), [email protected] (G. Rangasamy).

https://doi.org/10.1016/j.fuel.2022.126890
Received 27 July 2022; Received in revised form 17 September 2022; Accepted 22 November 2022
Available online 1 December 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
K. Radhakrishnan et al. Fuel 337 (2023) 126890

around 10 million ton per year finally reaches oceans as plastic waste generation. Aromatics and aliphatic chemicals were observed to be
[1]. This may lead to rise around 9–15 % of plastics in a year. Global produced during the catalytic pyrolysis of PE utilising HZSM-5. On the
consumption of plastic has increased by 10 % on an annual average. other hand, the usage of mesoporous MCM-41 resulted in a decrease in
Plastic is a petroleum-based substance that causes a depletion of the non- the amount of aromatic compounds generated due to its poor acid cat­
renewable source. Nearly 4 % of oil manufacture is used in production of alytic activity. There was a marked improvement in both the efficiency
plastics [2]. Plastic wastes are hazardous to the environment so the and quality of the resulting liquid oil during the pyrolysis process after
plastic can either be disposed or reused. It is recognized that that plastic the introduction of synthetic catalysts. The synthetic catalysts, on the
can be deposited in the ecosystem for a very long time. Continuous other hand, resulted to an increase in the expense of the pyrolysis pro­
deposition of this plastic in the ecosystem is critical to both aquatic and cess [9,10].
terrestrial organisms [3]. The various natural plastic degradation In this review, we examine the possibility of pyrolysis as a thermo­
mechanisms are auto-oxidation, photodegradation, thermal degrada­ chemical exchange procedure for the vaporization of plastic waste in a
tion, bio-degradation, thermos-oxidation. These mechanisms are taking systematic manner. Different pyrolysis types are explored, as well as the
place at a very inactive rate. On further discussion, the pollutants, such impact of operational variables such as vapor residence time, tempera­
as phenol, toluene, benzene and toluene were issued into water, soil & ture, catalyst type, as well the wastes of plastic type on quality, yield,
air as a consequence of plastics degradation affect undesirable problems, and uses of the cracked plastic goods. We summarize the feasibility of
such as effects on humans & animals’ physical condition & weakening of using pyrolysis method to convert various plastics into fuel conducted by
soil potency. Photodegradation change plastic wastes into minute a number of researchers. Multiple factors affect both product quality and
pieces, which floats over the surface of water bodies like pond, lake, output. This review aims to examine the several types of plastics waste
river, sea, ocean and can saturate through the food chain and finally pass pyrolysis procedures along with the quality and quantity of the products
to human, and cause disease to a human [4]. and different reactor types applied for the pyrolysis process. The
Primary reusing, secondary reusing, tertiary reusing, and quaternary application of pyrolysis plastic oil is reviewed. Year-wise consumption
recycling are the four harmful ways to manage plastic waste. Primary of plastic in India was represented in Table 1.
reusing is a technological method that uses only one type of unpolluted
and clean plastic trash to produce a product with the same fundamental 2. Types of plastics
structure and quality. The drawback of this type is expensive when
waste material is wasted which produce a new wastewater and, even Plastics play a significant role in human life. Plastic is being used in
more pertinently, plastic waste are typically made up of a mixture of many places because of its adaptability, durability, low cost, and light­
plastic products, often grouped as composite materials with some weight [11]. Plastic waste compounds are manufactured in various
additional materials, and are may be hard or almost unbearable to sectors namely automobile, residential, agricultural, construction, and
recycle. Subordinate mechanical reusing is the next step in the recycling electrical equipment, demoralization, toys, and packing materials have
process, which includes decontamination, melting, remoulding, size good growth and are either decomposed or recycled [12]. Plastic wastes
reduction, re-extruding, and pollutants removal. The benefit of this contain Polyvinyl Chloride (PVC), High-Density Poly Ethylene (HDPE),
technology is that it has a low operating cost. Gasification, hemolysis, Poly Ethylene Terephthalate (PET), Poly Propylene (PP), and Low-
pyrolysis, and partial oxidation as well as cracking solvolysis, are all Density Poly Ethylene (LDPE), among which PET and PP represent the
examples of tertiary recycling. Chemical processes are used to transform best portion of plastic waste [13].
large polymer molecules from plastic trash into smaller ones in this
approach. Fuels are created using this method. This technology can be
used to create new polymers and other items in specific instances. 2.1. Polyethylene terephthalate (PET)
Quaternary reusing is the last step in the waste incineration process for
energy recovery. It is the easiest way, yet it pollutes the environment PET has grown in popularity as a plastic packaging material for a
while having little effect on the ecosystem [5]. As previously stated, both variety of foods and beverages, including soft drink bottles, fruit juice
primary and secondary technologies have certain drawbacks, including containers, and mineral water. This is owing to its inherent character­
significant material loss, water pollution, high costs, and labor-intensive istics, which make it ideal for lightweight, pressure-resistant containers
operations. Plastics that have been recycled are more costly than fresh and high-capacity. Electrical insulation, magnetic tapes, X-ray printing
plastics, and they do not retain their original qualities. As a result, ter­ sheets, and other photographic films are some of the various uses for
tiary recycling can be a cost-effective and ecologically responsible PET. The widespread usage of PET would result in a build-up of PET
approach for producing high-value gasoline from plastic trash. garbage in landfills. The current procedure for dealing with accumulated
We can identify minimization, controlling, recycling, reduction, en­ plastic trash was to recycle PET waste. The bulkiness of the containers,
ergy recovery, reuse, and disposal in the hierarchy of waste management on the other hand, results in a high frequency of collections, which raises
[6]. Some companies show interest in the conversion of plastics into transportation expenses. PET trash must be divided into distinct grades
useful materials by pyrolysis method has increased over few years [7]. and colors to facilitate recycling, which makes recovery inefficient and
The recycling techniques are the most suitable techniques for decreasing uneconomical. As a result, another option for recovery of PET, the
the performance of plastic after many recycle.it is referred that pyrolysis method of pyrolysis, was investigated, and product yield has been
is the most used pyrolysis technique to yield petroleum products [8]. evaluated from many researchers.
Degradation is one of the technologies but many studies involved by Papari et al., used PET in a fixed bed reactors at 500 ◦ C to see if it
using specific kinds of microorganisms such as bacteria, to degrade the could be used in pyrolysis procedure to create liquid oil. The heating rate
plastic material. in this experiment was 10 ◦ C/min, and cleaning gas was N2. The output
Microporous and mesoporous catalysts have been used in numerous
research to transform plastic trash into oil and char. The utilisation of Table 1
HZSM-5 increased liquid oil output because of its high aromatic and Plastic consumption in India.
isoalkane component content. Pyrolysis of plastic waste was catalyzed S. NO CONSUMPTION (TONNES) YEAR Ref
by utilising the modified MCM-41 and HZSM-5. In their study, they 1 61,000 1996 [4]
found that using HZSM-5 led to the production of lighter hydrocarbons 2 3,00,000 2000
(C3-C4) with the highest concentration of aromatic chemicals. Hetero­ 3 4,00,000 2001
geneous catalysts HZSM-5 with mesoporous SiO2-Al2O3 or MCM-41 4 85,00,000 2007
5 1,60,00,000 2019
resulted in the highest liquid oil production with minimal gas

2
K. Radhakrishnan et al. Fuel 337 (2023) 126890

of this liquid oil was observed to be decreased than that of gaseous oil. the multiple uses. Polystyrene is not accepted in the roadside recycling
The liquid oil yield 23 wt%, whereas the gas product yield 77 %, without program, which only accepts cans, papers, glasses, and certain plastics.
any solid residue. A proximate composition based on Table 1 clearly Despite the fact that there is a category of plastic, most individuals don’t
states that PET has a relatively less volatile content around 86.8 % over place foam food packages in the plastic recycling bin and instead place it
other polymers with turbulent values of all above 90 %. This might in the general trash. Because of its low-density polystyrene foam,
explain the poor liquid yield. Polystyrene is often not separated and economically collected for the
recycling process. As a result, the only option to completely use PS waste
2.2. High-density polyethylene (HDPE) is to use the pyrolysis process to convert it into a more valuable oil
product instead of letting it dumped over the landfills indefinitely.
Milk bottles, detergent bottles, oil containers, Toys, and other items
are all made from HDPE. The different uses account for 17.6 % of the 3. Properties of plastics
plastic wastes classification, which is the 3rd most common plastic type
in a Public Solid Waste (PSW). Differences in polymers’ properties, they are chemically stable, and
Ahmad et al. using micro steel reactor investigated the HDPE py­ weightless, adaptable to many different shapes and sizes, superior
rolysis. The pyrolysis temperature was in-between 300 ◦ C and 400 ◦ C, insulation with a low thermal conductivity. They can absorb shock well
with a heating rate of around 5–10 ◦ C/minute. As a fluidizing medium, and won’t corrode, and resistance to haze and abrasion. These material
nitrogen gas was employed. They discovered that the largest overall are easily deformed and has poor dimensional stability. The recycling
conversion occurred during 350 ◦ C, in which liquid as the primary result properties of plastics was influenced by the rate of pyrolysis process.
harvest (80.8 % of weight.). The solid excess were quite high (33.05 wt Chemical composition of the feedstock, operation pressure, cracking
%) at 350 ◦ C, but it was decreased to 0.5 wt% at the maximum tem­ temperature, and residence time are some of the most important ele­
perature around 400 ◦ C [13]. ments that influence the plastic pyrolysis process and the molecular
distribution of the pyrolysis products. These considerations are summed
2.3. Polyvinyl Chloride (PVC) up in the next paragraphs of this section. (i) Chemical composition: The
chemical composition and the chemical structure of the plastics that are
Polyvinyl Chloride differs from other thermoplastic in that it is made going to be pyrolyzed are directly related to the products of the pyrolysis
up of 57 % Cl which is obtained from industrial-sized salts and 43 % C process. In addition to this, the pyrolysis processes are also affected by
which is obtained from petroleum feedstocks such as ethylene from the chemical make-up of the feedstock being used. In point of fact, waste
natural or oil gas, similar to other thermoplastic polymers such as plastics may already be polluted before they are recycled, which may
polypropylene (PP), polyethylene (PE), and polystyrene (PS), all of have implications for both the pyrolysis process and the goods it yields.
which can be relaxed by warming and are mainly resulting from the (ii) Cracking temperatures: Due to the fact that temperature is the pri­
lubricant. An PVC is good for electrical insulation because of its great mary factor in determining whether or not polymer materials will crack,
fire resistance due to its chlorine component. temperature is one of the most significant operating variables.
Increasing the temperature won’t work on all types of polymer mate­
2.4. Low-Density polyethylene (LDPE) rials; some of them are too brittle. The Van der Waals force is the force
that exists between molecules and is responsible for attracting molecules
Low-Density Polyethylene has greater branched than HDPE, which to one another and preventing the molecules from collapsing. When the
leads to a lower intermolecular force, subsequent in less tensile strength vibration of molecules becomes strong enough, the molecules on the
and stability. This LDPE, on the other hand, has superior ductility surface of the item will evaporate. (iii) Type of Reactor: The kind of
compared to HDPE as side diverging makes that structure less crystalline reactor used for plastic pyrolysis has a sizeable impact on the rate of heat
and easier to shape. It also has good water resistance and is consequently transfer, the proportion of plastics to pyrolysis products mixed in, the
frequently used in plastic bags, packing foils, waste bags, and other amount of time spent in residence, and the amount of reflux produced by
applications. All of these goods are often utilized in our everyday lives, the primary products. It is possible to categorize reactors as batch, semi-
and as a result, LDPE garbage has grown to become the 2nd largest batch, or continuous operations, or they can be categorized according to
plastic waste in Municipal Solid Waste (MSW) after Polypropylene [14]. the types of reactor beds used. The pyrolysis reactor can be broken down
LDPE pyrolysis to oil products has recently gotten a lot of interest from into three different types based on the feeding and product removal
academics as a technique to recover energy and decrease waste. procedures. These reactors are called batch, semi-batch, and continuous
reactors. In a batch reactor, the pyrolysis can begin either at the
2.5. Polypropylene (PP) beginning of the process or after all of the materials that were fed into
the reactor have been treated. The materials are fed into the reactor in
PP is a chemically and thermally resistant saturated polymer having batches. (iv) Residence Time: The concept of residence time is defined
a linear hydrocarbon chain. PP, unlike HDPE, did not melt below 160 ◦ C. differently throughout the various research studies. When talking about
PP has a lesser density compared to HDPE, and also it has a stiffness and the fast pyrolysis process or the continuous pyrolysis process, this term
higher durability, making it a better choice for the plastics sector. PP refers to the amount of time that the plastic spends in contact with the
makes up around 24.3 % of the plastic wastes class, which has the most heated surface of the reactor. On the other hand, in the slow pyrolysis
plastics in MSW. and batch processes, the term “residence time” refers to the amount of
time that elapses between the beginning of the heating of the feedstock
2.6. Polystyrene (PS) plastic and the extraction of the products. A longer residence time makes
it more likely that the basic products will be changed even more. This
Polystyrene is majorly done of petrochemical liquid-derived styrene leads to the production of more thermally stable products, like hydro­
monomer. Its structure is made up of a long hydrocarbon chain with a carbons with a low molecular weight and petroleum gases that don’t
group of phenyl attaches to any C-atom. Polystyrene is generally condense. (v) Pressure: The operating pressure has a considerable
colorless by nature, although it can be tinted with colorants. Its heat impact, not only on the products, but also on the pyrolysis process itself.
resistance, as well as its reasonable durability, strength, and lightweight Because the pyrolysis products have higher boiling points when sub­
make it ideal for usage in a range of industries, including electronics, jected to higher pressure, heavy hydrocarbons are further pyrolyzed in a
toys construction, food packaging, and medical appliance. The vast pressurized environment rather than evaporated at the specified oper­
quantity of Polystyrene in MSW accumulated in every year is reflected in ation temperature. (vi) Influence of Other Factors: The pyrolysis process

