Journal of Hazardous Materials 424 (2022) 127460

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Review

Conversion of plastic waste into fuels: A critical review

Ning Li a, Hengxin Liu a, Zhanjun Cheng a, Beibei Yan a, Guanyi Chen a, b, c, 1, *, Shaobin Wang d
a
School of Environmental Science and Engineering/Tianjin Engineering Research Center of Bio Gas/Oil Technology, Tianjin University, Tianjin 300072, China
b
School of Mechanical Engineering, Tianjin University of Commerce, Tianjin 300134, China
c
School of Science, Tibet University, Lhasa 850012, Tibet Autonomous Region, China
d
School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia

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

Editor: Dr. R Teresa Plastic wastes have posed serious threats to the environment, including decrease of soil nutrient effectiveness and
agricultural production as well as emerge of ecological instability. Fuel conversion from plastic waste is regarded
Keywords: as a promising strategy for its disposal and energy utilization. Plastic wastes can be converted into target fuels by
Plastic adjusting cracking of chemical bonds. Currently, numerous technologies regarding fuel conversion from plastic
Fuel
wastes have been reported, including conventional pyrolysis, novel heat treatment and advanced oxidation.
Pyrolysis
However, systematic summary and comparative analysis of different technologies are still scarcely reported. In
Catalytic cracking
Hydrothermal liquefaction this review, fuel conversion from plastic wastes was summarized comprehensively, highlighting novel heat
Advanced oxidation treatment and advanced oxidation technologies reported in recent years. Furthermore, the superiority and
drawbacks of each technology were analyzed, and future prospects of technology application were proposed.
With lower reaction temperature and higher-value fuel, novel heat treatment of plastics is more popular than
traditional one. Advanced oxidation can be controlled to convert plastics into fuels under room temperature and
pressure, guiding the new normal in energy utilization of plastic wastes. This review aims to provide inspiration
for energy utilization of solid waste, addressing the issues of white pollution and energy shortage.

1. Introduction
In recent years, the global demand of plastics has increased with the
continuous development of industry, agriculture and fishery. As a result,
more and more plastic wastes generate year by year. According to the
United Nations Environment Programme, the global production of
plastic wastes was about 360 million tons in 2018. As we all know,
plastic is a high molecular polymer with stable structure, which is hard
to be destroyed by microorganisms in nature. As a kind of solid
pollutant, plastic waste has posed serious threats to the environment in
the following aspects: (1) affect soil function and agricultural produc­
tion. The concentrations of dissolved organic nitrogen and phosphorus
decrease owing to the interaction between plastic wastes and humus,
thus affecting soil nutrient effectiveness (Pathan et al., 2020). Besides,
microplastics in the soil changes the isoelectric cohesive Coulomb and
van der Waals forces between soil particles, affecting the formation of
soil agglomerates (Machado et al., 2018). With plastic wastes mixed in
the soil, the pores of the root cell wall are blocked. As a result, the ab­
sorption of water and nutrients via root system is affected, leading to
reduction of output (Mbachu et al., 2021); (2) threaten the survival of
animals. Waste plastics on land surface or in water are easily taken by
animals, causing animal death; (3) produce microplastics and induce
ecological security. The toxic effect of plastic wastes refers to organism
adverse reactions generated by the invasion from plastic to organisms.
Microplastics can inhibit the expression of genes involved in oxidative
stress and transmembrane transport in the plant body, hence affecting its
growth (Zhou et al., 2020). More seriously, microplastics hinder the
extracellular transmission of cellular transport carriers and cause human

Abbreviations: PP, Polypropylene; PS, Polystyrene; PE, Polyethylene; LDPE, Low density polyethylene; PET, Polyethylene terephthalate; HDPE, High density
polyethylene; RH, Rice husk; WS, Wheat straw; HZSM-5, Hydrogen zeolite socony mobile-five; FCC, Fluid catalytic cracking; SZ, Sulfated zirconia; Ecat-1, Com­
mercial catalyst-one; PVC, Polyvinyl chloride; PAM, Polyacrylamide; PLA, Polylactic acid; PUR, Polyurethane; CNX|Ni2P, Carbon nitride/nickel phosphide; PVA,
Polyvinyl alcohol; PCBs, polychlorodiphenyls.
* Corresponding author at: School of Environmental Science and Engineering/Tianjin Engineering Research Center of Bio Gas/Oil Technology, Tianjin University,
Tianjin 300072, China.
E-mail address: chen@tju.edu.cn (G. Chen).
1
Postal address: No.135, Yaguan Road, Jinnan District, Tianjin City, P.R. China.

