SS symmetry

Review
Catalytic Pyrolysis of Plastic Waste and Molecular Symmetry
Effects: A Review
Saša Papuga 1 , Milica Djurdjevic 2, *, Andrea Ciccioli 3 and Stefano Vecchio Ciprioti 4, *

1 Faculty of Technology, University of Banja Luka, 78000 Banja Luka, Bosnia and Herzegovina
2 Faculty of Mechanical Engineering, University of Banja Luka, 78000 Banja Luka, Bosnia and Herzegovina
3 Department of Chemistry, Sapienza University of Rome, I-00185 Rome, Italy
4 Department of Basic and Applied Science for Engineering, Sapienza University of Rome, I-00161 Rome, Italy
* Correspondence: [email protected] (M.D.); [email protected] (S.V.C.)

Abstract: The present review addresses the latest findings and limitations in catalytic pyrolysis for
the processing of plastic waste into valuable fuels. Compared to thermal degradation of plastics,
catalytic pyrolysis provides better results in regards to the quality of the obtained liquid hydrocarbon
fuel. Different types of catalysts can be used in order to improve the thermal degradation of plastics.
Some of the most used catalysts are different types of zeolites (HUSY, HZSM-5, Hβ), Fluid Catalytic
Cracking (FCC), silica-alumina catalysts, or natural clays. There is a need to find affordable and
effective catalysts in the aim of achieving commercialization of catalytic pyrolysis of plastic waste.
Therefore, this study summarizes and presents the most significant results found in the literature in
regards to catalytic pyrolysis. This paper also investigates the symmetry effects of molecules on the
pyrolysis process.

Keywords: catalyst; pyrolysis; plastic waste; zeolites; symmetry effects

1. Introduction
Plastic is a non-degradable material that can persist in the environment for long
Citation: Papuga, S.; Djurdjevic, M.; periods of time [1]. On the other hand, it is a very special material with a great number
Ciccioli, A.; Vecchio Ciprioti, S. of advantages: it is affordable, versatile, light, and resistant [2,3]. Plastic originates from
Catalytic Pyrolysis of Plastic Waste petrochemicals and contains mostly hydrocarbons and some additives, such as antioxidants,
and Molecular Symmetry Effects: A flame retardants, and stabilizers, which make the material very bio-undegradable [4].
Review. Symmetry 2023, 15, 38. Thanks to its unvaluable properties, plastic can be used for many different functions [2].
https://doi.org/10.3390/ A total of 44.8% of all plastics produced in 2015 were used for packaging purposes, and
sym15010038 18.8% in the building and construction industry [5]. Other big plastic consumers are the
Academic Editor: Bozhidar Stefanov
textile industry, consumer and institutional products, transportation, and electronics [5].
The exponential growth of plastic production is shown in Figure 1 [6]. Chemical resistance
Received: 9 November 2022 is well known to be one of the most important properties of plastics. As a result, land,
Revised: 8 December 2022 water, and oceans become easily polluted by plastic waste, implying serious risks for the
Accepted: 14 December 2022 survival of living organisms [5] and important impacts on wildlife, natural surroundings,
Published: 23 December 2022
and human health [7–9].
The most used types of plastics are polyethylene (PE), polypropylene (PP), polyvinylchlo-
ride (PVC), polyethylene terephthalate (PET), and polystyrene (PS). Usually, their utilization
Copyright: © 2022 by the authors.
in daily life is in the form of mixtures of monomers, oligomers, and additives [10].
Licensee MDPI, Basel, Switzerland. Plastic waste is commonly found as a component in municipal solid waste, with PE
This article is an open access article and PS as the main components of the heterogeneous mixture [1]. Plastic waste consists of
distributed under the terms and different mixtures of plastic products, such as low- and high-density polyethylene (LDPE
conditions of the Creative Commons and HDPE, respectively), PP, PS, PVC, and PET. Plastic waste is bulkier than other organic
Attribution (CC BY) license (https:// residues and therefore a massive space is needed in landfills. This disadvantage is also re-
creativecommons.org/licenses/by/ sponsible for the high cost of disposal and incineration of plastic waste. Additionally, plastic
4.0/). waste incineration and disposal lead to abundant emissions of harmful compounds [11,12].

Symmetry 2023, 15, 38. https://doi.org/10.3390/sym15010038 https://www.mdpi.com/journal/symmetry

Symmetry 2023, 15, 38 2 of 19

Symmetry 2023, 14, x FOR PEER REVIEW 2 of 20

As seen in Figure 2, a high percentage of plastic waste was still landfilled across Europe in
2018 [13].

Figure 1. Exponential growth of plastic production over the years (adapted from [6]).

Plastic waste is commonly found as a component in municipal solid waste, with PE

and PS as the main components of the heterogeneous mixture [1]. Plastic waste consists
of different mixtures of plastic products, such as low- and high-density polyethylene
(LDPE and HDPE, respectively), PP, PS, PVC, and PET. Plastic waste is bulkier than other
organic residues and therefore a massive space is needed in landfills. This disadvantage
is also responsible for the high cost of disposal and incineration of plastic waste. Addi-
tionally, plastic waste incineration and disposal lead to abundant emissions of harmful
compounds [11,12]. As seen in Figure 2, a high percentage of plastic waste was still land-
filled
Figureacross Europe growth
1. Exponential in 2018of[13].
plastic production over the years (adapted from [6]).
Figure 1. Exponential growth of plastic production over the years (adapted from [6]).

Plastic waste is commonly found as a component in municipal solid waste, with PE

and PS as the main components of the heterogeneous mixture [1]. Plastic waste consists
of different mixtures of plastic products, such as low- and high-density polyethylene
(LDPE and HDPE, respectively), PP, PS, PVC, and PET. Plastic waste is bulkier than other
organic residues and therefore a massive space is needed in landfills. This disadvantage
is also responsible for the high cost of disposal and incineration of plastic waste. Addi-
tionally, plastic waste incineration and disposal lead to abundant emissions of harmful
compounds [11,12]. As seen in Figure 2, a high percentage of plastic waste was still land-
filled across Europe in 2018 [13].

Figure 2. Plastic waste management in Europe in 2018 (taken from [13]).