3
K. Radhakrishnan et al. Fuel 337 (2023) 126890

is also influenced to some degree by a number of additional factors, each Table 3

of which is discussed in the following paragraphs. For example, reactive Plastic wastes proximately analyzed.
additives like air, oxygen, or hydrogen may be present in the reaction for Plastic Ash Fixed Moisture Volatile HHV reference
a variety of reasons. However, their presence will interfere with the types content carbon content matter (MJ/
reactions and change the quality of the products. kg)
To promote effective heat/mass transmission waste plastics must be HDPE 1.4 0.3 0.0 95.5 49.2 [12]
smashed, crushed, then filtered to remove tiny molecules with a size of LDPE 0.5 0.0 0.4 96.7 46.4
<3 nm. The proximal and final analyses of various plastic wastes are PP 2 1.4 0.5 97.8 45
PS 0.0 0.3 0.3 98 40.5
shown in Tables 2 and 3. Plastic waste materials are a great option for PET 0.1 6.8 0.5 90.5 31.4
pyrolysis procedures that result in the high conversions of fuel products
because they have a high volatile component with a high nitrogen and
carbon content. over plastic into fuel oil is represented in Fig. 1.
The pyrolysis process produces either a liquid or a waxy plastic oil.
4. Pyrolysis process The wax produced is yellow in color, has more viscidness at normal
room temperature, also it is made up of hydrocarbon called alkane and
A thermal cracking process known as pyrolysis happens at temper­ alkene that have a high boiling point [17]. This process is characterized
atures exceeding 400 ◦ C in the absence of oxygen. Different types of by catalytic cracking of the oxygenated organic compounds and is
pyrolysis include 1) slow pyrolysis, 2) fast pyrolysis, and 3) ultra-quick accomplished via simultaneous dehydration, decarboxylation, and
pyrolysis, also known as flash pyrolysis [12]. This summarise the vari­ decarbonylation reactions occurring in the presence of suitable chemical
ations in temperature, heating rate,residence time, and the products catalysts. The catalytic cracking to transform wax like substance into
produced by each technique. liquid fuels. The majority of aliphatic chemicals, as well as poly­
The slow pyrolysis is the typical approach taken in the industry to aromatics and monoaromatics, make up liquid plastic oil. Not only being
alter the solid material and lower the oil output. Fast and ultra-quick a good forerunner for fuel purposes but this plastics lubricant may also
(flash) pyrolysis are useful for optimising the extraction of gases and oil. be applied as an intermediary and transformed into propylene and
Fast pyrolysis is the rapid thermal decomposition of carbonaceous ethylene by additional than breaking at exceptionally short contact
materials at moderate to high heating rates, in the absence of oxygen. periods and high temperatures. Butane, butadiene, propylene, ethane,
It’s the method most commonly employed in both formal research and ethylene, and methane are the primary gaseous species that make up the
practical settings. Bio-oil is the most valuable product. Pyrolysis is an “gas product” [18] (see Fig. 2).
endothermic reaction. The feedstock must be dry, composed of micro­
scopic particles (3 mm), and typically done at air temperature with rapid 4.1. Slow pyrolysis
quenching of the products. The procedure cannot start until all of these
conditions are met. 30–60 % liquid condensates, 15–35 % gases, and For the conversion of plastic waste utilizing several reactors and a
10–15 % char are produced. broad range of parameters, with or without the use of a catalyst, Table 4
Ultra-fast pyrolysis, also known as flash pyrolysis, is a specific kind of provides the slow pyrolysis details. During slow pyrolysis, the liquid
pyrolysis characterised by an extremely rapid thermal decomposition products are often oily rather than waxy. When pyrolyzing LDPE at
and a high rate of heating. Both gases and bio-oil are produced mostly as 5500 ◦ C, the oil production can reach up to 90 % by weight. The plastic
byproducts. There is a wide range of possible heating rates, from 100 to oil can be utilized immediately in in-stream boilers to generate power or
10,000 ◦ C per second, and typical residence times are relatively short. in other applications such as monomer recovery, carbon nanotube
Between 60 % and 80 % of the resources extracted are in the form of gas, manufacturing, and transportation fuels. Because of the lower fixation
whereas 10 % to 15 % of the resources extracted are in the form of char. carbon and greater volatile chemicals mixed with the plastic wastes, the
Depending on the feedstock, fast pyrolysis is employed for a liquid generated solid residue is lower than bio-based char (see Fig. 3).
generation. The liquid output from pyrolyzing polyolefin materials can Influence of plastic types: In the lack of a catalyst, pyrolysis of
reach up to 90 % by weight. The temperature during flash pyrolysis is plastics such as HDPE, LDPE, and PP produces liquid oil containing a
often more than 700 ◦ C, the feed which experiences the heating rate is large proportion of alkenes and alkanes, as seen in Table 4. To obtain the
exceedingly quick, and the vapor residence time is measured in milli­ gh conversion of high polyolefins, the temperature is set above 4500 ◦ C.
seconds. For biomass feedstocks, flash pyrolysis gives a larger propor­ When the temperature is below 450 ◦ C, the solid residue grows
tion of oil compared to fast pyrolysis, but for the plastic waste, it dramatically. Polystyrene is a material made out of a styrene monomer
changes, which produces more gas than the other products [15]. Solid that may form a liquid with very few aromatic chemicals like ethyl­
residues, liquid residues, and gas residues are the final products of this benzene, benzene, and toluene. Pyrolysis of polystyrene and polyolefin
pyrolysis of waste plastics. The pyrolysis process may be used for either produces a liquid oil that may be utilized as a good fuel. When pyro­
monomer recovery or fuel, which is particularly useful for dealing with lyzing PET AND PVC, the needed amount of hydrochloric acid and
plastic waste. The oil produced by rapid pyrolysis is a good petroleum benzoic acid can be produced. [19].
fuel source [16]. Because the absence of high oxygenated water and Influence of catalyst: For conventional pyrolysis process of plastic,
chemicals, the heating values of plastic oils are high, almost three times [20] employed a catalyst such as MCM-41, HZSM-5, FCC, HY, silica-
that of bio-based oils obtained from biomass feedstocks, and are alumina, and HUSY. Zeolite catalysts exhibit high oligomerization,
equivalent to diesel fuels [12]. The pyrolysis process of converting left- aromatization, isomerization, and cracking catalytic activity. Specific
phytochemical activities, such as micropore crystalline structure and
strong acidity, are found in zeolite. When contrasted to the uncatalyzed
Table 2 pyrolysis process, the HZSN5 crystal produces aromatic hydrocarbons
Various plastic wastes ultimate analysis. and polycyclic aromatic hydrocarbons. As a result, it was implicated in
Plastic Sulfur Nitrogen Hydrogen Carbon Oxygen Reference the percentage of gasoline. Furthermore, because to the accelerated
types cracking processes, zeolite catalysts often result in a much larger gas
HDPE 0.08 0.06 13 78 4 [12] generation. [21]. Light olefins may be produced using amorphous silica-
PP 0.08 0.02 14 84 1 alumina catalysts without any changes in aromatic product formation.
PS 0.08 0.07 9 90 1 [22] Zeolite-Y and ZMS-5 promote aromatic and branching hydrocarbon
PET NA 0.2 13 77 4
synthesis, as well as a significant increase in the fraction of hydrocarbon

4
K. Radhakrishnan et al. Fuel 337 (2023) 126890

Fig. 1. Pyrolysis Process of Converting Plastic Waste into Fuel Oil.

[13]. Catalyst reforming over Al-MCM-41 increases gasoline output

while reducing gas generation because of the catalyst’s low acid prop­
erties and big pore dimensions. The oil yield drops considerably in the
authority of the both ZSM-5 and Y-zeolite, favoring gas generation [23].
The variations in chemical and physical catalyst features, such as surface
area, pore size, and surface acidity, explain why Y-zeolite outperforms
ZSM-5 in terms of synthesis of aromatic compound.

4.2. Fast pyrolysis

The batch reactor is used for slow pyrolysis, whereas the continuous
reactor is used for quick pyrolysis. The char is quickly removed from the
reactor, which, when combined with continuous procedures, prevents
unwanted catalytic effects such as excessive vapour cracking, which,
Fig. 2. Batch Reactor System. when combined with short time of vapour residence, minimize sec­
ondary reactions of cracking, which results in production of higher
liquid. Fast pyrolysis may convert about 95 % of plastic wastes into wax
material, as shown in Table 5. When compared to polypropylene,
polyethylene has a greater wax output. Fast pyrolysis has a higher wax

Fig. 3. Fixed Bed Reactor System.

5
K. Radhakrishnan et al. Fuel 337 (2023) 126890

Table 4
Plastic wastes during slow pyrolysis.
Types of Ref Temperature catalyst Ratio of Feed Solid residue Liquid Gas Wax wt. Diesel wt. Gasoline wt. Monomer
Plastic no (oC) catalyst yield yield yield % % % recovery

HDPE [22] 450 No catalyst – 2 83 14 4 32 47 –

[22] 450 ZSM-5 20 3 35 66 0 0 35 –
[22] 450 Silica- 20 1 78 21 0 6 71 –
alumina
[21] 550 NONE 10 – 84 16 NA NA NA 11
[21] 550 HZSM5 10 1 17 72 NA NA NA 53
[16] 450 No catalyst 33 19 74 6 25 60 15 21
[16] 450 MCM 32 15 78 6 25 60 15 22
[16] 450 FCC 32 11 82 6 10 65 25 21
[16] 450 HZSM 31 4 81 15 23 62 25 21

LDPE [1] 425 No catalyst 10 42 45 11 <1 23 19 2

[1] 450 No catalyst 10 11 76 17 1 35 33 7
[1] 475 No catalyst 10 5 60 22 <1 36 27 16
[1] 425 HZSM-5 10 44 7 45 <1 <1 6 25
[1] 450 HZSM-5 10 11 16 72 0 0 15 44
[1] 475 HZSM-5 10 4 22 74 <1 <1 21 52
[1] 425 AL-MCM-5 10 48 40 10 1 6 30 7
[1] 450 AL-MCM-5 10 18 34 58 2 2 32 33
[1] 475 AL-MCM-5 10 4 42 54 1.3 4 36 36
[24] 550 NONE 10 – 93 14 NA NA NA 9
[21] 550 HZSM5 10 1 18 71 NA NA NA 59
[21] 550 HUSY 10 2 62 34 NA NA NA 22
[21] 550 HUSY 10 2 41 24 NA NA NA 31

PE [16] 500 Y-zeolite – 10 80 10 NA NA NA 4

[16] 500 ZSM-5 – 10 70 20 NA NA NA 5

PET [25] 550 No catalyst – 4 84 12 – – – –

PS [25] 550 No catalyst – 2 90 9 11 37 42 3

Table 5
Different plastic wastes during fast pyrolysis.
Type of Ref Temp Solid residue yield (wt. Liquid per wax yield Gas yield (wt. gasoline (wt. Diesel (wt. Wax (wt. Monomer recovery (wt.
Plastic No (oC) %) (wt.%) %) %) %) %) %)