https://doi.org/10.1016/j.jhazmat.2021.127460
Received 12 August 2021; Received in revised form 3 October 2021; Accepted 6 October 2021
Available online 8 October 2021
0304-3894/© 2021 Elsevier B.V. All rights reserved.
N. Li et al.
metabolic disorders (Nor et al., 2021). Also, microplastics ingested by
animals and accumulated in the gut, attacking the intestinal mucosa and
causing intestinal damage (Varo et al., 2021). On one hand, micro­
plastics refer to plastic particles less than 5 mm in size. Owing to the
great specific surface area of microplastics, it is prone to adsorb other
pollutants to trigger combined toxic effects. On the other hand, micro­
plastic belongs to polymer and requires more than 100 years to be
degraded in nature. The toxic effect of microplastics accumulates
gradually in food chain, affecting the stability of ecosystem (Zhang et al.,
2017); (4) cause white pollution. The plastic wastes in the environment
can affect the cityscape and pose a visual shock to people; (5) trigger
diseases. Plastic wastes in the ocean show higher charge and hydro­
philicity than that on land, which can be converted into microplastics in
the presence of microorganisms. Bacteria could accumulate and adhere
to the surface of plastic wastes easily, forming micro colonies and
resulting in damage to organisms in the ocean. For instance, with
physical injury from plastic wastes to coral, genus Vibrio on plastic
wastes can invade coral tissues and induce white syndrome (Lamb et al.,
2018; Rasool et al., 2021). Also, accidental ingestion of microplastics by
fish induces a false sense of satiety, thus reducing their food intake.
Decrease of fish population size and individual quality occurs due to
unavailability of growth energy (Mallik et al., 2021). Furthermore,
microplastics in the soil can be absorbed by plants, leading to growth
retardation and plant height inhibition (Xu et al., 2020). People feed on
plants, resulting in microplastics transfer to human body, which can
cause intestinal inflammation and affect human growth and develop­
ment readily (Yee et al., 2021). Therefore, it is particularly important for
the proper treatment and disposal of plastic wastes.
Large amounts of dioxins and polychlorodiphenyls (PCBs) can
generate via incineration of plastic wastes. Dioxins absorbed by human
respiratory tract trigger reproductive decline and blurred vision. The
dynamic balance of reactive oxygen species in plants is disrupted by
PCBs readily, causing free radical accumulation and plant damage. PCBs
ingestion by animals show acute hepatic necrosis and bone deformation
owing to PCBs accumulation in fatty tissues (Bursian et al., 2018; Sub­
ramanian et al., 2017; Yao et al., 2017). Also, landfill is one of the
common ways for plastic wastes treatment currently. Heavy metals (e.g.,
cadmium, copper and mercury) and pathogens carried by plastic wastes
enter the groundwater with rainwater washing. The contaminated
groundwater can induce heart failure and bone softening after humans
and animals consumption (Sall et al., 2020).
The energy utilization of plastic wastes is one of the effective ways
for its proper disposal. Fuel conversion from plastics can reduce harmful
emissions and pathogen contaminants compared to incineration and
landfill disposal. The species and density of oxidants can be regulated by
reaction parameters (e.g., temperature, reaction time and temperature
increasing rate) in fuel conversion from plastic wastes (Yin et al., 2021).
Furthermore, chemical bonds are broken selectively, and generate
C4-C18 gasoline hydrocarbon and diesel hydrocarbon fractions (Dogu
et al., 2021). In this way, most of the carbon and hydrogen elements are
stored in the liquid fuel, reducing the formation of polycyclic aromatic
hydrocarbons effectively (Gin et al., 2021; Liu et al., 2021). Also, fuel
conversion from plastic wastes via heat treatment is conducted with
anoxic condition at 250–600 ◦ C (Banu et al., 2020). Most of aerobic
pathogens intolerant to high temperature are eliminated during the heat
treatment of plastic wastes.
Currently, plastic wastes can be converted into fuels, fine chemical
feedstocks and functional materials via appropriate technologies (Chen
et al., 2021; Lin et al., 2010; Singh et al., 2020). Traditional heat
treatment, novel heat treatment and advanced oxidation technologies
have been reported for fuel conversion from plastic wastes (Fadillah
et al., 2021; Hibino et al., 2021; Dwivedi et al., 2021). Initially, gasifi­
cation as a conventional pyrolysis technology, could convert plastic
wastes into liquid fuel of C5-C20 aromatic and aliphatic hydrocarbon at