Waste-to-energy technologies
Waste-to-energy technologies can convert plastic
can convert plastic waste
waste into
into heat,
heat, hydrocarbon
hydrocarbon fuels, fuels,
and chemicals [14,15]. There are different ways to process plastic
and chemicals [14,15]. There are different ways to process plastic waste. Primary or me- waste. Primary or
mechanical
chanical recycling
recycling involves
involves grinding
grinding plastics
plastics andand producing
producing newnewgoods goods
withwith recycled
recycled ma-
material. During secondary recycling or incineration, calorific value
terial. During secondary recycling or incineration, calorific value is generated. Tertiary is generated. Tertiary
recycling or
recycling or pyrolysis
pyrolysis is is aa thermo-chemical process, where
thermo-chemical process, where the the polymer
polymer is is heated
heated under
under
an inert atmosphere causing polymer cracking [16–21]. In order
an inert atmosphere causing polymer cracking [16–21]. In order to limit char formation, to limit char formation,
pyrolysis should be performed in an oxygen-free or at least oxygen-poor atmosphere [22].
pyrolysis should be performed in an oxygen-free or at least oxygen-poor atmosphere [22].
During pyrolysis, plastic is heated to a certain temperature and oxygen is extracted from the
During pyrolysis, plastic is heated to a certain temperature and oxygen is extracted from
reaction chamber. Depending on the working conditions, such as temperature, heating rate,
the reaction chamber. Depending on the working conditions, such as temperature, heating
and residence
Figure 2.time,
Plasticthere
wastearemanagement
different types of pyrolysis
in Europe in of
2018 processes
(taken from that can be distinguished
[13]).
rate, and residence time, there are different types pyrolysis processes that can be dis-
by hydro-, oxidative, catalytic, steam, vacuum, microwave-, plasma, or electrical heating
tinguished by hydro-, oxidative, catalytic, steam, vacuum, microwave-, plasma, or electri-
pyrolysis [23]. Pyrolysis could
Waste-to-energy play an important
technologies role in
can convert plastic
plastic waste
waste management,
into since it fuels,
heat, hydrocarbon
cal heating pyrolysis [23]. Pyrolysis could play an important role in plastic waste manage-
is an environment-friendly solution, allowing forways
the production of liquidwaste.
fuels and other
ment, since it is an environment-friendly solution, allowing for the production of liquidor me-
and chemicals [14,15]. There are different to process plastic Primary
products for further applications [24].
chanical recycling involves grinding plastics and producing new goods with recycled ma-
fuels and other products for further applications [24].
Pyrolysis processes
terial. During have gained
secondary a lot of
recycling orattention in recent
incineration, times,value
calorific since isthey representTertiary
generated. a
Pyrolysis processes have gained a lot of attention in recent times, since they represent
basis to produce a second generation of synthetic fuels, materials, and
recycling or pyrolysis is a thermo-chemical process, where the polymer is heated underchemicals [19,25–28].
a basis to produce a second generation of synthetic fuels, materials, and chemicals [19,25–
Pyrolysis is a reaction
an inert atmosphere occurring
causingin polymer
the absence of oxygen,
cracking whereby
[16–21]. In orderorganic
to limitcompounds
char formation,
are decomposed,
pyrolysis shouldgenerating gaseous in
be performed andanliquid products.
oxygen-free or atOn theoxygen-poor
least contrary, theatmosphere
inorganic [22].
matrixDuring
usuallypyrolysis,
remains unaltered
plastic is [11,29,30].
heated to a certain temperature and oxygen is extracted from
During
the reaction chamber.of
the pyrolysis polymers,on
Depending macromolecules are broken
the working conditions, such down into smaller
as temperature, heating
molecules
rate, and residence time, there are different types of pyrolysis processes materials
[31]. The advantage of pyrolysis is the production of high energy that can be dis-
(char, tar, and gas)by
tinguished from low energy
hydro-, solid
oxidative, waste. The
catalytic, conversion
steam, vacuum,depends
microwave-,on the operating
plasma, or electri-
conditions used: the heating rate, maximum temperature, processing time
cal heating pyrolysis [23]. Pyrolysis could play an important role in plastic waste manage- at the maximum
temperature, pressure,
ment, since it is anand catalysts used [30,32–34].
environment-friendly solution,Theallowing
liquid products yield, as well
for the production of liquid
fuels and other products for further applications [24].
Pyrolysis processes have gained a lot of attention in recent times, since they represent
a basis to produce a second generation of synthetic fuels, materials, and chemicals [19,25–
Symmetry 2023, 15, 38 3 of 19

converting of raw material, which depends on the experimental conditions (process pa-
rameters), raw material type (waste or clean, synthetic plastics) and composition (mixture
or individual plastic types), reactor type, size of the sample’s particles, and time of the
reaction. Therefore, for each individual system or pyrolysis plant, it is necessary to clearly
define the operating parameters and to investigate the conditions for an adequate yield [35].
Volatile matter, together with ash content, are important factors in determining the liquid
yield. When the content in the volatile matter is high, a more abundant production of liquid
oils can be obtained. On the contrary, the ash content tends to reduce the amount of liquid
oils and increases the formation of char and gases [19].
Pyrolysis can be thermal or catalytic [36,37]. Thermal pyrolysis requires higher tem-
peratures (from 350 to 900 ◦ C), which can lead to a low molecular weight and low quality
products [11]. Gases evolved during pyrolysis have a high calorific value, and could be
used in different gas machines and engines for the generation of electricity without any
other treatments or modifications [38]. The addition of catalysts overcomes the limita-
tions of thermal pyrolysis, by reducing either the reaction temperature or the time [11].
Furthermore, the addition of catalysts improves conversion, reduces activation energy
of pyrolysis, and enhances the fuel quality. The most commonly used catalysts for the
pyrolysis of plastics are zeolites, polyciliate components, and clays [31,32,39]. Compared to
thermal pyrolysis, the catalytic process has the advantage of a lower process temperature,
a reduction of solid residues such as carbonized char and volatile fraction, shorter time
process, high product selectivity, and high-octane-number products. Zeolite-based catalysts
are the best option for the pyrolysis of plastic waste, and for co-pyrolysis of combined
plastic waste/biomass [40].
Processing of PVC is not preferred because it leads to the formation of hydrochloric
acid (HCl) that can damage process equipment and cause high-temperature corrosion. This
drawback can be solved by dechlorination, with an increase of the overall process costs.
In addition, PET pyrolysis leads to the formation of oxygenated aromatic hydrocarbons,
which cause the lowering of oil quality, decrease of liquid product yield, and damage of
the process equipment [41]. Generally, the presence of oxygen and halogen elements in the
structure of polymers lead to the reduction of liquid pyrolytic fuel quality [42]. Studies from
Li et al. [18] and Fivga and Dimitriou [43] have focused on the economic feasibility of the
plastic pyrolysis process. Both studies concluded that the process is economically feasible
when the capacity of the facility is scaled up. Another study on the pyrolysis of plastic was
reported by Iribarren et al. [44]. This study showed economic and environmental feasibility.
Additionally, the production of energy from the process was analyzed, pointing out that,
when compared with two traditional waste management approaches such as incineration
and landfilling, plastic pyrolysis shows good results.
The aim of this work is to present and analyze the available and current data on the
catalytic pyrolysis of waste, with the goal of providing the best examples and suggesting
experimental procedures of good practice, and to find gaps and pathways for further
development of this topic. The second section of this review explores the thermal pyrolysis
of plastic waste, while the third section covers catalytic pyrolysis, with particular reference
to the most used catalysts, providing a literature survey of studies on the catalytic pyrolysis
of plastic waste. Finally, the fourth section is focused on molecular symmetry effects in
pyrolysis processes.

2. Thermal Pyrolysis
Thermal (non-catalytic) pyrolysis of plastic waste is an endothermic reaction which
proceeds in the absence of catalysts [1]. In this process, polymer materials are heated to
very high temperatures, whereby macromolecules are broken down into smaller molecules.
Pyrolysis products are represented by a wide range of hydrocarbons, further classified into a
non-condensable gas fraction, liquid fraction (paraffins, olefins, naphthenes, and aromatics),
and solid residue. A variety of fuels can be recovered from the liquid fraction—in the
range of gasoline (C4–C12), diesel (C12–C23), kerosene (C10–C18), and motor oil (C23–C40).
Symmetry 2023, 15, 38 4 of 19

However, when the process temperature is high, there is an increased production of the
non-condensable gaseous fraction and, consequently, a decrease in that of liquid fuels,
such as diesel [11,45–48]. A significant yield of the gaseous fraction is obtained by thermal
pyrolysis due to the breaking of aliphatic chains in small fragments [49].
In general, the influence of temperature on the distribution of pyrolysis products
should be considered together with the influence of other process parameters, such as
carrier gas flow and reaction time, as well as other parameters such as the type of plastic,
the composition of the plastic mixture, and especially the type of configuration reactor
system [35]. Therefore, for each individual system or pyrolysis plant, it is necessary to
clearly define the above mentioned parameters, and investigate their effect on the yield [35].
Pyrolysis reactions usually take place in three steps: initiation, propagation, and
termination [11]. During initiation, the cracking of large polymer molecules into free
radicals occurs. Free radicals and molecular species are cracked into smaller radicals
and molecules in the propagation steps. Finally, the generated radicals are combined
together during the termination step to obtain stable molecules via the formation of covalent
bonds [50].
Thermal analysis can play a crucial role in determining the thermal behavior of
thermoplastic and thermoset components in mixtures that simulate real plastic waste.
These techniques, which in some cases are coupled with pyrolysis experiments in a pilot
scale reactor, can be used for the identification and characterization of polyolefins and
multilayer-packaging-based plastic waste or some thermoplastic components of WEEE
when they are subjected to a pyrolysis process [51,52].
There are several studies focused on the behavior of different WEEE, such as printed
circuit boards, keyboards, video cards, and telephone line at different temperatures. The
study of the thermal behavior of mixed plastics from packaging and electric equipment
residues revealed the advantages of applying pyrolysis feedstock recycling from an ener-
getic point of view [53].