PP [26] 668 3 43 54 40 – – 22
PP [26] 703 7 35 57 29 – – 25
PP [26] 746 5 29 66 36 – – 34
PE [26] 728 3 38 60 18 25 – 16
HDPE [26] 600 – 99 6 27 21 53 5
HDPE [27] 650 – 89 15 34 17 37 15
HDPE [27] 700 – 61 41 32 33 10 33
HDPE [27] 428 – 94 8 52 21 17 –
PP [27] 409 – 97 4 70 18 8 –
HDPE [28] 650 – 79 21 11 – 55 –
PVC [28] 740 48 27 16 – – – –

percentage than low pyrolysis, resulting in a short vapour residence time pyrolysis, which is carried out at temperature above 700 ◦ C. Benefits of
and fewer reactions of fracture. flash pyrolysis is that it occurs in milliseconds. Table 6 indicates that
Influence of temperature: Temperature is critical in the pyrolysis when plastic wastes are flash pyrolyzed, more gas is produced rather
process. Temperature increases gas yield, which can accelerate cracking than liquid. Flash pyrolysis may recover 75 wt% of monomers such as
processes while reducing oil output. Because of the kinetic mechanism ethylene and propylene, as mentioned by Kannan et al. [31] investigated
pyrolysis procedure, the temperature may affect the product’s quality. the temperature’s influence on monomer recovery by performing flash
Because of the conversion of long-chain paraffin into shorter molecules, pyrolysis of Low-Density Poly Ethylene in a micro-reactor with a mini­
high temperatures induce the creation of lesser waxy and higher oily mum volume transmission resistance at temperature between 550 and
compound. However, when temperature rises, decrease in the solid 950 ◦ C and a vapour residences period of 250 ms (olefin’s yield). They
residue yield is observed. According to plastic oil’s qualitative assess­ discovered that the temperature range between 950 and 1000 ◦ C is ideal
ment, high temperatures enable a rise in production of gasoline, which for recovering up to 68 % of monomers. Influence of vapor residence
correlates to a higher quantity of aromatic [29]. Production of propylene time [34]: The important parameters that impact the pyrolysis produc­
and ethylene increases as the temperature rises. tion yield and composition are temperature and vapour residence time.
Upgrading of pyrolysis plastic oil: Table 7 shows the judgment be­
4.3. Flash pyrolysis tween test plastic oil and diesel fuel derived from the mixed plastic
pyrolysis, comprising 58 wt% LDPE and HDPE, 27 wt% PP, 9 wt% PS,
The liquid product is converted to a gaseous product using flash and 5 wt% PET [58]. The distributions of carbon number the generated

6
K. Radhakrishnan et al. Fuel 337 (2023) 126890

Table 6
Different plastic wastes during flash pyrolysis.
Type of Plastic Ref Temp Vapor Residence time Wt. % of Liquid harvest Wt.% of Solid residue harvest Wt.% of the Gas harvest Wt. % of Monomer recovery
(oC)

LDPE [30] 900 0.75 – – 95 49

[27] 850 0.6 11.4 – 89 –
[31] 825 0.4 6 2 93 50.6
[32] 790 0.5 32.1 0. 63 66
[33] 1000 0.25 – – 100.3 77

production.
Table 7
Judgment of plastic lubricant and diesel - physicochemical properties.
6. Influence of various critical parameters over recycling
Properties Diesel Plastic oil
process: Pyrolysis method

Calorific value(mj/kg) 42 41 In Pyrolysis method, different parameters play a significant influence

Kinametic viscosity(cSt) 3.02 2.9
Flash point(oC) 50 46
on the product yield. Some elements impact the generation of ultimate
Calorific value(mj/kg) 42 41 final product such as gas, liquid oil, char, and pyrolysis of plastic.
Density (kg/m3) 820–850 734 Temperature, pressure, residence duration, reactor type, and catalyst are
Ash content (wt.%) 0.04 1 all essential characteristics. Controlling the parameter at various values
Cetane number 555 49
can result in the desired results.
Flash point (◦ C) 50 46
Fire point (◦ C) 56 51
Carbon residue (wt.%) 0.002 0.01
Aromatic content (wt.%) 11–15 32 6.1. Temperature
Carbon residue (wt.%) 0.002 0.01
One of the most significant factors in the process of pyrolysis is
temperature because it controls the breaking response of the chain of
Table 8 polymer. The bulk of the molecule are drawn together by the van der
Comparison of the fuel qualities of three types of gasoline fractions of HZSM-5 Waals attraction, as well as the temperature prevents them from
with different ratios of SiO2 / Al2O3. collapsing. The oscillations of the molecules in a system increase as the
SiO2/ Aromatics Olefins Benzene Octane Ref temperature rises, leading the molecule to use to evaporate from the
Al2O3 Volume % Volume % Volume % number surface of the object. A broken carbon chain occurs when the power
Required <35 <18 <1 95 [78]
generated by weak Van der Waals force along chain of polymers exceed
30 43.3 33.1 4.2 94.1 the temperature of the C–C bond in the chain according to Sobko et al.
80 13.5 61.2 1.3 86.7 [38].
280 6.9 68.9 0.46 85.9 Thermogravimetry analyzer was used to analyze and measure the
thermal degrading plastic behavior, which produces graphs which are of
two types. This thermogravimetry analysis curve (ie. T.G.) is one
plastic oil are as follows, according to the GC–MS results: Singh et al
example of a curve that analyses mass change as a role of time and
(2020) [5] found 35.4 wt% of C6–C9, 48.40 wt% of C10–C14, 13.216 wt
temperature. The derived thermogravimetry analysis (ie. D.T.G.) curve,
% of C15–C20, and 1.832 wt% of C20+. When pyrolysis plastic oil and
on the other hand, provides information on the deterioration phase that
diesel fuel are compared, the heating system and kinematic viscosity are
happened throughout the process, as shown by the number of peak
similar, but the plastic oil has a larger content of ash and a low cetane
points [37].
number than diesel.
In a study on the PET pyrolysis process, Cepeliogullar and Putun
et al., discovered that PET decomposition begins at 400 ◦ C, with a little
5. Degradation mechanism for pyrolysis of plastics
change in weight happening during temperature is in between 200 ◦ C
and 400 ◦ C. temperature at 4300 ◦ C, the materials loses least amount of
Cullis and Hirschler presented a comprehensive examination of the
weight [40]. As a result, PET degrades at temperatures between 3500
mechanism of polymer heat breakdown. The four techniques that have
and 5200 ◦ C. Similarly, while the substantial heaviness happened at two
been suggested are as follows: (i) end-chain scission or unzipping, (ii)
distinct temperature varieties, they did research on PVC and discovered
random-chain scission or fragmentation, (iii) chain stripping or side
that PVC might have various thermal behavior compared to other types
chain deletion, and (4) cross-linking. The molecular structure of the
of plastic. The first temperature range was 260 ◦ C to 385 ◦ C, which
polymer plays a significant role in determining the mode of decompo­
resulted in a limited weight loss of 63.25 % from the starting weight. The
sition that will occur: of char [80,81].
2nd temperature range, which was among 385 ◦ C and 520 ◦ C, resulted in
M*n → M* n − 1 + M(i) a weight decrease of roughly 21.74 % compared to the initial weight.
The weight loss of the material became minimal when the temperature
M*n − 1 → M* n − 2 + M(ii) was raised to 800 ◦ C (1.62 %). As a result, it was determined that the
Mn → Mx + My(iii) decomposition of PVC temperature is between 220 and 520 ◦ C [38].
According thermogravimetry analysis (T.G.) at various heating
Both Eqs. (1) and (2) reflect thermal degradation, however Eq. (3) values in the range from 10 ◦ C to 5 ◦ C/min, Chin et al., performed
shows the random degradation technique that occurs during polymer research on the HDPE pyrolysis process and observed that degradation
pyrolysis. The fourth type of process is known as cross-linking, and it is by thermal starts at 378 to 404 ◦ C and is finished at 517 ◦ C–539 ◦ C
one that typically occurs in thermosetting polymers during high tem­ [39,41]. Higher heating rates accelerate weight loss, resulting in a faster
perature heating. In this process, two neighbouring polymer chains that reaction time. Marcilla et al., discovered that HDPE has high breakdown
have been “stripped” might form a bond, which ultimately results in a occurred at 467 ◦ C in another thermal behavior research. This critical
chain network (a higher MW species). One such example is the temperature should be taken into account when using the pyrolysis

7
K. Radhakrishnan et al. Fuel 337 (2023) 126890

experiment to provide the better possible liquid yield [42]. cause more residues in the process. Excluding these, it is difficult to
Marcilla et al., studied on pyrolysis of LDPE and discovered that tiny discrete the residues from the substance at the completion of the trial.
quantity of liquid oil was generated when the temperature is kept in Sakata et al., employed batch reactors to investigate the PP and
between 360 ◦ C and 385 ◦ C. At 469 ◦ C–494 ◦ C, the greatest liquid yield is HDPE pyrolysis at 380 ◦ C and 430 ◦ C, respectively, in the presence and
obtained Marcilla et al., determined in another investigation that the absence of different types of catalyst. For some catalysts, via catalytic
most suitable temperature for obtaining high fluid oil was 550 ◦ C. The pyrolysis liquid oil was obtained which is even lesser than that produced
conversion of LDPE into oil began around 410 ◦ C, according to Onwudili from thermal pyrolysis, according to scientists [54]. In thermal pyroly­
et al. At temperatures below 410 ◦ C, a dark waxy substance appeared, sis, the yield of liquid from PP was 80 wt%, whereas the yield from
indicating that the oil conversion was incomplete. They discovered that HDPE was 69.3 wt%. The yield of liquid for both HDPE and PP was
for LDPE, the optimal temperature for obtaining the maximum liquid compact to 47–78.0 wt% and 49.8–67.80 wt%, individually, with the
was 425 ◦ C. As a result, it is established that LDPE thermal deterioration use of different catalyst for instance silica-alumina (SA-1) and HZSM-5.
occurred between 360 and 550 ◦ C [42]. However, using catalysts like mesoporous silica catalysts (FSM) and
According to Jung et al. PP has a lower thermal degradation tem­ silica-alumina (SA-2) boosted the yield of liquid for both polymers
perature than HDPE. They investigated the temperature’s effect on PP slightly greater than thermal pyrolysis, with an increase of roughly 1–7
and HDPE pyrolysis in a fluidized bed reactors and discovered that the wt%. As a result, various catalysts may react differently with different
HDPE and PP decomposition occurred between 400 ◦ C and 500 ◦ C using plastic types. However, it should be highlighted that the tendency for
derivative thermogravimetry analysis (DTG) curves. On comparing to coke to accumulate on surface of the catalyst may be one of the reasons
the fraction of HDPE, weight loss of the fraction of PP began at a low why the batch reactor catalyst’s efficacy has deteriorated over time [15].
temperature <400 ◦ C [28]. According to Marcilla et al., highest tem­ To pyrolyze PP at 450 ◦ C, Abbas-Abadi et al., employed semi-batch
perature for degradation of PP was 447 ◦ C, whereas the primary weight reactors using FCC catalysts. They observed that this experiment pro­
loss occurred at 467 ◦ C [42]. Jung et al., Theoretically, PP decomposed vided a 92.3 wt% liquid yield [55]. Seo et al. explored HDPE pyrolysis in
faster than HDPE as half of the C in the PP chain is tertiary C, making batch reactor with an agitator around 450 ◦ C. At 200 RPM, the stirrer
tertiary carbocation formation easier during degradation [28]. was whirling. Larger percentage of liquid oil was yielded on thermal
As a result of the preceding discussion, Temperature has been shown pyrolysis which would be equivalent about 84 wt% [56]. Furthermore,
to have the greatest influence on the rate of the reaction, which can the quantity of liquid product produced by catalytic pyrolysis employing
change the liquid, gas, and char product composition for all polymers. a comparable silica-alumina catalyst was greater than that obtained by
The product’s choice has a big impact on the required operating tem­ Sakata et al., which was 78 wt% vs 74.3 wt%. As a result, it was obvious
perature. A temperature of greater than 500 ◦ C is required. If a gas or that the stirrer in the batch reactor improved the mixing for the sub­
char outcome was sought, Fogler et al. was advised. If the liquid used stances and polymers within the reactor, hence increasing the liquid oil
instead, a temperature difference in the range between 300 and 500 ◦ C output [15]. Abbas-Abadi et al., conducted more research on semi-batch
was suggested, and this requirement is relevant to every polymers [45]. reactors with stirrers [55].
Batch, as well as semi-batch reactor, are the best reactors for updraft
6.2. Reactor types process of pyrolysis to create a higher liquid yield as the parameters can
be monitored easily, according to the literature review. However,
Reactor’s type has a big influence on how well the polymers and because coke growth on outermost layer of the catalyst, which would
catalysts mix, how long they stay in the reactor, how much heat they disturb the overall yield of the product, the reactor was not welcomed
transmit, and how efficient the reaction is at producing the end prod­ for catalytic pyrolysis. Furthermore, the batch method was better suited
ucts. In the laboratory conditions, most pyrolysis of plastic was done in for a laboratory experiment instead of larger-scale manufacturing as
semi-batch, batch such as Conical Spouted Bed Reactors (CSBR), fixed- high operation cost is required for feedstock recharge.
bed reactors, and fluidized bed. In the next subsections, the benefits
and drawbacks of each reactor will be examined. 6.2.2. Fixed and fluidized bed reactor
Even though it is cheap to install, it has some drawbacks, like the
6.2.1. Semi-Batch &Batch reactors inconsistent size of the particle and shape of the polymers which is used
Batch reactors are generally a method which is closed during the as feed, which might cause problems during the process feed. In addi­
reaction, without any reactant or product as input or outflow. One of the tion, the reaction has limited access for a catalyst’s surface area which is
major advantages of the batch reactor is that it may reach higher con­ available. Reactors are only used as secondary pyrolysis reactor in
versions by permitting the reactants to remain in the reactors for an particular instances. The products from principal pyrolysis may be
extended interval. The drawback of this batch reactor, according to simply supplied into fixed-bed reactor, which commonly contains the
Fogler et al., include product uncertainty from batch to batch-to-batch, gaseous and liquid phase. Using a two-step process, Fogler et al., Onu
cost of labor is high for each batch, and the large-scale manufacture is et al., and Vasile et al. investigated various plastic pyrolysis [45,58]. Few
difficult [45]. researches, however, are carried out in a two-step technique because it is
On considering, semi-batch reactors enable the possibility of reactant not expense and the results obtained are comparable to those obtained in
& product input. The semi-batch reactor has the advantage of allowing a single-step procedure [25,26,43,53,56,57].
reactants to be fed in desired time, improving reaction selectivity. Semi- Jung et al., selected fluidized bed reactors for PE & PP pyrolysis as it
batch reactors are better suited for smaller manufacturing since their delivers a practically steady temperature and high mass, resulting
labour costs are comparable to batch reactors. Certain scientists in py­ reactor with shorter holding time and a more homogeneous spectrum of
rolysis products laboratory-scale investigations preferred batch reactors goods. Pyrolysis of plastic in fluidized bed reactor was frequently carried
or semi-batch reactors because of their simple design and capacity to out at temperatures as less as 290 ◦ C–850 ◦ C for both catalytic and
easily manage operating parameters [25,44–52]. Pyrolysis in a batch thermal processes. Luo et al. examined the catalytic degrading of PP and
reactor a, as well as semi-batch reactor, is generally carried out at HDPE using a silica-alumina catalyst in a Fluidized Bed Reactor. Ac­
temperature around 300–800 ◦ C with both catalytic and thermal py­ cording to the author, PP generated an 87 wt% liquid composition at
rolysis. Several academics applied catalysts to polymers to increase 500 ◦ C, whereas HDPE generated an 85 wt% liquid composition. This
hydrocarbon production and enhance goods. In catalytic pyrolysis, the outcome was expected as the HDPE has better properties of strength
catalysts were mixed with the samples of plastic in a batch reactor. This compared to PP. As per outcome, a Fluidized Bed Reactor is decided to
approach’s downside is that coke tends to create on the catalyst’s sur­ be the best reactor for operating catalyzed plastic pyrolysis because of
face, reducing the catalyst’s efficacy over the time period and going to catalyst which can be reused multiple times without releasing it, which

