Progress in Energy and Combustion Science 93 (2022) 101021

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: [Link]/locate/pecs

Pyrolysis technology for plastic waste recycling: A state-of-the-art review

Leilei Dai a, b, Nan Zhou a, Yuancai Lv a, Yanling Cheng a, c, Yunpu Wang b, Yuhuan Liu b,
Kirk Cobb a, Paul Chen a, Hanwu Lei d, Roger Ruan a, *
a
Center for Biorefining and Department of Bioproducts and Biosystems Engineering, University of Minnesota, 1390 Eckles Ave., St. Paul MN 55108, United States
b
State Key Laboratory of Food Science and Technology, Engineering Research Center for Biomass Conversion, Ministry of Education, Nanchang University, Nanchang
330047, P.R. China
c
Biochemical Engineering College, Beijing Union University, No. 18, Fatouxili 3 Area, Chaoyang District, Beijing 100023, P.R. China
d
Department of Biological Systems Engineering, Washington State University, Richland, WA 99354, United States

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

Keywords: Discarded plastics can be converted to various fuels and chemicals to generate positive economic value instead of
Plastic waste polluting the environment. In the past few years, pyrolysis has attracted much attention in the industrial and
Pyrolysis scientific communities as a promising versatile platform to convert plastic waste into valuable resources.
Fuels
However, it is still difficult to fine-tune an efficient and selective pyrolysis process to narrow the product dis­
Chemicals
Circular economy
tribution for a feasible commercial production. Furthermore, traditional plastic-to-fuels technology looks like
another expensive way to burn fossil fuels, making no contribution to the plastic circular economy. By learning
from the developed plastic-to-fuels technology, achieving the conversion of plastic waste into naphtha or plastic
monomers that can be used for new plastic manufacturing in a closed-loop way is a more promising resource
recovery pathway. However, there is no comprehensive review so far about achieving plastic waste recycling/
upcycling by pyrolysis. This article will provide a critical review about the recovery pathways of plastic pyrolysis
based on the various products (fuels, naphtha, hydrogen, and light olefins). It will overview the recent advances
regarding plastic pyrolysis process and reactor design, introduce various recovery pathways based on the py­
rolysis process, summarize process optimization and catalyst development, discuss the present challenges for
plastic pyrolysis, highlight the importance and significance of creating a plastics’ circular economy, discuss the
economic feasibility, the environmental impact, and outlook for future development for plastic pyrolysis. This
review presents useful information to further develop and design an advanced pyrolysis process, with an
improved efficiency, desirable product selectivity, and minimum environmental impacts. It is helpful to
encourage more circular economy-oriented research aimed at converting waste plastics to naphtha and plastic
monomers instead of simply producing fuels from the scientific communities of chemistry, energy, and the
environment.

1. Introduction accompanied by a huge amount of plastic solid waste (PSW), with 6300
Mt of PSW being generated by the end of 2015 and most of them
Plastics are ubiquitous and have become an integral component of accumulating in landfills or the natural environment (Fig. 1).
modern society. Growing annual demand for plastics has been observed Global PSW pollution has led to serious environmental consequences
in the last few decades, due to the ever-increasing dependency on these both on land and in the oceans, because the PSW cannot easily be
versatile materials used in a variety of ways, such as food packaging, degraded in the natural environment, unlike biomass. The accompa­
hardware, electronics, and construction. This growing demand has been nying micro- and nano-plastic particles are threatening the ecosystem

Abbreviations: Psw, plastic solid waste; Vocs, volatile organic compounds; Pcdds, polychlorinated dibenzo-para-dioxins; Pcdfs, polychlorinated dibenzofurans; Pet,
polyethylene terephthalate; Hdpe, high density polyethylene; Ldpe, low density polyethylene; Pe, polyethylene; Pvc, polyvinyl chloride; Pp, polypropylene; Ps,
polystyrene; Pahs, polycyclic aromatic hydrocarbons; Csbr, conical spouted bed reactor; Sic, silicon carbide; (gc × gc-tofms), two-dimensional gas chromatography
coupled with time-of-flight mass spectrometry; GC–MS, Gas Chromatography-Mass Spectrometer; FTIR, Fourier Transform Infrared Spectroscopy; NMR, Nuclear
Magnetic Resonance; SEC, Size Exclusion Chromatography; PC, polycarbonate.
* Corresponding author.
E-mail address: ruanx001@[Link] (R. Ruan).

[Link]
Received 16 September 2021; Received in revised form 9 January 2022; Accepted 3 June 2022
Available online 5 August 2022
0360-1285/© 2022 Elsevier Ltd. All rights reserved.
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

and even human health [2,3]. Although this makes PSW disposal and operation, which can probably obtain valuable products, but these
management a matter of paramount importance, technological limita­ methods can only be done with uncontaminated and single-use plastics
tions pose a great constraint on the development of PSW recycling [4]. and produce polymers which have inferior properties to virgin materials
Without a bold shift in approach, PSW mismanagement may continue to [6]. Serious contamination and a high variety in plastics in the waste
worsen, thereby missing opportunities to harvest these valuable waste stream also affect the product quality from mechanical recycling that
materials. Developing a systematic and “circular economy” manner to dominates current recycling practices. Apart from mechanical recycling,
address PSW pollution and stop catastrophic ocean plastic pollution is current PSW recycling relies heavily on “quaternary” recycling which
imperative. results in contamination of nearby landscape surfaces, as well as air
Up to date, primary, secondary, tertiary, and quaternary recycling pollution emissions such as volatile organic compounds (VOCs), NOx,
methods for PSW have been developed, as shown in Fig. 2 [5]. Currently, SOx, polychlorinated dibenzofurans (PCDFs), and dioxins [7]. A more
primary and secondary recycling are widely applied, due to ease of promising recycling pathway, “tertiary” recycling, focuses on the

Fig. 1. Global primary plastics production, waste generation, recycling rate and disposal. a. Global production, use, and fate of plastics (in million metric tons) from
1950 to 2015. b. Cumulative plastic waste generation and disposal (in million metric tons). (Adapted from [1] with permission from Science).

2
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Fig. 2. Four main techniques of PSW recycling. (Adapted from [5] with permission from Elsevier).

Table 1
Main features and characteristics of thermochemical techniques. (Adapted from [14]).
Process types Incineration Gasification Hydrogenation Pyrolysis

Definition and Excess burning of feedstock whilst Defined as the treatment of PSW in Treatment of PSW under high Pyrolysis is a thermal degradation in
main recovering power and heat after steam oxygen deficient environment to pressure with hydrogen media to the presence of heat with a
objective generation. Air is used in abundance over produce fuel or synthesis gasses produce high quality products, surrounding inert atmosphere,
stoichiometric as an oxidizing agent. through gas reforming. syncrude oil. typical nitrogen or vacuum.
Main features ● Off gas is disposed with advanced ● Carbon in PSW is converted into ● Visbreaking is typically applied ● The process maximizes
electrostatic precipitators, fabric filters, syngas which comprises CO, H2, as a pretreatment process before degradation of PSW to liquid oil and
scrubbers, etc. and then send back to stack. CH4, and light hydrocarbons. hydrogenation. gas.
● The most common technologies are ● Residues including ash and slag ● The process is still in research ● The main product, liquid oil, can
fluidized bed combustion, moving grate, can be used as construction and development phases, be easily upgraded into
and rotary kiln. materials. requiring high cost catalysts. transportation fuels.
● The produced bottom ash can be treated ● Scrubbing is conducted to remove
for recovering iron, steel, aluminum, particulates, hydrocarbons, etc.
copper, and zinc. ● Syngas can be used for heat,
● Very low bottom ash, suitable for energy, or electricity generation.
landfill. Syngas can also be used to produce
transportation fuels (e.g. Fischer-
tropsch reaction, Methanol-to-
Gasoline process, etc.).

Main products ● High temperature flue gasses ● Syngas (H2 and CO) ● Syncrude ● CO, H2, and hydrocarbons
●Energy in form of heat and power ● CO2, H2O, and methane ● Natural gas equivalent
Operating The process is operated generally under The process is operated generally High pressures reaching 100 bars Open vent pressure to slightly above
conditions atmospheric pressure, with temperatures under atmospheric pressure, with in some sections with reaction atmospheric, with temperature
between 850 ◦ C and 1200 ◦ C. temperatures between 850 ◦ C and temperatures ranging from 350 ◦ C ranging from 300 ◦ C to 900 ◦ C.
1200 ◦ C. to 490 ◦ C.
Main Sulfur dioxide, nitrogen oxides, and Tar, H2S, and HCl HCl and residues H2S, and HCl
pollutants dioxins

depolymerization of PSW to produce fuels and chemicals that can be there would be less CO2 emission and toxic pollutants can be minimized.
alternatives to petroleum-based products. Here, considerable research Especially, polychlorinated dibenzo-para-dioxins (PCDD) and poly­
achievement has been accomplished, regarding the enzymatic degra­ chlorinated dibenzofurans (PCDF) can be mitigated largely in the py­
dation of plastics. But it was pointed out that the degradation capability rolytic conditions (lower than 600 ◦ C and the absence of oxygen)
of enzymes largely depends on the plastic types and given conditions [10–12]. Furthermore, pyrolysis shows specific advantages from the
[8]. Only a few plastic materials, such as polyethylene terephthalate perspective of environmental management, operating costs, product
(PET) and polyamides, can be enzymatically converted into oligomers or value, and alternative energy production. Techno-economic analysis
monomers due to the existing of hydrolysable bonds. Other common indicates that producing petroleum intermediates from PSW may have
plastics which contain saturated carbon–carbon backbones cannot be significant economic potential [13]. At this point, pyrolysis has been the
broken down to desirable molecules. focus of thermochemical recycling, and thermochemical recycling has
Comparatively speaking, thermochemical conversion of PSW is a always been at the center of PSW management when it comes to how to
quite popular and promising choice for PSW recycling. Compared with respond to the PSW pollution.
biological recycling, thermochemical recycling is easier to scale up and Current research about this topic mainly focuses on plastic pyrolysis
able to treat unsorted and contaminated waste. Table 1 shows main parameters optimization, catalyst development, kinetic analysis, and
features and characteristics of thermochemical techniques. Among reactor design, to improve product yield and selectivity [15–18].
thermochemical pathways, pyrolysis has gained more attention recently Various catalysts, such as Al-SBA-15 [19], fly ash synthesized natural
because it can achieve environmentally friendly conversion of PSW into catalyst [20], zeolites (ZSM-5, Y, □, etc.) [15,21] and, pillared clays
highly valuable fuels and chemicals [9]. Compared to incineration and [22], have been developed and used to enhance the pyrolysis oil yield by
gasification, pyrolysis is carried out in the absence of oxygen so that reducing wax formation and obtain a potentially valuable fuels or

3
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

chemicals. Operating conditions, including the key pyrolysis tempera­ production of different valuable products and provide a state-of-the-art
ture [23], residence time of vapors [24], and catalyst-to-reactant ratio review of this area. Furthermore, the emerging plastic-to-naphtha and
[25], have been optimized to improve plastic-to-fuel feasibility. Typical light olefins technologies that are able to contribute to the circular
types of reactors have been reported for plastic pyrolysis [24–26]. In plastic economy will be highlighted considering that they can be used as
terms of catalytic pyrolysis, in-situ catalysis mode and two-step system the feedstock for new plastic manufacturing by utilizing the existing
(pyrolysis-catalysis) are reported in the literature [27–29]. One chal­ petroleum refining facilities. In addition, techno-economic and envi­
lenge related to in-situ catalysis mode is that the impurities in the PSW ronmental considerations of PSW pyrolysis are discussed to encourage
could potentially deactivate the catalyst materials and the catalyst further study and investment. Overall, it will help researchers and in­
separation after reaction is much more tricky. In contrast, the dustrial partners to fully understand what is going on for plastic pyrol­
pyrolysis-catalysis system is divided into two stages where plastic is ysis and determine what else they can do or if plastic pyrolysis technique
decomposed to primary volatiles at around 500 ◦ C, and then passes is worth the investment.
through a catalytic reforming bed at a given temperature. The advan­
tages of two independent reactors in series are very clear, compared to 2. Conceptual design
the conventional one step pyrolysis/gasification process. First of all,
controlling the pyrolysis temperature and reforming parameters can be 2.1. Plastics
addressed separately, allowing independent temperature optimization
and injecting steam into the subsequent reforming reactor without There are many different types of plastics available in the market as
affecting the pyrolysis process. Second, the catalyst is separated from the shown in Fig, 3. It is unfortunate that only PET, high density poly­
PSW pyrolysis reactor, effectively avoiding the mass and heat transfer ethylene (HDPE), and low density polyethylene (LDPE) have been
issues posed by high plastic viscosity and making the catalyst recovery routinely recycled, with a recovery rate not much higher than 5% [33].
much easier. In addition, there is no contact between the reforming Generally speaking, both proximate analysis and elemental analysis of
catalysts and PSW feedstock so that the impurities present in the PSW various plastics are necessary to understand the pyrolysis process of
may no longer cause undesirable catalyst deactivation. plastics. Proximate and elemental analyses of different plastics are
This review primarily introduces recent advances in converting shown in Table 2. In terms of proximate analysis, volatile matter content
plastics to fuels, naphtha, light olefins, and hydrogen by catalytic py­ plays a key role in determining the pyrolysis oil yield, where more
rolysis. A few review articles summarized plastic pyrolysis for fuels volatile matter in a plastic lead to a higher pyrolysis oil yield. On the
production in the past few years, including process parameter conditions other hand, in order to obtain high quality petroleum-based products,
[30], examples of plastic-to-fuel processes [9], reactor design [31], and carbon and hydrogen are the desirable components instead of oxygen or
chemistry [32]. Different from them, the scope of the article will be chlorine.
narrowed to focus on catalytic pyrolysis of plastics for selective

Fig. 3. Various commercial plastics and corresponding applications. (Reprinted from [34] with permission from Elsevier).

4
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Table 2
Properties of different plastics.
Plastics SPI codesa Chemical structure Proximate analysis (wt.%) Elemental analysis (wt.%) Degradation temperature ( ◦ C) Ref.
FCb VMc Ash C H O Cl Td5% Temax

PET 1 13.15 86.85 0 62.50 4.21 33.29 0 400 435 [35–37]

HDPE 2 0 100 0 85.50 14.50 0 0 415 460 [38,39]

PVC 3 2.77 97.23 0 38.40 4.90 0 56.70 270 290, 465 [31,40,41]

LDPE 4 0.02 99.98 0 85.40 14.60 0 0 375 460 [40,42,43]

PP 5 0.03 99.97 0 86.44 14.46 0 0 355 470 [40,44,45]

PS 6 0 99.80 0.20 93.63 6.36 0 0 400 435 [35,46,47]

a
means codes defined by Society of the Plastics Industry.
b
represents fixed carbon.
c
represents volatile matter.

Fig. 4. Product distribution based on thermogravimetric analysis within the temperature range of 400–750 ◦ C. (Reprinted from [6] with permission from Elsevier).

2.2. Pyrolysis technology significantly increases. It appears that operating under higher temper­
atures may slightly facilitate the formation of aromatics. It is widely
2.2.1. Mechanism for plastic pyrolysis accepted that polyethylene pyrolysis can be illustrated by a free radical
During plastic pyrolysis, long chain polymers are broken into smaller mechanism (initiation), which is followed by random scission and
fractions, and the resulting oils and gasses are both highly valuable chain-end scission (secondary decomposition) and then recombination
precursors of fuels and chemicals [9,48]. Without using any catalyst, of different chains (termination), as shown in Fig. 5 [50,51]. Similarly,
pyrolysis of PP and PE at 500–600 ◦ C mainly produces PS pyrolysis is also considered to proceed via type free radical reactions
C20+hydrocarbons that are a solid wax product at room temperature that include β-scission, hydrogen abstraction, hydrogen transfer, radical
[49]. At higher temperatures, more gas and oil products can be formed, recombination, and disproportionation with the aromatic monomer,
which are composed of C1–C4 olefin mixtures, C5–C20 olefins and a dimer, and trimer as the main products [52–54]. Aromatic monomers
small amount of aromatics, respectively [49]. For example, thermal are mostly produced via unzipping reaction, where the terminal aro­
cracking of PE produces a wide range of hydrocarbons that are primarily matic ring falls off due to the fracture of C–C linkage between two ar­
composed of gasses (C1–C4), C5–C10 non-aromatic hydrocarbons, omatic rings. It can be seen from Fig. 6 that intramolecular hydrogen
mono-aromatics, and waxes (>C11) (Fig. 4). Wax yield experiences a transfer followed by □-scission contributes to the generation of aro­
linear drop with the increasing temperature, while the gas yield matic dimers. However, intermolecular hydrogen transfer followed by

5
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Fig. 5. Reaction mechanism of low-density polyethylene pyrolysis. (Adapted from [63] with permission from Elsevier).

□-scission gives a larger molecule containing three aromatic rings or Furthermore, an effective catalyst can improve the hydrocarbon distri­
more. On the other hand, aromatic dimers and trimers can be formed bution and selectivity, making it more suitable for upgrading to gaso­
through monomer recombination or intermolecular benzyl radical line, diesel, and jet fuels.
addition followed by □-scission [55,56]. However, PVC is totally
different because PVC pyrolysis, without catalysts, can still obtain a high 2.2.2. Process and reactor design
yield of liquid oil that consists of polycyclic aromatic hydrocarbons Unlike some other solid wastes, plastics have some undesirable
(PAHs) instead of wax [57]. It is widely accepted that poly vinyl chloride properties for pyrolysis, such as low thermal conductivity, sticky nature,
(PVC) pyrolysis can be recognized as a three-stage mechanism, including low softening and melting temperatures. Generally speaking, in a py­
(1) dechlorination accompanied with inner cyclization; (2) aromatic rolysis process, a higher heating rate is favorable for liquid oil produc­
chain scission; (3) release of 2–4 rings aromatics [57,58]. During the tion, and minimizes the drawbacks of secondary reactions, which could
PET pyrolysis, the major thermal degradation pathway is considered to cause the formation of more solid residues or gas products. In order to
include □-scission and retro-hydroalkoxylation, yielding benzoic acid achieve the high heat transfer and avoid clogging issues easily occurring
and vinylic products, where the bridging glycol O − C bond can be in pilot and industrial scale systems, advanced reactor designs need to be
cleaved and a β-H atom is transferred to the carbonyl O [59,60]. developed for pyrolyzing plastics based on the most important principle
Furthermore, the ester groups will be released to produce a large amount of improving the heat transfer during pyrolysis and enhancing the en­
of CO2, CO, and ethylene, in agreement with previously reported PET ergy efficiency of this process.
pyrolysis product distribution [61]. A batch reactor can be used to easily implement a plastic pyrolysis,
As we know, the activation energy of pyrolysis reactions will be but a batch system can also cause some problems, such as poor heat
lower if a catalyst is added, which is important for lowering energy transfer; non-continuous operations also pose a challenge for system
consumption of pyrolysis by reducing reaction temperature and/or scale-up [31,64]. Several reactor configurations have been proposed and
processing time. The catalyst can also facilitate the degradation of long developed to minimize heat transfer limitations and avoid common
chain polymers, and reduce or avoid wax formation [62]. In the processing issues in the pyrolysis of waste plastics. The simplest
above-mentioned polyethylene pyrolysis process, the presence of cata­ approach to improve heat transfer efficiency is stirring which assures
lyst can effectively lower the required energy for cracking the C–C and better thermal convection between the plastic feedstock and heat
the C–H bonds, thereby generating more carbonium ions [63]. transfer surfaces [65]. Based on this principle, some improved designs

6
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Fig. 6. Typical polystyrene pyrolysis reactions. (a) Random scission; (b) Unzipping reaction; (c) Intermolecular hydrogen transfer; (d) Intramolecular hydrogen
transfer. (Reprinted from [53] with permission from Elsevier).

have been developed, like the rotary kiln [66,67]. PSW samples are bed materials coated with melted polymer, improving the contact be­
mainly heated by conduction from the reactor walls; additional heat tween gas and solid phases is an effective to avoid the defluidization
carriers (such as metal or ceramic balls, or sand) also needs to be added problems. In this regard, a conical spouted bed reactor (CSBR) combines
to improve heat transfer inside the reactor. A helical screw plays an the advantages of the spouted bed regime with those of the conical ge­
important role in this system, not only for conveying the PSW feedstock ometry to provide high heat and mass transfer coefficients between gas
to the heating zone, but also evacuating any solid residue [68,69]. and solid phases, thereby avoiding the defluidization to some extent.
A fluidized bed reactor enables a pyrolysis process to be continuous, Another advantage of CSBR design over fluidized bed reactors is to
at high heating rates, and relatively short residence times, which have lower the reactant residence time to about 20 ms, thus avoiding unde­
been widely applied in plastic pyrolysis [16,70,71]. Jung et al. [70] sirable secondary reactions and alleviating coke formation [49,78]. As
developed a lab scale fluidized bed reactor to pursue the high yield of shown in Fig. 8, CSBR is divided into three regions, including the spout,
aromatics at high pyrolysis temperatures (650–750 ◦ C). The process annulus, and fountain. In order to achieve the spout status, the gas inlet
proposed by Park et al. [16,71,72] was also used to produce aromatics diameter would be 20–30 times larger than the particle diameter, but
from polyolefins without a catalyst, and the selectivity of aromatic hy­ the use of a draft tube can resolve this and affect other operation pa­
drocarbons in the pyrolysis oil could be up to 92%. In order to effectively rameters, such as spouting velocity, pressure drop, gas distribution, etc.
reduce the residence time and convert waste plastics to olefins with high [79,80]. The design of CSBR has been further developed for PSW py­
yield, Milne et al. [73] designed an internally circulating fluidized bed rolysis applications in the past decades. Research headed by Olazar
and confirmed its effectiveness. In spite of the many advantages of flu­ investigated the pyrolysis of different waste plastics, confirming CSBR’s
idized bed reactors, defluidization problems caused by the agglomera­ suitability for PSW processing, in terms of its hydrodynamic behavior
tion of the molten plastics and heat carriers need to be taken seriously. and versatility [49,61,81,82]. In the flash pyrolysis of polystyrene for
Once a well-fluidized bed loses fluidization partially or totally, the monomer recovery, bed temperature and gas flow rate in the CSBR
temperature gradient will be observed in the reactor and the contact of significantly affected the styrene yield, within the range from 50.8 wt.%
gas and solid particles will be affected significantly, both of which can to 70.6 wt.% [82]. The extremely vigorous mixing regime of particles
lead to side reactions, lower product quality, and potentially reduce the inside the CSBR enables catalysts to be easily and effectively utilized in
process efficiency. Seville et al. [74,75] concluded that the defluidiza­ the in-situ catalytic pyrolysis of PSW. In the catalytic pyrolysis of
tion can be attributed to an increased sintering rate and the tendency of polyolefins over HZSM-5, the resulting pyrolysis oil was composed of 60
particle to agglomerate at higher temperatures. Generally speaking, wt.% C2–C4 olefins, 10 wt.% single-ring aromatics, 15 wt.% nonaro­
agglomeration and defluidization occurs more easily if “sticky” bed matic C5–C11 hydrocarbons, and 14 wt.% C4- alkanes [83]. It was
materials or feedstock are used or the feedstock contains alkali elements. pointed out that polymer melting and catalyst coating with the melted
It was experimentally found that the bed pressure decreased signifi­ polymer can be facilitated in a CSBR, and the high heat and mass transfer
cantly due to the accumulation and growth of the agglomerates, thereby rates shortened the residence time of pyrolysis vapors to generate more
causing defluidization [76]. The inorganic compositions of feedstock primary pyrolysis products by minimizing any secondary reactions [84].
were the significant influence on the bed agglomeration, and both the Dielectric heating enables microwave irradiation to be a fast and
increase in bed particle size and temperature and the decrease of gas selective heating method, which has been widely applied in solid waste
velocity and static bed height accelerated the defluidization. If the initial pyrolysis [85–87]. Unlike the conventional pyrolysis process, in this
bed height is increased, the bed resistance will increase accordingly so alternative approach, microwave-absorbing materials are preferentially
that much more power input is needed for re-fluidizing the consolidated heated without initially increasing the temperature of the surrounding
bed [77]. Considering that defluidization is caused by agglomeration of pieces of the HDPE because plastics are transparent to microwave