3. Catalytic Pyrolysis
Catalytic pyrolysis involves the addition of a catalyst, with a higher conversion rate
of plastic into oils and higher quality of the products, which is related to the lower tem-
peratures and lower reaction time of the process [1,21]. Catalysts are also used in py-
rolysis for the optimization of product distribution and increase of product selectivity,
and provide yields similar to the conventional fuels, such as diesel and gasoline [54–57].
Catalysts are usually classified into two groups: homogeneous and heterogeneous. Gen-
erally, homogeneous catalysts are in a single phase (reactants, products, and catalysts are
in the same phase), i.e., liquid solution, while the heterogeneous catalysts are in solid
form [58,59]. The most used homogeneous catalysts for plastic pyrolysis are aluminum
chloride (AlCl3 ), potassium hydroxide (KOH), sodium hydroxide (NaOH), and sodium
methoxide (CH3 ONa). Commonly used acidic catalysts are hydrochloric, phosphoric,
sulphuric, and organic sulphonic acids. Homogeneous acid catalysts are preferred to base
ones, because of the lower activity of the latter [58].
Heterogeneous catalysts are mostly in the solid form, and they are added to solid or
liquid or gaseous compounds in the mixture [59]. Heterogeneous catalysts are of more com-
mon use, because of their easy separation from the liquid pyrolysis product, which allows
the catalyst to be reused and regenerated [60]. Another important advantage of heteroge-
neous catalysts over homogeneous ones is that they are non-corrosive. The surface area,
porosity, arrangement of functional groups, and acidity are important features for the pyrol-
ysis process [58,61]. Most used catalysts are the following: zinc oxide—ZnO; magnesium
oxide—MgO; calcium-carbonate—CaCO3; calcium carbide—CaC2; silicon dioxide—SiO2 ;
aluminum oxide—Al2 O3 ; silicon dioxide alumina doped—SiO2 -Al2 O3 ; zeolite Socony
mobil-5—ZSM-5; zeolite; red mud; and fluid catalytic cracking—FCC [54,55]. The FCC cata-
lysts are widely used in petroleum refineries for the cracking of heavy oils into gasoline and
liquid oil petroleum [1,60]. The FCC contains three parts: zeolite crystals and a non-zeolite
Symmetry 2023, 15, 38 5 of 19

acid matrix that is made of silica-alumina with a binder in the structure [61]. Silica-alumina
catalysts have Lewis acid sites, acting as electron acceptors, and Brönsted acid sites with
ionizable hydrogen atoms. Acidity of these catalysts influences the production of liquid oils
from the pyrolysis of waste plastics. When the acidity is very high, the production of liquid
oils is reduced [1]. The presence of open pores in zeolites is the most important feature of
this type of catalyst. Zeolites with high acidity are more active in the cracking process, thus
increasing the production of light olefins and decreasing the heavy fractions [1,62].

3.1. Catalyst Structure and the Pyrolysis Mechanism

Zeolite catalysts have a crystalline structure that contains primary structural TO4
tetrahedron units. T represents the central atom, mostly Si or Al, surrounded by O atoms
connecting the units to each other. Interconnection between the building units leads
to three-dimensional microporous structures with different geometries and structural
characteristics [62]. Zeolites also promote hydrogen transfer reactions, due to the presence
of many acid centers [8]. Silica-alumina catalysts and zeolites result in an increase of the
gaseous yield. Lighter molecules, supporting gas formation, are obtained as a consequence
of the increased cracking reactions and acidity [62]. Compared with zeolites, silica-alumina
catalysts can be assumed not to contain stable crystalline structures with pore volumes
larger than those in zeolites, which are microporous [63]. Many studies have been published
on the pyrolysis of plastic waste polymers due to the advantageous microporous structure
of ZSM-5 zeolite [42,64–66]. These papers also provide exhaustive surveys of the studies
performed on the catalytic pyrolysis of plastic waste in the presence of zeolites (ZSM-5).
The activation energy is known to decrease in the presence of catalysts, thus suggesting
an increase of the reaction rate, although no information is available on the value of the pre-
exponential factor. As a consequence, the use of catalysts reduces the optimum temperature
needed for the pyrolysis process allowing for energy saving, therefore reducing the most
relevant cost for industries [19].
Catalysts can be placed either in the pyrolysis reactor (in situ) or in a separate catalytic
bed (in-line). Catalysts, such as the protonated (H+ ) form of ZSM-5 orHZSM-5, protonated
form of Y zeolite (HY), protonated form of beta zeolite (Hß), and hierarchical H-style
ultra-stable Y HUSY zeolite, promote the carbocationic cracking of pyrolysis volatiles and
isomerization, oligomerization-cracking, and hydrogen transfer. The main properties of
catalysts that influence the cracking performance are strength and porosity. During the
catalytic processing of plastics, the polymer matrix melts upon heating and is dispersed
over the catalyst surface. Mechanisms of catalytic pyrolysis also include chain scission,
isomerization, oligomerization, H-transfer, and aromatization. The first step of polymer
cracking is ascribed to adsorption of the reactant molecule on the acid site, where it
undergoes protonation with the formation of carbonium ions. This intermediate promotes
the cracking of molecules. As a consequence, the reaction rate is mostly affected by acid site
strength, density, and distribution. A catalyst’s acid active site promotes cracking of olefinic
compounds and hydrogen transfer reactions. When catalyst sites are strongly acidic, the
formation of olefins (via end-chain scission) is favored, whereas, when the catalyst sites
are weakly acidic, the formation of waxes (random scission) is enhanced. The obtained
products (olefins or waxes) undergo further reactions to produce low-molecular-weight
compounds [62]. In the study carried out by Cai et al. [67], the catalytic pyrolysis of various
plastic types with Fe/Al2 O3 was studied in order to obtain high value hydrogen, aromatic
chemicals, and carbon nanotubes as reaction products. This work showed that plastic
polymers tend to decompose through a random scission mechanism, and ethylene obtained
from PE decomposition was more involved in the catalytic coke deposition with respect to
propylene (from PP decomposition), which further increased the amount of solid carbon.
Furthermore, high impact polystyrene (HIPS) and general-purpose polystyrene (GPPS)
deposited more carbon than that produced during the catalytic pyrolysis of polyolefin
plastics. This is explained by the difference in the molecular structure of the different plastic
types, because of the presence of benzene rings in the HIPS and GPPS structures. When
Symmetry 2023, 15, 38 6 of 19

GPPS and HIPS are heated to their degradation temperatures, the large polymer moiety
breaks up into smaller aromatic compounds such as styrene or styrene oligomers. When the
catalysts are used, the ethenyl group in the styrene molecule is removed and benzene rings
are accessible to produce high value hydrogen, aromatic chemicals, and carbon nanotubes
as reaction products. At the same time, C-C and C-H bonds in the ethenyl groups are
broken. On the catalyst, carbon atoms are dissolved and suddenly recombined by melting
iron, thus forming graphitic carbon. The residual hydrogen atoms are responsible for the
formation of low-molecular-weight gases. The heavier aromatic hydrocarbon compounds
are decisive for the carbon-generating process in comparison to micro alkane and olefin
molecules. Due to the higher degree of conversion into solid carbon, the amount of gaseous
products obtained from PS is lower than that produced from PE and PP [67].
Paula et al. [6] have performed thermal and catalytic pyrolysis of plastic waste (PE,
PP, PS) with ZSM-5 zeolites and modified mordenite (MOR). Mordenite was treated with
NaOH in order to improve the pore volume. By treatment with alkali, a mesoporous
morphology can be produced in the catalyst, thus preserving its acidity. Mordenite has
an irregular pore size, which could contribute to the occurrence of secondary reactions
taking place on the catalyst surface. Reactions on the catalyst surface may contribute to
bimolecular secondary processes and the production of aromatic compounds, which further
lead to lower conversion rates and increase light fraction hydrocarbons. Low conversion
rates can also be related to mono-dimensional channel systems and low mesoporosity,
which limited the catalyst’s access to polymer chains on the active sites. However, the
treated ZSM-5 catalyst showed better performance in the catalytic processing of plastics
compared to mordenite. Another study where the effect of small pores of the ZSM-5 catalyst
was discussed is reported in [42].