8
K. Radhakrishnan et al. Fuel 337 (2023) 126890

is advantageous given the industry’s high catalyst cost. It’s also more higher temperatures. The carbon number dispersion of the liquid
flexible on compared to a batch reactor as continuous operations may product changed to the low-molecular-weight- molecular - weight side
eliminate common raw material trying to charge and the process doesn’t when the pressure became high. Furthermore, the rate of creation of
have to be restarted as frequently. As a result, a Fluidized Bed Reactors double bonds was influenced by pressure. Pressure had a direct influ­
will be the best reactor for larger-scale operations from an economic ence on the disparition rate of C–C link in the polymer, according to
aspect [28,59,60]. Murata et al. When pressure was increased, the frequency of double
bond formation decreased, suggesting that pressure used to have a direct
6.2.3. Conical spouted bed reactor (CSBR) impact on the disparition rate of C–C link in the polyethylene. They
CSBR delivers excellent agitation with the capacity to handle a wide likewise noticed that pressure had a larger effect on residence time at
range of particle size, large particles, and particle density discrepancies minor temperatures. When the temperature rose over 430 ◦ C, however,
Fogler et al. [45]. According to Olazar et al., the CSBR had less attrition the effect of pressure on the duration of the stay became less obvious
and bed segregation compared to bubbling fluidized bed [61]. While [63]. Residence time is described as the normal period of time particles
using sticky substance, it also has significant transfer of heat among consume in the reactor, and it has an impact on product dispersion. A
phases and minimal defluidization difficulties. Moreover, numerous longer residence time increases primary product conversion, leading in
technical issues have developed in the functioning of this reactor, such more high thermal stability products such as low molecular weight hy­
as B. catalyst supply and section specifies (solid and liquid), making it drocarbon and non-condensable gas. Although the holding time has no
less cost-effective. Furthermore, it is problematic due to the high oper­ effect on product dispersal until that point, the process has a tempera­
ating expenses associated with its sophisticated design, which necessi­ ture limit that may alter product supply. Mastral et al. analyzed the
tates the employment of several motors in the system. Elordi et al., impact of dwell time and temperature on the distribution of HDPE
employed CSBR to execute pyrolysis of HDPE at 5000 ◦ C with a HY thermal fracturing products in a fluidized bed reactors. It was revealed
zeolite catalyst, leading in a gasoline percentage of 68.7 % (C5–C10), as that when the temperature is much <685 ◦ C, a longer residence duration
represented in Fig. 4 [62]. The oil has such an octane level of 96 RON, (2.57 s) resulted in significantly greater liquid yield. The residence
which was close to the regular grade. Arabiourrutia et al. on the other duration had less of an influence on the solid and vapour generation at
hand, used the CSBR to investigate the wax production and character­ temperatures over 685 ◦ C [64]. As a consequence, temperature and
ization of PP, LDPE, and HDPE pyrolysis at 450–600 ◦ C [19]. They residence time were discovered to be temperature-dependent factors
claimed that CSBR could handle sticky materials that would be tough to that may affect the delivery of plastic pyrolysis products at lower tem­
manage in a Fluidized Bed Reactor. The bubble bed concept was peratures. Greater pressure improved gaseous product yield and altered
particularly well suited to wax production using low-temperature py­ the molecular mass of mutually solid and vapour products, albeit this
rolysis. The wax production reduced as the temperature rise, according impact was only visible at high temperatures. According to the literature
to the authors. More wax is fractured into the gaseous or liquid products review, the bulk of studies focused on the thermal component of plastic
at rising temperatures. At approximately 80 wt%, LDPE and HDPE wax pyrolysis at air pressure. The residence time was not increased during
production are relatively equal, however PP wax production was greater the research since the influence might grow into low noticeable at higher
at a lower temperature of around 92 wt%. temperatures. Furthermore, from an economic aspect, network adapters
such as a compressor and a pressure gauge must be added to the entire
system. The cost of the procedure will increase if the issue of pressure is
6.3. Residence time and pressure included. However, depending on product distribution option, these two
characteristics should be considered, particularly while running at high
At a temperature increases of 0.1–0.8 MPa, Murata et al. examined speeds when operating at temperatures below 450 ◦ C.
the impact of stress on the pyrolysis HDPE result in continuous stirred
tank reactor. The gaseous product grew considerably from around 6 wt%
to 13 wt% at 410 ◦ C when the pressure was increased from 0.1 to 0.8
MPa, but only marginally from 4 wt% to 6 wt% at 440 ◦ C. This suggests
that pressure had a substantial influence on the gaseous product at

Fig. 4. Diagram of CSBR.

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K. Radhakrishnan et al. Fuel 337 (2023) 126890

6.4. Catalysts [66].

The yield of aromatics and light alkanes is also increased when the
6.4.1. Significance of catalysts ratio of SiO2 / Al2O3 in zeolite is reduced. Table 9 compares the gasoline
Acceleration of a chemical reaction is while remaining unaltered at fraction fuel qualities achieved with three kinds of HZSM-5 zeolite with
the conclusion is done by catalyst. Catalysts are frequently utilized in varying SiO2/Al2O3 ratios. As shown, the greatest tartness catalyst with
businesses and research to boost product selectivity and optimize the lower ratio of SiO2/Al2O3 resulted in a higher-octane number,
product dispersion. As a result, catalytic squalor is particularly greater aromatics, and benzene content, although lower dilution of
appealing for obtaining commercially valuable chemicals for example olefins. The scarcity of sulfur in the fuel composition allowed it to be
automobile fuel (gasoline and diesel) and C2–C4 alkenes, which are in combined with refinery stream to satisfy the EU standard, regardless of
high necessity in the petrochemical sector. When a catalyst is utilized, the fact that the octane number was lower and the aromatics, benzene,
the process’ initiation energy is reduced, resulting in a faster reaction and olefins standard exceed the European Union (EU) criteria (see
rate. As a result, the catalyst lowers the optimal temperature required, Table 10).
which is critical since the pyrolysis process consumes a lot of energy (it’s HMOR and HUSY are two more zeolite catalysts that are commonly
extremely endothermic), which makes it difficult to commercialize. utilized in plastic catalytic pyrolysis, in addition to HZSM-5. Garforth
Because heat is one of the most expensive factors in the sector, using the et al., examined the efficacy of three zeolite catalysts for HDPE pyrolysis:
catalyst might help save energy. Aside from that, numerous studies HZSM-5, HMOR, and HUSY, using a polymer to catalyst ratio of 40 %.
employed the catalyst to increase the hydrocarbon dispersion with the HZSM-5 was shown to have better activity of catalyst than HMOR and
aim to generate liquid which is pyrolyzed with qualities same as tradi­ HUSY in their experiments, owing to the little amount of residue left by
tional fuels such as diesel and gasoline. HZSM-5 (approximately 4.53 wt%), compared to 7.07 wt% & 8.93 wt%
Using heterogeneous catalysts changes the plastic waste conversion residues left by HMOR and HUSY, respectively. This demonstrates that
route differently from thermal degradation. These catalytic materials HZSM-5 outperforms other zeolites in terms of total product converted
have shown to be effective in the process of valorizing waste biomass. in plastic pyrolysis [67].
Using catalysts to activate high-energy bonds, these systems efficiently Distinct zeolites may have different product preferences in terms of
turn large biomass macromolecules into products with higher value. selectivity. Marcilla et al., investigated the working of HUSY and HZSM-
Heterogeneous catalysts can be used in the plastic waste conversion 5 on LDPE and HDPE in a batch reactor at a persistent temperature of
process to produce the desired liquid oils and gaseous hydrocarbons. 550 ◦ C and 20 wt.% polymers to catalyst ratio [68]. When compared to
Further, heterogeneous catalytic systems can help vary selectivity be­ HZSM-5 catalyst (HDPE = 17.3 wt%, LDPE = 18.3 wt%), HUSY catalyst
tween and within the two fractions by adjusting the catalyst acidity and recovered more liquid oil (HDPE = 41.0 wt%, LDPE = 61.6 wt%). The
pore structure. In the following sections, we will discuss the different HZSM-5 catalyst, on the other hand, produced a greater gaseous product
heterogeneous catalysts that have been investigated for the conversion (HDPE = 72.6 wt%, LDPE = 70.7 wt%). This demonstrates that product
of plastic waste and their effects on the end product. selectivity varies depending on the catalyst. Lin and Yen [70] found a
similar trend of product selectivity in PP pyrolysis utilizing the HUSY
6.4.2. Types of catalysts zeolites and HZSM-5.
The major two types of catalysts are heterogeneous (many phases are The influence of HZSM-5 on HDPE pyrolysis at 450 ◦ C with a cata­
involved) and homogeneous (just one phase is involved). Classic Lewis lytic to polymer ratio of 20 % was investigated by Seo et al. HZSM-5 had
acids, such as AlCl3, have been utilized as a homogeneous catalyst for a lower water yield of around 35 % but a higher gaseous output of 63.5
polyolefin pyrolysis [63]. However, due the liquid product combination %, according to the researchers. Hernández et al. found an even lower
can be clearly removed from the solid catalysts, heterogeneous catalyst liquid harvest of near 4.40 wt% and 86.10 wt% gaseous emission while
is the most commonly utilized. As a result, the heterogeneous catalyst is conducting HDPE pyrolysis at 500 ◦ C with the same catalytic to polymer
more cost-effective since diverse catalysts are expensive, and their reuse ratio as Seo et al. Lin and Yen employed HZSM-5 & HUSY zeolite cata­
is required. Zeolites in form of nanocrystalline, typical acid solids, meso- lysts in PP pyrolysis at 360 ◦ C with a catalyst to polymers ratio of 40 wt%
structured catalysts, metal assisted on carbon, and basic oxides are all to get a little amount of liquid product. Only 2.31 wt% and 3.75 wt% of
examples of heterogeneous catalysts, according to Aguado et al. [84]. liquid yield were achieved, respectively. Nonetheless, HZSM-5 showed
HUSY, HZSM-5, Hb, and HMOR are examples of nanocrystalline zeolites better coking resistance than HUSY catalyst when the product gas, such
that are commonly employed in plastic pyrolysis research. Non-zeolites as isobutane & isopentanes, stayed unchanged during operation while
catalysts including MCM-41, silica-alumina, and silicalite have also the olefins grows (pentene & butane) [56,68,69].
gotten a lot of interest in recent studies. As a result, the three main kinds Apart from direct plastic cracking, several researchers have looked at
of catalysts utilized in Single-atom catalysts (SAC), zeolite, plastic py­ the efficacy of zeolite catalysts in a two-step reaction method incorpo­
rolysis, and FCC, will be described in upcoming subheadings. rating heat and catalytic reactors in order. Aguado et al., investigated
the catalytic conversion of LDPE in a batch and fixed bed reactor in a
6.4.2.1. Zeolite catalyst. Glassy aluminosilicate strainers with open two-step reaction process. The batch reactor would break the plastic,
holes that have ion-exchange properties are known as zeolite. The and the vapors would be transferred to the fixed-bed reactors, where the
structure is made up of a 3D framework that connects the tetrahedral 10- wt% HZSM-5 catalysts would be installed. Pyrolysis was carried out
sides with oxygen atoms. Depending on the kind, different ratios of at temperatures ranging from 425 to 4750 ◦ C. According to the findings,
SiO2/Al2O3 are used to construct it. The zeolite reactivity is determined catalytic reforming using a zeolite catalyst resulted in a considerable rise
by the SiO2/Al2O3 ratio, which influences the pyrolysis end product. in the gas percentage. At the greatest temperature, the gaseous product
Artetxe et al., demonstrated that the HZSM-5 zeolite’s SiO2/Al2O3 had grown to 74.3 wt%, but only 21.9 wt% of liquid hydrocarbons had
ratio had a significant impact on the product yield fraction in HDPE been recovered [84]. As a result, the observed trend was strikingly
pyrolysis. The zeolite’s strong acidity was suggested by the low SiO2/ similar to that of direct catalytic cracking, which created a large quantity
Al2O3 ratio. When compared to the lowest acidic catalyst (SiO2/Al2O3 = of gaseous state product when the HZSM-5 catalyst was applied. Finally,
280), the most catalyst which are acidic (SiO2/Al2O3 = 30) was more it’s worth mentioning that using zeolite catalysts in plastic pyrolysis
vigorous during breaking waxes, resulting in greater light olefins and a merely increased the amount of volatile hydrocarbon produced. HZSM
reduced high percentage of C12–C20. The light olefins yield increased was advised for increased efficiency and longer cycle times since the
from 35.5 till 58.0 wt% when the ratio of SiO2/Al2O3 was reduced from catalyst’s deactivation rate was exceptionally low, making it more
280 to 30, but the harvest of C12–C20 declined from 28.01 to 5.30 wt% economical for regeneration.