7
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

irradiation. It has been found that microwave-assisted pyrolysis is able 2.3. Plastic pyrolysis oil characterization
to significantly minimize side reactions, compared to conventional py­
rolysis of plastic, and thereby more effectively control product distri­ Research and development of plastic pyrolysis in recent years mainly
bution [88]. A few studies have also confirmed the application potential focus on maximizing the selectivity and yield of target products by
in plastic pyrolysis [87,89]. Fig. 8 shows a typical microwave-assisted innovative catalyst design, optimizing the operating conditions and
pyrolysis reactor which was developed by Ruan’s group [90]. Rele­ reactor configurations. The most important thing is to characterize the
vant process operations, optimization, and improvements have been obtained liquid product. By a detailed chemical characterization of bio-
reported [90–93]. One advantage for this microwave pyrolysis reactor is oil, it would increase the knowledge of the chemical composition of
that plastic feedstock is heated by heat conduction from the high tem­ liquid product, which is necessary to optimize the process and determine
perature SiC balls which are stirred by a shaft, effectively increasing the its potential uses. Although progress has been made to analyze the liquid
heat transfer efficiency and achieving fast pyrolysis. Based on a 200 product, limited information has been obtained from traditional tools
kg/day lab-scale continuous microwave pyrolysis system, Ruanʼs group due to the large number of various compounds and coelutions in the oil.
has shown that pyrolysis of 1 kg HDPE chips consumed a total of 5 MJ Therefore, research focus needs to be shifted to developing a systematic
electrical energy [94]. At this time (2021) a California company has and comprehensive strategy to characterize the liquid product with the
achieved a processing capacity of up to 1 ton/day of PSW via this mi­ help of advanced instrumentation. The current pyrolysis oil character­
crowave pyrolysis system, for recovery of fuels and naphtha from waste ziation techniques are shown in Table 4 and the corresponding advan­
plastics, and has demonstrated the potential for commercial application. tages and disadvantages are also listed Table 4.
Several other up-to-date plastic pyrolysis reactor designs have also The chemical profile of PSW derived oils can determine if the liquid
been studied, to improve the pyrolysis process, and product yield and oil can be used as gasoline, diesel, other fuels, or as chemicals. For
quality, such as: (a) the molten salt pyrolysis reactor, and (b) thermal example, with the goal of producing naphtha as a potential feedstock for
plasma pyrolysis reactor. The advantages and disadvantages of these virgin plastic production, more C5–C12 paraffins and less aromatics are
plastic pyrolysis reactors are summarized in Table 3 and different py­ desirable in naphtha [109]. Branched hydrocarbons are essential com­
rolysis reactors are shown in Fig. 7. ponents to improve the physical properties, such as low melting point
and pour point, for using as transportation fuels [110]. The chemical
composition of the liquid oil is usually characterized by the gas

Table 3
Advantages, disadvantages, and real practices of various PSW pyrolysis reactors.
Reactor types Advantages Disadvantages Real practice References

Batch reactor Simple construction and operation; Low processing capacity; Long residence Operating condition: 3.5 L batch reactor, 100 g plastic [24,95,96]
Low investment time; Low heat transfer rate mixture, pyrolysis temperature of 500 ◦ C, Reaction time
of 30 min
Result: 65.2 wt.% of liquid yield with 69.7 of
monoaromatics; a positive energy balance (+700 kJ/kg)
Screw kiln Uniform heat transfer; Controllable Plugging risk; Possible heat transfer Operating condition: the reactor size of a 26.5 mm [97,98]
reactor residence time; Simple separation of difficulties at large scales; Poor mixing at diameter and a 500 mm length, pyrolysis temperature of
solid residue radial direction 500 ◦ C, 300 g plastic mixture/h, residence time of 15 s
Result: 5.5 wt.% liquid oil and 93.2 wt.% of wax
Fluidized bed High heat and mass transfer rate; Defluidization problems; High carrier gas Operating condition: the reactor size of a 710 mm high [16,
reactor Scale up; Good mixing; Good rate; Required particle size; High cylinder with 58 mm of internal diameter, pyrolysis 99-101]
control of operation parameters investment temperature of 500 ◦ C, 2 g HDPE in total, residence time
of 1.3–1.7 s
Results: 40.9 wt.% of liquids (mainly composed of
C10–C40 linear paraffins almost without aromatcs), 7.4
wt.% of wax
Conical spouted Extremely short residence time; Scale up; Bed material particle size Operating condition: 30 g of sands, LDPE flowrate of 60 [26,31,78,
bed reactor High heat transfer rate; Good limitation; Catalyst circulation g/h; residence time of around 12 s; pyrolysis temperature 82]
mixing; Good control of operation of 500 ◦ C
parameters Result: 69 wt.% of wax with the Mw of 1534 Da; HHV of
35.55 MJ/kg
Microwave- Fast, selective, and volumetric Heating dependence on waste dielectric Operating condition: 6 kg of silicon carbide balls used as [31,94,
assisted heating; Easy design and operation; properties; The limited processing capacity the microwave absorbents, HDPE feeding rate of 2 kg/h; 102-104]
pyrolysis Convenient start-up and shutdown due to the finite microwave penetration residence time of around 90 s; pyrolysis temperature of
reactor depth 500 ◦ C
Result: 33 wt.% of liquid oil (mainly composed of C6-C26
n-alkanes/alkenes), 41 wt.% of wax; if a ZSM-5 catalyst is
used, pyrolyzing 1 kg of HDPE requires 5 MJ electrical
energy, giving a 89.6% energy efficiency. Furthermore,
6.1 MJ of electrical energy potentially produced from gas
product enables this process to be energy self-sufficient.
Molten salt High heating transfer rate; No Scale up; High operation cost Operating condition: 13 kg of the tin and lead alloy used [31,105,
pyrolysis limitation on particle size as the molten metal bed, 300 g of HDPE, pyrolysis 106]
reactor temperature of 419–428 ◦ C
Result: 93.31 of liquid oil (48.8–52.1% of C4–C10,
30.9–33.6% of C11–C16, 16.9–17.9% of C17–C24 almost
without aromatics)
Plasma pyrolysis High heating transfer rate; Low Extremely high voltage; Scale up Operating condition: 270 W direct current thermal [107,108]
reactor investment; Ultra-fast reaction plasma, residence time of 30 min, pyrolysis temperature
velocity of 500 ◦ C, pressure = − 0.95 bar, 15 g LDPE sample
Result: 75.6 wt.% of liquid yield with aromatic
monomers and dimers as the main products

8
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

chromatography (GC)-flame ionization detection (FID) or Gas can be determined by simulated distillation. For those naphtha-range
Chromatography-Mass Spectrometer (GC–MS) analysis. Baena-González and kerosene-range hydrocarbons, GC-FID/MS can play a key role in
et al. [111] analyzed the composition of plastic waste pyrolysis oils by analyzing the chemical compositions and determining the correspond­
GC–MS, and intended to recover bitumen, solvents, and styrene by ing carbon yield. With regard to heavier compounds, FTIR, NMR, and
combining distillation and/or liquid-liquid extraction processing steps, SEC can be effectively combined to analyze the corresponding chemical
as needed. As evaluated by GC–MS, the chemical compositions of PSW properties.
derived liquid oils vary, depending on the chemical structure of the
beginning plastics. PS pyrolysis only obtained 79.5% of mono-aromatics 3. PSW pyrolysis for recovery of fuels or chemicals
and 11.5% di-aromatics, while the styrene content was as high as 53.5%
[67]. More complicated compound mixtures were generated from Since mechanical recycling of PSW is hampered by high pre-sorting
polyolefin plastics pyrolysis. The liquid oil from PE pyrolysis contained requirements and decreasing product quality in each cycle, chemical
55.5% aromatic, and 43.1% aliphatic compounds, while PP pyrolysis recycling can tackle these challenges and has attracted much interest
obtained 52.9% aromatic and 44.7% aliphatic compounds [67]. from scientific and industrial communities. Research and development
However, common GC–MS technique is only able to analyze some of on chemical recycling of PSW, especially pyrolysis, seem to have made
components in pyrolysis oil due to due to the insufficient resolution and significant progress. The use of pyrolysis to recycle highly valuable
the difficulty in detecting structural isomers. In this regard, two- products from PSW around the world shows a great potential. Espe­
dimensional gas chromatography (GC × GC) coupled with time-of- cially, transforming PSW to pyrolysis oil at an industrial scale, which can
flight mass spectrometry (TOF-MS) (GC × GC-TOFMS) that uses a be fed into the current petrochemical production network as a raw
non-polar column to separate compounds with similar chemical struc­ material and reduce the input of fossil resources, shows higher market
tures first and a polar column for the second dimension could be one of attractiveness. By feeding the PSW derived pyrolysis oils into the current
the most attractive options. Fan et al. [112] found more than 5100 petrochemical production network to manufacture virgin plastic prod­
compounds in characterizing the bio-oil produced from sewage sludge ucts, the loop for plastic re-use can be partially closed. In this regard,
pyrolysis using GC × GC-TOFMS, which is about 10 times as many as chemically recycled plastics can lead to lower CO2 emissions, compared
those identified by GC–MS. Tessarolo et al. [113] studied the detailed to using fresh fossil resources for plastics production.
chemical compositions of bio-oil by GC–MS and GC × GC-TOFMS with
the hope of allowing the improved usage of this attractive renewable 3.1. Fuels production from pyrolysis of psw
energy source in bio-fuels. Results showed that several coelutions pre­
sent in the GC–MS can be resolved by GC × GC-TOFMS and the number Pyrolysis of PSW to produce valuable liquid fuels suitable for
of compounds identified by GC × GC-TOFMS was much higher. transportation, is an effective pathway to optimize the PSW manage­
Although GC × GC-TOFMS analysis of bio-oil in biomass pyrolysis has ment towards zero landfilling, and minimize the carbon footprint of the
been developed, its application in analyzing plastic pyrolysis oil is transportation industry [116]. Commercial PSW pyrolysis plants have
lacking. been built in recent years, showing the feasibility of producing trans­
In order to further acquire the heavy hydrocarbons distribution that portation fuels from PSW at an industry scale. For example, a pyrolysis
can not be calibrated by GC-FID/MS and information for distinguishing plant with the capacity of 5–7 tons/day PSW was designed and
hydrocarbons in the liquid oil with the extremely similar structure, commissioned in South East Asia in 2014, with the aim to eliminate the
Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic PSW already in the landfill [116]. In this system, the oil yield was
Resonance (NMR), elemental analysis, and Size Exclusion Chromatog­ approximately 65 wt.% and it was demonstrated to be distilled into 27%
raphy (SEC) can be also applied. From 1H NMR spectra, protons attached gasoline and 70% diesel. Another batch-operated rotary kiln with a
to alkanes, olefins, and aromatics can be determined, and the percent­ volume of 35 m3 was assembled with a total processing capacity of 14
ages of different chemical groups can be obtained, by integrating the 1H tons/day of PSW in Eastern Europe in 2015 [116]. According to the
NMR spectra [114]. Chemical shifts, which are indicative of the func­ report, the top priority for successfully commercializing the product is to
tionalities of alkenes and alkanes are 4.5–6.5 ppm and 0.5–2.7 ppm, mitigate wax formation by using suitable catalysts, and optimizing the
respectively. The FTIR spectral analysis can also obtain similar results to process. But its throughput is limited by the batch operating mode,
NMR. C–H stretching vibrations of the chemical functional groups which prevents the catalyst from working at optimized conditions.
-CH3, -CH2, and -CH appeared at 2800–3000 cm− 1 and C = C stretching Although the produced fuel is unable to meet transportation standards,
vibrations were observed at approximately 1640–1650 cm− 1, indicating it can, at least, be used as a fossil fuel substitute. Many observations have
the presence of olefins. If aromatics also existed, a peak at 3000–3100 verified that production of liquid fuels from PSW via pyrolysis is
cm− 1 would appear. SEC analysis is able to acquire the molecular weight promising and commercially viable. In this regard, a great number of
distribution information of the plastic pyrolysis oil. On average, the studies have been conducted to develop new catalysts suitable for
molecular weight of an oil fraction with a lower boiling temperature, is different fuels production, and improve the pyrolysis process.
lower than that of a higher boiling temperature.
Currently, the most common tool used for pyrolysis oil character­ 3.1.1. Effects of temperature and residence time
ization is GC-FID/MS that can provide the detailed chemical composi­ Temperature is definitely one of the most important pyrolysis pa­
tions and the relative contents [19,115]. Considering that GC inlet rameters for controlling the cracking reaction of PSW, since the cracking
temperature and oven temperature is usually around 280 ◦ C, the heavy of PSW is largely dependent on the temperature ranges they are exposed
hydrocarbons with high boiling point can not be detected by to. One study indicated that 99.4 wt.% decomposition can result for a
GC/GC–MS. Despite of this, heavy hydrocarbons have small solubility in plastic mixture at 500 ◦ C [117]. Increasing the pyrolysis temperature
CH2Cl2 that is usually used as a solvent for GC analysis so that the in­ will promote the cracking of PSW, which in turn generates more gas and
formation about larger fractions may not be obtained accurately [110]. gradually eliminates wax in the products. When HDPE pyrolysis was
This could limit the understanding for the pyrolysis oil by only performed in a fluidized bed reactor at 650–850 ◦ C, the yield of the
GC/GC–MS analysis. Based on our knowledge, a PSW pyrolysis oil liquid (mainly composed of aliphatic hydrocarbons) was highest at 640
sample should be distilled into naphtha-range hydrocarbons (the boiling ◦
C (79.7 wt%), whereas only 9.6 wt% of liquid product (high aromatic
temperature˂170 ◦ C), kerosene-range hydrocarbons (170 ◦ C˂ the hydrocarbons) with high yields of gaseous products (86.4 wt%) was
boiling temperature˂280 ◦ C), diesel-range hydrocarbons (280 ◦ C˂ the obtained at 780 ◦ C [23]. Gracida-Alvarez et al. studied the effect of
boiling temperature˂400 ◦ C), and wax (the boiling temperature˃400 temperature on HDPE pyrolysis, and found that higher temperature was
◦
C) fractions first. The relative yields of different range hydrocarbons favorable for the formation of aromatics and light aliphatics and

9
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Fig. 7. Scheme of the pyrolysis process in different reactors. (Adapted from [94,97] with permission from Elsevier).

decreased the liquid yield due to the facilitated cracking of the pyrolysis
Table 4
vapors toward non-condensable gasses during catalytic pyrolysis of
Advantages and disadvantages of methods for plastic pyrolysis oil
characterization. plastic over an activated carbon catalyst. When the catalytic tempera­
ture was increased from 430 to 571 ◦ C, approximately 20% higher
Methods Advantages Disadvantages
selectivity of C8–C16 linear alkanes was obtained, and mono-ring aro­
GC-FID/MS Understanding the Limited inlet and column matics production also responded with a gradual increase. More gasses
detailed chemical temperature; Different
(mainly C1–C4 hydrocarbons) were also obtained in the ex-situ catalytic
compositions solubility of long chain
hydrocarbons in solvents reforming of plastic pyrolysis vapors, as the catalyst bed temperature
GC × GC-TOFMS Higher resolution in the Limited inlet and column increased from 500 to 600 ◦ C [122]. This finding indicated that the
chemical compositions in temperature; Different catalytic temperature changed the liquid oil compositions more effec­
the oil solubility of hydrocarbons tively than the catalyst type.
in solvents
Residence time defined for steady-state pyrolysis system is a measure
FTIR Obtaining chemical groups No information for detailed
information; No chemical compositions of the average time plastic feedstock spends in the pyrolysis reactor and
requirement for oil can be calculated by considering the total gas flow in the reactor and the
vaporization internal volume of the reactor. It is found to show very similar effects on
NMR Obtaining chemical groups No information for detailed
the PSW pyrolysis to reaction temperatures. Generally speaking, the
information; No chemical compositions
requirement for oil longer residence time could result in the over-cracking of PSW and in­
vaporization crease the chances for secondary reactions (further cracking, isomeri­
SEC Obtaining the molecular No information for zation, aromatization, alkylation, and hydrogenation/dehydrogenation
weight distribution chemical compositions/ reactions, etc.), obtaining higher yield of gas product. Mastral et al. [23]
information; No groups
studied effect of residence time on HDPE pyrolysis and observed that the
requirement for oil
vaporization longer residence times provided enhanced yields of gaseous products. In
Thermogravimetric Obtaining boiling No information for addition, longer residence time is favorable for the evolution of aro­
analysis temperature range chemical compositions/ matics [118]. More specifically, when pyrolyzing HDPE at a two-stage
groups
micropyrolysis reactor, low temperature (625 ◦ C) and short residence
Distillation, combined Accurate chemical profiles High cost; Time-consuming
technologies for naphtha, kerosene, time (1.4 s) produced diesel range hydrocarbons combined with gaso­
diesel, and wax line and gasses; moderate temperature (650 ◦ C) and short residence time
(1.4 s) mainly produced gasoline range hydrocarbons and gasses; high
temperature (675 ◦ C) and long residence time (5.6 s) primarily produced
facilitated the degradation to diesel range aliphatics and wax [118]. In a gasses and aromatics. All in all, longer residence time tends to facilitate
small pilot scale batch pyrolysis reactor, increasing the pyrolysis tem­ the secondary conversion of the primary products, and generates more
perature from 400 ◦ C to 450 ◦ C can obtain about 4% increase in oil yield, stable compounds, including aromatics and non-condensable gasses. It
while further temperature increases could cause a decrease in oil yield was interesting that Mastral et al. observed the interdependence of
[119]. It was also found that the increase of pyrolysis temperature temperature and residence time [123]. At a temperature lower than 685
enhanced the concentration of H2 in the gas product, however, there was ◦
C, longer residence time inversely resulted in a higher liquid yield for
no effect on the formation of CO or CO2 [120]. HDPE pyrolysis, while at temperatures above 685 ◦ C, the residence time
For a two-step pyrolysis-catalysis process, catalytic temperature also had no obvious influence on the liquid and gas yields.
plays a vital role in product yield and selectivity. It is indispensable for In order to study the effect of volatiles residence time on the prod­
driving the catalytic reaction to provide suitable catalytic temperature. ucts, two different set-ups were developed, a pyroprobe flash pyrolyzer
Zhang et al.’s [121] results indicated that a higher catalytic temperature that allows us to study the primary products due to near zero residence

10
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

time and negligible secondary reactions and a fluidized bed reactor semi-batch reactor [132]. It was found that lighter hydrocarbons can be
where the extent of the secondary reactions is significant [124]. They generated over medium-pore zeolites, as compared to large-pore zeo­
found that the increase of residence time can decrease the yields of lites, in the order of (lighter hydrocarbons) ZSM-5 ˂ mordenite ˂ β ˂ Y ˂
C4–C7 hydrocarbons in the thermal pyrolysis of HDPE, but the yields of Ultrastable Y (heavier hydrocarbons). In addition, the same order was
C4–C7 hydrocarbons increased with residence time in the presence of observed concerning the bond saturation (alkanes or olefins). This in­
HZSM-5 catalyst. During thermal degradation, some hydrocarbons dicates that the pore structure of zeolites largely affects product distri­
produced by primary reactions and by tar and heavy hydrocarbon bution, especially the ratio of alkanes to olefins. US-Y, Y, and β zeolites
cracking can be further cracked with the increasing residence time so mainly produced alkanes, whereas the major products were alkenes over
that the yields of C4–C7 hydrocarbons decreased. However, this mordenite and ZSM-5, due to rapid bimolecular hydrogen transfer re­
behavior is not detected under catalytic conditions. It was also reported actions, which is responsible for the generation of saturated hydrocar­
that the liquid yield during LDPE pyrolysis in a closed reactor decreased bons [133]. A similar study was conducted by Mordi et al., who tested
from 91.1 wt.% at zero residence time to 72.4 wt.% at residence time of the catalytic activity of H-mordenite, H-Theta-1, and H-ZSM-5 in the
60 min, and further to nearly 61 wt.% with the residence time increasing catalytic degradation of LDPE [134]. The major degradation compo­
to 120 min [125]. nents were C11–C19 hydrocarbons (mainly alkanes/alkenes) from
Overall, the high temperature and long residence time would pro­ H-mordenite or H-Theta-1, while the carbon chain length was no more
mote the cracking of polymers, leading to the production of more low- than 14 (mainly aromatics) over H-ZSM-5. It was interesting that
molecular-weight hydrocarbons and gas molecules, and the aromatic cracking initiation could be completed at the external surface of the
selectivity shows an upward trend with the increasing temperature and zeolite catalysts, or at the pore entrance, because polymer molecules
residence time. Basically, in order to provide maximum liquid products, were too large to enter the pore structure and access the internal active
the pyrolysis temperature should be precisely controlled and residence sites.
time needs to be minimized. For example, it is reported that the One important finding was that zeolite catalysts tended to show
decomposition temperature for PP is 378–456 ◦ C, whereas LDPE and higher selectivity than other catalysts, towards aromatics in most cases,
HDPE degrade at 437–486 ◦ C and 452–489 ◦ C, respectively [126]. A especially HY and ZSM-5. The aromatic formation mechanism mainly
further increase in reaction temperatures would lead to enhanced yields involves two stages, one of which is catalytic cracking to generate car­
of gaseous products. benium ions by Lewis acid site reactions, or carbonium ions via pro­
tonation of hydrocarbons on Bronsted acid sites. In the next step, these
3.1.2. Effect of catalysts intermediates were converted into aromatics via isomerization, oligo­
In a non-catalytic pyrolysis of PSW, carbon-carbon linkage in the merization, cyclization, Diels-Alder, and aromatization reactions on the
polymer chains can be broken randomly and no rearrangement of the surface of catalysts [135]. In this regard, Akubo et al. observed in the
fragments occurs, resulting in a wide distribution of products, such as catalytic pyrolysis of HDPE, in a fixed, two stage bed that Y zeolites with
light olefins, gasoline range, diesel range, and waxes [67,111]. Although transition metal promoters produced an oil product with aromatic
increasing temperature can improve the share of lighter hydrocarbons, content of over 80% [136]. The share of aromatics was much higher
the production of desirable fuels and chemicals with high selectivity is than in the non-catalytic process, where the aliphatic product content
still a great challenge. The use of a suitable catalyst with desirable was up to >99%. The single ring aromatic compounds, including
properties is necessary to narrow the product distribution and enhance toluene, ethylbenzene, and xylenes were dominate, although 2-ring and
target product selectivity. On one hand, the addition of a catalyst can multiple aromatics were also formed. A high yield of aromatic hydro­
lower the decomposition temperature of the plastic; on the other hand, carbons was also obtained in the catalytic fast pyrolysis of PS with
product selectivity can be modified towards a vast variety of valuable HZSM-5, Hβ, HY, and ultra-stable Y [137]. Ultra-stable Y catalyst
oils, such as gasoline [63], diesel [127], aromatics [128], and jet fuel showed the best shape selectivity for ethylbenzene and benzene for­
[129], which are fairly different from the product compositions for mation, and maximized the aromatic production.
non-catalytic pyrolysis. The product distribution from catalytic pyrolysis Mesoporous aluminosilicates (Al-MCM-41 and Al-SBA-15) with the
of plastic is controlled by catalyst properties, including acidity and pore tunable pore size of 1.5–30 nm allow plastic molecules or intermediates
structure, as shown in Fig. 8. With an increase of catalyst acidity, to enter the catalyst mesopores directly, mitigating the steric and
shorter-chain hydrocarbons would be generated, due to the facilitated diffusional hindrances, and greatly increasing the accessibility of inter­
cracking reaction. nal acid sites. It was then used in the catalytic cracking of plastics in
There is no doubt that catalytic pyrolysis of plastics sometimes shows 1996 for the first time, which confirmed the feasibility of this type of
several drawbacks, which may be caused by the inherent nature of the catalyst [138]. It was proposed that the growth around micelles is
catalysts used. For example, one main concern is catalyst deactivation. responsible for the synthesis of the ordered mesoporous aluminosilicates
The difficulty of regenerating the catalyst poses another challenge to this [139]. The templates are first formed by aggregating the micelles into
technology. In some cases, catalyst structure can be completely the hexagonal structures, and then the silica begins to condense around
destroyed in the catalytic process, significantly increasing the capital these templates. After calcination at high temperature, the templates are
cost. In addition, the activity and selectivity for the catalytic process removed and the ordered mesoporous structure is formed. The uniform
depends primarily on the catalyst type, and the corresponding reaction mesoporous distribution and ultra-high specific surface area enable it to
conditions, such as temperature, velocity, and atmosphere. In the pre­ show a higher conversion rate for polyolefins, as compared to amor­
vious studies, it was found that solid acids, used in the catalytic pyrolysis phous SiO2-Al2O3 [140]. Compared to ZSM-5, the acid strength of
of plastics, have been recognized as the most promising candidates [19, MCM-41 was lower, leading to the lower catalytic activity for cracking
130,131]. Therefore, different types of solid acids used for catalytic of HDPE and LDPE. It was interesting that the severe steric hindrances
pyrolysis of plastics are discussed below. caused by the narrow pores of ZSM-5 resulted in the lower catalytic
Zeolites are very common molecular sieves, which turns out to be activity for PP cracking while MCM-41 exhibited 99% conversion due to
one of the most suitable candidates for plastic cracking, due to the acidic the better accessibility of acid sites located in the mesopores.
properties and unique shape selectivity. Therefore, a great number of Zhang et al. [19] converted LDPE into a gasoline-type product using
studies concerning the screening of effective zeolites, and the investi­ the shape-selective Al-SBA-15 catalyst and the results showed a great
gation of the corresponding catalytic fundamentals have been con­ potential of Al-SBA-15 catalyst in the catalytic cracking of LDPE. When
ducted. The need for screening zeolite catalysts was highlighted by the silicon/aluminum molar ratio of Al-SBA-15 was 5, the temperature
Manos et al., who compared the catalytic performance of 4 zeolites at the 50% conversion was even lower than ZSM-5, regardless of the
(Ultrastable Y, Y, β, ZSM-5) during catalytic degradation of HDPE in a weaker acid sites. With ZSM-5 catalyst, the product contained a large