350–600 ◦ C under oxygen deprivation (Papari et al., 2021). Moreover,
combustible gases such as H2, CO and CH4 could also generate (Panda
2
Journal of Hazardous Materials 424 (2022) 127460
et al., 2010). Combustible gases and liquid fuel can be used directly as
secondary energy to realize energy utilization of plastic waste (Nanda
and Berruti, 2020). Hydrothermal liquefaction and catalytic cracking
are regarded as novel heat technologies. In this way, plastic waste is
converted to gaseous hydrocarbons and >C13 non-aromatic liquid fuel at
250–450 ◦ C (Shen, 2020; Budsaereechai et al., 2019). Furthermore,
plastic polymers are decomposed to H2 in the presence of ⋅OH species in
advanced oxidation systems (Weber and Ramasamy, 2020). At the same
time, organic products such as carboxylic acid and sulfonic acid are
formed, making plastic waste a carbon resource for the chemical in­
dustry. In addition, the CO2 produced in the process of advanced
oxidation, can be further converted to acetic acid with photoreduction
or electrocatalysis (Liu et al., 2012; Zhao et al., 2017).
Reviews on energy conversion of plastic waste into C5-C20 aromatic
and aliphatic hydrocarbon fuels have been reported by pyrolysis and
catalytic cracking (Al-Salem et al., 2017; Uzoejinwa et al., 2018; Wong
et al., 2015). The effects of pyrolysis and catalytic cracking parameters
on the composition and properties of target fuels were summarized
(Mohanraj et al., 2017; Anuar Sharuddin et al., 2016; Kunwar et al.,
2016). Noticeably, many new technologies have been reported
regarding the conversion of plastics into fuels in recent years, such as
hydrothermal liquefaction and advanced oxidation (Okolie et al., 2020;
Pichler et al., 2021). In hydrothermal liquefaction, plastic wastes can be
converted into superior oils at relatively lower temperature compared to
conventional pyrolysis. Besides, high purity oil can generate by plastic
conversion via advanced oxidation at room temperature and pressure.
However, systematic summary of new technologies and comparison of
different processes have not yet been published. This review provides
readers with novel technologies for fuel conversion from plastic wastes
and clarifies the superiority and drawbacks of different systems. In
addition, more efficient processes can be designed based on different
types of plastic wastes, promoting target fuels generation by further
parameter regulation in the system. Herein, this review focused on novel
heat treatment and advanced oxidation technologies for energy utili­
zation of plastics. The advantages and shortcomings of different tech­
nologies were also analyzed by comparison. Furthermore, the outlook of
future applicable technologies was conducted. Also, the unresolved is­
sues and development directions were proposed. This review aims to
improve summaries of technologies for converting waste plastics into
fuels, promoting the harmless disposal and energy utilization of organic
solid waste. This review could provide inspiration and reference for
researchers in the field of solid waste utilization.
2. Conversion technologies of plastic wastes into fuels
2.1. Traditional heat treatment
The pyrolysis process can realize the conversion of plastic wastes into
fuel by anaerobic heating at 350–600 ◦ C. By providing thermal energy to
meet the activation energy required for polymer cracking, the plastic
waste is converted into combustible gas and liquid oil. Liquid oil could
be obtained from the pyrolysis of polyvinyl chloride (PVC), of which the
calorific value was as high as 40 MJ/kg (Miranda et al., 1999). By
comparison, the calorific value of non-aromatic fuel produced by py­
rolysis of polystyrene (PS) at 350 ◦ C was slightly lower (40.6 MJ/kg)
(Bajad et al., 2017). Obviously, the calorific value of fuel obtained from
polypropylene (PP) pyrolysis is closer to that of gasoline (44 MJ/kg),
appearing as an alternative energy after treatment. PS pyrolysis at
500 ◦ C could produce 96.0% of aromatic hydrocarbon, of which C5-C12
liquid gasoline hydrocarbon accounted for 82.5% (Zhang et al., 2020).
The product composition via polyethylene (PE) pyrolysis at 400 ◦ C was
studied (Sarker et al., 2012b). Results showed the percentage of C3-C27
volatile olefins reached 97.0%. It can be seen that the pyrolysis oil from
plastic wastes contains a large amount of gasoline and diesel fractions.
However, it is unsuitable for direct use as fuel due to wide carbon
number distribution, low octane value of gasoline and large number of
N. Li et al. Journal of Hazardous Materials 424 (2022) 127460