3.2. Application of Zeolites for the Catalytic Pyrolysis of Plastic

PE, PP, PS, and PET were pyrolyzed in the presence of HZSM-5 zeolite in a tandem
micro-pyrolyzer. Pyrolysis was conducted in situ and ex situ. The in situ catalytic pyrolysis
of plastics gave a higher amount of solid residue and led to the production of aromatic
hydrocarbons, with the exception of PS. During the ex situ catalytic pyrolysis of PS, a
high amount of aromatics was produced compared to the in situ catalytic pyrolysis, with
a large production of styrene. In the case of PET, in situ catalytic pyrolysis generated a
large amount of CO2 and a small amount of CO, compared to the ex situ catalytic pyrolysis.
Pyrolysis of PE and PP yielded comparable amounts of alkenes and alkanes in ex situ and
in-situ catalytic pyrolysis, with the amount of produced alkene higher than the alkane
yield during ex situ catalytic pyrolysis. These results show that in situ and ex situ catalytic
pyrolysis of plastics have different reaction mechanisms [14]. Another study that also
confirmed catalytic pyrolysis of the polymers to depend on the chemical and physical
characteristics of the catalysts, and on the chemical and structural nature of polymers, was
reported by Marcilla et al. [16].
Colantonio et al. [68] investigated the pyrolysis of plastic residue from a material
recovery facility. The goal of this study was to investigated the effect of the HUSY catalyst
and hydrogen zeolite socony mobil-5 (HZSM5) catalyst on the quality of the pyrolysis
products. The plastic residue used as a feed was composed of 45 wt.% of PE, 30 wt.% of PP,
20 wt.% of PS, and 5 wt.% of PET. Thermogravimetric analysis showed that HUSY reduces
the degradation temperature of all plastic polymers, with the highest effect on polyolefins.
HZSM5 showed a significant effect on the degradation of PE. The pyrolysis reaction was
carried out in a laboratory semi-batch reactor at 370, 450, and 650 ◦ C, on the basis of TG
analysis. The use of zeolites resulted in a reduction of the heavy oil fraction and inhibition
of wax formation. HUSY showed the best results in regards to the monoaromatic yield,
whereas, HZSM5 influenced the production of gases.
A noticeable improvement in the production of light oil to the detriment of tar was
obtained in a recent study [68], which carried out catalytic pyrolysis of thermoplastics
extracted from waste electrical and electronic equipment (WEEE) using various catalysts
Symmetry 2023, 15, 38 7 of 19

prepared from fly ash. The pyrolytic degradation of common polymers found in packaging
materials was recently studied in [69]. The cracking temperature affects the type and
number of the segments produced, with higher temperatures favoring the conversion of the
polymer chains to monomers and the release of smaller molecules, and lower temperatures
are more likely to produce oligomers. Faujasite (FAU) zeolites typically induced the
formation of char due to their large cavity volume where secondary reactions can take
place [70].
The pyrolysis of multilayered plastic and mixed resin plastic waste in the presence
of the iron-modified zeolite ZSM-5 catalyst was examined in the study carried out by
Kremer et al. [71]. The FTIR analysis showed that PET was present in the exterior part of the
packaging, mixed with PE and PP. Some packaging also contained small amounts of PA. The
study showed how the activation energy of pyrolysis decreases in the presence of a catalyst
and that the catalyst lowered the content of polyaromatic compounds. Kinetic analysis of
the pyrolysis of non-recyclable plastics and its influence on the product yield was studied
by Kremer et al. [41]. In this study, plastic waste that was not mechanically recyclable was
used. The plastic waste was separated from PVC, so that the main components of the used
feedstock were PE, PET, PA, PP, and a very small amount of PS. Two different catalysts were
employed in the pyrolysis process. The first catalyst was FCC, and the second one was iron
(III) oxide (Fe2 O3 ) loaded on the zeolite support ZSM-5 (Fe-ZSM). Pyrolysis was conducted
in a fixed-bed reactor, and TG and DTG analyses were carried out at 5, 10, and 15 ◦ C. The
study concluded that the order of polymer degradation was PS < PET < PP < LDPE < HDPE.
The decomposition temperature of pure PS was in the range between 350 and 450 ◦ C. PET
degradation occurs in the temperature range between 390 and 470 ◦ C, whereas PP, LDPE,
and HDPE require the highest temperatures (450–510 ◦ C) for degradation. In the presence
of catalysts, the pyrolysis of plastic waste is faster and the formation of wax is evidently
reduced [41]. Another kinetic study on the pyrolysis of waste plastic polymers (PP, PE,
PET, and PS) and three synthetic mixtures, representing commingled post-consumer plastic
waste output from recovery facilities, was reported by Tuffi et al. [72]. Volatilization that
occurs in one step of mass loss is complete for all polymers tested, with the exception of
PET, because of the formation of complex aromatic compounds [72].
Nanoporous MCM-41 (mobil composition matter no. 41), which has suitable properties
for catalytic applications of polymers, such as the specific area and pore size, can be used
for the degradation of PET [73]. The effect of pore shape on the catalytic performance of
zeolites during HDPE degradation was investigated in the presence of several zeolites with
different pore sizes. Good results (high conversion rates of HDPE) were obtained using
BEA and MFI zeolites, due to their bent pores, which slowed down catalytic deactivation
because of carbon deposit, defeating the formation of longer molecules. Sudden blocking
of linear pores by a small amount of carbon deposit decreased the MOR zeolite’s activity.
FAU zeolite had large pores connected through supercages, leading to better mass transfer
and a high yield of liquids. On the other side, MWW zeolite had numerous large pores that
influenced the slow diffusion of cracked products, enhancing yields of small hydrocarbons.
By taking all these findings into account, it can be concluded that the pore shape of the
studied zeolites was a crucial parameter for the determination of catalytic activity and
product selectivity in the degradation of polymers [74].
Catalytic pyrolysis of HDPE on HZSM-5 and iron-alumina pillared montmorillonite
(FAMO) was performed in a conical spouted bed reactor. The acid sites of catalysts affect
the activity and the cracking products. When the acid site is stronger, the produced
hydrocarbon mixture is lighter. In view of the bulky nature of polymers, another important
factor for the activity of catalysts is the availability of the acid sites. In the pyrolysis
performed with the HZSM-5 catalyst, the high activity and high selectivity for gases could
be explained by the strong acidity of the zeolite, related to the easy and full access to
acid sites located on its outer surface. On the other hand, FAMO showed low selectivity
towards gases, because of the lower acid strength of catalyst site. However, when pyrolysis
Symmetry 2023, 15, 38 8 of 19

is performed at a temperature of 550 ◦ C, the catalyst showed a better performance in the

production of diesel-range products [75].
Garforth et al. [76] have investigated the catalytic pyrolysis of HDPE at temperatures
between 290 and 430 ◦ C in a fluidized-bed reactor using HZSM-5, H-mordenite zeolite
HMOR, HUSY, and SAHA catalysts. This study showed that initial cracking of HDPE has
to be restricted to the outer surface and pore entrances of the zeolite, and the subsequent
initial cracked products are decomposed within the catalyst. Zeolite catalysts, namely
HZSM-5, HMOR, and HUSY, were more effective in the conversion of polymers into
volatile hydrocarbons than SAHA. Another study focused on the influence of the zeolite
catalyst (ZSM-5) and red mud was carried out by Lopez et al. [77]. ZSM-5 and red mud
were tested on a plastic mixture simulating the municipal plastic waste. Pyrolysis was
performed in semi-batch reactor at 440 and 500 ◦ C, respectively. ZSM-5 produced a higher
proportion of gases and liquids with aromatics compared to the thermal process. Red mud
also showed positive results in plastic waste degradation, although higher temperatures
were required than in the process with ZSM-5 [77].