11
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Fig. 8. Effect of different acid catalysts on product distribution during catalytic pyrolysis of polyolefins. (Reprinted from [31] with permission from Elsevier).

amount of mono-aromatic, such as benzene, toluene, ethylbenzene and feedstocks, the shape selectivity and long catalyst lifetime cannot be
xylenes, which was completely different from Al-SBA-15 catalyst. observed [142]. In the catalytic pyrolysis of LDPE, HZSM-5 gave a sig­
Al-SBA-15 gave rise to a well-defined gasoline-type product which was nificant increase in the light olefins and aromatics by eliminating
mainly composed of C4–C10 alkenes/alkanes. The catalytic activity of heavier hydrocarbons, while mesoporous Al-MCM-41 catalyst exhibited
Al-SBA-15 was attributed to the following features: (1) the large pore no shape selectivity with a wide range of hydrocarbons. To improve the
size which allowed LDPE chains to fully access the Brønsted sites of the shape selectivity of mesoporous materials, “relay catalysis process” was
catalyst; (2) the modulated strength of acid sites was favorable for developed, in which several catalysts are used in tandem. Recently,
controlling the cracking of LDPE, and generating more gas; (3) the Ratnasari et al. [143] effectively converted waste plastics to gasoline
wide-pore system improved the diffusion of gasoline-like hydrocarbons range hydrocarbons (C8–C12) over MCM-41/ZSM-5 catalysts. Pyrolysis
and minimized secondary cracking reactions. Similar conclusions were volatiles passed through a mesoporous MCM-41 catalyst layer followed
drawn by Socci et al. in the catalytic cracking of LDPE over mesoporous by a microporous ZSM-5 zeolite with the aim of controlling the product
Al-SBA-15 materials [141]. Due to the higher diffusional efficiency of distribution more accurately. Highest selectivity (97.72%) of gasoline
reactants in the mesoporous structure of the Al-SBA-15 catalysts range hydrocarbons was obtained at the a MCM-41:ZSM-5 ratio of 1:1,
compared to ZSM-5, a higher selectivity of the gasoline range hydro­ which was higher than the single use of ZSM-5 or MCM-41. It indicated
carbons was obtained. The density and strength of the Brønsted acid that the high surface and large pore volume were favorable for catalytic
sites, pore structure, and the Al content, had a significant effect on the cracking of the heavy hydrocarbons in the primary pyrolysis vapors to
pyrolytic product distribution. lighter molecules, which were then easier to enter into ZSM-5 micro­
Although these mesoporous materials with high surface area and pores for further reforming reactions.
well-defined larger pores show great potential to process bulky plastic As mentioned above, the catalytic pyrolysis of plastics over zeolites

12
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

clays is lower than zeolite catalysts but higher than pure silica. Although
less active than USY zeolite, clays led to higher liquid yield in the cat­
alytic pyrolysis of PE at around 600 K, with gasoline range hydrocarbons
being the major products [151]. Alkenes dominated in the oil product
from the clay-catalyzed process, instead of aromatics. It was due to the
milder acidity as compared to USY zeolite, thereby mitigating the
hydrogen-transfer secondary reactions. At the same time, a smaller
amount of coke was formed on the surface of clays. In the catalytic
pyrolysis of PS, Kaolin was confirmed as an effective catalyst, giving a
higher liquid yield than the non-catalytic pyrolysis process with aro­
matic hydrocarbons being the main components [152].
To further improve the catalytic performance of clays, modification
techniques change the pore structure and acidity, with the aim of tuning
or narrowing the resulting hydrocarbons distribution. Although kaolin
catalyst has a certain cracking ability to convert polymers to diesel range
hydrocarbons, the HCl modified clay can further crack the diesel frac­
tion into shorter chain hydrocarbons (C6–C11) because HCl modifica­
Fig. 9. Relationship between molecular kinetic diameter, pore diameter and
tion is able to create more active functional groups, resulting in stronger
pore ring number of different zeolites. (Reprinted from [150] with permission
acidity [153]. Stefanis et al. modified the smectite clays by acid
from the Royal Society of Chemistry).
restructuring or oxide intercalation assembly and tested their perfor­
mance in the catalytic cracking of PE [154]. The chemical profile and
proceeds initially by the acid sites present in the outer surface or large
yield of liquid product both reflected that clay-based catalysts with
pores, and then the smaller intermediates can subsequently enter the
weaker acidity mitigated the over-cracking toward small molecules,
zeolite micropores for further cracking or other secondary reactions,
giving higher liquid product yield. Several restructured or pillared clays
which is controlled by the acidity and the pore channel architecture of
had different structures, leading to an activity different from each other.
the zeolites. For example, cyclohexane with a kinetic diameter of 0.6 nm
Most clays gave aliphatic hydrocarbons as the major products except
is unable to enter the micropores of ZSM-5 zeolite (10 membered ring
HSA (a modified saponite clay). Li et al. [22] also developed various
channels with size of 0.56 nm) due to steric hindrance imposed by the
transition metal pillared clays to produce diesel range hydrocarbons and
micropore size, but it can access the acid sites inside the micropores of Y
hydrogen from mixed plastics. The high catalytic activity of modified
zeolite (12 membered ring channels with size of 0.74 nm) [144].
clays was attributed to the moderate acidity, high surface area, and
However, the C6H3(C3H7)3 possessing approximately 0.82 nm pore
uniformly dispersed metal oxide particles on the support.
channels can not enter the micropores of Y zeolite, as shown in Fig. 9.
In addition to these materials, fluidized catalytic cracking (FCC)
Theoretically, strong Brønsted acid sites that determines the cracking
catalysts composed of crystalline zeolites, acid SiO2-Al2O3, and binding
performance of zeolites are attributed to the acidic protons linked to the
agents are proposed as promising catalysts for catalytic cracking of
Si-O-Al bridge bond inside micropores [145]. Therefore, enhancing the
plastics. Although the spent equilibrium FCC showed lower catalytic
accessibility of the zeolite acid sites could improve product distribution
activity than the silica–aluminas, this can be compensated by using more
and catalyst lifetime in the catalytic cracking of polyolefins over zeo­
spent FCC catalysts. Taking the economical factor into account, the
lites. Unlike conventional zeolites which are mainly composed of mi­
negligible cost of the spent FCC catalyst enables it to be more suitable for
cropores, hierarchical zeolites are characterized by their multimodal
industrial application. Rodríguez et al. [155] conducted catalytic
microporous− mesoporous-macropore pore size distribution with a
cracking of HDPE pyrolysis waxes in a CREC riser simulator reactor,
considerable share of mesopores, enabling them to be more active for
with the goal to study the effect of the FCC equilibrium catalyst prop­
plastic cracking. In this regard, significant advances have come due to
erties on product distribution. As a whole, three FCC catalysts produced
the application of hierarchical zeolites. Lee et al. [146] compared hi­
similar product compositions, while with less acidic catalyst the naphtha
erarchical ZSM-5 zeolite with conventional one in the catalytic cracking
fraction contained less aromatics and more olefins. The spent FCC
of PE, finding that hierarchical ZSM-5 showed higher catalytic activity
catalyst was also used to crack HDPE in a conical spouted bed, restricting
(about 95% of conversion) due to a high external surface and a rapid
the formation of aromatics and paraffins and giving rise to the lumps of
mass transfer. Caldeira et al. [147] tested two hierarchical Beta zeolites
gasoline fraction and light olefins [84]. The spent catalyst possesses
obtained from reorganization of the protozeolitic nanounits and the use
meso‑ and macroporous pores which allow plastic molecules to diffuse
of a silanization agent. Both hierarchical Beta zeolites can achieve
for cracking and micropores in the zeolite crystals which give a higher
higher plastic conversion (67.3 wt.% and 97 wt.%) than the conven­
shape selectivity to gasoline range hydrocarbons and light olefins.
tional Beta sample. The results obtained indicate that the HDPE cracking
Metal oxides, with a multivalent nature, and special acid–base
activity is strongly related with the acid sites within the micropores, so
properties, have been widely used in heterogeneous catalysis reactions
the overall catalytic activity largely depends on the accessibility to the
[156,157]. Various metal oxides have been tested in catalytic cracking
acid sites. Silva et al. [148] also confirmed that hierarchical ZSM-23
of plastics, showing potential to catalyze the thermal cracking of poly­
demonstrated the higher conversion efficiency and lower energy level
mers and/or the reforming of pyrolysis intermediates in the volatiles
in catalytic cracking of PE compared to the microporous ZSM-23.
into more stable products (Table 5) [25,158,159]. Ten years ago, Shah
Quantitative analysis of the accessibility of Brønsted acid sites shows
et al. [160] attempted to achieve the maximum conversion of LDPE into
that a larger number of accessible Brønsted acid sites exists in hierar­
chemicals using a wide range of acidic and basic metal oxides and cal­
chical ZSM-5 (64.3%) than the parent ZSM-5 (6.25%) [149]. It enables
cium carbide. An interesting finding is that metal oxides, such as MgO,
the decomposition temperature of LDPE to decrease to 420 ◦ C, which is
Al2O3, and ZnO, are more suitable for the production of polar and aro­
originally 453 ◦ C with the use of parent ZSM-5.
matic products, while CaC2 should be adopted if aliphatic products are
Other materials used for catalytic cracking of PSW are clay-based
desirable.
catalysts. The huge reserves and low price of this type of material
Al2O3 is a very common catalyst/support in the catalytic pyrolysis of
make these attractive to be used for catalysts in industry. These mate­
solid wastes. Fe–Ce@Al2O3 was used to catalytically convert poly­
rials are found to have a naturally layered structure, between which
carbonate (PC) plastic waste into aromatic hydrocarbons at 650 ◦ C
different metal oxides can be intercalated (pillared clay). The acidity of
[161]. Three preparation methods, including co-precipitation,

13
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

impregnation, and physical mixing, were compared. Experimental re­ low temperature of 280 ◦ C. Compared to the conventional long-chain
sults showed that co-precipitation gave rise to the highest content of alkyl-aromatic production, this one-step process is much simpler and
monocyclic aromatic hydrocarbons. It was attributed to weaker acid less energy-intensive and gets rid of organic solvents used in the con­
sites, larger pore volume, higher surface area, and uniformly dispersed ventional process. More importantly, up to 80 wt.% of
metal oxides. Transition metals (Fe, Co, and Ni) were able to effectively low-molecular-weight liquid/wax products was obtained, with negli­
improve the basicity of the Al2O3 support [162]. When used in the gible amounts of light gasses produced. The stability testing of
catalytic pyrolysis of PS, β-chain-breaking was facilitated, thereby Pt/γ-Al2O3 catalyst indicates that the intrinsic activity of the catalyst
leading to a higher selectivity of styrene monomers. Different metal stays unchanged regardless of the decreasing liquid/wax yield in the
species (Ni, Cu, Ce, Co, and La) were also screened in the catalytic py­ second run. However, the issue for this process is the long reaction time
rolysis of PS waste foams, at temperatures ranging from 400 to 500 ◦ C to in a batch reactor increasing the difficulty in scaling it up.
obtain the highest conversion of PS, and more desirable product com­ It is noteworthy that, inspired by the macromolecule deconstruction
ponents [163]. Cu/Al2O3 was found to be the best candidate for PS enzymes, an artificial processive catalyst (SiO2-supported Pt nano­
conversion, with the highest styrene yield of 63.59%. particles) was designed for PE hydrogenolysis, into diesel and lubricant-
Recently, a significant breakthrough was made in the PE conversion range alkanes with high selectivity [165]. The key is to develop suffi­
over Al2O3 supported Pt catalyst [164]. PE was effectively converted to ciently narrow pores to enable the headfirst adsorption of a PE chain and
valuable long-chain alkyl-aromatics and alkyl-naphthenes by combining accessibility to the active sites (Pt species) positioned near the end of the
exothermic hydrogenolysis and endothermic aromatization at a very pores, selectively breaking one type of bond at a regular interval from

Table 5
Effects of different catalysts on liquid yield and product distribution in the plastic pyrolysis.
Catalysts Feedstock Reaction conditions Liquid Product distribution Refs
yield (wt.
%)

Natural zeolite PS Catalytic pyrolysis temperature of 450 ◦ C, 54 91% of aromatics [166]

Reaction time 75 min
Spent FCC catalyst HDPE Catalytic pyrolysis temperature of 500 ◦ C, 60 50% of non-aromatic C5–C11 hydrocarbons, 8–10% of [84]
feeding rate of 1 g/min, 30 g of catalyst C12–C20 hydrocarbons, 10% of wax
Equilibrium FCC HDPE Catalytic pyrolysis temperature in the 500− 560 57–80 20–30% of C5–C12 hydrocarbons, 35–50% C13–C20 [155]
catalysts waxes ◦
C range, catalyst/feedstock ratio fixed at 5 gcat/ hydrocarbons, 2–10% C20+hydrocarbons
gwax, contact time of 6 s
Conventional/ HDPE Catalytic pyrolysis temperature of 380 ◦ C, Around 13% of C5-C12 aromatics, 30% of C5-C12 alkanes, [147]
hierarchical Beta Plastic to catalyst mass ratio of 100 25% of olefins
Ni/Mo/Fe/Ga/Ru/Co- HDPE Pyrolysis temperature of 600 ◦ C, Catalytic 31–43 Around 80–95% of aromatics, 5–20% of aliphatic [136]
Y-zeolites temperature of 600 ◦ C, HDPE to catalyst ratio of hydrocarbons
1:2
MCM-41 and ZSM-5 HDPE Pyrolysis temperature of 500 ◦ C, Catalytic 83.15 97.72% of gasoline range hydrocarbons, 95.85% of aromatics [143]
temperature of 500 ◦ C, MCM-41:ZSM-5 ratio of
1:1, HDPE to catalyst ratio of 1:2
MgO HDPE Pyrolysis temperature of 500 ◦ C, Catalytic 37 36% of C5-C12 aromatics, 38% of C5-C12 alkenes, 11% of [25]
temperature of 450 ◦ C HDPE:MgO of 15:1 C5-C12 alkanes
ZnO LDPE 10% ZnO addition, 50 kPa pressure 72 56.2% of 7-C36 alkanes, 30% of C9-C18 alkenes, mainly [167]
composed of diesel range hydrocarbons
Ni/CuO PS Pyrolysis temperature of 390 ◦ C, reaction time of 93.5 68.9% of aromatics, 21.29% of olefins, 2.2% of oxygenates [168]
90 min
Sulphated ZrO2 PET Pyrolysis temperature of 450 ◦ C, residence time 41.4 27.5 wt.% of benzoic acid, 13.9 wt.% of other aromatic [169]
of 20 s, catalyst to plastic mass ratio of 3 wt.% compounds
ZnO PET Pyrolysis temperature of 450 ◦ C, Catalytic 83.9% of aromatics, 16.1% of oxygenates [170,
MgO temperature of 700 ◦ C PET:metal oxides of 1:20 38.7% of aromatics, 61.3% of oxygenates 171]
TiO2 38.9% of aromatics, 61.1% of oxygenates
ZrO2 43.9% of aromatics, 56.1% of oxygenates
CaO 99.7% of aromatics, 0.3% of oxygenates
ZnO PS Pyrolysis temperature of 450 ◦ C, 60 min heating 84.7 85.8% of aromatics [172]
time and 1:0.2 feed to catalyst ratio
Kaolin clay PP Catalytic pyrolysis at 600 ◦ C, plastic to catalyst 22 30–40% of aromatics, 25–35% of straight alkenes, 5–10% of [153]
ratio of 9 cycloparaffins, 2–7% of straight alkanes
Fe/Al PE Catalytic pyrolysis at 300 ◦ C, 60 No aromatics, 100% of aliphatics [154]
oxide-pillared clay Reaction time of 3 h
Sewage sludge derived PE, PP and catalytic temperature at 600 ◦ C with a residence 46.6 Monocyclic aromatics of up to 75.3%, styrene of 29.1%, and [173]
char PS time of 1 s xylene of 12.5%
Coconut-shell HDPE Feed to catalyst ratio of 1:0.6, catalytic pyrolysis 47.59 1.08% of cycloparaffin, 52.57% of n-paraffin, 32.18% of [174]
activated carbon temperature of 400 ◦ C, operation time of 45 min olefin, 4.53% of aromatic
Coconut sheath PS and PP Microwave pyrolysis at 900 W and with a 84.30 80.58% of aromatic content (toluene (3.39%), styrene [86]
activated carbon polymer to an absorbent ratio of 10:1, reaction (67.58%), ethylbenzene (1.82%) and α-methyl styrene
time of 176 s (1.71%)) and 11.29% of olefinic content,
Phosphoric acid- LDPE Catalytic pyrolysis at 500 ◦ C, catalyst to LDPE 75.3 93.13 area% of jet fuel-ranged hydrocarbons, (39.11% of [175]
activated biomass ratio of 1 C8–C16 alkanes, 54.02% of ˂C16 aromatics)
char
Biomass-derived LDPE Catalytic pyrolysis temperature of 500 ◦ C, 72 65.3% of C8–C16 alkanes and 33.4% of aromatic [176]
activated carbon/ catalyst to LDPE ratio of 2, and char to MgO ratio hydrocarbons (< C16)
MgO of 1
ZnCl2-activated PE, PP and Catalytic pyrolysis temperature of 500 ◦ C, 51.8 27% of alkanes, 23.8% of alkenes, 47.5% of aromatics [177]
biochar PS catalyst to LDPE ratio of 1:4 (mostly in the diesel range)
KOH-activated PE, PP and Catalytic pyrolysis temperature of 500 ◦ C, 42.6 43.1% of alkanes, 2.2% of alkenes, 44.7% of aromatics [178]
biochar PS catalyst to LDPE ratio of 1:4 (mostly in the diesel range)

14
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

the chain end. The obtained shorter chain hydrocarbons will be des­ Generally speaking, developing carbon materials from solid wastes
orbed, and released from the shell/core structure. This catalyst enables would be much cheaper than any other sources, which is especially
plastics-to-diesel/lubricant technique to be more reliable and promising. important for PSW conversion. This section of the literature review will
MgO and CaO are two typical base metal oxides used in the catalytic summarize recent progress made in the development of carbonaceous
conversion of PSW, which are effective for enhancing the cracking materials to be used in the catalytic cracking of PSW to produce valuable
process and altering product distribution. In the catalytic pyrolysis of fuels and/or chemicals.
LDPE over MgO, 96.0% of gasoline-range hydrocarbons can be obtained, Sewage sludge char from direct high temperature carbonization was
with 56.3% C5–C12 aliphatics being the main components [25]. The used to catalyze the conversion of waste plastic mixture into an
possible mechanism for the MgO-catalyzed upgrading of LDPE pyrolysis aromatic-rich oil [181]. In this study, acid sites caused by aluminum
vapors was also proposed in this study. As mentioned above, the poly­ phosphate and dehydrogenation caused by -P = O and sulfides were able
olefin cracking can generate long and short chain radicals which are to promote aromatization; simultaneously, calcium oxide and iron spe­
converted into stable alkanes or olefins by hydrogen transfer reactions. cies in the char were favorable for ring-opening reactions, thereby
The first step for MgO catalyst is that the base catalyst is able to abstract preventing the formation of heavy aromatics. At a temperature of 600 ◦ C
the hydrogen proton attached to the long chain hydrocarbons, forming a and a residence time of 1 s, 75.3% selectivity of monocyclic aromatics
carbanion. The obtained carbanion is easy to be fragmented into shorter could be obtained. In the PET pyrolysis, a carbon-supported Pd catalyst
chain alkenes via β-scission (Fig. 10). This is the reason why gasoline was added to prevent the formation of hazardous materials, such as
range hydrocarbons can be obtained in the catalytic pyrolysis of LDPE polycyclic hydrocarbons and biphenyl derivatives [182]. When the
over MgO. The β-scission process is terminated by utilizing the proton carbon-supported Pd catalyst loading ratio was 0.05, the concentrations
from the MgO surface, and long chain alkanes will be generated of 2-naphthalenecarboxylic acid and biphenyl-4-carboxylic acid were
(Fig. 10). On the other hand, the free radicals may be recombined into reduced by 44% and 79% respectively.
long chain alkanes or cracked into smaller fragments which go through Considering that biomass production and processing industry give
cyclization and dehydrogenation to form aromatics. Kumagai et al. rise to a lot of low-cost by-products, the synthesis of carbon materials
[158] investigated the catalytic conversion of PET over CaO, with the from abundant biomass wastes would be feasible, cost-effective, and
focus on the CaO deterioration effect. The presence of CaO significantly promising [183]. Juliastuti et al. [174] prepared an activated carbon
facilitated the decarboxylation reaction, obtaining 83.6% selectivity of produced from coconut shell pyrolysis and used it as the pyrolytic
aromatic hydrocarbons. However, the catalytic activity decreased catalyst in a microwave-assisted pyrolysis of HDPE. Results showed that
gradually with repeated runs, which means the increase in oxygenates. the total yield of liquid and gas could reach 99.22% and the main
Observed from scanning electron microscopy images, CaO was thor­ components in the oil were cycloparaffins and n-paraffins, accounting
oughly sintered, resulting in the reduction of its basicity. for 54.09%. When activated carbon was used in a microwave batch
Besides these, transition metals have also been tested for catalytic reactor for catalytic pyrolysis of PS, the highest oil yield was 93.04 wt.%
pyrolysis of plastics, with different effects on the product formation. with aromatics being the main products [184]. Rex et al. [185] also
Kumagai et al. [170] studied the PET pyrolysis over various metal oxides synthesized different activated carbons from rice husk, corn husk, and
(ZnO, MgO, TiO2, and ZrO2) using tandem µ‑reactor-GC/MS and found coconut sheath, respectively, which were used as microwave absorbents
that benzene-rich aromatic hydrocarbons were the major products. ZnO and catalysts, simultaneously in the microwave pyrolysis of a waste
has the strongest basicity, maximizing the decarboxylation effect and plastic mixture. The product oil was mainly composed of gasoline range
resulting in the 88.8% benzene. In contrast, MgO, TiO2, and ZrO2 with hydrocarbons, with the highest styrene recovery of 67.58% in this
lower basicity, exhibits lower catalytic performance for the decarbox­ process.
ylation reaction, and a higher decarboxylation temperature was also Lei and his co-workers have developed H3PO4-activated biomass
observed, compared to ZnO. In a HDPE pyrolysis-catalytic cracking carbon material and studied the effect of acid concentration on heating
process, CuCO3 was used as a catalyst to achieve effective conversion of rate and carbonization time, with the ultimate goal of optimizing H3PO4
waste HDPE into liquid hydrocarbons [179]. The liquid hydrocarbon concentration to obtain the optimum activated carbon yield, and
fuel collected was mainly composed of paraffins, olefins, and aromatics textural characteristics from biomass precursors [186]. Subsequently,
and applied to successfully power a petrol-engine of a bike, showing the they attempted to produce jet fuel range hydrocarbons from PSW over
potential to use in petrol and diesel engines. Wu et al. [180] synthesized the activated carbon [121,175]. It turns out that up to 100% selectivity
a Ni-Ce based catalyst where the Ni-Ce core was encapsulated by a silica of jet fuel range hydrocarbons (71.8% alkanes and 28.2% aromatics) can
shell, with the hope of effectively mitigating the sintering of nano­ be obtained at the optimized conditions. The acidity of activated carbon
particles at high temperature. This catalyst showed excellent catalytic plays a critical role in determining the catalyst activity, where weak
activity and coking resistance ability in hydrogen production. It was acidity is favorable for jet fuel-ranged alkane formation, and strong
reported that sulphated zirconia was an effective catalyst for recovering acidity increases aromatics. Further, increasing catalytic reaction tem­
benzoic acid through PET pyrolysis due to its high acidity, with up to perature can also promote aromatization reactions, generating more
27–32 wt% benzoic acid yield [169]. More importantly, catalytic py­ aromatics, and releasing more hydrogen as well. They also combined
rolysis of PET in the presence of sulphated zirconia for benzoic acid biomass derived activated carbon and MgO as catalysts in the catalytic
production can be achieved at temperatures below 525 ◦ C, which is pyrolysis of LDPE; so, the pyrolysis vapors went through a MgO catalyst
much lower than the non-catalytic pyrolysis temperature (600 ◦ C). layer, followed by a biomass-derived activated carbon layer [176].
Carbonaceous materials derived from organic solid wastes have been Similarly, 100% jet fuel range hydrocarbons can be obtained at the
recognized as a promising candidate for catalysts, or support in het­ desired experimental conditions. The synergy effect between these two
erogeneous catalysis, due to excellent surface properties, such as catalysts, was seen on the hydrogen production, with 94.8 vol% of
controllable surface area and porosity, low synthesis cost, and high hydrogen in the gas product. Catalyst stability testing showed that corn
stability. Some researchers pay attention to this type of abundant and stover derived biochar is able to catalyze the LDPE degradation without
inexpensive material and have developed many different carbonaceous wax formation after 20 regeneration-reuse cycles [187].
materials for use as catalysts. From literature sources regarding carbon- Using ZnCl2 as an activation agent, enables the specific surface area
based catalysts used in the catalytic pyrolysis of PSW, it can be seen that of biochar to increase significantly, and the Zn species leads to more
organic solid wastes are the more popular feedstocks for carbon catalyst Lewis acid sites, which promotes the Diels–Alder reaction, hydrogen
preparation in order to reduce catalyst costs. Although plastic-to-fuels transfer, and dehydrogenation progress in the catalytic pyrolysis of PSW
technology has been developed very well, the price of plastic based [177]. ZnCl2-activated biochar increased the selectivity of aromatics to
liquid fuels still cannot compete with the existing petroleum industry. 47.5%, with two-ring aromatics being significantly enriched. Sun et al.