olefins. Hence, further upgrading of the pyrolysis oil is needed. As shown

in Table 1, mixed plastic wastes pyrolyzed to obtain chlorinated oil,
which was further refined to light liquid fraction including alkanes and
aromatics. The chlorine content of the light fraction reduced and the oil
composition was closer to gasoline and diesel products after refining
(Lopez-Urionabarrenechea et al., 2015). Overall, fuels with high calo­
rific value (>40 MJ/kg) can generate by plastic pyrolysis at scale, alle­
viating energy crisis potentially.
The efficiency of fuel conversion from plastic wastes is mainly
related to heating rate, pyrolysis temperature and feed composition. The
effect of heating rate on fuel conversion process of low density poly­
ethylene (LDPE) was investigated. It was found that the yield of non-
aromatic liquid oil decreased from 80.4% to 76.5% with ramp rate
increasing from 6 ◦ C/min to 10 ◦ C/min. The yield of the above products
further decreased to 71.1% with heating rate increasing to 14 ◦ C/min
(FakhrHoseini and Dastanian, 2013; Singh et al., 2019a) pyrolyzed
PE/PP/PS mixed plastic wastes slowly (10 ◦ C/min) at 500 ◦ C and found
the major products were C5-C14 aromatics and aliphatic hydrocarbons.
Comparatively, the mixed waste plastics were mainly converted to
gaseous products such as methane and ethane under fast pyrolysis
(20 ◦ C/min). In addition, pyrolysis of PE and polyethylene terephthalate
(PET) was conducted at heating rate of 15 ◦ C/min and 20 ◦ C/min,
respectively. PE was converted into >C13 non-aromatic high-value fuels
while PET was turned into aromatic fuels (Cheng et al., 2020; Singh
et al., 2019b). Therefore, slow pyrolysis can promote the conversion of
plastic into high-value liquid fuels and reduce the formation of
by-products.
As shown in Fig. 1a, the effect of pyrolysis temperature on fuel
production from mixed plastics (PP and LDPE) was investigated. The
yield of C5-C12 gasoline fraction increased from 18.3% to 48.6% with
temperature rising from 220 ◦ C to 275 ◦ C (Shah et al., 2010). Besides,
the yield of diesel hydrocarbon in PP pyrolysis rose from 57.3% to 69.8%
with the increase of pyrolysis temperature from 250 ◦ C to 300 ◦ C. The
production of naphthenic hydrocarbons increased while that of diesel
hydrocarbon decreased to 63.2% under higher temperature (400 ◦ C) Fig. 1. (a) Effect of pyrolysis temperature on oil yield from PP and LDPE; (b)
Pyrolysis mechanism of mixed plastic wastes. The Fig. 1(a) is taken from
(Ahmad et al., 2014). The impact of temperature on PP pyrolysis in a
Ref. (Prurapark et al., 2020) with copyright permission.
vertical cracking reactor was investigated. The fuel yield declined from
74.4% to 50.3% when the temperature increased from 550 ◦ C to 625 ◦ C
(Jin et al., 2018). After being understood the influence of related pa­ the diesel percentage by pyrolysis of PP alone was 46.3%, which
rameters, high density polyethylene (HDPE) and PET have been con­ improved by 9.3% and 5.2% after mixing with RH and WS (Suriapparao
verted to kerosene, gasoline and diesel fractions successfully (Prurapark et al., 2020). It was reported that fuel could be obtained by co-pyrolysis
et al., 2020). Consequently, high temperature pyrolysis (>550 ◦ C) of of red oak with HDPE at 575 ◦ C, of which the calorific value reached
plastic wastes is detrimental to the formation of liquid hydrocarbons. It 35.2 MJ/kg, much higher than that with HDPE pyrolysis alone (Xue
is crucial to select pyrolysis temperature rationally according to the et al., 2015). Co-pyrolysis of biomass and plastics required less micro­
target products. wave energy or thermal energy. Also, the loss of thermal conductivity
The effect of feedstock on the pyrolysis of PS and PP was studied. It was low, which is conducive to generating high-value fuels and
was observed that the yield of diesel fraction obtained by pyrolysis of improving the pyrolysis efficiency. In the future, co-pyrolysis of plastic
single PS was 20.8%, which increased slightly to 27.4% and 26.7% after wastes with other biomass can be tried to enhance the target fuel for­
addition of rice husk (RH) and wheat straw (WS) respectively. Besides, mation to the desired level.