10
K. Radhakrishnan et al. Fuel 337 (2023) 126890

Table 9
Plastic pyrolysis summary.
Plastic- Reactor used parameters Yield of oil (wt. Yield of Gas (wt. Yield of Solid (wt. Ref.
type Pressure Temp Time Heating rate(oC/ %) %) %) No.
(oC) duration mins)

PET Fixed Bed – 500 – 10 23.1 76.9 0 [78]

– 1 atm 500 – 6 38.89 52.13 8.9 [78]
Horizontal steel – 350 30 20 80.88 17.24 1.88 [79]
Semi-batch 1 atm 400 – 7 82 16 2 [80]
batch – 450 60 – 74.5 5.8 19.7 [80]
HDPE Semi batch 1 atm 450 – 25 91.2 4.1 4.7 [77]
Fluidized bed – 500 60 – 85 10 5 [61]
Batch – 550 – 5 84.7 16.3 0 [72]
Fluidized batch – 650 20–25 – 68.5 31.5 0 [72]
PVC Fixed bed – 500 – 10 12.3 87.7 0 [37]
Vacuum bed 2 kpa 520 – 10 12.79 0.34 28.14 [80]
Pressurized 0.8–4.3 425 60 10 89.5 10 0.5 [1]
batch Mpa
Batch – 430 – 6 75.6 8.2 7.5 [79]
LDPE – 1 atm 500 – 3 80.41 19.34 0.16 [82]
Fixed bed – 500 20 10 95 5 0 [79]
batch – 550 – 5 93.1 14.6 0 [72]
Fluidized bed 1 atm 600 – – 51.0 24.2 0 [78]
Horizontal steel – 300 30 20 69.82 28.84 1.34 [79]
Batch 1 atm 380 – 3 80.1 6.6 13.3 [43]
PP Semi-batch 1 atm 400 – 7 85 13 2 [77]
Semi-batch 1 atm 450 – 25 92 4.1 3.6 [78]
– 1 atm 500 – 6 82.12 17.76 0.12 [78]
batch – 740 – – 48 49.6 1.6 [80]
Pressurized 1.36 Mpa 425 60 10 97 2.5 0.5 [81]
PS batch
Semi batch 1 atm 400 – 7 90 6 4 [72]
Batch – 500 150 – 96.7 3.27 0 [82]
batch – 581 – – 89.5 9.9 0.6 [80]

petroleum and acceptable gasoline fraction. ’Spent FCC catalyst’ is FCC

Table 10
catalyst that has been utilized and may generally be achieved from in­
Diesel, plastic oil and hydrogenated plastic oil – physioco-chemical properties.
dustrial FCC procedures in petroleum refineries. It is useful and maybe
Properties Upper Plastic Hydrogenated Diesel Low Limit reused in the pyrolysis process despite various levels of pollution. In a
Limit Pyrolysis Plastic Standard
stirred semi-batch reactors at 400 ◦ C, Kyong et al., studied the influence
Standard Oil Pyrolysis Oil EN590
En590 of wasted FCC catalyst on the pyrolysis of PS, LDPE, PP and HDPE. 200 g
of reactants is added with 20 g of catalyst and heated at a rate of 7 ◦ C/
Pour point – − 30 − 20 − 15 –
(oC)
min [72]. As a consequence, all polymers generated over 80 % fluid oil,
Density 840 771 851 837 820 with PS producing the most (around 90 wt% liquid yields). The fluid
(Kg/m3) yields were grouped in this sequence depending on the plastic types: PS
Calculated – 60 62 52 46 > PP > PE (HDPE, LDPE). The yield of gas phase products was in the
Cenane
opposite order from that of liquid products, as follows: PE > PP > PS.
index
Kinematic 4.5 1.78 3.5 2.31 2 Because PS included a benzene ring, which formed a more stable
viscosity structure, it was less fractured than the gaseous product. Overall, it was
(mm2 /s) shown that wasted FCC catalyst still has good catalytic activity, with
Fire point – 30 72 82 – liquid yields more than 80 % for samples of all plastics. It is also cheap as
(oC)
Flash point – 20 65 72 55
the catalyst can be reusable.
(oC) The efficiency of wasted FCC catalyst in comparison to HDPE ther­
Wt. % of 0.1 0.01 0.01 0.01 – mal pyrolysis without catalyst was tested using the similar factors as
Content Kyong et al., but at a greater temperature of 430 ◦ C. The liquid oil
of Ash
production rise slightly from 75.5 to 79 wt%, but the gas phase product
Conradson – 0.1 0.1 0.18 –
carbon decreased slightly from 20.0 to 19.4 % wt. % when the catalyst was
residue utilized, according to the results of the experiment. With the catalyst
(wt.%) present, however, the quantity of residue solid left decreased dramati­
Gross – 45 45 46 – cally from 4.5 to 0.9 wt%. Furthermore, when the first fluid develop­
calorific
value
ment was seen at around 350 ◦ C, catalytic pyrolysis decreases the
(Mj/kg) reaction temperature of HDPE. The first liquid was generated after 30
min of non-catalyzed pyrolysis at 430 ◦ C. This means that using leftover
FCC catalysts in thermal pyrolysis improved the overall product con­
6.4.2.2. Fluid catalytic splintering. Non-zeolite acid matrix is used to version while also increasing the pace of reaction [72].
make the binder and crystals of zeolite is commonly known as Si-Al. Due To increase liquid oil output, FCC catalysts were advised to be used in
to its excellent thermal stability and product selectivity, Zeolite-Y has plastic pyrolysis. In terms of cost, the use of the “used FCC catalyst” was
been the major components of FCC catalyst over more than 40 years also advantageous. However, to avoid dominance of coke and gaseous
[69]. In the petroleum refining business, FCC catalyst is often employed product, the ratio of catalyst/polymer must be within 20 % by weight.
to fracture heavy oil fractions into simpler and more LPG from crude