3.3. Application of Natural Catalysts for Plastic Pyrolysis

In order to make the catalytic pyrolysis more affordable, catalyst costs need to be
reduced, because scaling up the process on the continuous scale requires a large amount of
catalysts that further influences the overall cost of the process [58]. Naturally occurring
silica-rich zeolites (clinoptilolite and mordenite) can be used for plastic pyrolysis [64].
Several studies closely examined the application of natural zeolites [78–81]. Natural zeolites
frequently have impurities such as Na, Mg, Ca, K, Ti, and Fe that can promote further
reactions, therefore, could not be used for the process on a larger scale [64].
Clays may be used as catalysts for plastic degradation. However, they require higher
temperatures for pyrolysis than zeolites. Clays act like solid acid catalysts and they have
been used in the petroleum industry before zeolites were discovered. Because of their
affordable price and availability, clays were extensively studied and applied for the plastic
pyrolysis process. The acidity and activity of clays can be enhanced by pillaring them (PILC)
and, subsequently, by applying an acid treatment. Layered clay forms a two-dimensional
porous network, with a microporous size larger than zeolites. PILC have a grid of voids
and they are not as flexible as the parent clays [82]. Mixed plastics (HDPE, PS, PP, and PET)
have been pyrolyzed in the presence of modified pillared clays (PILC) and Al-PILC [83].
Budsaereechai et al. [54] have investigated the application of pelletized bentonite clay as a
catalyst for the pyrolysis of PS, PP, LDPE, and HDPE. As previously stated, PS contains
mainly aromatic hydrocarbons (gasoline-range), whereas longer aliphatic hydrocarbons
(for diesel engines) are present in PP, LDPE, and HDPE. The pelletized form of catalysts
eliminates the pressure drop and reduces the pyrolysis processing time. Furthermore, due
to the high acidity of the bentonite catalyst, no wax is formed during the process.
Experiments were carried out by Auxilio et al. [84] on five zeolitic and clay-based
catalysts (pelletized and powdered zeolite-based catalysts and clay) for the pyrolysis of
virgin HDPE, HDPE waste, and mixed plastic waste. A two stage thermo-catalytic process
was detected and monitored in a bench scale reactor, with a continuous feeding system.
This work outlined important information for the possible upscaling process: diesel fuel
can be produced by two-stage thermo-catalytic cracking, by optimizing the waste plastic
composition. The acid strength of the catalysts is crucial for reaching a good selectivity
of the hydrocarbon fraction, since a higher acidity leads to gasoline formation, whereas
a lower-to-mild acidity leads to the formation of diesel. In addition, mesopore volume is
an important factor for avoiding catalyst coking, especially when the mesopore volume
is small and the coke formation is more prominent; a pelletized form of the catalyst is
favorable over a powder form, because it avoids the large pressure drop in the reactive
distillation column [84].
Symmetry 2023, 15, 38 9 of 19

Five different plastic types (HDPE, LDPE, PP, PS, and PET) were mixed and pyrolyzed
in a fixed-bed reactor (temperature up to 400 ◦ C, 90 min). Natural catalysts (clays and
dolomite) and a synthetic catalyst (pelletized zinc oxide) were used for the plastic pyrolysis.
Based on the calculations of liquid and gas yields, the study has concluded that the use of
natural catalysts does not give a significantly different amount of fuel yields compared to
synthetic catalysts [31]. Thermal and catalytic pyrolysis of PP, LDPE, and HDPE, as well
as mixtures of these three materials, were carried out in a batch reactor, in the presence of
calcium bentonite. The presence of a catalyst had accelerated the reaction and improved
the quality of the condensable fraction. Furthermore, the reaction time decreased with the
increase of the catalyst concentration. This means that the reaction rate increased with
increasing the catalyst concentration, due to the high surface area and the catalyst’s acidity.
The ideal catalyst-to-plastic ratio is found to be 1:3 at 500 ◦ C [17]. By using this optimal
ratio, the highest yields of liquids were obtained: 88.5 wt.% for PP, 82 wt.% for LDPE,
82.5 wt.% for HDPE, and 81 wt.% for mixed plastics [17].
An interesting study was carried out by Nguyen et al. [85] in which the pyrolysis of
PP waste plastics in the presence of natural-clay-mineral NCM, with LaFeO3 nanoparticles,
was studied. The degradation of PP was investigated using thermogravimetry (TG) and
differential scanning calorimetry (DSC). The results showed that pyrolysis of PP takes
place between 460 and 480 ◦ C, and the formation of coke was observed on the surface
of the catalyst. The study also reported that in the presence of the catalyst the cracking
component consisted of 49.3% and 34.4% of alkenes and alkanes, respectively. Recently,
a comprehensive overview of polystyrene pyrolysis was reported in the literature [86].
The effects of temperature, reactor type, and catalysts on the oil yield were also discussed.
When bentonite catalysts are used for the pyrolysis of PS, mostly styrene compounds were
formed. On the other hand, zinc catalysts promoted better selectivity of the end products,
while the spent FCC catalyst was highly efficient in the production of liquid yields. Calcium
oxide represents an economical and very effective catalyst in the depolymerization of PS
into styrene compounds.
A modified natural zeolite was used by Miandad et al. [87] as a catalyst for the
pyrolysis of plastics containing PP, PS, PET, and PE. In order to improve the catalytic
properties, natural zeolites from Saudi Arabia were treated in a novel thermal activation
process followed by an acid treatment with HNO3 . The degradation of PET and PE
require higher temperatures compared to other types of plastic. PE is a long chain branch
structure and its degradation occurs via random chain scission, which requires a high
temperature. The decomposition of PET follows the ester link random scission, where
oligomers are formed as the resulting compounds. The highest amount of liquid oil is
obtained via the catalytic pyrolysis of PS in comparison with those obtained through the
catalytic degradation of PE and PP. Liquid oil produced from the catalytic pyrolysis with
two selected catalysts showed high aromatic content with aliphatic and other hydrocarbon
compounds. The obtained liquid oils had higher heating values (HHV) in the range of
conventional diesel.