Table 1
Fuel conversion from plastics via traditional heat treatment.
Type of plastics Conditions Products Yield (%) Refs.

PET T = 400/425/450 ◦ C C10-C14 kerosene / (Prurapark et al., 2020)

HDPE T = 575 ◦ C, Ratio of plastics to biomass = 1:4 Liquid oil 57.6 (Xu et al., 2020)
PE/PP/PS (Mixture) T = 500 ◦ C, Heating rate = 20 ◦ C/min C5-C19 liquid oil 50.9 (Singh et al., 2019a)
PS T = 500 ◦ C, Filling ratio of heat carrier = 15% C5-C12 liquid oil 82.5 (Zhang et al., 2017)
PE T = 400 ◦ C Liquid oil 92.0 (Sarker et al., 2012a)
LDPE/PP (Mixture) T = 275 ◦ C, Time = 80 min C5-C12 gasoline fraction 48.6 (Shah et al., 2010)
PP T = 550 ◦ C Liquid oil 74.4 (Jin et al., 2018)
LDPE T = 500 ◦ C, Heating rate= 6 ◦ C/min Liquid oil 80.4 (FakhrHoseini and Dastanian, 2013)
PP T = 300 ◦ C C6-C16 naphtha 50.0 (Ahmad et al., 2014)
PP T = 450 ◦ C, Ratio of plastics to RH = 1:1 C6-C14 diesel 55.6 (Suriapparao et al., 2020)
PS T = 350 ◦ C, Time = 40 min Liquid oil 88.0 (Bajad et al., 2017)
PE/PP/PS/PET/PVC (Mixture) T = 500 ◦ C, Time = 30 min C5-C16 liquid oil 87.0 (Lopez-Urionabarrenechea et al., 2015)

PET: Polyethylene terephthalate; HDPE: High density polyethylene; PE: Polyethylene; PP: Polypropylene; PS: Polystyrene; LDPE: Low density polyethylene; PVC:
Polyvinyl chloride; T: Temperature; RH: Rice husk.