15
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Fig. 10. The possible mechanism for the MgO-catalyzed upgrading of LDPE pyrolysis vapors. (Adapted from [25] with permission from Elsevier).

[178] investigated the effect of biochar catalysts, activated with species polymerized from the pyrolytic volatiles accumulate on the
different chemical agents (ZnCl2, KOH, and H3PO4) on the plastic py­ catalyst surface, thereby covering the active sites and resulting in cat­
rolysis. Brønsted and Lewis acid sites created by H3PO4 and ZnCl2 both alytic activity loss [190]. It has been reported that olefin oligomerization
facilitated the aromatization process, leading up to 66% and 47.6% of and condensation reactions were the main causes for coke formation
aromatics, respectively. [191]. As shown in Fig. 11, catalyst deactivation caused by coke depo­
Catalyst deactivation is one of the barriers for the PSW pyrolysis sition takes place through several pathways. In terms of a supported
process, which impacts the process efficiency, economics, and the metal catalyst, the first deactivation pathway is to form carbide by
optimization of operating conditions at large-scale production. It is strong chemisorption as a monolayer or create multilayers by phys­
mainly caused by coke deposition and poisoning of active sites, both of isorption, hindering access to the active sites. The metal particles and
which contribute to the loss of catalytic activity in the catalytic cracking other active sites can even be covered totally, which enables reactants to
of plastics. Previous studies stress that the acidity and pore structure of be inaccessible to these active sites. The blockage of catalyst pores is also
cracking catalysts are two key factors to determine the deactivation able to prevent reactants from contacting the active site inside the mi­
resistance ability [188,189]. Therefore, the next parts will discuss the cropores of catalysts. Generally speaking, coke properties are mainly
coke deposition and active site poisoning during the catalytic pyrolysis studied from the perspective of its content, location, morphology, and
of plastics. chemical nature. Temperature programmed oxidation (TPO) technique
Coke deposition means that large-molecular-weight carbonaceous is able to accurately measure the amount of coke deposited on the

16
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

catalyst surface. Barbarias et al. tested the coke amount by this tech­ aliphatic chains, indane and indene, were the main components in the
nique, and found that the coke deposition rate in the catalytic reforming soluble coke, extracted from the spent HZSM-5 catalyst.
of HDPE pyrolysis volatiles over a commercial Ni-Ca/Al2O3 catalyst Marcilla et al. [196] studied the effect of temperature on coke for­
varied from 0.1 to 6.1 mgcoke g−cat1 g−HDPE
1
, depending on the catalytic mation in the catalytic cracking of LDPE over HZSM-5 and HUSY zeo­
temperature, space-time and steam/plastic ratio [192]. lites. Results showed that the higher the cracking temperature, the lower
Ibánez et al. [194] identified coke in the sequenced pyrolysis–­ the coke content deposited on the catalyst surface. The amount of coke,
cracking of HDPE over an HZSM-5 zeolite catalyst at a temperature of using the HZSM-5 zeolite (approximately 5%) is much lower than that of
500 ◦ C and a continuous feed of HDPE (1 g min− 1). They observed that HUSY zeolite (approximately 15%), which can be due to the difference
waxes are the precursors of coke formation during the initiation period, of pore sizes. They also calculated the pore volumes which were inac­
while light olefins could lead to the steady coke formation over time on cessible to the adsorbate (VA) and occupied by coke (VR), with the aim of
stream by condensation and oligomerization in the subsequent sections. determining the possible location of the coke. VR/VA ratio should be
Two types of coke were determined by TG-TPO analysis, one of which about 1 with the simple pore filling, while the ratio would be lower than
(coke I) was aliphatic hydrocarbons generated from the degradation of 1 with the channels and intersections being blocked. It should be noted
waxes and located on the outside of mesoporous and microporous pores. that increasing cracking temperature leads to a larger share of coke,
Another one (coke II) was aromatic hydrocarbons, either inside the insoluble in dichloromethane, that are chiefly poly-aromatic
zeolite pores or in the exterior of the zeolite pores, which were formed compounds.
by degrading coke I or oligomerizing and condensing light olefins. Apart Another cause of catalyst deactivation is the presence of poisons in
from coke I and coke II, wax itself or molten plastic could play a role in the catalytic cracking of PSW. Poisonous materials in the feedstock
covering the active sites on the surface of catalysts. If weight hour space would cover a part of active sites on the catalyst surface, or compete
velocity for a continuous plastic pyrolysis is too high, wax itself or with the reactants, thus suppressing the catalyst activity. In most liter­
molten plastic can not be immediately cracked, momentarily or endur­ ature, the used feedstock is very pure plastic without any poisons, like
ingly blocking the mass transfer channel. Considering that TG-TPO is not LDPE powder, which is not a problem at all. When a huge amount of
able to analyze the coke type and location, Castaño et al. [195] gave PSW needs to be handled by pyrolysis, it is inevitable to have a small
more in-depth insights into the coke formation in the cracking of HDPE amount of N and S in the PSW. The good news is that, in the catalytic
in the presence of HZSM-5, Hβ and HY zeolites. They observed in the cracking of plastic mixtures with 0.23% of N and 0.07% of S, over
Raman spectra, that a more graphite-like coke was formed as the pore different zeolite catalysts, the presence of N and S had little influence on
size of the zeolite increased. It was found from UV–vis spectroscopy that the catalytic cracking [197]. However, in the catalytic cracking of
the micropore size of the larger zeolite, condensation of higher LDPE− lube oil mixture with 4000 ppm of S and 85 ppm of N, the
poly-condensed aromatics, was also confirmed by solid-state 13C presence of N and S led to lower activities, as compared to the pure LDPE
CP-MAS NMR profiles. Although soluble coke is mainly composed of pyrolysis [198].
aromatics, the spent HZSM-5, Hβ, and HY zeolites gave rise to different With the catalyst deactivation being inevitable in the catalytic
aromatic families. For example, single-ring aromatics with two or more cracking of PSW, regeneration is able to save the catalyst repalcement

Fig. 11. The deactivation mechanism of a supported metal catalyst caused by coke deposition. (i) carbon chemisorption or physisorption hindering the access to
reactants; (ii) metal particle encapsulation or full covering of active sites; (iii) pore plugging; (iv) degradation of catalyst structure. (Reprinted from [193] with
permission from Elsevier).

17
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

costs, and thus enable a more cost-effective industrial process. Catalyst different mass and heat transfer rates would alter the plastic conversion
regeneration largely depends on the deactivation mechanism, and process, thereby affecting the product distribution and compositions. In
cannot be implemented if an irreversible deactivation happens, such as isothermal and dynamic experiments, PP pyrolysis shows considerable
de-alumination and zeolite amorphization [199]. As mentioned above, discrepancies of parameters, stemming from heat transfer limitations or
coke deposition is one of the main causes for catalyst deactivation in the complex degradation mechanisms [204]. Ceamano et al. [205] observed
catalytic cracking of plastics. Serrano et al. [199] explored the deacti­ significant longitudinal temperature profiles inside large PE samples
vation mechanism of nano-crystalline HZSM-5 zeolites in the catalytic during pyrolysis, and stressed that PE samples should be melted and
cracking of PE. He observed a reversible deactivation, caused by coke then coated onto sand particles in order to maximize the contact surface
deposition, and an irreversible or permanent deactivation caused by for heat transfer. They also studied the thermal decomposition kinetics
other factors. It was also found that the coke deposited on the HZSM-5 of HDPE, observing two causes of discrepancies from the experimental
catalyst, with larger external surface area, is less aggressive and easier results [206]. One of them is caused by an imperfect heat transfer be­
to remove, than the conventional microporous nano-crystalline tween plastic particles and reactor/plastic particles. Adjusting the
HZSM-5. In this case, a thermal decomposition curve is an effective amount of feedstock and heating rate was able to potentially resolve the
way to acquire information about carbonaceous deposit removal, tem­ heat transfer issues. It should be noted that an excellent gas–solid con­
perature, and reaction conditions. For example, Xie et al. [200] observed tact in the spouted bed reactor was also favorable to minimize heat and
that a thermal degradation curve of a used catalyst, derived from cata­ mass transfer limitations, keeping the bed in an isothermal condition
lytic dehydration of glycerol, stayed unchanged after 500 ◦ C, indicating [207]. In addition, a two-step pyrolysis process was developed by Zassa
coke can be eliminated at 500 ◦ C. Kassargy et al. [201] attempted to et al. with the aim of mitigating the heat transfer limitations of a
remove coke, derived from catalytic cracking of PE by combustion at multiphase reactor system [208]. In this system, the plastic melting and
500 ◦ C for 3 h, and showed a positive result that the regenerated USY pyrolysis are separated, allowing uniform melting of the polymer before
zeolite, after the first 8 cycles, still possessed a comparable catalytic decomposition. In this way, the light olefins yield was significantly
activity to the fresh catalyst. Although the USY zeolite, after 14 cycles of improved, with up to 75 wt.% of the gas being ethylene at the optimum
regeneration, was still able to catalyze the PE decomposition, the crys­ conditions.
talline structure was destroyed, and Bronsted sites density significantly Aguado et al. [209] used a conical spouted bed reactor to study the
decreased, leading to the production of the liquid hydrocarbons with kinetics of PS pyrolysis at temperatures ranging from 450 ◦ C to 550 ◦ C
higher carbon number. and compared the results with data derived from thermogravimetry
Another way to determine full combustion of the coke is to detect the (TGA) and a micro-reactor with extremely high heating rate. The inev­
concentration of CO2 coming out from the combustion system, when 100 itable mass and heat transfer limitations between PS and sand at high
vol% oxygen is used as the inert atmosphere [202]. In the thermal temperatures led to the lower activation energy in the spouted bed
regeneration of a Ni-based commercial catalyst, that was deactivated in reactor as compared to TGA. Non-crystalline PS is not able to coat the
the catalytic reforming of HDPE pyrolysis volatiles, the sintering of Ni0 sand particles uniformly with a fine layer after the glass transition, so
active sites made it impossible to fully recover its initial activity, after that higher transfer limitations would be expected. The results
high temperature calcination [202]. Considering that high temperature confirmed the highly suitable characteristics of this new reactor for PS
may increase the possibility of catalyst structure change, non-thermal pyrolysis, stemming from the following advantages: bed isothermicity,
plasma was proposed as a regeneration technique by oxidizing the compatibility with particles of various sizes, excellent gas-solid contact,
coke on the deactivated catalysts at a very low temperature [203]. With alleviated particle agglomeration, small segregation, and shorter resi­
the high concentration of ozone induced by plasma, 97.4% of the coke dence time of the pyrolysis volatiles.
can be eliminated at 250 ◦ C. As far as I am concerned, non-thermal The previous reports indicate that the competition between degra­
plasma regeneration, almost without destroying the catalyst skeleton dation and vaporization during PSW pyrolysis should be analyzed
structure, would be very promising. If the catalytic activity can be suc­ carefully [210,211]. Generally speaking, polymer molecules are too
cessfully recovered by this technique, the service life of the catalysts will large to vaporize, so they should be converted into small molecules
be largely extended in the real industry. Unfortunately, it is hard to before vaporization [32]. Formed small molecules that are dispersed in
precisely control the temperature of plasma reactor in a long-time the bulk phase and generate bubbles would be diffused into the interface
treatment and the scaling up of the non-thermal plasma technology is between condensed bulk and vapor phase. Finally, these small molecules
a challenge requiring more input. are able to move through the interface into the vapor phase. In a small
All in all, zeolites are the most common catalysts in the catalytic scale pyrolysis process, the rate-determining step in the volatilization
cracking of PSW due to high catalytic activity for gasoline or diesel range process of polymers is the degradation process where the
hydrocarbons production, although metal oxides, carbon materials, and rate-determining step is the rate of bond rupture within the polymer
clays show good cracking ability. In particular, hierarchical zeolites with molecules, since the sample size and thickness are so small that the
meso/macro pores are able to improve the diffusion of polymer chains, diffusion limitation can be minimized [210]. However, in large-scale
thereby enhancing the activity and extending the catalyst lifetime. reactors, diffusional limitations during the volatilization of polymers
Borrowed from the petroleum industry, this type of catalyst would be the are expected. On one hand, the surface area plays a vital role in the rate
most promising candidates for large-scale production. Catalyst deacti­ of volatilization, since the rate depends on the fraction of molecules in
vation is mainly caused by coke deposition and poisoning of active sites, the surface layer that have an energy equal to or greater than the min­
both of which contribute to the loss of catalytic activity during catalytic imum kinetic energy needed to break away from the surface. On the
pyrolysis of plastics. In the future, the focus should be to design the other hand, the vaporization rate is also determined by the diffusional
catalyst structure and regulate the acidity to enable better production of rate within the bulk phase that is inversely proportional to the sample
desirable hydrocarbons and longer catalyst life. thickness. It is expected that solid, liquid, and gas phases would be
present simultaneously during this process. In light of the multi-phase
3.1.3. Mass and heat transfer complexity of PSW pyrolysis, an extensive detailed analysis of the
Mass and heat transfer is always a big issue for the pyrolysis process, characteristics of all three phases should account for the mass and heat
which depends on the reactor design, although few literature references transfer phenomena during PSW pyrolysis. However, the inherent
have studied it. It is especially important for PSW due to the low thermal complexity of the problem of polymer pyrolysis makes the imple­
conductivity of this material. For plastic pyrolysis, particle temperature mentation of the multi-phase simulations remarkably challenging. Un­
inside the reactor plays the key role because plastic cannot start to fortunately, these challenges have not been addressed, so that there is an
degrade until the temperature reaches a certain point. Obviously, important research gap, yet to be filled, regarding the effect of mass and

18
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

heat transfer on the degradation behavior of PSW. economy of plastics. However, as we mentioned in the introduction, the
One of the effective ways to investigate the heat and mass transfer is in-situ catalysis has the shortcoming that the inorganics (in particular
making use of dimensionless numbers such as pyrolysis numbers (Py), alkalines) in the real-world PSW would physically block and chemically
Biot number (Bi), Péclet number (Pe), and Lewis number (Le) poison acid sites.
[212–215], which are useful in assessing the performance and limita­ Based on the insufficiency of existing catalytic pyrolysis process for
tions of pyrolysis reactors (Table 6). Py numbers determine whether the production of light olefins, Eschenbacher et al. [221] and Artetxe et al.
pyrolysis process is governed by the reaction kinetics (Py≫ 1) or con­ [205,222] developed a two-step (pyrolysis-catalysis) system with the
ductive/convective heat transfer in the particle (Py≪ 1). In the case of goal of maximizing the yields of waxes (C21+) and C12− C21 hydrocar­
Bi≫ 1, heat transfer through intraparticle conduction is slower than bons in the pyrolysis reactor and then effectively cracking the produced
external heat transfer through convection. In contrast, the external heat volatiles in the cracking stage. With a bare steam-treated HZSM-5, at
transfer would dominate the pyrolysis process. If Py≪ 1 and Bi≫ 1 are higher temperature (700 ◦ C), the total yield of light olefins reached 69
simultaneously obtained, thermal gradients can be observed inside the wt% (19% ethylene, 22% propylene, 10% 1,3-butadiene, and 18% other
particles and thus the reaction rate inside the particle is significantly C4 olefins) [221]. The total yield of light olefins (C2–C4) was further
lower than the surface of the particle. The case of Pe≫ 1 means that enhanced to 77 wt.% with the yields of ethylene, propylene, and butene
convective mass transfer from the particle is much faster than the being 40.4, 19.5, and 17.5 wt%, respectively, at 900 ◦ C [222]. The high
diffusion of volatilizing molecules through the reacting particle. For an yield of light olefins can contribute to regulating and controlling the
analogous comparison in the heat transfer phenomena, Le≫ 1 indicates temperature for each step, where the pyrolysis temperature was opti­
that the intra-particle heat transfer occurs much faster than the mass mized at 500 ◦ C to yield 93 wt % of long chain hydrocarbons and further
transfer. tuning the catalytic temperature achieved the desirable outcomes. The
addition of a HZSM-5 zeolite catalyst in the catalytic reforming stage
3.2. Valuable gas from pyrolysis of PSW was able to reduce the temperature to below 550 ◦ C [205]. A maximum
of 62.9 wt.% of light olefins can be obtained with the yields of ethylene,
Apart from the production of liquid hydrocarbons by PSW pyrolysis, propylene and butene being 10.6, 35.6 and 16.7 wt.%, respectively, at
obtaining valuable gas byproducts, such as light olefins and hydrogen, this condition. More importantly, the byproduct of aromatics would
with high selectivity, is another feasible recycling method. Apparently, never go beyond 13 wt.%. Similar results were also observed in the
light olefins can be used to produce new plastic products, creating a catalytic cracking of HDPE pyrolysis waxes over HZSM-5 zeolite cata­
circular economy for plastic waste. Hydrogen produced from PSW py­ lysts [223]. The catalyst with a SiO2/Al2O3 ratio of 30 showed the
rolysis can be recognized as the “blue hydrogen” or even “green highest light olefin yield (58 wt%), with the yields of ethylene, pro­
hydrogen” that greatly mitigates carbon emissions as compared to fossil- pylene, and butenes being 9.5, 32, and 16.5 wt%, respectively. These
based hydrogen, making a contribution to carbon neutrality. This sec­ collective studies highlight the importance of identifying a more effi­
tion will discuss the production of light olefins and hydrogen from py­ cient catalyst capable of reducing reaction temperature and tuning
rolysis of PSW in detail. product distribution.
Elordi et al. [78] studied the catalytic activity of HZSM-5, HY and Hβ
3.2.1. Light olefins zeolite-based catalysts during catalytic pyrolysis of HDPE, with the main
Light olefins, including ethylene and propylene, are the feedstock for products being light olefins and fuel range hydrocarbons. HZSM-5 zeo­
the production of plastics and many other downstream chemicals. Ad­ lite-based catalyst show a high yield of light olefins of approximately 58
vancements in the PSW-to-light olefins technology have led to a circular wt.% once equilibrated. An important finding is that the yield of light
economy of plastics instead of linear use, enabling the PSW to stay in the olefins has a strong relationship with the pore size of the zeolite catalysts
economy and out of the environment. Kaminsky et al. [216] took the being used. The HZSM-5 catalyst, with the smallest pore size, gives rise
lead in light olefins production by pyrolysis of plastics, and successfully to the highest yield of light olefins; then the Hβ and HY zeolites obtain
obtained high yields of light olefins consisting of approximately 36% higher yield of light olefins due to larger pores. In addition, the com­
ethylene, 15% propylene, 9% 1-butene and butadiene. Rather than using ponents of light olefins are also affected by the catalyst pore size. The
catalyst materials, however, their results was obtained based on the large pore size is favorable for the formation of butenes, whereas pro­
increase of temperature and the addition of steam. This example reveals pylene and ethylene are the main components for the HZSM-5 catalyst,
how steam improve the production of light olefins during catalytic py­ with the smallest pore size.
rolysis of PSW.
For catalytic pyrolysis of polyolefins, relatively low yields (˂40 wt%) Table 6
of light olefins were usually reported based on in-situ catalysis mode and Dimensionless numbers which are useful in assessing reactor performance and
the moderate catalyst temperature (around 500 ◦ C). For example, a limitations. (Adapted from [32] with permission from Elsevier).
spent fluid catalytic cracking (FCC)catalyst agglomerated with 50 wt% Characteristic Dimensionless Values Significance
bentonite can produce as low as 28 wt% of C2–C4 olefins at 500 ◦ C [84]. phenomena number
The same studies also assessed the use of a spent FCC catalyst at the
Reaction kinetics λ Py ≫ 1 Pyrolysis controlled by
moderately catalytic pyrolysis of PSW, finding that 21–38 wt.% of light PyI =
ρCp L2 k reaction kinetics.
olefins were observed [217–219]. A novel catalytic reactive distillation h Py ≪ 1 Pyrolysis controlled by heat
PyII =
approach based on in-situ catalysis mode was also developed to produce ρCp Lk transfer.
light olefins from HDPE [48], where the product can be collected only Heat transfer hL Bi ≫ 1 Heat transfer limitation due to
Bi =
intra-particle thermal
when the molecular weight of the pyrolysis products is low enough to
λ
gradients.
exit the cooling coil as a gaseous stream. At the operating temperature of Bi ≪ 1 Heat transfer limitation due to
500 ◦ C and 1% (w/w) of HZSM-5 (catalyst to polymer ratio), almost external convection.
100% of the HDPE can be converted into gaseous products of a specific Mass transfer PK Pe ≫ 1 Release of volatiles controlled
Pe =
Dμ by diffusion.
range. The product analysis shows that the volatile products fell into the
Pe ≪ 1 Release of volatiles controlled
range between C2 to C8, with light olefins accounting for the majority by convective mass transfer.
(approximately 50 wt%), in particular propylene and butenes. By tuning μλ Le ≫ 1 Negligible internal heat
Le =
the reaction conditions, the middle olefins within the range of C5 to C11 PKρCp transfer effects.
can also be produced in this system [220]. This distillation-based py­ Le ≪ 1 Negligible internal mass
transfer effects.
rolysis approach provides a proof of concept that promotes a circular