3.4. Application of Other Types of Catalysts for the Catalytic Pyrolysis of Plastic
An interesting study was conducted by Cocchi et al. [88], where the plastic film residue
(PFR) from plastic waste recycling (polyolefin mixture residual) was pyrolyzed in the pres-
ence of coal fly ash (CFA) and CFA-derived zeolites, aiming at investigating the catalyst’s
effect on yields and the quality of the obtained oils. CFA-derived zeolites were produced
from CFA by melting in the presence of NaOH, followed by a hydrothermal method
NaX/CFA, and by a further acidification HX/CFA. The best results were achieved with
HX/CFA, since it reduced the endothermic contribution, and, at the same time, improved
the gas and oil yield, as well as the selectivity towards the gasoline-range products.
Symmetry 2023, 15, 38 10 of 19

Dai et al. [89] have studied the conversion of polyolefin waste into low aromatic
naphtha in a microwave pyrolysis reactor. Various catalysts were screened in order to
choose the best one for the conversion of HDPE into shorter-chain olefins with the smallest
aromatic selectivity. Mesoporous silica SBA-15(SiO2 )-supported metal catalysts (Al, Co,
Ni, Zn, etc.) were tested for the pyrolysis process. Among the tested catalysts, Zn/SBA
showed to be the most promising candidate for the pyrolysis of polyolefins. Integration of
ZnO altered the mesoporous structure of SBA-15 (Santa Barbara Amorphous) catalyst and
increased its acidity. This led to higher catalytic activity for the conversion of polyolefins
into shorter hydrocarbon chains with a low aromatic selectivity. In the same study, zeolites
were also tested and their performances compared with that of SBA-15 for the pyrolysis of
polyolefins. In particular, USY and ZSM-5 were chosen for this reaction. In comparison
to SBA-15 catalysts, zeolites seem to have a better cracking performance, but the main
constituents in the liquid oil were aromatic hydrocarbons, which are not suitable for
converting naphtha into plastic monomers [89].
Hydrocracking of LDPE was monitored over commercial zirconia nano powders with
a fixed amount of sulfate and various amounts of Pt [65]. The addition of Pt on sulfated
zirconia resulted in an increase in the catalyst’s acidity and reduction in the crystallinity of
ZrO2 . As a consequence, when higher concentrations of Pt were used, gasoline production
was increased.

4. Comparison between Thermal and Catalytic Pyrolysis

Many examples were found in the literature where thermal and catalytic pyrolysis of
plastic waste were considered and their performances compared. In this section, a short
survey of some of the most relevant results is reported.
Thermal pyrolysis of PP and HDPE were investigated by Ahmad et al. [90], by carrying
out the pyrolysis reaction in a steel microreactor. The conversion for PP was 98.66% (liquid:
69.82%, gas: 28.84%, and residue: 1.34%) at 300 ◦ C, while the conversion for HDPE at
350 ◦ C was also high, 98.12% (liquid: 80.88%, gas: 17.24%, and residue: 1.88%). Both liquids
obtained by pyrolysis of PP and HDPE showed fuel-like criteria.
Thermal degradation and catalytic pyrolysis of real-world waste plastics and single
plastic components (PE, PP, PS, and PET) were studied by Muhammad et al. [91]. Pyrolysis
was conducted in fixed-bed reactor, and zeolite HZSM-5 was used as a catalyst. Feedstock
sample of the real-world plastic contained mostly PE, PP, and PET. The thermal pyrolysis of
waste plastic yielded a high amount of oil/wax (81–97 wt.%). By addition of a catalyst the
amount of oil/wax decreased to between 44 and 51 wt. %. The TG analysis of individual
plastic polymers showed that the degradation temperature of PS is around 420 ◦ C, which
is lower than those of PET and PP (around 480 ◦ C). Thermal and catalytic pyrolysis of
HDPE waste was studied under an inert atmosphere at 450 ◦ C in a packed bed reactor [92].
Various bed materials (sand, cement, and white clay) were tested to investigate the thermal
cracking of HDPE. Sodium hydroxide, HUSY, and Hß zeolite were used to enhance the
pyrolysis of HDPE. The highest yield of liquids during thermal degradation of HDPE
(82%) was obtained by using a powder bed reactor. In the catalytic pyrolysis, each catalyst
was examined with each type of reactor bed. The yield of the products changed when
HUSY or Hß were used as a catalyst, with changing of the reactor bed material. Another
study where plastics were processed by thermal and catalytic pyrolysis was reported by
Saeaung et al. [93]. In this study, HDPE, LDPE, PP, and PLA were obtained. The effect
of pyrolysis temperature and catalyst on the liquid composition and yield were studied.
Thermal pyrolysis of HDPE and LDPE yielded high amounts of waxes. On the other side,
the thermal degradation of PP and PLA led to the formation of liquids and waxes. The
TG curves of HDPE, LDPE, and PP showed only one step of mass loss occurring between
400 and 500 ◦ C, because of the similar chemical bonds between the molecular structures.
In addition, only one step is expected in the TG curve of PLA, but at lower temperatures
(300–400 ◦ C). The maximum degradation temperatures were found at 490, 473, 454, and
371 ◦ C for HDPE, LDPE, PP, and PLA, respectively. The difference in the degradation
Symmetry 2023, 15, 38 11 of 19

temperatures can be ascribed to the chemical structure of each plastic type. HDPE has a
linear structure, whereas LDPE is more branched. As a consequence, the heat transfer can
be favored within the latter matrix. In another study [37], the authors used polyethylene
film waste and different catalysts, aiming to investigate the influence of their presence on
the formation of high-quality liquid oil. The best results, in terms of the reduction of wax
consistency, were obtained by using HUSY, Zeocelcliopilolite, HBEA, and Na-Y-Geace.
Thermal and catalytic pyrolysis of LDPE, HDPE, and PP, and mixtures of LDPE and
PP, were performed under a nitrogen atmosphere in a laboratory-scale batch reactor at
460 ◦ C. For the catalytic pyrolysis run, a zeolite-type catalyst was used. The application
of a catalyst reduced the degradation temperature of the polymers, which implied a
reduction of the energy consumption of the process. Thermal cracking of PP yielded about
86 and 94 wt.% of liquids for PP and LDPE, respectively [36]. The effect of the catalyst
fraction (powdered acidic ultrastable Y zeolite—HUSY) on the pyrolysis of HDPE was
also investigated [94]. The study showed how the conversion to volatile products changes
with the catalyst fraction in the system with two different reactor temperatures (693 and
643 K), under a nitrogen atmosphere for 25 min. It was found that at 643 K the catalyst
fraction of 11 or 20% was not enough for the complete reaction of the polymer. When the
temperature was increased to 693 K, the conversion decreased when the catalyst fraction
was increased. At this temperature, 11% of catalyst was enough to accomplish the whole
polymer conversion. Adding more catalyst would lead to the negative effect of converting
more polymer into coke. Secondary reactions took place when the strength of the acid sites
of higher catalyst fractions was high. Furthermore, the overcracking of primary products
into smaller molecules was found, owing to the secondary reactions, so that more gaseous
products were obtained. Consequently, the product distribution was shifted towards lighter
hydrocarbons. Raveh-Amitet et al. [95] have examined thermal and catalytic pyrolysis of
HDPE with ZSM-5 and Zeolite Y. The decomposition of HDPE was also monitored with
and without catalysts using TG. Among the tested zeolites, ZSM-5 [25] led to the most
significant decrease of the decomposition temperature. This result is worth noting, since a
decrease of temperature leads to a lower energy consumption. Susatriawan et al. [96] have
investigated the effects of zeolite size during the occurrence of the pyrolysis of LDPE. It
was concluded that the smaller size of the zeolite influenced the rates of both heat transfer
and pyrolysis, the pyrolysis temperature, the reaction rate, and the yield of oil.
Plastics from waste electrical and electronic equipment, namely WEEE, can be also
pyrolyzed in order to obtain oil yields. In the study by Santella et al. [70], this type of waste
was pyrolyzed in a bench-scale semi-batch reactor. Plastic was thermally and catalytically
pyrolyzed. HUSY and HZSM-5 were used as catalysts in the catalytic run, at a temperature
of 400 ◦ C. The thermal run was conducted at 400, 600, and 800 ◦ C. The highest oil yields
were obtained in the presence of HZSM-5, and at 600 and 800 ◦ C without catalysts. More
solid particles were collected when HUSY was used. The presence of catalysts contributed
to reach higher yields of lighter and viscous oil yields, and the products contained a higher
concentration of monoaromatics under catalytic conditions, when compared to the oil
produced in the thermal pyrolysis run. Waste polypropylene plastic was treated with
pyrolytic (thermal and catalytic) processes using a batch reactor and FCC as a catalyst.
Thermal pyrolysis gave the maximum amount of liquid oil, while the catalytic pyrolysis
reduced its yield, and increased that of gas [97]. Finally, Onwudili et al. [98] used FCC, Y,
and ZSM-5 zeolites for the catalytic pyrolysis of a plastic mixture containing HDPE, LDPE,
PP, PS, and PET that simulated municipal solid waste. The application of catalysts resulted
in an increase of the gas yield and a decrease in that of oil.
Finally, all the information gathered for thermal and catalytic pyrolysis are summa-
rized in the Table 1.
Symmetry 2023, 15, 38 12 of 19

Table 1. Comparison between thermal and catalytic pyrolysis.