3
N. Li et al.
The conversion mechanism of mixed plastic wastes to fuel by py­
rolysis is shown in Fig. 1b. Heat is absorbed by plastics, inducing
thermal-initiation reactions at 350–600 ◦ C (Eq. (1)). Long-chain free
radicals generated by random breakage of PE and PP, or end fracture of
PS, which can be converted to paraffin and diolefin via hydrogen
transfer (Eq. 2). Besides, Vinyl can be formed through beta-scission of
long chain radicals. Moreover, the reorganization and aromatization
occur in vinyl, promoting the formation of alkanes and olefins (Eqs.
(3–8)). When free radicals, cations and anions are presented in the ter­
minal of plastic molecules, the bond energy at this position is distinct
from that of the neighboring groups. Hence, the plastic is susceptible to
suffer end-break degradation. In this model, pyrolysis starts at the end of
plastic molecular chain. The molecular weight of the plastic diminishes
slowly during the reaction. Besides, a large amount of monomeric matter
releases. In general, most of the vinyl polymers in the α-substituted
position are degraded via this reaction pattern. Random degradation
occurs anywhere in the polymer chain, and the plastic is decomposed
into small molecular fragments. However, no monomeric substance is
produced during the degradation process and the active site is not
required in the polymer chain to drive the reaction. Typically, vinyl
polymers such as polystyrene and polyacrylonitrile are fragmented by
random chain breaking mode. The main reaction equations of mixed
plastic wastes in pyrolysis are listed as follows:
(1) Thermal-initiating reaction:
(1)
∆
− R − (R)n − R − → − R − (R)n − R
(2) Chain-breaking reaction:
− R − (R)n − R∙ → − R − (R)n − R∙ + R (2)
(3) Chain-terminating reactions:
R∙ + R∙ → R− R (3)
R∙ + RO∙→ OR (4)
R∙ + ROO∙→ ROOR (5)
RO∙ + RO∙ → ROOR (6)
RO∙ + ROO∙→ ROR + O2 (7)
ROO∙ + ROO∙→ ROOR + O2 (8)
2.2. Novel heat treatment
2.2.1. Catalytic cracking
Catalytic cracking refers to the heating process of mixed catalysts
with plastic wastes, aiming to obtain liquid oil. By adding catalysts, the
activation energy can be reduced. As a result, the cracking of plastic
wastes and the production of liquid oil are facilitated. With high calorific
value and excellent performance, cracked oil has the potential to sub­
stitute fossil energy such as oil and diesel. The composition and prop­
erties of PS cracked oil under natural zeolites catalysis was examined.
The cracked oil was composed of aromatic hydrocarbons, including
styrene, ethylbenzene, benzene, asphaltene, and toluene. The calorific
value of the obtained fuel was as high as 45 MJ/kg, which is extremely
similar to the quality of conventional diesel fuel (Miandad et al., 2017).
Besides, PP cracking was performed under azoisobutylnitrile catalysis,
obtaining C8-C12 aliphatic hydrocarbons and cycloalkanes (Siddiqui,
2009). In comparison with direct pyrolysis, catalytic cracking of plastics
could generate liquid oil with narrower carbon number distribution.
Moreover, the yield of gasoline and kerosene fractions was enhanced.
4
Journal of Hazardous Materials 424 (2022) 127460
In catalytic cracking process, the plastic conversion is regulated by
temperature, flow rate of scrubbing gas, ratio of catalyst to plastic and
catalyst properties. The effect of temperature on the conversion of HDPE
to fuels with HZSM-5 catalyst was studied. As shown in Table 2. The
yield of C12-C18 diesel fraction raised from 14.3% to 41.7% as temper­
ature increased from 400 ◦ C to 450 ◦ C (Miskolczi et al., 2004). Also,
HDPE could be converted to C7-C16 alkanes by HZSM-5 catalysis at
400 ◦ C (Fig. 2a). The main products were aromatics and alkanes after
the temperature further increased by 40 ◦ C (Pan et al., 2018). In addi­
tion, by optimizing the pyrolysis temperature, the conversion of PP to