19
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

3.2.2. Hydrogen temperature of 600 ◦ C and a reforming temperature of 800 ◦ C. Experi­

Selective production of hydrogen by plastic pyrolysis represents an mental results indicated that CNTs can be formed in quantity, on nickel,
important advance, because hydrogen has a great potential to serve as a iron. and cobalt based catalysts, while copper based catalyst had the
fuel in future energy supplies. Each year over 50 million tons of H2 need opposite result, with only trace amounts of CNTs. Of the catalysts tested,
to be produced to support the agricultural and chemical industries all Fe based catalyst gave the highest hydrogen yield. Ni-Fe bimetallic
over the world, 96% of which is currently obtained from steam catalyst was developed and used in the pyrolysis-catalysis of waste
reforming of fossil fuels [224]. Therefore, PSW-to-hydrogen technology plastics, showing a potential catalytic performance [232]. The presence
might be able to address two global challenges: PSW pollution and H2 of Ni and Fe was able to play a different role, where Fe showed a higher
fuel production, if this technology can be developed and advanced to the cracking ability, producing more hydrogen and solid carbon, while the
commercial stage in the near future. Ni improved the thermal stability and graphitization degree of CNTs.
Generally speaking, two fixed bed reactors for the two-stage process The highest H2 yield was 7.24 g/100 g plastic sample, with H2 con­
are easier to be designed and operated at the laboratory scale. Approx­ centration of around 70 vol% and carbon yield was 46 g/100 g plastic
imately 0.2–0.3 g H2/g plastics was obtained in such a two-stage process sample. They compared the results with other studies, confirming the
at the pyrolysis temperature of 500 ◦ C and the catalytic reforming superior catalytic performance. By further comparing the carbon ma­
temperatures ranging from 600 ◦ C to 900 ◦ C [225]. Without a catalyst, terials produced in different catalytic temperatures, it can be found that
the H2 yield was only 0.015 g H2/g plastics, but this H2 yield was higher temperature is favorable for improving carbon deposition and
significantly increased to 0.25 g H2/g plastics by using a Ni–Mg–Al high quality ordered carbon nanotubes should be produced at higher
catalyst. At the high reforming temperature of 800 ◦ C, the yield of gas than 700 ◦ C [233]. That could be due to the fact that complex carbon
derived from PS decomposition was still very low (11.2 wt.% related to precursors produced at lower temperatures made the dissociation and
the mass of plastic) without a catalyst and steam; in contrast, a 94.1 wt. dehydrogenation more difficult to grow graphitic layers. Ru/γ− Al2O3
% yield can be obtained after adding the Ni–Mg–Al catalyst and steam was found to be very effective for steam reforming of PS pyrolysis vapors
[226]. Furthermore, increasing the catalytic reforming temperature and to hydrogen-rich gas, and lowering the temperature by 200 K as
the steam injection can improve the hydrogen production. However, compared to a conventional Ni-based catalyst [234]. Understandably,
scaling up the fixed bed reactor could encounter the heat and mass with a drop in reforming temperature, less thermal input would be
transfer limitation due to the inherent nature of this type of reactor. required, leading to an increase of thermal efficiency for the whole
The use of fluidized bed reactors for the two stage process has been process.
proposed. The pioneering studies conducted by Czernik and French Although the above-mentioned studies have suggested that two-step
combined two fluidized beds to achieve a continuous plastic pyrolysis- process is able to produce high purity hydrogen, it has also been
reforming process, showing clear advantages and yielding hydrogen at demonstrated that one-step (in-situ catalysis mode) process may also be
80% of the stoichiometric potential, with PP as the feedstock [227]. promising in the catalytic deconstruction of PSW into hydrogen and
Barbarias et al. [228] tested hydrogen production from different plastics high-value carbons [88]. The one-step microwave-initiated process fa­
in an original two-step reaction system, where the plastic pyrolysis was cilitates catalytic scission of chemical C–H bonds over an active FeAlOx
achieved at 500 ◦ C in a conical spouted bed reactor, followed by a cat­ catalyst by generating huge temperature gap (over 400 ◦ C) between the
alytic reforming process at 700 ◦ C in a fluidized bed reactor. The good catalyst and substance. Therefore, a high hydrogen yield of
mixing during a conical spouted bed enables the PSW feedstock to be 55.6 mmol/g plastic can be obtained, with over 97% of the theoretical
heated uniformly and timely, thereby minimizing a possibility of partial mass of hydrogen being extracted from the deconstructed plastic. The
or incomplete pyrolysis, and the subsequent fluidized bed is favorable results are based on very small microwave batch experiments (0.3–0.4 g
for improving the catalyst utilization efficiency. Based on this reactor, plastics processed for each run), so the largely different mass and heat
polyolefins gave the highest yield of hydrogen (34.8–37.3 wt%) while PS transfer and limited microwave penetration depth for a large scale
and PET were much lower, with hydrogen yields being 29.1 wt.% and operation could affect the process efficiency and product selectivity.
18.2 wt.% respectively. Based on these results and Table 2, it could be
hypothesized that the hydrogen production is linearly associated with 3.3. Naphtha production from pyrolysis of PSW
the hydrogen content of plastics.
Recently, co-production of H2 and high-value carbon nanotubes Although plastic-to-fuels technology enables the reduction of PSW,
(CNTs) by a two-stage process, has also been reported. In this process, fuels are currently burned to provide heat or electricity, causing serious
using a proper catalyst, hydrogen can be produced with high selectivity, greenhouse gas emission. In this way, the demand for virgin plastics
and carbon nanotubes will be simultaneously deposited on the catalyst. cannot be offset, and the virgin plastics are still produced from fossil
Wu et al. [229] processed real-world waste plastics through sources. Some researchers even claim that this solution is not recycling;
pyrolysis-reforming over a Ni-Mn-Al catalyst, with the aim of producing it is really just another expensive and complicated way to burn fossil
hydrogen and high value CNTs. The highest hydrogen yield of 94.4 fuels. However, manufacturers and end-users are challenged to utilize
mmol H2 g− 1 plastic can be obtained in the presence of the Ni-Mn-Al recycled plastics instead of fossil based plastics although they hope that
catalyst and steam, and multi-walled CNTs with parallel graphene 100% of packaging could be recyclable. As mentioned in the Introduc­
layers were clearly observed, based on SEM and TEM images. Unfortu­ tion part, the current recycling method (melting and remolding) often
nately, the purity of the CNTs were affected by the presence of chloride encounters a challenge because the recycled plastics does not perform as
in the waste plastics, even though the polyvinyl chloride content was well as virgin plastics. Without a bold shift in approach, it is very
very low (0.3 wt.%). Given the importance of steam in the catalytic difficult to achieve the goal set of plastic circular economy. The good
reforming of plastic pyrolysis vapors, they studied the effect of steam news is that emerging and scaling technology is developed to convert
content on the hydrogen production and the quality of CNTs from the PSW to naphtha that gets back into circulation as a new feedstock for
perspective of purity [230]. For LDPE, PP, and PS, more hydrogen was plastic product (Fig. 12). In the petroleum industry, naphtha-to-plastic
produced by increasing the steam injection rate. In terms of PS, the monomers technology (steam cracking) is very mature. If we are able
highest CNT yield (32 wt.% plastic conversion to CNTs) was achieved to produce naphtha through PSW pyrolysis and ensure it to meet the
when the steam injection rate was 0.25 g h− 1. feedstock requirements for petrochemical cracking process, plastic-to-
Regarding the pyrolysis-reforming of PSW for clean hydrogen pro­ plastic chemical recycling could not only be comparable to the more
duction with high-value CNTs as a by-product, catalyst would play a prevalent technique called “mechanical recycling” but also enable the
vital role in the hydrogen yield and CNTs quality. Acomb et al. [231] same quality to the virgin plastics, and be suitable for complicated
screened different metals supported on Al2O3 at the pyrolysis plastic mixtures. To be honest, the PSW-to-naphtha technology is really

20
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

accelerating solutions for a more circular recycled plastics supply chain clear demand is to expand capacity and improve technologies to create a
at scale. circular economy for plastics. These practical examples indicate that it is
It is known that some major companies aim to promote PSW recy­ totally possible to return more PSW to supply chains than is currently in
cling towards increasing the share of recycled plastics in the market. In play today, giving the credit to the innovation developed and scaled by
this potential circular-economy, one of the most important sectors is to technology providers. Unfortunately, the scientific community has not
turn PSW into pyrolysis oil used as feedstock for new plastic products. yet been devoted to this technology too much. Based on current litera­
The corresponding pilot scale results presented to consumers show that tures, the main components of liquid oil produced from PSW pyrolysis
the pyrolysis oil (recycled naphtha) based plastics have the same quality are unsaturated hydrocarbons and aromatics [16,19,220,236]. In the
and application capability as those manufactured from fossil oil. It also petroleum industry, the steam cracking for light olefins production re­
pointed out that this PSW recycling method is complementary to me­ quires the C5–C12 saturated hydrocarbons as much as possible, with a
chanical recycling, for the time being, because some sorted single- minimum amount of aromatic. It was found that in the in-situ catalytic
stream plastics can be recycled mechanically. For a plastic mixture pyrolysis of HDPE at 500 ◦ C (Al2O3 pillared montmorillonite clay and
which cannot be mechanically sorted efficiently, this chemical recycling HDPE mixture with the ratio of 1:1), over 50% C5–C12 alkanes and
for converting PSW back to naphtha for new plastic production should about 15% of aromatics can be obtained, with the liquid yield of 60–70
be more reasonable. It should be noted that this virgin-quality recycled wt.% [237]. However, in light of the drawbacks of the in-situ catalysis
plastic from pyrolysis to naphtha could increase availability of plastics including fast deactivation of catalyst caused by the impurities in the
for food-grade products, because the mechanically recycled plastics are real-world plastics, discontinuous process, higher operation cost, and
not allowed to enter into food packaging. low heat and mass transfer, ex-situ catalytic reforming of plastic pyrol­
Recently, Ruan’s group has licensed continuous microwave-assisted ysis volatiles for naphtha production was developed [238]. That was an
pyrolysis technology [94] to a California company for converting PSW to ex-situ tandem catalysis process, where the first catalytic reforming zone
low-carbon and low-sulfur fuels and high quality naphtha. That could be was intended to improve the cracking of plastic pyrolysis wax into
a great step to deal with the PSW by pyrolysis technology. More shorter chain olefins, and the second lower-temperature catalytic
importantly, the system is modular, compact, and portable so that it can reforming zone was intended for the hydrogenation process to convert
be fixed on small boats and large ships, making it flexible in a number of olefins to alkanes without high pressure or the use of external hydrogen
ocean cleaning scenarios. The California company has also been (Fig. 13). In the first catalytic zone, polyolefin cracking proceeded via
expanding its processing capability, currently (2021) with a capacity of free radicals, mainly consisting of initiation, chain propagation, and
1–5 t/day PSW. Another big company in Skive, Denmark is also working termination. Initiation reactions primarily include random cracking and
hard to develop technology which can recover naphtha from PSW, with end chain cracking, which break C–C bonds of the long chains of poly­
the goal of creating a circular value chain. What makes this company olefins, generating free radicals and molecules. The formation of car­
unique is that they designed an effective catalyst for hydrocracking of benium ions in the initiation reactions was demonstrated to work by
plastic pyrolysis volatiles. It turns out that the catalyst could alter the abstraction of a hydride ion on the acid site of the catalyst. Then,
molecular structure of hydrocarbons, obtaining desirable components. propagation reactions occurred, to keep the cracking reactions going,
This company built the first testing facility in 2014, confirming that meaning that the free radicals generated during the initiation reactions,
pyrolysis of PSW to produce desirable products by the unique technol­ broke off during the β-scission reactions. β-scission reactions enable the
ogy was feasible. By now, they have started the first production facility large free radicals generated from the initiation reactions, to be cracked
in Skive, Denmark and the factory was successfully scaled to 20,000 tons into C5–C12 olefins and smaller free radicals. Finally, the chain propa­
of PSW per year. In the future, they plan to build more and larger fa­ gation reaction is terminated by desorbing the surface carbenium ions,
cilities across Europe, or even the world. forming C5–C12 olefins and hydrions. The main function of Al2O3 pil­
In order to further advance the plastic-to-naphtha technology, the lared M− clay in the second catalytic zone would be to convert the

Fig. 12. Plastic-to-naphtha technology roadmap. (Reprinted from [235] with permission from Elsevier).

21
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

obtained short chain olefins to C5–C12 paraffins via hydrogen transfer million and 49.1%, respectively. If the concentrated solar power is used
reactions. Most of the olefins were converted into paraffins with the as an energy source, the TCI would present a 20% increase and the ROI
simultaneous formation of aromatics. The issue for this process is that would decrease by 11%. Westerhout et al. [242] compared different
the low cracking ability of the first catalytic zone shortens the process reactors from the perspective of the techno-economic analysis. They
lifetime, thereby highlighting the importance of new cracking catalysts drew a conclusion that the ROIs of a bubbling fluidized bed reactor
with higher stability. operated at 740 ◦ C and a circulating fluidized bed reactor operated at
In terms of plastic-to-naphtha technology, the top priority right now 840 ◦ C are 21.7% and 29.5%, respectively, which are both higher than a
should be to increase the selectivity of naphtha range aliphatic hydro­ rotating cone reactor operated at 625 ◦ C with the ROI of 14.2%. They
carbons by developing better cracking catalysts and simultaneously also estimated the TCI for a 50,000 t/yr pyrolysis plant would be be­
mitigate the aromatic formation. Generally speaking, aromatic forma­ tween USD 7.84 and 11.2 million. The specific production cost of the
tion could be promoted by a synergic effect between Brønsted acid sites plastic oil was estimated, based on a plastic-to-heavy fuel plant with a
(aromatization) and Lewis acid sites (dehydrogenation), while catalytic capacity of 100 kg PSW/h [13]. At this scale, the cost of plastic based
cracking process largely relies on the Brønsted acid sites [239,240]. In heavy fuel oil was about £0.87/kg, which is much higher than the price
this regard, the isolation of Lewis acid sites will suppress the aromatic of the market product, whereas the value can be reduced significantly by
formation without affecting the catalytic cracking ability of catalysts. further scaling up, showing improved economic feasibility. If the pro­
Further research should focus on the catalyst or catalytic system cessing capacity of the pyrolysis plant is able to reach 100,000 kg/h, it
development and process optimization. This plastic-to-naphtha tech­ will be profitable within a year.
nology is an important strategy for a bio-based circular plastics econ­ A waste HDPE refinery for processing 500 tons/day was designed,
omy. However, an effective production process for high alkane content and the corresponding techno-economic analysis was conducted [243].
naphtha that is able to attract industrial partners is still missing. It is also As shown in Fig. 14, the products obtained from the refinery process,
difficult to recover plastics containing oxygen or nitrogen, because the with four sections, would include plastic monomers (ethylene and pro­
catalytic reforming process for oxygen and nitrogen removal requires pylene), aromatics, low- and high-molecular weight hydrocarbon
higher cost. At a time when the plastic-to-naphtha technology is strug­ (MWHC) mixtures. According to the capital cost estimation, including
gling to make money, manufacturers would like to feed clean polyolefins the fixed capital investment, total project investment and total installed
to existing facilities to produce high quality naphtha for downstream cost, and indirect costs (engineering, consulting, construction, etc.) are
vendors. the highest for both the base and heat integrated cases. In this study, the
net present value (NPV) obtained from discounted cash flow analysis
4. Techno-economic analysis was used as an indicator to estimate the economic feasibility of the
HDPE refinery process. Results showed that the heat integrated refinery
The costs of PSW pyrolysis recycling, which will determine if it can had the NPV of 383.1 MM USD while the NPV of the base case was
be commercialized in the market, can be affected by many factors, such 366.75 MM USD. Sensitivity analysis was also conducted to study the
as labor, maintenance, transportation, capital investment, electricity, effect of ten parameters (total project investment, internal rate of return,
heat, and other plant utilities. The techno-economic evaluation of this corporate tax rate, HDPE cost, electricity cost, ethylene price, propylene
process is essential to reduce the underlying costs of the process and price, aromatics mixture price, low MWHC price, and high MWHC price)
improve the corresponding supply chain. This assessment and resulting on NPV. It was found that the NPV decreased with the increase of the
recommendations will be beneficial to establish a sound strategic design HDPE cost, electricity cost, and federal + State corporate tax linearly.
for the production of fuels or chemicals from PSW pyrolysis. The return More importantly, when the HDPE cost goes beyond 460 USD/tonne, the
on investment (ROI) and total capital investment (TCI) are two impor­ NPV would be negative, enabling the project to be economically un­
tant factors used to evaluate the performance of a PSW pyrolysis plant feasible. However, it was suggested that the HDPE refinery process, with
(Table 7). Jiang et al. [241] conducted a techno-economic evaluation of economic sustainability, was quite promising.
the molten solar salt pyrolysis of PSW, and found that the TCI and ROI of As described in the study by Larrain et al. [244], PSW pyrolysis can
a 8000 t/yr plant would be USD 3.63 million and 27.6%, respectively, be classified into open-loop and closed-loop recycling processes. A
with the pyrolysis gas being used to power the plant. When it is scaled up closed-loop recycling process represents a plastic-to-naphtha technology
to a 16,000 t/yr plant, the TCI and ROI could increase to USD 6.44 as naphtha is a feedstock for new plastic production; while an open-loop

Fig. 13. Reaction mechanism for catalytic reforming of HDPE pyrolysis volatiles by a tandem catalysis. (Reprinted from [238] with permission from Elsevier).

22
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

recycling process means that PSW will be converted into waxes used for [251]. However, pyrolysis can significantly reduce the greenhouse gas
other applications. They compared the economic performance of the two emissions, pollutants emission, and requirement for landfill space; it also
processes. The economic assessment indicates that open-loop recycling provides much greater resource savings than landfill and a comparable
presents a better economic performance when compared to close-loop level to those for incineration [252,253]. According to an LCA study,
recycling, with the higher price of output product. To enable these integrating carbon nanotubes production to the plastic pyrolysis process
recycling processes to be feasible and cost-effective, the minimum PSW is favorable for further reduction of climate change impact, fossil
processing capacity for open-loop and close-loop recycling should be 70, depletion, radiation potentials, and human toxicity [254]. Furthermore,
000 t/year and 115,000 t/year, respectively. The supply of PSW feed­ a higher PET share in the PSW feedstock, can increase the impact to the
stock must be ensured as well. environment.
Designing for circularity has gained wide interest in the plastic in­ Greenhouse gas (GHG) emissions are the major environmental
dustry, requiring manufacturers and users to rethink how to recycle burden for PSW pyrolysis. Many years ago, the first study of GHG
PSW. Recovering ethylene monomer via pyrolysis of polyolefins is an emissions from PSW pyrolysis was conducted, based on a British Pe­
emerging field, which follows the principles of a circular economy. troleum polymer cracking process (BP process) with a mixture of poly­
Somoza-Tornos et al. [245] explored the economic benefits of this ethylene terephthalate (PET) and polyolefins as a feedstock [255]. This
technical route in the chemical industry. The main contributors to the study found that the GHG emissions were 1.7 kg CO2 equiv/kg plastics,
capital cost of the PE-to-ethylene process include the installation of the which was lower than other processes, such as landfill, combustion, and
pyrolysis reactor (accounting for 12%), the compressors of the main hydrocracking. Similar results that the pyrolysis process produced less
process (accounting for 18%), the energy used for the refrigeration cycle GHG emissions were obtained from other studies [256,257]. These
(accounting for 32%), and the heat exchanger network (accounting for studies also pointed out that GHG emission savings can be improved by
15%). Economic assessment results showed that ethylene recovered suppressing the use of fossil based raw materials. Iribarren et al. [258]
from PE pyrolysis was able to offer a highly competitive cost of 0.386 conducted the LCA of a pyrolysis process, coupled with catalytic
€/kg that is much lower than the standard naphtha-based cost (0.835 €/ reforming, and targeting gasoline and diesel production within the
kg). They drew a conclusion that converting waste PE to ethylene via cradle-to-gate scope. In this study, the GHG emissions were 2.44 kg CO2
pyrolysis seems feasible based on the proposed market assumptions in equiv/kg gasoline. On the other hand, Gracida-Alvarez et al. [259]
this assessment. analyzed the life cycle carbon footprint of a HDPE refinery design in
detail, and provided the effect of regional electricity grids on GHG
5. Environmental considerations emissions. This study indicates that the proposed refinery process of
HDPE is able to produce high quality plastic monomers and aromatics
Life cycle assessment (LCA) plays an important role in identifying the with less GHG emissions as compared to those from fossil oil, assuming
environmental impacts of a product throughout its life cycle [247,248]. American average grid electricity.
This tool can be used to compare different life cycles for alternative Apart from the emissions in the pyrolysis process, the GHG emission
products and processes. As shown in Fig. 15, four stages (the goal and during the conversion of plastic pyrolysis oil, is another aspect for
define the system boundary, mass and energy flows, life cycle impact environmental considerations. By comparing the GHG emissions of fuels
assessment for all processes, and sensitive analysis) need to be imple­ obtained from PSW pyrolysis and crude oil refinery, Gracida-Alvarez
mented. The final results obtained are beneficial to the product et al. found that pyrolysis fuels caused 8% lower emissions per mega­
improvement and to minimize the underlying impact of the process. joule [260]. A similar conclusion was also observed in another study
Alston et al. [249] evaluated the environmental impact of the pyrolysis, [261]. Life-cycle GHG emissions of plastic-derived ultralow sulfur diesel
incineration, and landfill of waste electrical and electronic equipment, were reduced by 1% to 14%, compared to petroleum diesel, depending
containing up to 25% plastics via LCA analysis. They found that the main on the co-product utilization technology. But the study by Kalargaris
impact for landfill was in terms of requirements for huge land space and et al. showed that all measured emissions (NOx, HC, CO, CO2) experi­
pollutants emission. In addition, persistent organic pollutants, such as enced an increase with the addition of plastic pyrolysis oil in the diesel
polycyclic aromatic hydrocarbons and polychlorinated biphenyls, can fuel [262]. In this regard, creating a circular economy by converting
be released from landfilling [250]; what is worse is that pollution and PSW into naphtha or light olefins could significantly reduce the GHG
soil contamination may serve as breeding ground for pests and diseases emission.

Table 7
literature reports on economic evaluation of pyrolysis of PSW.
Reactors Products Plant scale (ton/ TCI (USD ROI Production cost (USD million/ Refs
yr) million) yr)

Molten salt reactor powered by pyrolysis gas Pyrolysis oil/wax 4000 3.63 10.7% 1.76 [241]
Pyrolysis oil/wax 8000 4.41 27.6% 2.51
Pyrolysis oil/wax 16,000 6.44 49.1% 3.55
Molten salt reactor powered by concentrated solar Pyrolysis oil/wax 4000 4.34 9.4% 1.74
power
Pyrolysis oil/wax 8000 5.40 24.1% 2.38
Pyrolysis oil/wax 16,000 8 41.2% 3.34
Bubbling fluidized bed Ethylene and 50,000 8.2 21.7% 4.3 [242]
propylene
Circulating fluidized bed Ethylene and 50,000 10.4 14.2% 5.4
propylene
Rotating cone reactor Ethylene and 50,000 7.3 29.5% 4.5
propylene
Fluidised bed reactor Pyrolysis oil/wax 7000 5.40 25% 2.9 [13]
Pyrolysis oil/wax 70,000 15.1 50% 5.7
Pyrolysis oil/wax 700,000 91.8 100% 34
Fluidised bed reactor Gasoline/diesel 10,000 16.0 4.17% 5.9 [246]
Gasoline/diesel 60,000 42.4 23.8% 29.3
Gasoline/diesel 120,000 63.3 35.7% 56.2

23
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Fig. 14. The detailed HDPE refinery process. A-100 represents pyrolysis section. A-200 represents monomer separation section. A-300 represents aromatics
extraction section. A-400 represents hydrotreatment section. (Reprinted from [243] from permission from ACS Publications).

Fig. 15. The life cycle assessment framework.