11
K. Radhakrishnan et al. Fuel 337 (2023) 126890

6.4.2.3. SAC-Single-atom catalysts. In order to attain a more sustainable in a 500 mL beaker to be washed. To eliminate metals that might clog
future, it is very necessary to work on the development of catalytic the pores, the samples of carbon were immersed in 200 mL 0.1 N HCl
processes that are both more effective and less harmful to the environ­ was continuously stirred using magnetic stirrer for at least 4 h. After
ment in order to convert biomass into chemicals with added value. In soaking, the AC sample was rinsed with deionized water until it reached
recent years, cutting-edge single-atom catalysts (SACs) and single-atom a neutral pH 6–7. AC sample was dried for at least 24 h at 105 ◦ C in an
alloys (SAAs) have proven to be promising materials to overcome the oven. In a single neck flat bottom flask which is of 500 mL volume, 10 g
issues associated with conventional catalytic approaches, and their of AC and 150 mL of concentrated sulfuric acid (96 % H3PO4) were
utilisation in the process of biomass valorization has become a field that added for the sulfonation procedure. Using an oil bath, the flash was
is experiencing rapid expansion. The Catalytic co-pyrolysis method were heated at 100–140 ◦ C for 300 min with steady stirring. For each
employed in the existence of single-atom catalysts (SACs) to convert experimental run, in a reflex system, the reaction was carried out about
plastics waste into highest yield fuels. Bronsted acid spots with ionic 5–9 h, depending on the specified parameters of the reaction. The
hydrogen atoms and Lewis acid sites that accept electrons are found in samples were cooled to room temperature after the reaction and the
the unorganized acid catalyst silica-alumina. The mole ratio of SiO2/ samples were transferred to a beaker that contains DI Water in it. Vac­
Al2O3 is used to determine the acid content of a silica-alumina catalyst. uum filtration was used to separate the mixture once it had cooled down.
Silica-alumina’s acidic strength, unlike zeolite, is determined in other Using hot DI water (>80 ◦ C) the solid residues were washed until no
direction, with a higher SiO2/Al2O3 ratio suggesting a high acid sulfate ions were identified using wash water. The sulfate ions were
strength. Spite of the fact both are commercial silica-alumina, SA-2 detected using barium chloride (BaCl2). To make the SAC-based catalyst,
(SiO2/Al2O3 = 4.99) has a higher tartness than SA-3(SiO2/Al2O3 = the sample which is washed was dried at 105 ◦ C for at least 36 h.
0.27). The acidity of the catalyst has a significant impact on the ultimate Synthesis of Al/Fe2O3 nanocomposites: Commercial coconut shell
finished manufactured goods of pyrolysis plastic. Sakata et al., looked Activated Carbon, with 852 m2/g surface area and a pore capacity of
into the catalytic effect of acidity (ZSM-7, SA-1, SA-3) on the allocation about 0.42 cm3/g, is acquired from Aladdin and employed as a support
of pyrolysis of HDPE products. With 10 g of HDPE and 1 g of catalyst, the for catalysis, according to LijunJin et al. [81]. The Activated Carbon was
testing was performed in a semi-batch reactor around 430 ◦ C⋅NH3 mashed and mesh sieved to 80e100, and vacuum oven-dried at 110C for
Thermal Desorption (TPD) was used to measure the acidity of the cat­ 6 h before Fe and Al2O3 were added. A standard impregnation process
alysts, and the findings were as follows: SA-2 > ZSM-7 > SA-3. As an was used to make supported Fe and Al2O3 catalysts. In a nutshell, the
output, it was seen that SA-3 catalyst with low acidity produced high oil appropriate quantity of Al(NO3)3 and Fe(NO3)3 metal salts were first
(74.3 wt%), observed by SA-2 (67.8 %), and ZSM-7 (57.8 %). (49.8 wt dissolved at room temperature in a solution combined of 10 g ethanol
%). ZSM-7 generated more vapors but had a lower water yield than the and 30 g of distilled water. To remove the solvent, immediately the
other 2 acid catalysts because it had more acid sites. Uddin et al., mixture was evaporated at 85 ◦ C for 2 h before being vacuum dried
examined the effect of SA-3 on LDPE and HDPE at same temperatures around 120 ◦ C for 2 h. The samples which were dried was exposed to
and catalyst-polymer ratio. Their liquid oil production figures were heat at 250 ◦ C for 30 min, then to 350 ◦ C at 3 ◦ C/min for 30 min, then to
quite similar to those of Sakata et al., When the SA-3 catalyst was uti­ 600 ◦ C for 60 min, and finally to 870 ◦ C for 120 min under an N2 at­
lized, pyrolysis of HDPE and LDPE yielded 77.4 wt% and 80.2 wt%, mosphere of 100 mL/min. xFeyAl/ AC was the name given to the
individually [71]. The lower amount yield of liquid observed was ex­ resulting samples (x is the mass % of Fe metal; y means the mass % of
pected due to HDPE’s linear chain, which made it stiffer than LDPE. Al2O3 in the catalyst). For contrast, the samples with 40 wt% Fe loading
Sakata et al., tested the efficacy of SAC upon PP around 380 ◦ C, in was just heated upto 450 ◦ C and maintained for 60 min for decompo­
addition to HDPE and LDPE, but this time with two different catalyst sition of nitrate with N2 environment, resulting in Fe/AC-40 percent.
interaction modes: vapor and fluid stage [13]. The substance was Without any additional H2 reduction, the resulting samples were
combined with a PP pallet and filled in the batch reactor as liquid stage. crushed and sieved to an 80e100 mesh as the catalyst.
In contrast to the vapor, the catalyst was suspended over a stainless-steel
net 10 cm from bottom of the reactor. They discovered that the catalyst 7. By-products of plastics
in liquid mode generated a greater liquid product (68.8 wt%) than the
SAC because the waxy residue dissolved into lighter hydrocarbon. In the The by-products obtained by the plastics pyrolysis are gas and char.
vapour phase, however, the catalyst produced a greater gaseous product In pyrolysis, numerous factors like heating rate, temperature, pressure,
(35 wt%) because the hydrocarbon further degraded into the gas phase and residence duration have an important impact on the proportion of
product over the SAC. As a result, the catalyst mode was a critical by-products. Below is some information on the by-products that were
component to consider, as it altered the distribution of the end product produced.
in plastic pyrolysis.
Synthesis of crystals: SAC-catalysts were made in two steps: (1) the 7.1. Char
synthesis of activated carbon (AC) and (2) the sulfonation of the AC. The
modified process reported was used to produce AC. In a 500 mL beaker, In general, a slow rate of heating at a very lower temperature and a
the corncob was soaked in 56.50 % H3PO4 as the chemical activating longer residence time will maximize char in the process of pyrolysis.
agent. The samples were placed in the fume hood and coated with While formation of char is generally low in the rapid pyrolysis process,
paraffin film for 24 h. In a 500 mL beaker, in phosphoric acid (56.50 % consideration should be given to the belongings and uses of char to boost
H3PO4) the corncob was soaked, here the H3PO4 acts as the activating the pyrolysis of plastic potential. Jamradloedluk et al., investigated the
chemical agent. The samples were placed in the fume hood and coated charring characteristics of HDPE plastic waste generated during pyrol­
with paraffin film for 24 h. After that, the samples which are impreg­ ysis. A closer analysis showed that volatile constituents and solid carbon
nated were put in a 105 ◦ C oven overnight. The precursors which are are the main components of coal (>97 % by weight), while ash and
activated were carbonized in a microwave oven (Sineo MAS-II batch moisture are the minorities [74]. Coal’s calorific value was approx.
2.45 GHz) after chemical activation. The microwave oven was filled 18.84 MJ / kg. In addition, the lower sulfur content makes it suitable for
with impregnated samples in a three-neck quartz flask reactor which is fuel use, for example when burning with coal or some other wastes Jung
with a volume of 500 mL. An illustration of the carbonization system et al., noted that carbon creation increased with increasing temperature.
which is microwave-assisted may be seen elsewhere Nitrogen with 99 % The formation of char increased from 2 wt% to 4 wt% During the PP
purity was purged in the reactor for 30mins at 1000 mL/min prior to pyrolysis and from 0.7 wt% to 2 wt% [28]. During the PE pyrolysis with a
pyrolysis [80]. At 700 W microwave power, the process of carbonization rise in temperature from 6680 ◦ C to 7460 ◦ C. Sadly, up to 98.9 % of the
was set at 450 ◦ C for 30 min. The collected carbon products were placed char formed from both polymers was made up of inorganic components,

12
K. Radhakrishnan et al. Fuel 337 (2023) 126890

which came from inorganic compounds in the raw - materials portion. 7.3. Oil
Use of char as a fuel proved challenging in this case due to the significant
amount of inorganic elements. It may, however, be utilised as a road­ The primary goal of this review paper was to examine how a number
ways as a construction material. of factors can affect the ability to produce large quantities of high-
The charred can be used as an adsorptive in bath water purification quality oil. The study by Chen et al. [88] titled “Use of supercritical
to eliminate metal particles through enhancement processing. Bernando water for the liquefaction of polypropylene into oil” was deemed to be
et al., studied the multistage enrichment of semi-coke through the highly thorough in its examination of the impact of time and tempera­
combined pyrolysis of plastic waste PP, PE, and PS. The enhanced ture on the distribution of the product, as well as its comparison of the
charcoal’s adsorption characteristics were investigated, and the results elemental analysis of the liquid product created with the fuel that is
revealed that the charcoal was primarily a porosity and super hygro­ currently in use. High oil products with yields of up to 91 % are achieved
scopic with methylene blue dye adsorption capacities ranging from 3.59 at temperatures of 425 and 450 ◦ C, after a reaction period of 120 and 30
to 22.2 mg/g. This suggests that the enhanced characters must be min, respectively. The oil yield has a larger H/C ratio than gasoline and
excellent at adsorbing large particles. As a result of the coal upgrading diesel, but its higher heating value (HHV) varies from 46.3 to 49.3 MJ/
procedures, the carbon wastes from pyrolysis may be utilised as pre­ kg, making it competitive with gasoline’s HHV (47.7 MJ/kg), indicating
cursors for the adsorbents [75]. Other possible uses for pyrolysis coal its good quality. It has been demonstrated that the properties of con­
include as a feedstock for activated carbon synthesis and as a dry fuel for ventional fuels are similar to one another in terms of heating value,
boilers. density, viscosity, boiling point distribution, and carbon number [73].
Similar results were seen with the oil refined by the liquefaction tech­
7.2. Gas nique from recycled plastics. Thus, there is a good possibility that the oil
can be further processed into a different fuel. Estimates for energy use,
As per Prabir et al., the optimal conditions for maximum gas gen­ energy efficiency (Eout/Ein), and GHG emissions from a variety of
eration in the pyrolysis process were high temperatures and lengthy recycling processes and systems are provided in Table 8. Though it re­
residence durations. These circumstances, on the other hand, are dia­ quires a relatively low quantity of process energy input, the liquefaction
metrically opposed to the criteria utilized to optimize oil output [76]. In method has been cited for its great energy efficiency [89].
practice, gas generation in the polyolefins pyrolysis and PS plastics is
minimal, ranging from 5 to 20 % by weight, and is highly dependent on 8. Advantages and dis advantages of pyrolysis process
the type of polymers in the pyrolysis and temperature. Onwudili et al.,
looked at the effects of temperature and various kind of plastics [44] like Pyrolysis plants, as opposed to traditional incineration plants, can be
LDPE, PS, and combinations of these materials in pyrolysis. The gas situated geographically close to the place of generation, and they do not
released by the combination at 350 ◦ C was found to be greater than the generate any toxic dioxins in the process. In addition, pyrolysis facilities
pyrolysis of separate polymers. At 425 ◦ C, the gas generation increased are highly effective at transforming trash into valuable goods, such as
to 8.6 wt%, which was greater than PS pyrolysis alone but lesser than synthetic oil that may be used as fuel. Pyrolysis plants, as opposed to
LDPE. Pyrolysis of PS generated some coal but no considerable gas incinerators, which burn trash at extremely high temperatures, use a
products at the same temperature. Pyrolysis of LDPE, on the other hand, process that takes place at a lower temperature and, as a result, produce
generated more gas except coal during this temperature. As a result, the fewer harmful byproducts and lower levels of carbon emissions. Because
author remark that the amount of gas generated by the combination had this technology enables rapid conversion of a wide variety of raw ma­
a substantial impact on the LDPE component, whereas coal composition terials into bio-oil, it is essential that it be capable of controlling the
is closely associated to PS. The plastic mixture’s gas output was gradu­ reactor. In power plants and other industrial settings that use steam
ally raised to 12.8 wt% at 4500 ◦ C. boilers or internal combustion engines, pyrolysis oil that is created as a
When PET and PVC plastics are pyrolyzed, they produce a lot of gas byproduct of the conversion of solid waste has showed promise as a
comparing to other polyolefin plastics and polystyrene. The quantity of viable alternative energy source. Finding effective options for getting rid
gas formed during the pyrolysis of plastic waste PVC (87.7 % wt.%) and of solid wastes is something that should be done, as there is a growing
PET (76.9 % wt.%) is substantially larger than yield of liquid at 5000 ◦ C, population, more garbage, and less room available in landfills [85].
according to [65,77] found the same pattern during pyrolysis of PET at One of the drawbacks is that the method results in higher overall
constant temperature when 52.130 wt% of the Gas result was stored. costs. This indicates that it is only financially feasible for businesses that
This implies that PVC and PET have primarily degraded at this tem­ have substantial quantities of garbage that they can transform into
perature as a gaseous product. PET only required a small amount of biofuel. It is important to keep in mind that this process calls for a steady
energy to convert to other chemical structures, resulting in higher gas supply of fuel; if the facility is unable to obtain sufficient waste material
generation during pyrolysis. Alternatively, during the pyrolysis of PVC, for processing, it will not be able to operate at its maximum capacity. In
a dehydrochlorination phase might occur, resulting in a large volume of spite of this, when the benefits and drawbacks of the process, in terms of
gas being emitted rather than on the product in liquid phase. both the environment and the economy, are compared with one another,
The components of the gas is determined by the feeding material. it is difficult to say that pyrolysis and other processes that are analogous
[78] investigate the pyrolysis of PVC, PET, HDPE, PS, PP, and LDPE to it are the processes of the future. They offer solutions to such a wide
separately and discovered that methane, ethane, hydrogen, ethene, variety of issues that it is well worth the effort required to surmount the
propane, butene, and butane were the primary gas components formed difficulties that are inherent to their business model. This is due to the
during pyrolysis of each plastic. PET, on the other hand, additional gas fact that the advantages of dealing with plastic waste in this manner
components are produced such as carbon monoxide and carbon dioxide, considerably outweigh the disadvantages. The toxic fugitive emissions
while PVC additionally formed hydrogen chloride. The calorific value of are released during the polymerization process. In many urban areas,
the gas generated during the pyrolysis process is also considerable. Ac­ plastic trash is routinely burned in the open, releasing harmful fumes
cording to Jung et al., the gas generated by PE & PP pyrolysis only has a that harm the ecosystem. Carbon monoxide, chlorine, hydrochloric acid,
greater calorific value of 42.0 to 50.1 MJ/kg. As a result, the pyrolysis amines, nitride, styrene, benzene, butadiene, CCL, and acetaldehyde are
gas has a lot of promise as a source of heat in pyrolysis plants. Addi­ just some of the many harmful pollutants that can be released. Trash
tionally, if isolated from other gas components, ethene and propane can made of thermo-set plastics like SMC and FRP, as well as multi-layered
be used as a chemical raw material to generate polyolefins. Pyrolysis gas and metalized bags and sachets, presents a variety of difficulties when it
may also be utilized to generate energy in gas turbines and for direct comes to disposal. Mixed trash, especially when it contains plastic, is a
ignition in boilers without requiring flue gas treatment [28]. source of interference and challenges for landfills, recycling centres, and