C5-C9 gasoline was achieved at 360 ◦ C (Sarker et al., 2012a). Therefore,
in contrast to conventional pyrolysis, the decomposition of plastics can
be accelerated by catalytic cracking at relatively low temperatures. The
effect of temperature on HDPE conversion by FCC catalyst was investi­
gated. The proportion of C5-C12 aliphatic hydrocarbons decreased from
86.2% to 81.1% with temperature increasing from 420 ◦ C to 510 ◦ C
(Abbas-Abadi et al., 2013). Besides, the HDPE catalytic cracking was
conducted with silica alumina. The yield of C6-C8 cycloalkanes
decreased from 75.3% to 72.9% as the temperature increased from
400 ◦ C to 500 ◦ C (Luo et al., 2000). After optimising the related pa­
rameters, PE was converted into C6-C9 aliphatic hydrocarbons success­
fully (Fushimi and Gaffney, 2014). Hence, relatively high temperature
(>400 ◦ C) can inhibit the formation of gasoline hydrocarbons.
The influence of N2 flow rate on catalytic cracking of plastic waste
was summarized. Mixed plastic wastes (PE/PP/PS) was converted into
fuels with HZSM-5 catalyst at 360 ◦ C. The yield of C1-C9 aliphatic and
aromatic hydrocarbons increased from 90.3% to 91.2% with N2 flow
rate rising from 270 mL/min to 420 mL/min. When the N2 flow rate
reached 900 mL/min, the production of the above fuels decreased to
88.1% (Lin and Yang, 2005). Also, a mixture of PE, PP and PS plastic
wastes was decomposed via fluid catalytic cracking (FCC). With growth
in the flow rate of N2 from 300 mL/min to 600 mL/min, the output of
combustible gases (e.g., benzene, styrene, toluene and xylene) increased
by 1.1%. Further enlarging the N2 flow rate to 900 mL/min, a 2.2%
increase of combustible gases yield was realized (Lin, 2009). Therefore,
the cost of plastic wastes conversion would decrease via selecting
appropriate flow rate of gas.
The catalyst composition plays an important role in LDPE conver­
sion. The catalytic decomposition of LDPE by Pt loading sulfated zir­
conia (SZ) at 250 ◦ C was investigated. With the growth of Pt
concentration in SZ from 0.4% to 1.2%, the output of C5-C12 alkanes
increased by 16.2% (Utami et al., 2018). The catalytic cracking of mixed
plastics (PP/PE/PS) by different Ni/Si-Al catalysts was conducted at
410 ◦ C. The content of C5-C12 aliphatic hydrocarbons rose from 70.2%
to 78.5% with the increase of molar ratio of Si and Al from 0:1–1:1
(Wang and Wang, 2011). Obviously, the excellent performance of metal
catalysts was shown in the catalytic cracking of plastic wastes, which
promoted the formation of C5-C12 aliphatic hydrocarbons.
The catalyst mass presents significant influences on catalytic
cracking of plastics. The conversion of mixed plastics (PE/PP/PS) was
investigated with different mass ratios of catalysts at 400 ◦ C. As the mass
ratio of commercial catalyst (ECat-1) to plastic waste increased from
1:10–3:5, the yield of C5-C9 aromatics and C1-C4 combustible gases
decreased by 5.3% and 1.6%, respectively (Lin and Yang, 2007). The
catalytic cracking of PS by SiO2/Al2O3 at 300 ◦ C was reported. A 9.1%
decrease of styrene output was found owing to an increase of the mass
ratio of catalyst to PS from 1:20–1:10 (Owusu et al., 2018). Moreover,
with the mass ratios of catalysts (BaTiO3、HZSM-5 and CuCO3) to
polymer reaching 1:19, 1:10 and 1:9, LDPE and HDPE were converted to
C5-C9 aromatic and >C13 non-aromatic fuels respectively (Ahmad et al.,
2013; Marcilla et al., 2009; Singh et al., 2018). Once the mass ratio of
catalyst to plastics is exceeded the optimal value, agglomeration of
catalysts occurs, leading to reduced surface area, lower catalytic effi­
ciency and easier generation of carbon. Therefore, the catalyst dosage in
the catalytic cracking of plastics should not be too large. Catalytic
cracking of PP could produce diesel fraction with Ni-Mo/Laponite
N. Li et al. Journal of Hazardous Materials 424 (2022) 127460