6. Challenges breakthroughs and advance the plastic pyrolysis technology into the
commercial stage, continued efforts are suggested to address the
From an industrial level, many start-ups have been taking action on following challenges.
the PSW pyrolysis technology, and have built several promising facil­
ities, with the hope of keeping more PSW out of landfills and our envi­ (1) Theoretically, the pyrolysis system and technology can be
ronment. In the scientific community, the constantly updated plastic customized to produce a product based on the needs of cus­
decomposition/reforming mechanism and advanced catalysts/systems tomers, ranging from heavy oil to gasoline, naphtha, or jet fuels.
demonstrate the potential feasibility of high-quality products produced However, the real world PSW is extremely complicated, probably
from PSW. The coming years will tell whether the pyrolysis technology containing pigments, dyes, coatings, paper, metal foils, glass and
is able to make a real change for PSW recycling/upcycling. To achieve metal fragments etc., which might affect the quality and purity of

24
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

fuels. Accepting the fact that mixed PSW will, in reality, normally hydrogen separation, are still hampering this potential industrial
contain some level of PVC, more advanced systems are required application. Therefore, compared to plastic-to-fuels or naphtha
to separate the PVC from the real-world plastic mixture or remove technologies, valuable gas production seems to be less popular for
the hydrochloric acid in the final liquid product. In this regard, investors, partners, and customers due to the need of developing
the scientific and industrial community has been developing new downstream process (separation and purification of the
commercial PVC and other impurities removal system based on complicated gas).
multi-spectral sorting machinery with artificial intelligence. For (5) Besides, it should be noted that converting aromatic PSW back to
other potential contaminants in the real world plastic waste that aromatic monomers by pyrolysis, is also highly recommended for
can not be identified by the spectroscopic technology, a variety of a circular economy. In this pathway, the selective decomposition
technologies can be applied to further purify the plastic waste, of aromatic PSW into desirable monomers requires an effective
such as air separation systems, hydrocyclones for separating and unique catalyst, which facilitates the cleavage of C–O or C–C
liquid from solid, and integrated water/acid/alkaline/solvent bonds between aromatic rings. Recently, Jing et al. [263] pro­
washing systems. vided the first example of selectively producing aromatic mono­
(2) In terms of catalyst material, what restricts its development is the mers from PS, PET, PC, or their mixtures, via catalytic
steric and diffusional hindrance of the large polymer molecules hydrogenolysis, achieving 75–85% monomers yield. But this
within the zeolite micropores, which is inspiring new consider­ process involved an expensive catalyst (Ru/Nb2O5), high
ation for mesoporous or hierarchical materials, such as MCM-41 hydrogen pressure, and toxic octane as a solvent. If the recom­
and SBA-15. Although hierarchical zeolites are expected to mended pyrolysis-catalysis process can obtain the similar results,
improve the catalytic activity and product selectivity by tailoring it should be quite promising and favored by the industry from the
the porosity and acidity, increasing catalyst stability and standpoint of process economic and environmental consider­
regeneration-reaction cycles is still a great challenge. In cases ation. Additional research and development are needed to further
where mesoporous materials show superior diffusion to micro­ develop new catalysts and optimize the process, in order to make
porous counterparts, evidence of longer lifetime for mesoporous it suitable for commercial grade aromatic monomers production
materials during catalytic pyrolysis of PSW is generally lacking. from aromatic plastic wastes.
(3) The high percentage of olefins in the pyrolysis oil also limits the
economic feasibility, whether used as fuels or a raw material for 7. Concluding remarks and outlook
new plastics manufacturing. When the pyrolysis oil is planned to
be used in the transportation fuel industry, an excessive amount This review shows that research in catalytic pyrolysis of plastics is very
of olefin is not permissible since they may lead to the formation of attractive, especially in recent years when the government and the public
unwanted gums inside engines. With regard to the steam cracking are aware of the hazards of ever-increasing plastic pollution. Although
in the petroleum industry, the most desirable compositions are encouraging progress has been made, recent changes in the collection and
C5–C12 paraffins, with less amounts of olefins and aromatics. sorting of complex PSW and longer-term trends in the demand for creating
Until now, there are no reports for producing plastic-derived a plastic circular economy require further developments in the areas of the
naphtha with the same quality as fossil naphtha. So, selective plastic pyrolysis oil characterization, reactor designs, and catalysts. From
production of naphtha-range alkanes, with minimal amounts of the perspective of oil characterization, distillation coupled with a com­
olefins and aromatics, can be considered a significant step for­ bination of GC-FID/MS, FTIR, NMR, SEC is recommended to strengthen
ward for PSW pyrolysis. But continued research efforts may fundamental understanding of complicated pyrolysis oil product.
achieve expected results by developing promising catalysts. If Although different reactors have been developed, there is no direct
plastic-based naphtha can be used as an alternative to fossil way to compare their performance based on the current studies. Heat
naphtha for plastic monomers, without any changes needed in and mass transfer limitation should be evaluated by establishing accu­
the existing petrochemical infrastructure, pyrolysis is expected to rate kinetic models, which allow to successfully simulate the real tem­
open up new possibilities for closed-loop recycling PSW on a large perature and product distributions, to better describe the three-phase
scale. In light of the production of plastic-derived naphtha, PE nature of PSW pyrolysis. It should be noted that a two-step process
and PP could be the most attractive feedstock because catalytic composed of pyrolysis followed by catalytic reforming is expected to
cracking of PE and PP with the linear molecular structure is open up new possibilities for large-scale treatment of PSW, since it al­
favorable for paraffinic naphtha production, but aromatic plastics lows a higher activity and product selectivity. After much effort is
will mainly produce aromatics. Certainly, advanced collection focusing on the catalyst development and process optimization for high
and sorting systems may be possible to separate PE and PP out quality fuel production, the plastic-to-fuels technology has been
from plastic mixture, but processing industrial plastic waste, such demonstrated in the commercial stage, which will provide a reference
as automobile units and agricultural films, which are mostly for the development of plastic circular economy.
composed of PE and PP, into naphtha is more promising and cost- Recently different studies have been conducted on catalyst devel­
effective. opment for PSW pyrolysis, but the catalyst lifetime and detailed coke
(4) Another option for PSW pyrolysis is to maximize the light olefins formation mechanism are unclear during the process. Firstly, it is
and/or hydrogen, which is absolutely advantageous over incin­ important to make use of extensive product information (dry gas,
eration or direct landfill. However, unlike the plastic-to-naphtha liquified petroleum gas, gasoline, diesel, and wax) for evaluating cata­
technology, this strategy is unable to match the current facilities lyst performance based on the carbon efficiencies of each group. Sec­
in the petrochemical industry. It requires a big capital invest­ ondly, in-depth characterization should be performed for analyzing the
ment, making marginally profitable PSW recycling even less structure changes and macromolecule species present in the structure
practical. Although researchers have verified the feasibility of with time on stream. Furthermore, the identification of initiator frag­
hydrogen production from PSW via pyrolysis, some issues, such ments for coke formation by in-situ reaction monitoring would enable
as expensive catalysts, the hydrogen storage dilemma, and the analysis of coke species evolvement.

25
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

In order to create a plastic circular economy by recovering raw [6] Al-Salem S, Lettieri P, Baeyens J. The valorization of plastic solid waste (PSW) by
primary to quaternary routes: from re-use to energy and chemicals. Prog Energy
materials from PSW pyrolysis for manufacturing new plastic products,
Combust Sci 2010;36:103–29.
an important field of research calls for more input. That is to develop [7] Al-Salem S, Lettieri P, Baeyens J. Recycling and recovery routes of plastic solid
advanced catalysts and processes to convert PSW to naphtha, light ole­ waste (PSW): a review. Waste Manage (Oxford) 2009;29:2625–43.
fins, and aromatic monomers as alternatives to the current fossil re­ [8] Wei R, Tiso T, Bertling J, O’Connor K, Blank L, Bornscheuer U. Possibilities and
limitations of biotechnological plastic degradation and recycling. Nat Catal 2020;
sources for new plastic production. Future development of selectively 3:867–71.
catalytic pyrolysis of PSW would greatly benefit from more in-depth [9] Kunwar B, Cheng H, Chandrashekaran S, Sharma B. Plastics to fuel: a review.
knowledge of fundamental mechanisms. This urges us to place more Renew Sustain Energy Rev 2016;54:421–8.
[10] Wang Z, Li J, Burra K, Liu X, Li X, Zhang M, et al. Synergetic Effect on CO2-
emphasis on experimental studies to go beyond observational findings Assisted Co-Gasification of Biomass and Plastics. J Energy Res Technol 2021;143:
toward efforts that address how changes to each catalyst characteristic 031901.
(acid/active site distribution, pore connectivity, framework architec­ [11] Singh P, Déparrois N, Burra K, Bhattacharya S, Gupta A. Energy recovery from
cross-linked polyethylene wastes using pyrolysis and CO2 assisted gasification.
tures, etc.) alter the reaction pathways and its corresponding impact on Appl Energy 2019;254:113722.
product selectivity. In light of the complexity of the polymer chains [12] Gerasimov G. Comparative analysis of PCDD/Fs formation during pyrolysis and
pyrolysis, the model compounds, for example eicosane, can be used for incineration of medical waste. In: IOP Conference Series: Earth and
Environmental Science. IOP Publishing; 2019, 022116.
reaction mechanism explanation. In situ characterization techniques [13] Fivga A, Dimitriou I. Pyrolysis of plastic waste for production of heavy fuel
would capture the reaction intermediates that are useful information for substitute: a techno-economic assessment. Energy 2018;149:865–74.
determining reaction pathways and increase our understanding of [14] Al-Salem S. Feedstock and optimal operation for plastics to fuel conversion in
pyrolysis. Plastic to Energy 2019:117–46.
catalyst deactivation as well. Regarding the steric and diffusional hin­
[15] Elordi G, Olazar M, Artetxe M, Castaño P, Bilbao J. Effect of the acidity of the
drance of the polymer chains during catalytic reactions, the effective HZSM-5 zeolite catalyst on the cracking of high density polyethylene in a conical
solution for further improving the performance of hierarchical zeolites is spouted bed reactor. Appl Catal A 2012;415-416:89–95.
to finely balance the interplay between the catalytic active sites located [16] Park K, Jeong Y, Guzelciftci B, Kim J. Two-stage pyrolysis of polystyrene:
pyrolysis oil as a source of fuels or benzene, toluene, ethylbenzene, and xylenes.
in the micropores and the accessibility of these sites provided by the Appl Energy 2020;259:114240.
mesopores. It is also necessary to develop a reliable strategy to evaluate [17] Klaimy S, Ciotonea C, Dhainaut J, Royer S, Casetta M, Duquesne S, et al. Flash
the effectiveness of hierarchical zeolites by comprehensively consid­ Catalytic Pyrolysis of Polyethylene over (Alumino)silicate Materials.
ChemCatChem 2020;12:1109–16.
ering the influence of absolute porosity values and active sites. These [18] Zhao D, Wang X, Miller J, Huber G. The Chemistry and Kinetics of Polyethylene
insights will guide us to predict the chain length distribution of products Pyrolysis: a Feedstock to Produce Fuels and Chemicals. ChemSusChem 2020;13
and fine-tune the catalyst structure to meet different product demands. (7):1764–74.
[19] Zhang Z, Gora-Marek K, Watson J, Tian J, Ryder M, Tarach K, et al. Recovering
On the other hand, the solution to a complicated PSW mixture is waste plastics using shape-selective nano-scale reactors as catalysts. Nature
suggested to be separated into polyolefins, aromatic plastics, and others, Sustainab 2019;2:39–42.
and then a proper waste plastics decontamination process may be [20] Gaurh P, Pramanik H. Production of benzene/toluene/ethyl benzene/xylene
(BTEX) via multiphase catalytic pyrolysis of hazardous waste polyethylene using
implemented to meet the requirement for the target downstream low cost fly ash synthesized natural catalyst. Waste Manage (Oxford) 2018;77:
application of pyrolysis oil. In this regard, polyolefins are suitable for 114–30.
naphtha and light olefins/hydrogen production, while aromatic plastics [21] Elordi G, Olazar M, Lopez G, Castaño P, Bilbao J. Role of pore structure in the
deactivation of zeolites (HZSM-5, Hβ and HY) by coke in the pyrolysis of
should be targeted to produce aromatic monomers. However, if the PSW
polyethylene in a conical spouted bed reactor. Appl Catal B 2011;102:224–31.
mixture sorting is not realistic or economical, the mixture of naphtha, [22] Li K, Lei J, Yuan G, Weerachanchai P, Wang J-Y, Zhao J, et al. Fe-, Ti-, Zr- and Al-
light olefins, and aromatic monomers can be directly produced from the pillared clays for efficient catalytic pyrolysis of mixed plastics. Chem Eng J 2017;
plastic mixture, following by an aromatic extraction process to separate 317:800–9.
[23] Mastral FJ, Esperanza E, Garcı́a P, Juste M. Pyrolysis of high-density polyethylene
aromatic monomersfrom naphtha. in a fluidised bed reactor. Influence of the temperature and residence time. J Anal
Appl Pyrolysis 2002;63:1–15.
[24] López A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A. Influence of time
Declaration of Competing Interest and temperature on pyrolysis of plastic wastes in a semi-batch reactor. Chem Eng
J 2011;173:62–71.
[25] Fan L, Zhang Y, Liu S, Zhou N, Chen P, Liu Y, et al. Ex-situ catalytic upgrading of
The authors declare that they have no known competing financial vapors from microwave-assisted pyrolysis of low-density polyethylene with MgO.
interests or personal relationships that could have appeared to influence Energy Convers Manage 2017;149:432–41.
[26] Arabiourrutia M, Elordi G, Lopez G, Borsella E, Bilbao J, Olazar M.
the work reported in this paper. Characterization of the waxes obtained by the pyrolysis of polyolefin plastics in a
conical spouted bed reactor. J Anal Appl Pyrolysis 2012;94:230–7.
[27] Xue Y, Johnston P, Bai X. Effect of catalyst contact mode and gas atmosphere
Acknowledgments
during catalytic pyrolysis of waste plastics. Energy Convers Manage 2017;142:
441–51.
We acknowledge the financial support from National Natural Science [28] Wang K, Johnston P, Brown R. Comparison of in-situ and ex-situ catalytic
Foundation of China (No. 21766019, 21878137), China Scholarship pyrolysis in a micro-reactor system. Bioresour Technol 2014;173:124–31.
[29] Shafaghat H, Lee H, Tsang F, Oh D, Jae J, Jung S, et al. In-situ and ex-situ
Council (CSC), Xcel Energy, Resynergi, and University of Minnesota catalytic pyrolysis/co-pyrolysis of empty fruit bunches using mesostructured
MnDrive Environment Program (MNE12) and Center for Biorefining. aluminosilicate catalysts. Chem Eng J 2019;366:330–8.
[30] Anuar Sharuddin S, Abnisa F, Wan Daud W, Aroua M. A review on pyrolysis of
plastic wastes. Energy Convers Manage 2016;115:308–26.
References [31] Lopez G, Artetxe M, Amutio M, Bilbao J, Olazar M. Thermochemical routes for
the valorization of waste polyolefinic plastics to produce fuels and chemicals. A
[1] Geyer R, Jambeck J, Law K. Production, use, and fate of all plastics ever made. Sci review. Renewable Sustainable Energy Rev 2017;73:346–68.
Adv 2017;3:e1700782. [32] Dogu O, Pelucchi M, Van de Vijver R, Van Steenberge P, D’Hooge D, Cuoci A,
[2] Gigault J, Halle A, Baudrimont M, Pascal P, Gauffre F, Phi T, et al. Current et al. The chemistry of chemical recycling of solid plastic waste via pyrolysis and
opinion: what is a nanoplastic? Environ Pollut 2018;235:1030–4. gasification: state-of-the-art, challenges, and future directions. Prog Energy
[3] Rillig M, Lehmann A. Microplastic in terrestrial ecosystems. Science 2020;368: Combust Sci 2021;84:100901.
1430–1. [33] Rahimi A, García J. Chemical recycling of waste plastics for new materials
[4] Sharma D, Bapat S, Brandes W, Rice E, Castaldi M, Valorization B. Technical production. Nat Rev Chem 2017;1:1–11.
feasibility of zero waste for paper and plastic wastes. Waste Biomass Valoriz [34] Rajmohan K, Yadav H, Vaishnavi S, Gopinath M, Varjani S. Perspectives on bio-oil
2019;10:1355–63. recovery from plastic waste. Current Develop Biotechnol Bioengin 2020:459–80.
[5] Singh N, Hui D, Singh R, Ahuja I, Feo L, Fraternali F. Recycling of plastic solid [35] Encinar J, González J. Pyrolysis of synthetic polymers and plastic wastes. Kinetic
waste: a state of art review and future applications. Composites Part B 2017;115: study. Fuel Process Technol 2008;89:678–86.
409–22.

26
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

[36] Mendes L, da Costa, Pereira P. Optical microscopy as a tool to correlate [65] Murata K, Brebu M, Sakata Y. The effect of silica–alumina catalysts on
morphology and thermal properties of extruded PET/PC reactive blends. Mater degradation of polyolefins by a continuous flow reactor. J Anal Appl Pyrolysis
Sci Applic 2011;99:1033–40. 2010;89:30–8.
[37] Shah J, Jan M. Effect of polyethylene terephthalate on the catalytic pyrolysis of [66] Zhang Y, Ji G, Ma D, Chen C, Wang Y, Wang W, et al. Exergy and energy analysis
polystyrene: investigation of the liquid products. J Taiwan Inst Chem Eng 2015; of pyrolysis of plastic wastes in rotary kiln with heat carrier. Process Saf Environ
51:96–102. Prot 2020;142:203–11.
[38] Zannikos F, Kalligeros S, Anastopoulos G, Lois E. Converting Biomass and Waste [67] Zhang Y, Ji G, Chen C, Wang Y, Wang W, Li A. Liquid oils produced from
Plastic to Solid Fuel Briquettes. J Renew Energy 2013;2013:360368. pyrolysis of plastic wastes with heat carrier in rotary kiln. Fuel Process Technol
[39] Awad A, Abd El-Wahab A, El-Gamsy R, Abdel-latif M. A study of some thermal 2020;206:106455.
and mechanical properties of HDPE blend with marble and granite dust. Ain [68] Rackl M, Günthner W. Experimental investigation on the influence of different
Shams Engin J 2019;10:353–8. grades of wood chips on screw feeding performance. Biomass Bioenergy 2016;88:
[40] Xu F, Wang B, Yang D, Hao J, Qiao Y, Tian Y. Thermal degradation of typical 106–15.
plastics under high heating rate conditions by TG-FTIR: pyrolysis behaviors and [69] Aramideh S, Xiong Q, Kong S, Brown R. Numerical simulation of biomass fast
kinetic analysis. Energy Convers Manage 2018;171:1106–15. pyrolysis in an auger reactor. Fuel 2015;156:234–42.
[41] Pan Y, Castillo-Rodríguez M, Wang D. Mesoporous metal oxide/pyrophosphate [70] Jung S, Cho M, Kang B, Kim J. Pyrolysis of a fraction of waste polypropylene and
hybrid originated from reutilization of water treatment resin as a novel fire polyethylene for the recovery of BTX aromatics using a fluidized bed reactor. Fuel
hazard suppressant. Mater Chem Phys 2018;203:49–57. Process Technol 2010;91:277–84.
[42] Vollmer I, Jenks M, Roelands M, White R, van Harmelen T, de Wild P, et al. [71] Park K, Jeong Y, Kim J. Activator-assisted pyrolysis of polypropylene. Appl
Beyond mechanical recycling: giving new life to plastic waste. Angew Chem Int Energy 2019;253:113558.
Ed 2020;59(36):15402–23. [72] Park K, Jeong Y, Guzelciftci B, Kim J. Characteristics of a new type continuous
[43] Li X, Zhang H, Li J, Su L, Zuo J, Komarneni S, et al. Improving the aromatic two-stage pyrolysis of waste polyethylene. Energy 2019;166:343–51.
production in catalytic fast pyrolysis of cellulose by co-feeding low-density [73] Milne BJ, Behie L, Berruti F. Recycling of waste plastics by ultrapyrolysis using an
polyethylene. Appl Catal A 2013;455:114–21. internally circulating fluidized bed reactor. J Anal Appl Pyrolysis 1999;51:
[44] Gersten J, Fainberg V, Hetsroni G, Shindler Y. Kinetic study of the thermal 157–66.
decomposition of polypropylene, oil shale, and their mixture. Fuel 2000;79: [74] Compo P, Pfeffer R, Tardos G. Minimum sintering temperatures and
1679–86. defluidization characteristics of fluidizable particles. Powder Technol 1987;51:
[45] Kassargy C, Awad S, Burnens G, Kahine K, Tazerout M. Gasoline and diesel-like 85–101.
fuel production by continuous catalytic pyrolysis of waste polyethylene and [75] Siegell J. High-temperature de fluidization. Powder Technol 1984;38:13–22.
polypropylene mixtures over USY zeolite. Fuel 2018;224:764–73. [76] Chaivatamaset P, Sricharoon P, Tia S, Bilitewski B. The characteristics of bed
[46] Özsin G, Pütün A. Insights into pyrolysis and co-pyrolysis of biomass and agglomeration/defluidization in fluidized bed firing palm fruit bunch and rice
polystyrene: thermochemical behaviors, kinetics and evolved gas analysis. Energy straw. Appl Therm Eng 2014;70:737–47.
Convers Manage 2017;149:675–85. [77] Lu H, Cao J, Macri D, Guo X, Liu H, Gong X. Experimental study on defluidization
[47] Praveen Kumar K, Srinivas S. Catalytic Co-pyrolysis of Biomass and Plastics behaviours and its influence factors during gas switching fluidization. Powder
(Polypropylene and Polystyrene) Using Spent FCC Catalyst. Energy Fuels 2020; Technol 2021;380:106–14.
34:460–73. [78] Elordi G, Olazar M, Lopez G, Amutio M, Artetxe M, Aguado R, et al. Catalytic
[48] Santos E, Rijo B, Lemos F, Lemos M. A catalytic reactive distillation approach to pyrolysis of HDPE in continuous mode over zeolite catalysts in a conical spouted
high density polyethylene pyrolysis – Part 1 – Light olefin production. Chem Eng bed reactor. J Anal Appl Pyrolysis 2009;85:345–51.
J 2019;378:122077. [79] Neto J, Duarte C, Murata V, Barrozo M. Effect of a draft tube on the fluid
[49] Elordi G, Olazar M, Lopez G, Artetxe M, Bilbao J. Product Yields and dynamics of a spouted bed: experimental and CFD studies. Drying Technol 2008;
Compositions in the Continuous Pyrolysis of High-Density Polyethylene in a 26:299–307.
Conical Spouted Bed Reactor. Ind Engin Chem Res 2011;50:6650–9. [80] Nagashima H, Ishikura T, Ide M. Effect of the tube shape on gas and particle flow
[50] Kumar S, Panda AK, Singh RK. A review on tertiary recycling of high-density in spouted beds with a porous draft tube. Can J Chem Eng 2009;87:228–36.
polyethylene to fuel. Resour Conserv Recycl 2011;55:893–910. [81] Lopez G, Artetxe M, Amutio M, Elordi G, Aguado R, Olazar M, et al. Recycling
[51] Ueno T, Nakashima E, Takeda K. Quantitative analysis of random scission and poly-(methyl methacrylate) by pyrolysis in a conical spouted bed reactor. Chem
chain-end scission in the thermal degradation of polyethylene. Polym Degrad Eng Process 2010;49:1089–94.
Stab 2010;95:1862–9. [82] Artetxe M, Lopez G, Amutio M, Barbarias I, Arregi A, Aguado R, et al. Styrene
[52] Kruse T, Woo O, Wong H, Khan S, Broadbelt L. Mechanistic modeling of polymer recovery from polystyrene by flash pyrolysis in a conical spouted bed reactor.
degradation: a comprehensive study of polystyrene. Macromolecules 2002;35: Waste Manage (Oxford) 2015;45:126–33.
7830–44. [83] Elordi G, Olazar M, Lopez G, Artetxe M, Bilbao J. Continuous Polyolefin Cracking
[53] Zhou J, Qiao Y, Wang W, Leng E, Huang J, Yu Y, et al. Formation of styrene on an HZSM-5 Zeolite Catalyst in a Conical Spouted Bed Reactor. Ind Engin Chem
monomer, dimer and trimer in the primary volatiles produced from polystyrene Res 2011;50:6061–70.
pyrolysis in a wire-mesh reactor. Fuel 2016;182:333–9. [84] Elordi G, Olazar M, Castaño P, Artetxe M, Bilbao J. Polyethylene Cracking on a
[54] Kruse T M, Sang Woo O, Broadbelt L J. Detailed mechanistic modeling of polymer Spent FCC Catalyst inn a Conical Spouted Bed Reactor. Ind Engin Chem Res 2012;
degradation: application to polystyrene. Chem Eng Sci 2001;56:971–9. 51:14008–17.
[55] Dean L, Groves S, Hancox R, Lamb G, Lehrle R. Pyrolysis-GC and MS applied to [85] Foong S, Liew R, Yang Y, Cheng Y, Yek P, Mahari W, et al. Valorization of biomass
study oligomer formation in the degradation of polystyrene and styrene waste to engineered activated biochar by microwave pyrolysis: progress,
copolymers. Polym Degrad Stab 1989;25:143–60. challenges, and future directions. Chem Eng J 2020;389:124401.
[56] Ohtani H, Yuyama T, Tsuge S, Plage B, Schulten H. Study on thermal degradation [86] Rex P, Masilamani I, Miranda L. Microwave pyrolysis of polystyrene and
of polystyrenes by pyrolysis-gas chromatography and pyrolysis-field ionization polypropylene mixtures using different activated carbon from biomass. J Energy
mass spectrometry. Eur Polym J 1990;26:893–9. Inst 2020;93(5):1819–32.
[57] Gui B, Qiao Y, Wan D, Liu S, Han Z, Yao H, et al. Nascent tar formation during [87] Jiang H, Liu W, Zhang X, Qiao J. Chemical recycling of plastics by microwave-
polyvinylchloride (PVC) pyrolysis. Proc Combust Inst 2013;34:2321–9. assisted high-temperature pyrolysis. Global Challe 2020;4:1900074.
[58] Zhou J, Gui B, Qiao Y, Zhang J, Wang W, Yao H, et al. Understanding the [88] Jie X, Li W, Slocombe D, Gao Y, Banerjee I, Gonzalez-Cortes S, et al. Microwave-
pyrolysis mechanism of polyvinylchloride (PVC) by characterizing the chars initiated catalytic deconstruction of plastic waste into hydrogen and high-value
produced in a wire-mesh reactor. Fuel 2016;166:526–32. carbons. Nat Catal 2020;3(11):902–12.
[59] Levchik S, Weil E. A review on thermal decomposition and combustion of [89] Voiry D, Yang J, Kupferberg J, Fullon R, Lee C, Jeong H, et al. High-quality
thermoplastic polyesters. Polym Adv Technol 2004;15:691–700. graphene via microwave reduction of solution-exfoliated graphene oxide. Science
[60] Samperi F, Puglisi C, Alicata R, Montaudo G. Thermal degradation of poly 2016;353:1413–6.
(ethylene terephthalate) at the processing temperature. Polym Degrad Stab 2004; [90] Zhou N, Zhou J, Dai L, Guo F, Wang Y, Li H, et al. Syngas production from
83:3–10. biomass pyrolysis in a continuous microwave assisted pyrolysis system.
[61] Artetxe M, Lopez G, Amutio M, Elordi G, Olazar M, Bilbao J. Operating conditions Bioresoure Technol 2020;314:123756.
for the pyrolysis of poly-(ethylene terephthalate) in a conical spouted-bed reactor. [91] Wang Y, Zeng Z, Tian X, Dai L, Jiang L, Zhang S, et al. Production of bio-oil from
Ind Eng Chem Res 2010;49:2064–9. agricultural waste by using a continuous fast microwave pyrolysis system.
[62] Kassargy C, Awad S, Burnens G, Kahine K, Tazerout M. Experimental study of Bioresour Technol 2018;269:162–8.
catalytic pyrolysis of polyethylene and polypropylene over USY zeolite and [92] Wang Y, Wu Q, Yang S, Yang Q, Wu J, Ma Z, et al. Microwave-assisted catalytic
separation to gasoline and diesel-like fuels. J Anal Appl Pyrolysis 2017;127:31–7. fast pyrolysis coupled with microwave-absorbent of soapstock for bio-oil in a
[63] Ding K, Liu S, Huang Y, Liu S, Zhou N, Peng P, et al. Catalytic microwave-assisted downdraft reactor. Energy Convers Manage 2019;185:11–20.
pyrolysis of plastic waste over NiO and HY for gasoline-range hydrocarbons [93] Zhou J, Liu S, Zhou N, Fan L, Zhang Y, Peng P, et al. Development and application
production. Energy Convers Manage 2019;196:1316–25. of a continuous fast microwave pyrolysis system for sewage sludge utilization.
[64] Inayat A, Klemencova K, Grycova B, Sokolova B, Lestinsky P. Thermo-catalytic Bioresour Technol 2018;256:295–301.
pyrolysis of polystyrene in batch and semi-batch reactors: a comparative study.
Waste Manag Res 2021;39(2):260–9.