13
K. Radhakrishnan et al. Fuel 337 (2023) 126890

solid waste treatment facilities. Estimates for the years 2018–2019 say 9.5. Catalytic degradation
that the 70 largest cities in India make about 6,000 metric tonnes of
plastic trash every day [86,87]. The creaking reaction is carried out using specific catalysts in the
catalytic degradation process. The catalyst presence in the reactor re­
9. Other recycling process duces the temperature and time of the reaction. The technique produces
a product with a significantly narrower C atom number distribution and
9.1. Gasification a peak at lighter hydrocarbon, which occurs at low temperatures. To
make procedure more appealing from an economic standpoint, the cost
Gasification is the use of gasification agents to convert liquid C-based should be cut further. This technique might be improved by reusing and
materials, solid into gaseous products which is combustible. Through a actual catalysts in smaller amounts. This technology might be evolved
number of heterogeneous processes, a gasification is able to have a into a cost-effective trade polymers recycling procedure to address the
direct the fuel to be fast converted into gas. Gasification is a two-step pressing ecological issue of plastic waste dispersal. It also has a stronger
process that starts with the biomass which is partially combusted to plastics breaking capacity and a reduced solid residue content in the
produce char and gas, then uses charcoal to reduce the resulting gases, product. Various steps involved in catalytic degradation: Starting a
principally CO2 and H2O, into CO and H2. Based upon the reactor’s conversation Heat causes random breakdown of the main chain’s C–C
operating and design conditions, the process can also create methane bond, resulting in hydrocarbon radicals. The ability to reproduce. The
and other higher hydrocarbon [76]. hydrocarbon radical decomposes to yield lesser hydrocarbons like pro­
The three basic elements of a gasification system are as follows: pylene, then undergoes scission and H-radical abstraction from another
hydrocarbons to form a new hydrocarbon radical. Recombination or
1. gasifier – produce combustible gas disproportionation of two radicals.
2. gas purification system - removes hazardous substances
3. recovery system 10. Conclusions and future aspects

9.2. Blending This study describes the conversion plastic waste using pyrolysis
process into valuation commodities and fuels. Plastic garbage, which is
It may easily be burned in boilers to generate power. According to harmful both to aquatic and terrestrial environments, might be ther­
Damodharan et al., a diesel engine may run plastic oil without requiring mochemically transformed into useful products like wax, gasoline, and
any changes to the current engine architecture [26]. The overall pre­ fuels. Slow pyrolysis yields more oil compared to waxy hydrocarbon
sentation of the blending diesel and plastic oil in a single-piston four- blends, but quick pyrolysis yields waxy hydrocarbon blends. This is due
blow VCR diesel engine was quite excellent, according to Awasthi and to differences in vapor residence lengths; in slow pyrolysis, longer
Gaikwad [35], especially as well as a 20.0 wt% of plastics lubricant residence times allow paves way for more chances cracking processes,
pyrolysis. Singh et al. [27] demonstrated in an experiment that a 50 % which breaks large molecules into small or lighter fragments. In plastic
blend of plastic oil and diesel may be simply used in conventional diesel pyrolysis, catalysts enhance the synthesis of aromatics in the phase of
engines. liquid and the gas production. Secondary cracking processes are aided
by higher pyrolysis temperatures, resulted in more waxy substances
9.3. Hydrogenation being transformed to oily and gas products. In pyrolysis oils, PE and PP
create many aliphatic compounds, whereas PS produces more aromatic
According to Mangesh et al. [36], the hydrogenation process occurs hydrocarbons. Up to 70 % of olefin monomer, involving 50 % of
due to the presence of three factors: an unsaturated molecule, a catalyst, ethylene, may be improved using flash pyrolysis around 950 ◦ C and 200
and hydrogen. The transmission of H-pair to the unsaturated chemical is ms of vapor residence time, making it a feasible monomer recovery
facilitated by heterogeneous catalysts, that allows the reaction to technique. Plastic oils could be mixed with diesel as a fuel in standard
happen at a low pressure and temperature. Hydrogenation, for an diesel engine.
example, convert alkene to alkane in plastic oil. Because of the high Using a co-occurrence analysis, we were able to identify-four pri­
concentration of unsaturated compound in plastic oil, many several mary research contexts in the area of plastic pyrolysis. Among these
storage instability difficulties might arise over time. Pyrolysis oil hy­ promising areas is a new approach based on machine learning to analyse
drogenation can turn unsaturated molecules into saturated and make the the kinetics and reaction mechanism for complex feedstock, as well as
oil better stable at temperatures around 700 ◦ C, pressure above 70 bar, thermal and kinetic analysis on plastic degradation. Research into the
and the catalyst’s presence (like ZSM-5). It has been suggested that a impact of different catalysts on pyrolysis performance, as well as the co-
combination of blending and hydrogenation be employed to enhance the pyrolysis of biomass and polymers, are two further areas of active
quality of plastic oil to attain level of EN590 standard. investigation. Research into the extracted publications has uncovered a
Below are petroleum qualities of diesel, plastic’s lubricant, and hy­ slew of new scientific interests emerging around these hubs, all of which
drogenated plastic’s lubricant, as well as the EN590 standard value are will advance the state of the art in the study of plastic pyrolysis. We also
mentioned in Table-8. [30]. believes that transition from a linear to a circular economy surrounding
plastic must find a solution to a major worry. This issue cannot be solved
9.4. Liquid-liquid extraction simply. The existing infrastructure and technologies have a restricted
capability for choosing and processing a wide variety of polymers into
Due to a significant ignition delay, the higher pungent plastic oils high-value feedstocks. This is because there are limits on these abilities.
content, especially the derived from mixed polymers pyrolysis Investments in applied research and the construction of new facilities
comprising polystyrenes, causes drop in performance of engine com­ are crucial, but so are policies that improve the plastics industry’s cur­
bined with an emissions increase. Chandran et al. reported a low cetane rent value chain and the retrofitting of existing infrastructure for the
number fuel, which are produced by more aromatic content and it is not purpose of managing and sorting plastic waste.
recommended for the traditional diesel engines because it might induce
combustion [37]. As a result, before using plastic oil in diesel engines, CRediT authorship contribution statement
aromatic chemicals may be isolated and removed using solvent extrac­
tion. Tsuji et al., demonstrated the effectiveness of sulfonate as a solvent K. Radhakrishnan: Investigation, Data curation, Resources, Writing
for the separation of aromatic chemicals [20]. – original draft. P. Senthil Kumar: Conceptualization, Methodology,

14
K. Radhakrishnan et al. Fuel 337 (2023) 126890

Validation, Supervision. Gayathri Rangasamy: Conceptualization, [24] Bagri R, Williams PT. Catalytic pyrolysis of polyethylene. J Anal Appl Pyrolysis
2002;63:29–41.
Methodology, Validation, Supervision. L. Praveen Perumal: Data
[25] Miskolczi N, Bartha L, Deák G, Jóver B, Kalló D. Thermal and thermo-catalytic
curation, Formal analysis, Resources. S. Sanaulla: Data curation, degradation of high-density polyethylene waste. J Anal Appl Pyrolysis 2004;72:
Formal analysis, Resources. S. Nilavendhan: Data curation, Formal 235–42.
analysis, Resources. V. Manivasagan: Data curation, Formal analysis, [26] Damodharan D, Kumar BR, Gopal K, De Poures MV, Sethuramasamyraja B.
Utilization of waste plastic oil in diesel engines: A review. Rev Environ Sci Bio/
Resources. K. Saranya: Data curation, Formal analysis, Resources. Techn 2019;18:681–97.
[27] Singh R, Ruj B, Sadhukhan A, Gupta P. Thermal degradation of waste plastics
under non-sweeping atmosphere: Part 1: Effect of temperature, product
Declaration of Competing Interest optimization, and degradation mechanism. J Environ Manag 2019;239:395–406.
[28] Jung S-H, Cho M-H, Kang B-S, Kim J-S. Pyrolysis of a fraction of waste
polypropylene and polyethylene for the recovery of BTX aromatics using a
The authors declare that they have no known competing financial fluidized bed reactor. Fuel Process Technol 2010;91:277–84.
interests or personal relationships that could have appeared to influence [29] Berrueco C, Mastral FJ, Esperanza E, Ceamanos J. Production of waxes and tars
the work reported in this paper. from the continuous pyrolysis of high-density polyethylene. Influence of Operation
Variables Energy Fuels 2002;16:1148–53.
[30] Kaminsky W, Predel M, Sadiki A. Feedstock recycling of polymers by pyrolysis in a
Data availability fluidised bed. Polym Degrad Stab 2004;85:1045–50.
[31] Kannan P, Al Shoaibi A, Srinivasakannan C. Temperature effects on the yield of
gaseous olefins from waste polyethylene via flash pyrolysis. Energy Fuels 2014;28:
Data will be made available on request.
3363–6.
[32] Sodero SF, Berruti F, Behie LA. Ultrapyrolytic cracking of polyethylene—a high
References yield recycling method. Chem Eng Sci 1996;51:2805–10.
[33] Milne BJ, Behie LA, Berruti F. Recycling of waste plastics by ultrapyrolysis using an
internally circulating fluidized bed reactor. J Anal Appl Pyrolysis 1999;51:157–66.
[1] Al-Salem SM, Antelava A, Constantinou A, Manos G, Dutta A. A review on thermal
[34] Scott DS, Czernik SR, Piskorz J, Radlein DSAG. Fast pyrolysis of plastic wastes.
and catalytic pyrolysis of plastic solid waste (PSW). J Environ Manag 2017;197:
Energy Fuels 1990;4:407–11.
177–98.
[35] Awasthi PK, Gaikwad A. Comparison of power outputs of different blends of
[2] Ray R, Thorpe R. A comparison of gasification with pyrolysis for the recycling of
pyrolysis plastic oil, diesel with pure diesel on single cylinder 4-S (VCR) diesel
plastic containing wastes. Int J Chem React Eng 2007;5:1–14.
engine. Int J Mech Prod Eng Res Dev 2017;7:255–62.
[3] Kumar S, Prakash R, Murugan S, Singh R. Performance and emission analysis of
[36] Mangesh V, Padmanabhan S, Tamizhdurai P, Narayanan S, Ramesh A. Combustion
blends of waste plastic oil obtained by catalytic pyrolysis of waste HDPE with
and emission analysis of hydrogenated waste polypropylene pyrolysis oil blended
diesel in a CI engine. Energy Convers Manag 2013;74:323–31.
with diesel. J Hazard Mater 2020;386:121453.
[4] Butler E, Devlin G, McDonnell K. Waste polyolefins to liquid fuels via pyrolysis:
[37] Chandran, M., Tamilkolundu, S., Murugesan, C. Characterization Studies: Waste
review of commercial state-of-the-art and recent laboratory research. Waste
Plastic Oil and Its Blends. Energy Sources Part A Recover. Util. Environ. Eff. 2019,
Biomass-Valorization 2011;2:227–55.
42, 281–29.
[5] Singh, A., Sharma, T.C., Kishore, P. Thermal Degradation Kinetics and Reaction
[38] Sobko AA. Generalized Van der Waals-Berthelot equation of state. Dokl Phys 2008;
Models of 1,3,5-Triamino-2,4,6-TrinitrobenzeneBased Plastic-Bonded Explosives
53:416–9.
Containing Fluoropolymer Matrices. J. Therm.4,566-580.
[39] Kumar S, Singh RK. Recovery of hydrocarbon liquid from waste high density
[6] Canopoli L, Fidalgo B, Coulon F, Wagland S. Physico-chemical properties of
polyethylene by thermal pyrolysis. Braz J Chem Eng 2011;28:659–67.
excavated plastic from landfill mining and current recycling routes. Waste Manag
[40] Cepeliogullar O, Putun AE. Utilization of two different types of plastic wastes from
2018;76:55–67.
daily and industrial life. In: Ozdemir C, Sahinkaya S, Kalipci E, Oden MK, editors.
[7] Rajmohan K, Yadav H, Vaishnavi S, Gopinath M, Varjani S. Perspectives on Bio-Oil
ICOEST Cappadocia 2013. Turkey: ICOEST Cappadocia; 2013. p. 1–13.
Recovery from Plastic Waste; Elsevier BV: Amsterdam. The Netherlands 2020:
[41] Chin BLF, Yusup S, Al Shoaibi A, Kannan P, Srinivasakannan C, Sulaiman SA.
459–80.
Kinetic studies of co-pyrolysis of rubber seed shell with high density polyethylene.
[8] Zhang F, Zhao Y, Wang D, Yan M, Zhang J, Zhang P, et al. Current technologies for
Energy Convers Manage 2014;87:746–53.
plastic waste treatment: A review. J Clean Prod 2021;282:124523.
[42] Marcilla A, García-Quesada JC, Sánchez S, Ruiz R. Study of the catalytic pyrolysis
[9] Gaca P, Drzewiecka M, Kaleta W, Kozubek H, Nowinska K. Catalytic degradation of
behaviour of polyethylene–polypropylene mixtures. J Anal Appl Pyrol 2005;74:
polyethylene over mesoporous molecular sieve MCM-41 modified with heteropoly
387–92.
compounds. Polish J Environ Stud 2008;2008(17):25–35.
[43] Marcilla A, Beltrán MI, Navarro R. Evolution of products during the degradation of
[10] Lin YH, Yang MH, Yeh TF, Ger MD. Catalytic degradation of high density
polyethylene in a batch reactor. J Anal Appl Pyrol 2009;86:14–21.
polyethylene over mesoporous and microporous catalysts in a fluidised-bed
[44] Onwudili JA, Insura N, Williams PT. Composition of products from the pyrolysis of
reactor. Polym Degrad Stab 2004;86:121–8.
polyethylene and polystyrene in a closed batch reactor: effects of temperature and
[11] Aguado J, Serrano D, Miguel GS, Castro M, Madrid S. Feedstock recycling of
residence time. J Anal Appl Pyrol 2009;86:293–303.
polyethylene in a two-step thermo-catalytic reaction system. J Anal Appl Pyrolysis
[45] Fogler HS. Elements of chemical reaction engineering. 4th ed. New Jersey: Pearson
2007;79:415–23.
Education Inc.; 2010.
[12] Kunwar B, Cheng H, Chandrashekaran SR, Sharma BK. Plastics to fuel: A review.
[46] Jan MR, Shah J, Gulab H. Catalytic degradation of waste high-density polyethylene
Renew Sustain Energy Rev 2016;54:421–8.
into fuel products using BaCO3 as a catalyst. Fuel Process Technol 2010;91:
[13] Kumar S, Panda AK, Singh R. A review on tertiary recycling of high-density
1428–37.
polyethylene to fuel. Resour Conserv Recycle 2011;55:893–910.
[47] Adnan SaJ, Jan MR. Thermo-catalytic pyrolysis of polystyrene in the presence of
[14] Papari S, Bamdad H, Berruti F. Pyrolytic conversion of plastic waste to value-added
zinc bulk catalysts. J Taiwan Inst Chem Eng 2014;45:2494–500.
products and fuels: A review. Materials 2021;14:2586.
[48] García RA, Serrano DP, Otero D. Catalytic cracking of HDPE over hybrid
[15] Sakata Y, Uddin MA, Muto A. Degradation of polyethylene and polypropylene into
zeolitic–mesoporous materials. J Anal Appl Pyrol 2005;74:379–86.
fuel oil by using solid acid and non-solid acid catalysts. J Anal Appl Pyrol 1999;51:
[49] Kim SS, Kim S. Pyrolysis characteristics of polystyrene and polypropylene in a
135–55.
stirred batch reactor. Chem Eng J 2004;98:53–60.
[16] Young-HwaSeo., Kyong-HwanLee., Dae-HyunShin., 2003, Investigation of catalytic
[50] Cardona SC, Corma A. Tertiary recycling of polypropylene by catalytic cracking in
degradation of high-density polyethylene by hydrocarbon group type analysis
a semibatch stirred reactor: use of spent equilibrium FCC commercial catalyst. Appl
Journal of Analytical and Applied Pyrolysis 70, 383-398.
Catal B Environ 2000;25:151–62.
[17] Scott Lovett., Franco Berruti., and Leo A, Behie.,1997. Ultrapyrolytic Upgrading of
[51] Adrados A, De Marco I, Caballero B, López A, Laresgoiti M, Torres A. Pyrolysis of
Plastic Wastes and Plastics/Heavy Oil Mixtures to Valuable Light Gas Products.
plastic packaging waste: a comparison of plastic residuals from material recovery
Ind. Eng. Chem, 36, 4436-4444.
facilities with simulated plastic waste. Waste Manage 2012;32:826–32.
[18] Williams PT, Williams EA. Fluidised bed pyrolysis of low-density polyethylene to
[52] Uemura Y, Azeura M, Ohzuno Y, Hatate Y. Flash-pyrolyzed product distribution of
produce petrochemical feedstock. J Anal Appl Pyrolysis 1999;51:107–26.
major plastics in a batch reactor. J Chem Eng Jpn 2001;34:1293–9.
[19] Arabiourrutia M, Elordi G, Lopez G, Borsella E, Bilbao J, Olazar M.
[53] Lee K-H, Shin D-H. Characteristics of liquid product from the pyrolysis of waste
Characterization of the waxes obtained by the pyrolysis of polyolefin plastics in a
plastic mixture at low and high temperatures: influence of lapse time of reaction.
conical spouted bed reactor. J Anal Appl Pyrolysis 2012;94:230–7.
Waste Manage 2007;27:168–76.
[20] Tsuji T, Hasegawa K, Masuda T. Thermal cracking of oils from waste plastics.
[54] Shah J, Jan MR, Mabood F, Jabeen F. Catalytic pyrolysis of LDPE leads to valuable
J Mater Cycles Waste Manag 2003;5:102–6.
resource recovery and reduction of waste problems. Energy Convers Manage 2010;
[21] Miandad R, Barakat MA, Aburiazaiza AS, Rehan M, Nizami AS. Catalytic pyrolysis
51:2791–801.
of plastic waste: A review. Process Saf Environ Prot 2016;102:822–38.
[55] Abbas-Abadi MS, Haghighi MN, Yeganeh H, McDonald AG. Evaluation of pyrolysis
[22] Lopez G, Artetxe M, Amutio M, Bilbao J, Olazar M. Thermochemical routes for the
process parameters on polypropylene degradation products. J Anal Appl Pyrol
valorization of waste polyolefinic plastics to produce fuels and chemicals.
2014;109:272–7.
A Review Renew Sustain Energy Rev 2017;73:346–68.
[56] Seo Y-H, Lee K-H, Shin D-H. Investigation of catalytic degradation of highdensity
[23] Marcilla A, Beltra MI, Navarro R. Thermal and catalytic pyrolysis of polyethylene
polyethylene by hydrocarbon group type analysis. J Anal Appl Pyrol 2003;70:
over HZSM5 and HUSY zeolites in a batch reactor under dynamic conditions. Appl
383–98.
Catal B 2009;86:78–86.