Thermal Pyrolysis Catalytic Pyrolysis

Requires high temperatures Lower reaction temperature
Better conversion rate, with reduction in reaction time,
Resulting oils have low quality
temperature, and activation energy
Gases from the process can be used for different gas engines Improved oil quality and better distribution of hydrocarbons
Production of a wide range of HC and solid residues Smaller fractions of solid residue
Homogeneous or heterogeneous catalysts

5. Molecular Symmetry Effects in Pyrolysis Processes

No studies are available in the literature specifically focused on the relevance of
molecular symmetry in the pyrolysis of plastics. However, some conclusions can be drawn
on the basis of the research carried out on the effects of molecular symmetry and steric and
geometrical issues caused by different molecules that are subjected to pyrolysis process,
especially in the presence of catalysts. In this section, relevant examples are presented and
the results critically discussed.
Several studies have explored the different aspects of molecular symmetry of certain
molecules when pyrolysis takes place under different experimental conditions. In the study
by Serinyel et al. [99], pyrolysis of the four symmetric ethers, diethyl ether (DEE), di-n-
propylether (DPE), di-isopropylether (DIPE), and di-n-butyl ether(DBE),was performed
in a jet-stirred reactor, and the main products were CO, CH4 , H2 , and C2 H4 . Furthermore,
all ethers produced the n/2 alcohol and olefin as the result of a molecular reaction (to a
small extent). This study aimed to give new kinetic information on the product analysis
of the four symmetric ethers. Another study dealt with pyrolytic decompositions of
symmetrical and unsymmetrical organotellurium (II)-compounds: Pr2 Te, di-tert-butyl
telluride Bu2 Te, (allyl)2 Te, (2-metylally)2 Te, and (3-metyl-3-butenyl)2 Te. A combination
of gas chromatography and gas chromatography/mass spectroscopy were applied and
it was found that the pyrolytic decomposition occurs via bond homolysis [100]. In recent
years, many authors focused their attention on the analysis of degradation kinetics of
polymers and plastic waste [101,102]. In the study by Tian et al. [103], the kinetic behavior
and release of evolved gases during the pyrolysis of waste tea was investigated by the
TG-FTIR technique. As far as the kinetic analysis was concerned, three model-free, and
three model-fitting models were selected for describing the mechanism of the pyrolysis
process. The results showed that the three-dimension diffusion (spherical symmetry) model
(D3) fits well to model the pyrolysis mechanism of waste tea. Diffusion mechanisms were
also determined for the reaction kinetics of the degradation of nanocomposite materials
based on copolymers of styrene and n-butyl methacrylate with either graphene oxide or
functionalized graphene oxide [104].
Haas and Ring [105] have examined the thermal degradation of SiH4 and Si2 H6 in the
presence of C2 H2 . This decomposition was studied with orbital symmetry considerations.
The activity of a catalyst is mainly determined by its structures. Since the catalysts have a
certain degree of porosity, and the pores have an irregular shape, it is difficult in this case
to analyze the symmetry effects of catalysts.
In the pyrolysis of macromolecules such as waste plastic or any other material, where
the aim is to produce diesel or oil, the size of the zeolites pores is crucial, since it does
(or does not) allow the diffusion of heavy compounds. As already noted, (Section 3.2),
zeolites are microporous, but there is the possibility of forming mesopores in order to
overcome this limitation. One possibility is to use organic surfactants during the synthesis
of zeolites. Another option is dealumination, which comes together with damaging of
the crystal matrix and the decrease of active acid sites [42]. The size of the pores is an
important factor in determining the products and reactants that can reach the active sites of
the catalyst [106].
 does not) allow the diffusion of heavy compounds. As already noted, (Section 3.2), zeolites
are microporous, but there is the possibility of forming mesopores in order to overcome
this limitation. One possibility is to use organic surfactants during the synthesis of zeo-
lites. Another option is dealumination, which comes together with damaging of the crystal
Symmetry 2023, 15, 38 matrix and the decrease of active acid sites [42]. The size of the pores is an important factor 13 of 19
in determining the products and reactants that can reach the active sites of the catalyst
[106].
A basic scheme of polymer degradation in the presence of an acid catalyst is pre-
A basic scheme of polymer degradation in the presence of an acid catalyst is presented
sented in Figure 3. Thermal cracking takes place on the outer surface of the solid catalyst,
in Figure 3. Thermal cracking takes place on the outer surface of the solid catalyst, while
while the internal
the internal pores behave
pores behave as channels
as channels for selective
for selective passagepassage and breakdown
and further further breakdown
of larger
of
hydrocarbons. As a consequence, gases are mainly produced in the in
larger hydrocarbons. As a consequence, gases are mainly produced the small
small pores,pores,
while
while
waxeswaxes are produced
are produced on theside
on the outer outer sidecatalyst.
of the of the catalyst. At thesurface,
At the catalyst catalystlow-molecular-
surface, low-
molecular-weight
weight hydrocarbons hydrocarbons
are producedare produced that areatvolatile
that are volatile at the reaction
the reaction temperature
temperature and can
and can diffuse through the molten polymer film as final products, or can
diffuse through the molten polymer film as final products, or can react further within react further
the
within the pores. The catalytic reaction is improved by microporous catalysts,
pores. The catalytic reaction is improved by microporous catalysts, producing gases and producing
gases and the
lowering lowering the liquid
liquid product product
yield, with yield,
a betterwith a better
quality thanquality thanofincatalytic
in the case the casepyrolysis
of cata-
lytic pyrolysis with
with macropores [107].macropores [107].

Polymercracking
Figure3.3.Polymer
Figure crackingover
overaasolid
solidacid
acidcatalyst
catalyst[107].
[107].