27
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

[94] Zhou N, Dai L, Lv Y, Li H, Deng W, Guo F, et al. Catalytic pyrolysis of plastic [125] Onwudili J, Insura N, Williams P. Composition of products from the pyrolysis of
wastes in a continuous microwave assisted pyrolysis system for fuel production. polyethylene and polystyrene in a closed batch reactor: effects of temperature and
Chem Eng J 2021;418:129412. residence time. J Anal Appl Pyrolysis 2009;86:293–303.
[95] Shah S, Khan Z, Raja I, Mahmood Q, Bhatti Z, Khan J, et al. Low temperature [126] Anene A, Fredriksen S, Sætre K, Tokheim L. Experimental study of thermal and
conversion of plastic waste into light hydrocarbons. J Hazardour Mater 2010;179: catalytic pyrolysis of plastic waste components. Sustainability 2018;10:3979.
15–20. [127] Mangesh VL, Padmanabhan S, Tamizhdurai P, Ramesh A. Experimental
[96] Das P, Tiwari P. Valorization of packaging plastic waste by slow pyrolysis. investigation to identify the type of waste plastic pyrolysis oil suitable for
Resources, Conserv Recycl 2018;128:69–77. conversion to diesel engine fuel. J Cleaner Prod 2020;246:119066.
[97] Campuzano F, Brown R, Martínez J. Auger reactors for pyrolysis of biomass and [128] Sun K, Themelis N, Bourtsalas A, Huang Q. Selective production of aromatics from
wastes. Renew Sustain Energy Rev 2019;102:372–409. waste plastic pyrolysis by using sewage sludge derived char catalyst. J Cleaner
[98] Al-Salem S, Yang Y, Wang J, Leeke G. Pyro-oil and wax recovery from reclaimed Prod 2020;268:122038.
plastic waste in a continuous auger pyrolysis reactor. Energies 2020;13:2040. [129] Huo E, Lei H, Liu C, Zhang Y, Xin L, Zhao Y, et al. Jet fuel and hydrogen produced
[99] Sharifzadeh M, Sadeqzadeh M, Guo M, Borhani T, Murthy Konda N, Garcia M, from waste plastics catalytic pyrolysis with activated carbon and MgO. Sci Total
et al. The multi-scale challenges of biomass fast pyrolysis and bio-oil upgrading: Environ 2020;727:138411.
review of the state of art and future research directions. Prog Energy Combust Sci [130] Serrano D, Aguado J, Escola J. Developing Advanced catalysts for the conversion
2019;71:1–80. of polyolefinic waste plastics into fuels and chemicals. ACS Catal 2012;2:
[100] Wong S, Ngadi N, Abdullah T, Inuwa I. Current state and future prospects of 1924–41.
plastic waste as source of fuel: a review. Renew Sustain Energy Rev 2015;50: [131] Maity A, Chaudhari S, Titman J, Polshettiwar V. Catalytic nanosponges of acidic
1167–80. aluminosilicates for plastic degradation and CO2 to fuel conversion. Nat Commun
[101] del Remedio Hernández M, García Á, Marcilla A. Catalytic flash pyrolysis of HDPE 2020;11:1–12.
in a fluidized bed reactor for recovery of fuel-like hydrocarbons. J Anal Appl [132] Manos G, Garforth A, Dwyer J. Catalytic degradation of high-density polyethylene
Pyrolysis 2007;78:272–81. over different zeolitic structures. Ind Eng Chem Res 2000;39:1198–202.
[102] Beneroso D, Monti T, Kostas E, Robinson J. Microwave pyrolysis of biomass for [133] Manos G, Garforth A, Dwyer J. Catalytic degradation of high-density polyethylene
bio-oil production: scalable processing concepts. Chem Eng J 2017;316:481–98. on an ultrastable-Y Zeolite. Nature of Initial polymer reactions, pattern of
[103] Foong S, Liew R, Yang Y, Cheng Y, Yek P, Wan Mahari W, et al. Valorization of formation of gas and liquid products, and temperature effects. Ind Eng Chem Res
biomass waste to engineered activated biochar by microwave pyrolysis: progress, 2000;39:1203–8.
challenges, and future directions. Chem Eng J 2020;389:124401. [134] Mordi R, Fields R, Dwyer J. Thermolysis of low density polyethylene catalysed by
[104] Luque R, Menéndez J, Arenillas A, Cot J. Microwave-assisted pyrolysis of biomass zeolites. J Anal Appl Pyrolysis 1994;29:45–55.
feedstocks: the way forward? Energy Environ Sci 2012;5:5481–8. [135] Liu R, Sarker M, Rahman MM, Li C, Chai M, Nishu, et al. Multi-scale complexities
[105] Stelmachowski M. Thermal conversion of waste polyolefins to the mixture of of solid acid catalysts in the catalytic fast pyrolysis of biomass for bio-oil
hydrocarbons in the reactor with molten metal bed. Energy Convers Manage production – a review. Prog Energy Combust Sci 2020;80:100852.
2010;51:2016–24. [136] Akubo K, Nahil M, Williams P. Aromatic fuel oils produced from the pyrolysis-
[106] Stelmachowski M. Feedstock recycling of waste polymers by thermal cracking in catalysis of polyethylene plastic with metal-impregnated zeolite catalysts.
molten metal: thermodynamic analysis. J Mater Cycles Waste Manage 2014;16: J Energy Inst 2019;92:195–202.
211–8. [137] Wang J, Jiang J, Sun Y, Zhong Z, Wang X, Xia H, et al. Recycling benzene and
[107] Tang L, Huang H, Hao H, Zhao K. Development of plasma pyrolysis/gasification ethylbenzene from in-situ catalytic fast pyrolysis of plastic wastes. Energy
systems for energy efficient and environmentally sound waste disposal. Convers Manage 2019;200:112088.
J Electrostat 2013;71:839–47. [138] Aguado J, Serrano D, Romero M. Catalytic conversion of polyethylene into fuels
[108] Gabbar H, Aboughaly M, Stoute C. DC thermal plasma design and utilization for over mesoporous MCM-41. Chem Commun 1996:725–6.
the low density polyethylene to diesel oil pyrolysis reaction. Energies 2017;10: [139] Soler-Illia G, Sanchez C, Lebeau B, Patarin J. Chemical strategies to design
784. textured materials: from microporous and mesoporous oxides to nanonetworks
[109] Karaba A, Dvořáková V, Patera J, Zámostný P. Improving the steam-cracking and hierarchical structures. Chem Rev 2002;102:4093–138.
efficiency of naphtha feedstocks by mixed/separate processing. J Anal Appl [140] Aguado J, Sotelo J, Serrano D, Calles J, Escola J. Catalytic conversion of
Pyrolysis 2020;146:104768. polyolefins into liquid fuels over MCM-41: comparison with ZSM-5 and
[110] Liu S, Kots P, Vance B, Danielson A, Vlachos D. Plastic waste to fuels by amorphous SiO2− Al2O3. Energy Fuels 1997;11:1225–31.
hydrocracking at mild conditions. Sci Adv 2021;7:eabf8283. [141] Socci J, Osatiashtiani A, Kyriakou G, Bridgwater T. The catalytic cracking of
[111] Baena-González J, Santamaria-Echart A, Aguirre J, González S. Chemical sterically challenging plastic feedstocks over high acid density Al-SBA-15
recycling of plastic waste: bitumen, solvents, and polystyrene from pyrolysis oil. catalysts. Appl Catal, A 2019;570:218–27.
Waste Manage (Oxford) 2020;118:139–49. [142] Serrano D, Aguado J, Escola J, Rodríguez J, San Miguel G. An investigation into
[112] Fan H, He K, Wang J. Study of sewage sludge pyrolysis liquids using the catalytic cracking of LDPE using Py–GC/MS. J Anal Appl Pyrolysis 2005;74:
comprehensive two-dimensional gas chromatography/time-of-flight mass 370–8.
spectrometry. Fuel 2016;185:281–8. [143] Ratnasari D, Nahil M, Williams P. Catalytic pyrolysis of waste plastics using
[113] Tessarolo N, dos Santos L, Silva R, Azevedo D. Chemical characterization of bio- staged catalysis for production of gasoline range hydrocarbon oils. J Anal Appl
oils using comprehensive two-dimensional gas chromatography with time-of- Pyrolysis 2017;124:631–7.
flight mass spectrometry. J Chromatogr A 2013;1279:68–75. [144] Zhokh A, Serebrii T, Strizhak P. Diffusion of C6 cyclic hydrocarbons in ZSM-5
[114] Chandrasekaran S, Sharma B. 7 - Fuel properties associated with catalytic zeolite: from single nanocrystal to packed pellet. Microporous Mesoporous Mater
conversion of plastics. editor. In: Al-Salem SM, editor. Plastics to energy. William 2020;292:109773.
Andrew Publishing; 2019. p. 173–220. [145] Katada N, Suzuki K, Noda T, Sastre G, Niwa M. Correlation between brønsted acid
[115] Nakaji Y, Tamura M, Miyaoka S, Kumagai S, Tanji M, Nakagawa Y, et al. Low- strength and local structure in Zeolites. J Phys Chem C 2009;113:19208–17.
temperature catalytic upgrading of waste polyolefinic plastics into liquid fuels [146] Lee J, Park S, Saha S, Cho S, Seo G. Liquid-phase degradation of polyethylene (PE)
and waxes. Appl Catal, B 2021;285:119805. over MFI zeolites with mesopores: effects of the structure of PE and the
[116] Faussone G. Transportation fuel from plastic: two cases of study. Waste Manage characteristics of mesopores. Appl Catal, B 2011;108-109:61–71.
(Oxford) 2018;73:416–23. [147] Caldeira V, Peral A, Linares M, Araujo A, Garcia-Muñoz R, Serrano D. Properties
[117] Diaz Silvarrey L, Phan A. Kinetic study of municipal plastic waste. Int J Hydrogen of hierarchical beta zeolites prepared from protozeolitic nanounits for the
Energy 2016;41:16352–64. catalytic cracking of high density polyethylene. Appl Catal, A 2017;531:187–96.
[118] Gracida-Alvarez U, Mitchell M, Sacramento-Rivero J, Shonnard D. Effect of [148] Silva B, Sousa L, Sarmento L, Alencar S, Quintela P, Silva A. Kinetic study of
temperature and vapor residence time on the micropyrolysis products of waste thermocatalytic degradation of UHMWPE over microporous and hierarchical
high density polyethylene. Ind Eng Chem Res 2018;57:1912–23. ZSM-23 zeolite. Appl Catal, B 2020;267:118699.
[119] Miandad R, Nizami A, Rehan M, Barakat M, Khan M, Mustafa A, et al. Influence of [149] Zang Y, Wang J, Gu J, Qu J, Gao F, Li M. Cost-effective synthesis of hierarchical
temperature and reaction time on the conversion of polystyrene waste to pyrolysis HZSM-5 with a high Si/TPA+ ratio for enhanced catalytic cracking of
liquid oil. Waste Manage (Oxford) 2016;58:250–9. polyethylene. J Solid State Chem 2020;291:121643.
[120] Singh R, Ruj B. Time and temperature depended fuel gas generation from [150] Shi J, Wang Y, Yang W, Tang Y, Xie Z. Recent advances of pore system
pyrolysis of real world municipal plastic waste. Fuel 2016;174:164–71. construction in zeolite-catalyzed chemical industry processes. Chem Soc Rev
[121] Zhang Y, Duan D, Lei H, Villota E, Ruan R. Jet fuel production from waste plastics 2015;44:8877–903.
via catalytic pyrolysis with activated carbons. Appl Energy 2019;251:113337. [151] Manos G, Yusof IY, Papayannakos N, Gangas NH. Catalytic Cracking of
[122] Onwudili J, Muhammad C, Williams P. Influence of catalyst bed temperature and Polyethylene over Clay Catalysts. Comparison with an Ultrastable Y Zeolite. Ind
properties of zeolite catalysts on pyrolysis-catalysis of a simulated mixed plastics Engin Chem Res 2001;40:2220–5.
sample for the production of upgraded fuels and chemicals. J Energy Inst 2019; [152] Hadi B, Sokoto A, Garba M, Muhammad A. Effect of neat kaolin and CuO/Kaolin
92:1337–47. on the yield and composition of products from pyrolysis of polystyrene waste.
[123] Mastral F, Esperanza E, Berrueco C, Juste M, Ceamanos J. Fluidized bed thermal Energy Sources Part A 2017;39:148–53.
degradation products of HDPE in an inert atmosphere and in air–nitrogen [153] Luo W, Hu Q, Fan Z, Wan J, He Q, Huang S, et al. The effect of different particle
mixtures. J Anal Appl Pyrolysis 2003;70:1–17. sizes and HCl-modified kaolin on catalytic pyrolysis characteristics of reworked
[124] del Remedio Hernández M, Gómez A, García ÁN, Agulló J, Marcilla A. Effect of polypropylene plastics. Energy 2020;213:119080.
the temperature in the nature and extension of the primary and secondary [154] De Stefanis A, Cafarelli P, Gallese F, Borsella E, Nana A, Perez G. Catalytic
reactions in the thermal and HZSM-5 catalytic pyrolysis of HDPE. Appl Catal, A pyrolysis of polyethylene: a comparison between pillared and restructured clays.
2007;317:183–94. J Anal Appl Pyrolysis 2013;104:479–84.

28
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

[155] Rodríguez E, Palos R, Gutiérrez A, Vela FJ, Arandes J, Bilbao J. Effect of the FCC [184] Prathiba R, Shruthi M, Miranda L. Pyrolysis of polystyrene waste in the presence
equilibrium catalyst properties and of the cracking temperature on the production of activated carbon in conventional and microwave heating using modified
of fuel from HDPE pyrolysis waxes. Energy Fuels 2019;33:5191–9. thermocouple. Waste Manage (Oxford) 2018;76:528–36.
[156] Wang Y, Arandiyan H, Scott J, Bagheri A, Dai H, Amal R. Recent advances in [185] Rex P, Masilamani I, Miranda L. Microwave pyrolysis of polystyrene and
ordered meso/macroporous metal oxides for heterogeneous catalysis: a review. polypropylene mixtures using different activated carbon from biomass. J Energy
J Mater Chem A 2017;5:8825–46. Inst 2020;93:1819–32.
[157] Wang S, Dai G, Yang H, Luo Z. Lignocellulosic biomass pyrolysis mechanism: a [186] Villota E, Lei H, Qian M, Yang Z, Villota S, Zhang Y, et al. Optimizing microwave-
state-of-the-art review. Prog Energy Combust Sci 2017;62:33–86. assisted pyrolysis of phosphoric acid-activated biomass: impact of concentration
[158] Kumagai S, Yamasaki R, Kameda T, Saito Y, Watanabe A, Watanabe C, et al. on heating rate and carbonization time. ACS Sustain Chem Eng 2018;6:1318–26.
Aromatic hydrocarbon selectivity as a function of CaO basicity and aging during [187] Wang C, Lei H, Qian M, Huo E, Zhao Y, Zhang Q, et al. Application of highly
CaO-catalyzed PET pyrolysis using tandem µ-reactor-GC/MS. Chem Eng J 2018; stable biochar catalysts for efficient pyrolysis of plastics: a readily accessible
332:169–73. potential solution to a global waste crisis. Sustain Energy Fuels 2020;4:4614–24.
[159] Ji M, Chen L, Que J, Zheng L, Chen Z, Wu Z, et al. Effects of transition metal [188] Yu Q, Sun H, Sun H, Li L, Zhu X, Ren S, et al. Highly mesoporous IM-5 zeolite
oxides on pyrolysis properties of PVC. Process Saf Environ Prot 2020;140:211–20. prepared by alkaline treatment and its catalytic cracking performance.
[160] Shah J, Jan MR, Mabood F, Jabeen F. Catalytic pyrolysis of LDPE leads to Microporous Mesoporous Mater 2019;273:297–306.
valuable resource recovery and reduction of waste problems. Energy Convers [189] Pérez-RamÃ-rez J, Verboekend D, Bonilla A, Sn AbellÃ3. Zeolite catalysts with
Manage 2010;51:2791–801. tunable hierarchy factor by pore-growth moderators. Adv Funct Mater 2009;19:
[161] Wang J, Jiang J, Meng X, Li M, Wang X, Pang S, et al. Promoting aromatic 3972–9.
hydrocarbon formation via catalytic pyrolysis of polycarbonate wastes over Fe- [190] Argyle M, Bartholomew C. Heterogeneous catalyst deactivation and regeneration:
and Ce-loaded aluminum oxide catalysts. Environ Sci Technol 2020;54:8390–400. a review. Catalysts 2015;5:145–269.
[162] Jing L, Yu Y, Zhou X, Hu C. Study on the catalytic pyrolysis of polystyrene. Chem [191] Barbarias I, Lopez G, Amutio M, Artetxe M, Alvarez J, Arregi A, et al. Steam
Res Appl 2009:10. reforming of plastic pyrolysis model hydrocarbons and catalyst deactivation. Appl
[163] Çelikgöğüs Ç, Karaduman A. Thermal-catalytic pyrolysis of polystyrene waste Catal, A 2016;527:152–60.
foams in a semi-batch reactor. Energy Sources Part A 2015;37:2507–13. [192] Barbarias I, Artetxe M, Lopez G, Arregi A, Bilbao J, Olazar M. Influence of the
[164] Zhang F, Zeng M, Yappert R, Sun J, Lee Y, LaPointe A, et al. Polyethylene conditions for reforming HDPE pyrolysis volatiles on the catalyst deactivation by
upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization. coke. Fuel Process Technol 2018;171:100–9.
Science 2020;370:437–41. [193] Ochoa A, Bilbao J, Gayubo A, Castaño P. Coke formation and deactivation during
[165] Tennakoon A, Wu X, Paterson A, Patnaik S, Pei Y, LaPointe A, et al. Catalytic catalytic reforming of biomass and waste pyrolysis products: a review. Renew
upcycling of high-density polyethylene via a processive mechanism. Nat Catal Sustain Energy Rev 2020;119:109600.
2020;3(11):893–901. [194] Ibáñez M, Artetxe M, Lopez G, Elordi G, Bilbao J, Olazar M, et al. Identification of
[166] Miandad R, Barakat M, Rehan M, Aburiazaiza A, Ismail I, Nizami A. Plastic waste the coke deposited on an HZSM-5 zeolite catalyst during the sequenced
to liquid oil through catalytic pyrolysis using natural and synthetic zeolite pyrolysis–cracking of HDPE. Appl Catal, B 2014;148-149:436–45.
catalysts. Waste Manage (Oxford) 2017;69:66–78. [195] Castaño P, Elordi G, Olazar M, Aguayo A, Pawelec B, Bilbao J. Insights into the
[167] Tekade S., Gugale P., Gohil M., Gharat S., Patil T., Chaudhari P., et al. Pyrolysis of coke deposited on HZSM-5, Hβ and HY zeolites during the cracking of
waste polyethylene under vacuum using zinc oxide. Energy Sourc, Part A. 2020: polyethylene. Appl Catal, B 2011;104:91–100.
1–15. [196] Marcilla A, Gómez-Siurana A, Valdés F. Influence of the final “ageing”
[168] Nisar J, Ali G, Shah A, Shah M, Iqbal M, Ashiq M, et al. Pyrolysis of expanded temperature on the regeneration behaviour and location of the coke obtained in
waste polystyrene: influence of nickel-doped copper oxide on kinetics, the HZSM-5 and USY zeolites during the LDPE cracking. Appl Catal, A 2008;334:
thermodynamics, and product distribution. Energy Fuels 2019;33:12666–78. 20–5.
[169] Diaz-Silvarrey L, McMahon A, Phan A. Benzoic acid recovery via waste poly [197] Wei T, Wu K, Lee S, Lin Y. Chemical recycling of post-consumer polymer waste
(ethylene terephthalate) (PET) catalytic pyrolysis using sulphated zirconia over fluidizing cracking catalysts for producing chemicals and hydrocarbon fuels.
catalyst. J Anal Appl Pyrolysis 2018;134:621–31. Resour Conserv Recycl 2010;54:952–61.
[170] Kumagai S, Yamasaki R, Kameda T, Saito Y, Watanabe A, Watanabe C, et al. [198] Serrano D, Aguado J, Escola J, Garagorri E. Performance of a continuous screw
Catalytic pyrolysis of poly(ethylene terephthalate) in the presence of metal oxides kiln reactor for the thermal and catalytic conversion of polyethylene–lubricating
for aromatic hydrocarbon recovery using tandem μ-reactor-GC/MS. Energy Fuels oil base mixtures. Appl Catal, B 2003;44:95–105.
2020;34:2492–500. [199] Serrano D, Aguado J, Rodríguez J, Peral A. Catalytic cracking of polyethylene
[171] Kumagai S, Yamasaki R, Kameda T, Saito Y, Watanabe A, Watanabe C, et al. over nanocrystalline HZSM-5: catalyst deactivation and regeneration study.
Tandem μ-reactor-GC/MS for online monitoring of aromatic hydrocarbon J Anal Appl Pyrolysis 2007;79:456–64.
production via CaO-catalysed PET pyrolysis. React. Chem. Eng 2017;2:776–84. [200] Xie Q, Li S, Gong R, Zheng G, Wang Y, Xu P, et al. Microwave-assisted catalytic
[172] Adnan Shah J, Jan M. Thermo-catalytic pyrolysis of polystyrene in the presence of dehydration of glycerol for sustainable production of acrolein over a microwave
zinc bulk catalysts. J Taiwan Inst Chem Eng 2014;45:2494–500. absorbing catalyst. Appl Catal, B 2019;243:455–62.
[173] Sun K, Themelis N, Bourtsalas A, Huang Q. Selective production of aromatics from [201] Kassargy C, Awad S, Burnens G, Upreti G, Kahine K, Tazerout M. Study of the
waste plastic pyrolysis by using sewage sludge derived char catalyst. J Cleaner effects of regeneration of USY zeolite on the catalytic cracking of polyethylene.
Prod 2020;268:122038. Appl Catal, B 2019;244:704–8.
[174] Juliastuti S, Hisbullah M, Abdillah M. High density Polyethylene plastic waste [202] Barbarias I, Artetxe M, Lopez G, Arregi A, Santamaria L, Bilbao J, et al. Catalyst
treatment with microwave heating pyrolysis method using coconut-shell performance in the HDPE pyrolysis-reforming under reaction-regeneration cycles.
activated carbon to produce alternative fuels. Mater Sci Engin 2018;334:012015. Catalysts 2019;9:414.
[175] Wan K, Chen H, Zheng F, Pan Y, Zhang Y, Long D. Tunable production of jet-fuel [203] Li X, Lv Z, Shao S, Zhu Y, Cheng J, Dong W. Regeneration of deactivated
range alkanes and aromatics by catalytic pyrolysis of LDPE over biomass-derived hierarchical La/Hi-ZSM-5 for catalytic pyrolysis of rape straw assisted by ozone
activated carbons. Ind Eng Chem Res 2020;59:17451–61. from nonthermal plasma. Energy Fuels 2020;34(11):14159–68.
[176] Huo E, Lei H, Liu C, Zhang Y, Xin L, Zhao Y, et al. Jet fuel and hydrogen produced [204] Bockhorn H, Hornung A, Hornung U, Jakobströer P. Modelling of isothermal and
from waste plastics catalytic pyrolysis with activated carbon and MgO. Sci Total dynamic pyrolysis of plastics considering non-homogeneous temperature
Environ 2020;727:138411. distribution and detailed degradation mechanism. J Anal Appl Pyrolysis 1999;49:
[177] Sun K, Huang Q, Chi Y, Yan J. Effect of ZnCl2-activated biochar on catalytic 53–74.
pyrolysis of mixed waste plastics for producing aromatic-enriched oil. Waste [205] Artetxe M, Lopez G, Amutio M, Elordi G, Bilbao J, Olazar M. Light olefins from
Manage (Oxford) 2018;81:128–37. HDPE cracking in a two-step thermal and catalytic process. Chem Eng J 2012;
[178] Sun K, Huang Q, Ali M, Chi Y, Yan J. Producing aromatic-enriched oil from mixed 207-208:27–34.
plastics using activated biochar as catalyst. Energy Fuels 2018;32:5471–9. [206] Ceamanos J, Mastral J, Millera A, Aldea M. Kinetics of pyrolysis of high density
[179] Singh MV, Kumar S, Sarker M. Waste HD-PE plastic, deformation into liquid polyethylene. Comparison of isothermal and dynamic experiments. J Anal Appl
hydrocarbon fuel using pyrolysis-catalytic cracking with a CuCO3 catalyst. Pyrolysis 2002;65:93–110.
Sustain Energy Fuels 2018;2:1057–68. [207] Niksiar A, Sohrabi M, Pyrolysis A. Mathematical modeling of waste plastic
[180] Wu S-L, Kuo J, Wey M. Thermal degradation of waste plastics in a two-stage pyrolysis in conical spouted beds: heat, mass, and momentum transport. J Anal
pyrolysis-catalysis reactor over core-shell type catalyst. J Anal Appl Pyrolysis Appl Pyrolysis 2014;110:66–78.
2019;142:104641. [208] Della Zassa M, Favero M, Canu P. Two-steps selective thermal depolymerization
[181] Sun K, Themelis N, Bourtsalas A, Huang Q. Selective production of aromatics from of polyethylene. 1: feasibility and effect of devolatilization heating policy. J Anal
waste plastic pyrolysis by using sewage sludge derived char catalyst. J Cleaner Appl Pyrolysis 2010;87:248–55.
Prod 2020;268:122038. [209] Aguado R, Olazar M, Gaisán B, Prieto R, Bilbao J. Kinetics of polystyrene pyrolysis
[182] Park C, Kim S, Kwon Y, Jeong C, Cho Y, Lee C, et al. Pyrolysis of polyethylene in a conical spouted bed reactor. Chem Eng J 2003;92:91–9.
terephthalate over carbon-supported Pd catalyst. Catalysts 2020;10:496. [210] Wall L, Madorsky S, Brown D, Straus S, Simha R. The depolymerization of
[183] Zhou Y, Haynes R. Sorption of heavy metals by inorganic and organic components polymethylene and polyethylene. J Am Chem Soc 1954;76:3430–7.
of solid wastes: significance to use of wastes as low-cost adsorbents and [211] Simha R, Wall L. Some aspects of depolymerization kinetics. J Polym Sci 1951;6:
immobilizing agents. Crit Rev Environ Sci Technol 2010;40:909–77. 39–44.