15
K. Radhakrishnan et al. Fuel 337 (2023) 126890

[57] Kyong HL, Nam SN, Dae HS, Seo Y. Comparison of plastic types for catalytic [74] Jamradloedluk J, Lertsatitthanakorn C. Characterization and utilization of char
degradation of waste plastics into liquid product with spent FCC catalyst. Polym derived from fast pyrolysis of plastic wastes. Proc Eng 2014;69:1437–42.
Degrad Stab 2002;78:539–44. [75] Bernando M. Physico-chemical characterization of chars produced in the
[58] Onu P, Vasile C, Ciocilteu S, Iojoiu E, Darie H. Thermal and catalytic copyrolysis of wastes and possible routes of valorisation. Portugal: Chemical
decomposition of polyethylene and polypropylene. J Anal Appl Pyrol 1998;49: Engineering. Universidade Nova de Lisboa; 2011. p. 27–36.
145–53. [76] Prabir B. Biomass gasification and pyrolysis. Practical design and theory. USA:
[59] Vasile C, Pakdel H, Mihai B, Onu P, Darie H, Ciocalteu S. Thermal and catalytic Elsevier Inc.; 2010.
decomposition of mixed plastics. J Anal Appl Pyrol 2000;57:287–303. [77] Fakhrhoseini SM, Dastanian M. Predicting pyrolysis products of PE, PP, and PET
[60] Luo G, Suto T, Yasu S, Kato K. Catalytic degradation of high density polyethylene using NRTL activity coefficient model. Hindawi Publishing Corporation 2013:1–5.
and polypropylene into liquid fuel in a powder-particle fluidized bed. Polym [78] Williams PT, Williams EA. Interaction of plastics in mixed-plastics pyrolysis.
Degrad Stab 2000;70:97–102. Energy Fuel 1998;13:188–96.
[61] Olazar M, Lopez G, Amutio M, Elordi G, Aguado R, Bilbao J. Influence of FCC [79] Gartzen Lopez, Maider Amutio, Gorka Elordi, avier Bilbao, and Martin Olazar.
catalyst steaming on HDPE pyrolysis product distribution. J Anal Appl Pyrol 2009; Cracking of High-Density Polyethylene Pyrolysis Waxes on HZSM-5 Catalysts of
85:359–65. Different Acidity. Ind. Eng. Chem. Res. 2013, 52, 31, 10637–10645.
[62] Elordi G, Olazar M, Castaño P, Artetxe M, Bilbao J. Polyethylene cracking on a [80] Wendy Mateoaa Hanwu, Leia Elmar Villotaab, Moriko Qiana Yunfeng Zhaoa,
spent FCC catalyst in a conical spouted bed. Ind Eng Chem Res 2012;51:14008–17. Erguang Huoa Quigfa Zhanga, Xiaona Lina Chenxi, Wanga Zhiyang Huanga,
[63] Murata K, Sato K, Sakata Y. Effect of pressure on thermal degradation of “Synthesis and characterization of sulfonated activated carbon as a catalyst for bio-
polyethylene. J Anal Appl Pyrol 2004;71:569–89. jet fuel production from biomass and waste plastics”.Bioresource Technology. 297,
[64] Mastral FJ, Esperanza E, Berrueco C, Juste M, Ceamanos J. Fluidized bed thermal 122411.
degradation products of HDPE in an inert atmosphere and in air– nitrogen [81] Lijun Jin, Huanhuan Si, Jianbo Zhang , PingLin .2013, Preparation of activated
mixtures. J Anal Appl Pyrol 2003;70:1–17. carbon supported Fe–Al2O3 catalyst and its application for hydrogen production
[65] Ivanova SR. Selective catalytic degradation of polyolefins. Prog Polym Sci 1990;15: by catalytic methane decomposition.International Journal of Hydrogen. 38,10373-
193–215. 10380.
[66] Artetxe M, Lopez G, Amutio M, Elordi G, Bilbao J, Olazar M. Cracking of high [82] Panda AK, Singh RK, Mishra DK. Thermolysis of waste plastics to liquid fuel. A
density polyethylene pyrolysis waxes on HZSM-5 catalysts of different acidity. Ind suitable method for plastic waste management and manufacture of value added
Eng Chem Res 2013;52:10637–45. products—a world prospective. Renew Sustain Energy Rev 2010;14:233–48.
[67] Garfoth AA, Lin YH, Sharratt PN, Dwyer J. Production of hydrocarbons by catalytic [84] Aguado J, Sotelo JL, Serrano DP, Calles JA, Escola JM. Catalytic conversion of
degradation of high density polyethylene in a laboratory fluidizedbed reactor. Appl polyolefins into liquid fuels over MCM-41: comparison with ZSM-5 and amorphous
Catal A Gen 1998;169:331–4. SiO2–Al2O3. Energy Fuels 1997;1997(11):1225–31.
[68] Marcilla A, Beltran MI, Navarro I. Thermal and catalytic pyrolysis of polyethylene [85] Hu Q, Ok YS, Wang C-H. Sustainable and highly efficient recycling of plastic waste
over HZSM-5 and HUSY zeolites in a batch reactor under dynamic conditions. Appl into syngas via a chemical looping scheme. Environ Sci Technol 2022;56:8953–63.
Catal B Environ 2008;86:78–86. [86] Kumar Jha K, Kannan TTM. Recycling of plastic waste into fuel by pyrolysis - a
[69] Hernández MR, Gómez A, García ÁN, Agulló J, Marcilla A. Effect of the review. Mater Today: Proc 2021;37:3718–20.
temperature in the nature and extension of the primary and secondary reactions in [87] Alam SS, Husain Khan A, Khan NA. Plastic waste management via thermochemical
the thermal and HZSM-5 catalytic pyrolysis of HDPE. Appl Catal A Gen 2007;317: conversion of plastics into fuel: a review. Energy Sources Part A 2022;44:1–20.
183–94. [88] Chen W-T, Jin K, Linda Wang N-H. Use of supercritical water for the liquefaction of
[70] Lin YH, Yen HY. Fluidised bed pyrolysis of polypropylene over cracking catalysts polypropylene into oil. ACS Sustainable Chem Eng 2019;7(4):3749–58.
for producing hydrocarbons. Polym Degrad Stab 2005;89:101–8. [89] Ahamed Kameel NI, Wan Daud WMA, Abdul Patah MF, Mohd Zulkifli NW.
[71] Marcilly CR. Where and how shape selectivity of molecular sieves operates in Influence of reaction parameters on thermal liquefaction of plastic wastes into oil:
refining and petrochemistry catalytic processes. Top Catal 2000;13:357–66. A review. Energy Conversion Management: X 2022;14:100196. https://doi.org/
[72] Kyong HL, Sang GJ, Kwang HK, Nam SN, Dae HS, Park J, et al. Thermal and 10.1016/j.ecmx.2022.100196.
catalytic degradation of waste high density polyethylene (HDPE) using spent FCC
catalyst. Korean J Chem Eng 2003;20:693–7.
[73] Uddin MA, Muto A, Kanada Y, Koizumi K, Murata K. Catalytic degradation of Further reading
polyethylene into fuel oil over mesoporous silica (KFS-16) catalyst. J Anal Appl
Pyrol 1997;43:15–25. [83] Cullis CF, Hirschler MM. The Combustion of Organic Polymers. Oxford Clarendon
Press; 1981.

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