Theporous
The porousstructure
structure isisimportant
important when
when catalysts
catalysts are
are used
used inin situ
situ [108].
[108]. IfIfthe
thecatalyst
catalyst
is used directly, the material recovery, which is one of the main goals [109],
is used directly, the material recovery, which is one of the main goals [109], is difficult, is difficult,
because the
because the catalyst
catalyst pores
pores are
areblocked,
blocked,since
sinceplastic
plasticfeedstock
feedstock becomes
becomes sticky
sticky[1].[1].
However,
How-
when catalysts are used directly, the quality of the obtained liquid oils is
ever, when catalysts are used directly, the quality of the obtained liquid oils is improved, improved, but
formation of coke or impurity is more greatly favored. The tridimensional
but formation of coke or impurity is more greatly favored. The tridimensional porous porous structure
of the ZSM-5
structure of thecatalyst
ZSM-5results
catalystinresults
less coke deposition
in less because of
coke deposition the circulation
because of aromatic
of the circulation of
coke, forerunner to the outer part of zeolite micropores. The increase in
aromatic coke, forerunner to the outer part of zeolite micropores. The increase in the sur- the surface area
improves
face the interaction
area improves between the
the interaction catalyst
between theand pyrolysis
catalyst and gas, whichgas,
pyrolysis results
whichin cracking
results
to gaseous products. Y zeolite has a high surface area and it contributes to the formation of
in cracking to gaseous products. Y zeolite has a high surface area and it contributes to the
gaseous products, while a natural catalyst with a low surface area favors the formation of
formation of gaseous products, while a natural catalyst with a low surface area favors the
liquid products [58]. Polyethylene can diffuse into the HZSM-5 pores in contrast to that
formation of liquid products [58]. Polyethylene can diffuse into the HZSM-5 pores in con-
observed for other polymers such as polypropylene. In addition, polyethylene’s branches
trast to that observed for other polymers such as polypropylene. In addition, polyeth-
and chain ends can diffuse into the HZSM-5 pores and make contact with the acid sites,
ylene’s branches and chain ends can diffuse into the HZSM-5 pores and make contact with
thus causing an increase in the catalytic reactivity. HZSM-5 has strong and weak acid sites,
the acid sites, thus causing an increase in the catalytic reactivity. HZSM-5 has strong and
while HUSY has only weak acid sites. Strong acid sites are able to favor the degradation
weak acid sites, while HUSY has only weak acid sites. Strong acid sites are able to favor
and cracking of heavy hydrocarbons [63].
the degradation and cracking of heavy hydrocarbons [63].
Small pores influence the diffusion of vapors and small molecules into the cavities,
Small pores influence the diffusion of vapors and small molecules into the cavities,
with subsequent conversion of these molecules into aromatic compounds. The bigger size
with subsequent conversion of these molecules into aromatic compounds. The bigger size
of the catalyst cavities is an advantage for the conversion of macromolecules into smaller
species and for the reduction of mass transfer resistance of the intermediate compounds.
However, long-chain or branched structures cannot enter cavities and they crack on the
catalyst surface. Unfortunately, this cracking process leads to coke formation and the
deactivation of catalysts.
A study on the connections between polymers (polyethylene) and the contact surface
of zeolites as catalysts with different characteristics (hierarchical and standard Beta zeolites,
Y zeolite, ZSM-5, ZSM-12, and MCM-22) was conducted by Calderia et al. [108]. The hierar-
chical Beta zeolite resulted to have a superior external area because of the use of a bulky
silanized agent in the synthesis. In the cracking reactions, the polymeric macromolecules
mostly interacted in the outer surface of the catalysts because of diffusional limitations.
Zeolites with bigger external area values—hierarchical Beta, standard Beta, ZSM-5, and
MCM-22—required lower temperatures for degradation, with a high conversion efficiency.
Symmetry 2023, 15, 38 14 of 19

Microporous zeolite material shows high thermal stability and stronger acid sites. However,
the selection of the zeolite has to be focused on target selectivity, which further implies
that HZSM-5 zeolite enhances the production of olefins, whereas hierarchical Beta and
HY zeolites promote the production of middle distillates [110]. In addition, the kinetics of
the plastic pyrolysis reaction, in the presence of the ZSM-5 zeolite catalyst, modified with
iron (III) oxide, was recently investigated [111]. The improvement of the reactivity on the
catalyst’s surface is due to the doping of the zeolite with iron.
Plastic degradation in the presence of heterogeneous catalysts experiences mass-
transfer limitations because of the bulky and viscous origin of the plastic polymers. In order
to overcome this constraint, very structured mesoporous silica can be used as a catalyst.
The ordered mesopores allow better diffusion of the polymers, and they can also improve
plastic cracking by speeding up the degradation rate and increasing the yield of liquid
products [62]. A number of studies have examined the catalytic pyrolysis of plastics with
mesoporous catalysts [64,112–116].
Y zeolites were found to positively affect the selectivity and thermal stability of
catalytic plastic degradation. They increased the formation of light hydrocarbons, and
moved the selectivity towards gasoline and diesel fuels with lower olefin concentration.
Furthermore, this specific type of catalyst allows a high number of reuses, and shows
effective performances in plastic conversion at lower temperatures (<500 ◦ C) compared to
other catalysts. Thus, less acidic Y zeolites with lower alumina content (higher Si/Al ratio)
reduces the cracking activity, while Y zeolites with a lower Si/Al ratio produce high yields
of aromatic hydrocarbons such as benzene and toluene. This is due to the combination of
different factors, such as high surface area, large pores, and strong acid sites, as the most
important [72].
The use of catalysts leads to the production of valuable liquid fuels with a narrow
hydrocarbon distribution in the petrol range (C5 ~C12 ) [58]. Furthermore, the decrease of
the reaction temperature reduces the energy supplied as heat for the extremely endothermic
reactions involved in the process. A better conversion of plastic is obtained by using an acid
catalyst with meso- and micropores. Polymer cracking occurs in mesopores and further
cracking is favored by the presence of micropores [58].
Structure–property relationships can be used to assess the potential applications of
symmetrical and unsymmetrical azoalkanes of the general formula R0 −N = N−R and
related azoxy, hydrazone, as well as azine, derivatives as novel flame retardants for
polypropylene, either alone or in combination with commercially available flame retar-
dants [117]. Although bromine-containing compounds—in combination with antimony
oxide—are very efficient flame retardants [118,119], attention is given to monitor the Br
content [118,119] and to try to reduce its amount, in the effort to develop more environment-
friendly systems [117].

6. Conclusions
Plastic utilization is increasing all over the world, and the problem of plastic waste
generation is a growing concern. Plastic waste pyrolysis seems to be a promising method
for plastic waste reduction. Pyrolysis of plastic waste is an oxygen-free process, which
results in polymer cracking with the formation of gaseous and liquid products that can be
used as valuable chemicals or fuels.
Plastic pyrolysis can be thermal or catalytic. However, the results of many studies
available in the literature lead to conclude that the latter presents more benefits com-
pared with the former. Some of the most important advantages include the supposed
increase of the pyrolysis rate due to the reduction of activation energy, narrow hydrocarbon
distribution in the products, and the decrease of reaction time.
Catalysts can be homogeneous or heterogeneous, with the latter more often applied
due to their easy separation from the liquid products. The most commonly applied catalysts
for plastic pyrolysis are zeolites, natural clays, and silica-alumina catalysts. However, the
reaction products depend on the type of applied catalyst. The activity of the catalyst
Symmetry 2023, 15, 38 15 of 19

depends on its structure. Therefore, as far as the pyrolysis of plastic polymers is concerned,
the size of the catalyst pores is an important factor influencing the pyrolysis outcome. The
presence of ordered mesopores provides a more effective diffusion of the polymer molecules
leading to better cracking, with the polymer cracking taking place in the mesopores, and
further cracking enhanced by micropores.
Although molecular symmetry is not usually considered in the literature addressing
the pyrolysis of plastics, some conclusions were drawn in the present investigation by taking
into account some case studies on the pyrolysis of molecular substances different from
plastics. In these examples, the effects of molecular symmetry and steric and geometrical
issues, especially in the presence of catalysts, have been critically discussed.
This paper shows that thermal and catalytic pyrolysis of plastic wastes are extensively
studied processes, and that the number of publications investigating this topic is strongly
increasing, thus demonstrating the intensive academic and business attention for this
matter in recent years. An improvement of the investigation on catalytic pyrolysis with
particular reference to the composition and morphology of the catalysts used seems to be
expected in the foreseeable future.

Author Contributions: Conceptualization, S.P. and M.D.; methodology, S.V.C.; investigation, M.D.;
data curation, S.P., M.D., A.C. and S.V.C.; writing—original draft preparation, S.P., M.D. and S.V.C.;
writing—review and editing, S.P., M.D. and S.V.C.; visualization, A.C.; supervision, S.V.C. All authors
have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

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