29
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

[212] Van Geem K, Faravelli T, Manenti F, Ranzi E. Chapter 6 - Kinetic modeling of the [242] Westerhout R, Van Koningsbruggen M, Van Der Ham A, Kuipers J, Van
pyrolysis chemistry of fossil and alternative feedstocks. Computer Aided Chemical Swaaij WPMJCER. Design. Techno-economic evaluation of high temperature
Engineering: Elsevier; 2019. p. 295–362. pyrolysis processes for mixed plastic waste. Chem Eng Res Des 1998;76:427–39.
[213] Di Blasi C. Modeling and simulation of combustion processes of charring and non- [243] Gracida-Alvarez U, Winjobi O, Sacramento-Rivero J, Shonnard D. System
charring solid fuels. Prog Energy Combust Sci 1993;19:71–104. analyses of high-value chemicals and fuels from a waste high-density
[214] Pyle D, Zaror C. Heat transfer and kinetics in the low temperature pyrolysis of polyethylene refinery. part 1: conceptual design and techno-economic
solids. Chem Eng Sci 1984;39:147–58. assessment. ACS Sustain Chem Eng 2019;7:18254–66.
[215] Lédé J. Reaction temperature of solid particles undergoing an endothermal [244] Larrain M, Van Passel S, Thomassen G, Kresovic U, Alderweireldt N, Moerman E,
volatilization. Application to the fast pyrolysis of biomass. Biomass Bioen 1994;7: et al. Economic performance of pyrolysis of mixed plastic waste: open-loop versus
49–60. closed-loop recycling. J Cleaner Prod 2020;270:122442.
[216] Kaminsky W, Schlesselmann B, Simon C. Olefins from polyolefins and mixed [245] Somoza-Tornos A, Gonzalez-Garay A, Pozo C, Graells M, Espuña A, Guillén-
plastics by pyrolysis. J Anal Appl Pyrolysis 1995;32:19–27. Gosálbez G. Realizing the potential high benefits of circular economy in the
[217] Ali S, Garforth A, Harris D, Rawlence D, Uemichi Y. Polymer waste recycling over chemical industry: ethylene monomer recovery via polyethylene pyrolysis. ACS
“used” catalysts. Catal Today 2002;75:247–55. Sustain Chem Eng 2020;8:3561–72.
[218] Lin Y, Yang M. Catalytic pyrolysis of polyolefin waste into valuable hydrocarbons [246] Sahu J, Mahalik K, Nam H, Ling T, Woon T, bin Abdul Rahman M, et al.
over reused catalyst from refinery FCC units. Appl Catal, A 2007;328:132–9. Feasibility study for catalytic cracking of waste plastic to produce fuel oil with
[219] Mertinkat J, Kirsten A, Predel M, Kaminsky W. pyrolysis A. Cracking catalysts reference to Malaysia and simulation using ASPEN Plus. Environ Prog Sustain
used as fluidized bed material in the Hamburg pyrolysis process. J Anal Appl Energy 2014;33:298–307.
Pyrolysis 1999;49:87–95. [247] Guinee J, Heijungs R, Huppes G, Zamagni A, Masoni P, Buonamici R, et al. Life
[220] Santos E, Rijo B, Lemos F, Lemos M. A catalytic reactive distillation approach to cycle assessment: past, present, and future45. Environ Sci Technol; 2011. p. 90–6.
high density polyethylene pyrolysis – Part 2 – middle olefin production. Catal [248] Khoo H, Conservation Recycling. LCA of plastic waste recovery into recycled
Today 2021;379:212–21. materials, energy and fuels in Singapore. Resour Conserv Recycl 2019;145:67–77.
[221] Eschenbacher A, Varghese R, Abbas-Abadi M, Van Geem K. Maximizing light [249] Alston S, Arnold J. Environmental Impact of pyrolysis of mixed WEEE plastics
olefins and aromatics as high value base chemicals via single step catalytic part 2: life cycle assessment. Environ Sci Technol 2011;45:9386–92.
conversion of plastic waste. Chem Eng J 2022;428:132087. [250] Melnyk A, Dettlaff A, Kuklińska K, Namieśnik J, Wolska L. Concentration and
[222] Artetxe M, Lopez G, Elordi G, Amutio M, Bilbao J, Olazar M. Production of light sources of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated
olefins from polyethylene in a two-step process: pyrolysis in a conical spouted bed biphenyls (PCBs) in surface soil near a municipal solid waste (MSW) landfill. Sci
and downstream high-temperature thermal cracking. Ind Eng Chem Res 2012;51: Total Environ 2015;530-531:18–27.
13915–23. [251] Cheng H, Hu Y. Municipal solid waste (MSW) as a renewable source of energy:
[223] Artetxe M, Lopez G, Amutio M, Elordi G, Bilbao J, Olazar M. Cracking of high current and future practices in China. Bioresour Technol 2010;101:3816–24.
density polyethylene pyrolysis waxes on HZSM-5 catalysts of different acidity. Ind [252] Alston S, Arnold J. Environmental impact of pyrolysis of mixed WEEE plastics
Eng Chem Res 2013;52:10637–45. part 2: life cycle assessment. Environ Sci Technol 2011;45:9386–92.
[224] Iulianelli A, Liguori S, Wilcox J, Basile A. Advances on methane steam reforming [253] Antelava A, Damilos S, Hafeez S, Manos G, Al-Salem S, Sharma B, et al. Plastic
to produce hydrogen through membrane reactors technology: a review. Cataly solid waste (PSW) in the context of life cycle assessment (LCA) and sustainable
Rev 2016;58:1–35. management. Environ Manage 2019;64:230–44.
[225] Wu C, Williams P. Pyrolysis–gasification of post-consumer municipal solid plastic [254] Ahamed A, Veksha A, Yin K, Weerachanchai P, Giannis A, Lisak G. Environmental
waste for hydrogen production. Int J Hydrogen Energy 2010;35:949–57. impact assessment of converting flexible packaging plastic waste to pyrolysis oil
[226] Wu C, Williams P. Pyrolysis–gasification of plastics, mixed plastics and real-world and multi-walled carbon nanotubes. J Hazard Mater 2020;390:121449.
plastic waste with and without Ni–Mg–Al catalyst. Fuel 2010;89:3022–32. [255] Perugini F, Mastellone M, Arena U. A life cycle assessment of mechanical and
[227] Czernik S, French R. Production of hydrogen from plastics by pyrolysis and feedstock recycling options for management of plastic packaging wastes. Environ
catalytic steam reform. Energy Fuels 2006;20:754–8. Prog 2005;24:137–54.
[228] Barbarias I, Lopez G, Artetxe M, Arregi A, Bilbao J, Olazar M. Valorisation of [256] Gear M, Sadhukhan J, Thorpe R, Clift R, Seville J, Keast M. A life cycle assessment
different waste plastics by pyrolysis and in-line catalytic steam reforming for data analysis toolkit for the design of novel processes–a case study for a thermal
hydrogen production. Energy Convers Manage 2018;156:575–84. cracking process for mixed plastic waste. J Cleaner Prod 2018;180:735–47.
[229] Wu C, Nahil M, Miskolczi N, Huang J, Williams P. Processing real-world waste [257] Al-Salem S, Evangelisti S, Lettieri P. Life cycle assessment of alternative
plastics by pyrolysis-reforming for hydrogen and high-value carbon nanotubes. technologies for municipal solid waste and plastic solid waste management in the
Environ Sci Technol 2014;48:819–26. Greater London area. Chem Eng J 2014;244:391–402.
[230] Acomb J, Wu C, Williams P. Control of steam input to the pyrolysis-gasification of [258] Iribarren D, Dufour J, Serrano D, Management W. Preliminary assessment of
waste plastics for improved production of hydrogen or carbon nanotubes. Appl plastic waste valorization via sequential pyrolysis and catalytic reforming.
Catal, B 2014;147:571–84. J Mater Cycles Waste Manage 2012;14:301–7.
[231] Acomb J, Wu C, Williams P. The use of different metal catalysts for the [259] Gracida-Alvarez U, Winjobi O, Sacramento-Rivero J, Shonnard D. System
simultaneous production of carbon nanotubes and hydrogen from pyrolysis of analyses of high-value chemicals and fuels from a waste high-density
plastic feedstocks. Appl Catal, B 2016;180:497–510. polyethylene refinery. Part 2: carbon footprint analysis and regional electricity
[232] Yao D, Wu C, Yang H, Zhang Y, Nahil M, Chen Y, et al. Co-production of hydrogen effects. ACS Sustain Chem Eng 2019;7:18267–78.
and carbon nanotubes from catalytic pyrolysis of waste plastics on Ni-Fe [260] Gracida-Alvarez U, Keenan L, Sacramento-Rivero J, Shonnard D. Resource and
bimetallic catalyst. Energy Convers Manage 2017;148:692–700. greenhouse gas assessments of the thermochemical conversion of municipal solid
[233] Yao D, Li H, Dai Y, Wang C. Impact of temperature on the activity of Fe-Ni waste in Mexico. ACS Sustain Chem Eng 2016;4:5972–8.
catalysts for pyrolysis and decomposition processing of plastic waste. Chem Eng J [261] Benavides P, Sun P, Han J, Dunn J, Wang M. Life-cycle analysis of fuels from post-
2021;408:127268. use non-recycled plastics. Fuel 2017;203:11–22.
[234] Namioka T, Saito A, Inoue Y, Park Y, Min T, Roh S, et al. Hydrogen-rich gas [262] Kalargaris I, Tian G, Gu S. Combustion, performance and emission analysis of a DI
production from waste plastics by pyrolysis and low-temperature steam reforming diesel engine using plastic pyrolysis oil. Fuel Process Technol 2017;157:108–15.
over a ruthenium catalyst. Appl Energ 2011;88:2019–26. [263] Jing Y, Wang Y, Furukawa S, Xia J, Sun C, Hülsey M, et al. Towards the circular
[235] Dai L, Zhou N, Li H, Wang Y, Liu Y, Cobb K, et al. Catalytic fast pyrolysis of low economy: converting aromatic plastic waste back to arenes over Ru/Nb2O5
density polyethylene into naphtha with high selectivity by dual-catalyst tandem catalyst. Angew Chem Int Ed 2021;133(10):5587–95.
catalysis. Sci Total Environ 2021;771:144995.
[236] López A, de Marco I, Caballero B, Laresgoiti M, Adrados A, Aranzabal A. Catalytic
pyrolysis of plastic wastes with two different types of catalysts: ZSM-5 zeolite and
Red Mud. Appl Catal, B 2011;104:211–9. Leilei Dai is a PhD candidate at the University of Minnesota.
[237] Dai L, Zhou N, Lv Y, Cheng Y, Wang Y, Liu Y, et al. Chemical upcycling of waste His research interests include catalytic microwave-assisted
polyolefinic plastics to low-carbon synthetic naphtha for closing the plastic use pyrolysis of soild wastes for the production of fuels, chem­
loop. Sci Total Environ 2021;782:146897. icals, and materials. He has 20 publications with a Google H
index of 30. He also served as a peer reviewer for many jour­
[238] Dai L, Zhou N, Lv Y, Cobb K, Cheng Y, Wang Y, et al. Pyrolysis-catalysis for waste
polyolefin conversion into low aromatic naphtha. Energy Convers Manage 2021; nals, such as Bioresource Technology, Applied Thermal Engi­
245:114578. neering, Science of the Total Environment, Fuel. .
[239] Gao P, Wang Q, Xu J, Qi G, Wang C, Zhou X, et al. Brønsted/Lewis Acid Synergy
in Methanol-to-Aromatics Conversion on Ga-Modified ZSM-5 Zeolites, As Studied
by Solid-State NMR Spectroscopy. ACS Cataly 2018;8:69–74.
[240] Yarulina I, De Wispelaere K, Bailleul S, Goetze J, Radersma M, Abou-Hamad E,
et al. Structure–performance descriptors and the role of Lewis acidity in the
methanol-to-propylene process. Nat Chem 2018;10:804–12.
[241] Jiang G, Wang J, Al-Salem S, Leeke G. Molten solar salt pyrolysis of mixed plastic
waste: process simulation and technoeconomic evaluation. Energy Fuels 2020;34:
7397–409.

30
L. Dai et al. Progress in Energy and Combustion Science 93 (2022) 101021

Nan Zhou (1992) received his BS (2013) in Energy and Power Kirk Cobb is a retired chemical process design engineer, after
Engineering at Xi’an Jiaotong University and MSc (2015) in working for 45 years, primarily in the oleo-chemicals industry.
Biosystems Engineering at Oklahoma State University. He is He completed a B.S. in Chemical Engineering at Ohio Univer­
currently a PhD candidate at University of Minnesota. His- sity during 1968–1972, and completed an M.S. in Chemical
research interests include energy and material recovery from Engineering at Michigan State University in 1973. He worked
organic solid wastes, and applications of non-thermal plasma in the pharmaceutical and detergent industries, early in his
technology and microwave technology. He has co-authored 38 career, and then spent more than 20 years working for the
publications with an h-index of 16 . chemical division of a large paper company, focusing on crude
tall oil and fatty acid distillation projects, and downstream
projects that converted distilled pine rosin and distilled fatty
acids into commercial products such as polymers, adhesive
resins, and printing ink resins. Process design work, both
domestic and international, always included mass and energy
balance evaluations, plant utilities, and related environmental issues. During the last 15
years of his career, Kirk felt compelled to use his engineering expertise to address the
growing concern of global climate change, and took his experience in the oleo-chemicals
Dr. Yuancai Lv is a teacher at Fuzhou University. He got her industry to the expanding biofuels industry. While doing consulting work in the biofuels
Ph.D from South China University of Technology, and M.S, B.S industry, he recommended a process technology to a client, which had been used for de­
from Fuzhou University. He has been part of Center for Bio­ cades in oleo-chemicals, as a unique process method for methyl ester production. Although
refining at University of Minnesota as a visiting scholar since the client later received a patent for this technology, Kirk was named in the corporate sale
2019. Since 2012, he has been focusing on the development of of that client, as having rights to future use of that technology. Kirk has written numerous
environmental materials and the recycling of solid waste. So technical articles which have been published in industrial periodicals, such as Biodiesel
far, he has obtained 5 grants including the National Natural Magazine, Biomass Magazine, and Render Magazine. Even in retirement, Kirk remains
Science Foundation of China and Fujian Natural Science enthusiastically focused on issues related to climate change, has written numerous letters
Foundation National, gained 5 Chinese invention patent and to the editor on this topic, which have been published in the Minneapolis Star Tribune. For
published 33 research articles. Currently, he has been the re­ many years, Kirk has remained a member of the American Chemical Society, and served as
viewers of several journals including Chemical Engineering the chairman of a local ACS section (many years ago!). To reduce his carbon footprint, he
Journal, Water Research, Journal of Hazardous Materials, now drives an EV .
Chemosphere and Energy & Fuel. His-interests involves syn­
thesis of biomass materials, nitrogen fixation with non-thermo plasma and water pollution
control .
Dr. Paul Chen is a research professor at the University of
Minnesota, USA. He also serves as the Program Director of the
Center for Biorefining at the University of Minnesota. He
Dr. Yanling Cheng is an adjunct associate professor at the earned his BSc and MSc degrees from South China Agricultural
University of Minnesota, USA, a professor at the Beijing Union University in 1983 and 1983 respectively, and obtained his
University, China. She got her Ph.D from China University of PhD degree at the Queen’s University of Belfast, UK, in 1994.
Mining and Technology (Beijing), and M.S, B.S from Chang­ His-main research interests include biological material and
chun University of Technology. Dr. Cheng’s research focuses food processing, biomass conversion, alternative biomass re­
on value-added processes and systems development for various sources, biorefining, and biobased product development, waste
by-products, residues and wastes from food and agricultural mitigation and utilization, environment protection, sustainable
productions, sustainable development, renewable energy and agriculture, food safety, and healthy foods. He is/was an
wastewater treatment. Dr. Cheng has published over 90 papers investigator of numerous USDA, DOE, and DOT funded projects
in refereed journals, co-authored three books, and holds 9 related bioenergy production. He has more than 230 papers, 2
patents. She has supervised over 60 undergraduate and grad­ books, 13 book chapters published with Google Scholar metrics of citations: 12,870, h-
uate students at Beijing Union University (BUU). She has index: 59, and i10-index: 172 .
received over 20 grants totaling over 10 million Chinese yuan
in various funding for research, including major funding from Chinese Ministry of S&T,
Beijing City Government, and industries since 2010. She has served as an editorial board
member of 1 journal, and peer reviewer for several journals . Dr. Hanwu Lei is an Associate Professor of Bioenergy and
Bioproducts Engineering of Biological Systems Engineering at
Washington State University. He received his B.S. from Jian­
gnan University and M.S. and Ph.D. from the University of
Dr. Wang Yunpu is a professor at Nanchang University. He Minnesota, Twin Cities, in Biosystems and Agricultural Engi­
received MSc (2012) and PhD (2020) at Nanchang University. neering. Dr. Lei has been working with biomass-derived car­
His-research interests include energy conversion and efficient bon, activated carbon, carbon catalyst production, carbon and
utilization of agricultural and forestry biomass and other solid zeolite catalysis, syngas and hydrogen production, bio aro­
wastes. He has published more than 100 scientific research matics, and bio-jet fuels. His-research investigates the mecha­
papers in the past 5 years, with an h-index of 25, i10-index of nisms responsible for the generation of fuel components and
51, and over 1800 citations . high-value chemicals and bioproducts from biomass and
municipal solid wastes including plastic wastes, and address
fundamental and applied questions in conversions. Dr. Lei has
published over 137 peer-reviewed journal articles and book chapters with an h-index of
40, i10-index of 95, and over 5336 citations. He is co-editing with international partners
for international peer-reviewed journals for the past 13 years .

Dr. Roger Ruan is a professor at the University of Minnesota,

Dr. Yuhuan Liu is a professor at Nanchang University. He USA. He received his from University of Illinois at Urbana-
received his B.S. from Fujian Agriculture and Forestry Uni­ Champaign. He is a fellow of ASABE and a fellow and IFT.
versity and Ph.D. from Nanchang University. He has been He has published over 500 papers in refereed journals, two
working with solid waste utilization, biobased product devel­ books, and 20 book chapters, and holds 18 US patents. He is
opment, waste management, environment protection, and also a top cited author in the area of agricultural and biological
sustainable agriculture. He has published over 200 peer- sciences with an h-index of 74, i10-index of 350, and over
reviewed journal articles and book chapters. He serves as a 21,000 citations. He has received over 180 projects totaling
reviewer for international peer-reviewed journals in the past over US$45 million in various funding for research, including
15 years . major funding from USDA, DOE, DOT, DOD, and industries. He
has served as Editor-in-Chief, associate editor, guest editor or
editorial board member of many journals. He has given over
300 keynote lectures, invited symposium presentations, com­
pany seminars, and short courses, and has been a consultant for government agencies, and
many local, national, and international companies and agencies in bioprocess engineering,
food engineering, and renewable energy and environment areas .

31