Table 2
Fuel conversion from plastics via novel heat treatment.
Type of plastics Catalyst Conditions Products Yield Refs.
(%)

PE/PP/PS Commercial equilibrium T = 400 ◦ C, Time = 30 min, N2 flow rate = 600 mL/min, C5-C9 gasoline 56.5 (Liang et al., 2013)
(Mixture) catalyst RCP = 1: 10
HDPE BaTiO3 T = 350 ◦ C, Time = 30 min, RCP = 1: 19 C6-C16 liquid oil 68.6 (Ahmad et al., 2013)
PE/PP/PS Ni/Si-Al T = 410 ◦ C, Time = 60 min, Ratio of Si to Al= 1: 1 C5-C12 gasoline 78.5 (Wang et al., 2014)
(Mixture)
PE/PP/PS HZSM-5 T = 360 ◦ C, Time = 20 min, N2 flow rate = 420 mL/min, C1-C4 gases 91.2 (Lin and Yang, 2005)
(Mixture) RCP = 2: 5
HDPE Ni/Al2O3 T = 400 ◦ C, Time = 120 min, RCP = 1: 50, P = 1 Mpa C7-C27 liquid oil 78.1 (Pan et al., 2018)
PS Natural zeolite T = 450 ◦ C, Time = 75 min, RCP = 1: 10, Heating rate Ethylbenzene 60.8 (Miandad et al., 2017)
= 10 ◦ C/min
PE/PP/PS Commercial equilibrium T = 390 ◦ C, N2 flow rate = 900 mL/min, RCP = 3: 7 Combustible 84.6 (Lin, 2009)
(Mixture) catalyst gases
LDPE Pt-promoted SZ T = 250 ◦ C, Pt ratio = 1.5% Olefins 55.6 (Utami et al., 2018)
PS SiO2/Al2O3 T = 300 ◦ C, Time = 120 min, RCP = 1: 20 Liquid oil 59.6 (Owusu et al., 2018)
HDPE HZSM-5 T = 550 ◦ C, RCP = 1: 10, Heating rate = 5 ◦ C/min Combustible 72.6 (Marcilla et al., 2009)
gases
HDPE HZSM-5 T = 450 ◦ C, Time = 60 min, RCP = 3: 97 C12-C18 diesel 41.7 (Miskolczi et al., 2004)
HDPE CuCO3 T = 500 ◦ C, RCP = 1: 19 Liquid oil 94.0 (Singh et al., 2018)
PP HZSM-5 T = 360 ◦ C, RCP = 1: 19 C3− C25 liquid oil 92.0 (Sarker et al., 2012a)
LDPE Cu@TiO2 T = 300 ◦ C, Time = 30 min, RCP = 1: 19 C13-C19 liquid oil 86.4 (Ukarde and Pawar, 2021)
PE sugarcane bagasse T = 280 ◦ C, Time = 60 min, RCP = 17: 3 Bio-oil 31.5 (Baloch et al., 2020b)
HDPE / T = 425 ◦ C, Time = 60 min, P = 0.62 Mpa, S = Deionized Diesel 45.0 (Jin et al., 2020)
water
PS / T = 490 ◦ C, Time = 10 min, P = 30 Mpa, S = Deionized Ethylbenzene 50.0 (Bai et al., 2019)
water
PS / T = 350 ◦ C, Time = 30 min, P = 25 Mpa, S = Pure water Liquid oil 85.4 (Sarker et al., 2012b)
LDPE sugarcane bagasse T = 280 ◦ C, Time = 75 min, S = Ethanol Bio-oil 32.3 (Baloch et al., 2020b)
PP/PS/PET / T = 300 ◦ C, Time = 30 min, P = 25 Mpa, S = Deionized Liquid oil 32.0 (Seshasayee and Savage,
(Mixture) water 2021)
PS / T = 350 ◦ C, Time = 60 min, S = Ethanol Liquid oil 84.7 (Ahmad et al., 2020)
PP / T = 425 ◦ C, Time = 120 min, P = 23 Mpa, S = Deionized C6-C13 liquid oil 64.7 (Chen et al., 2019)
water

PE: Polyethylene; PP: Polypropylene; PS: Polystyrene; HDPE: High density polyethylene; LDPE: Low density polyethylene; PET: Polyethylene terephthalate; HZSM-5:
Hydrogen zeolite socony mobile-five; T: Temperature; RCP: Ratio of catalyst to polymer; P: Pressure; S: Solvent; SZ: sulfated zirconia.

catalyst (mass ratio of Ni-Mo/Laponite to PP = 1:10), of which C10-C25
aliphatic hydrocarbons accounted for 64.1% (Mangesh et al., 2020).
Also, PP cracking with FCC catalyst was studied at 1:10 mass ratio of
catalyst to PP. Results showed the percentage of C12-C22 aliphatic hy­
drocarbons reached 85.8% (Lee et al., 2002). Therefore, FCC catalyst is
more conducive to diesel conversion from PP than Ni-Mo/laponite.
The catalytic cracking process of PE, PP, PS, PET and PVC mixture is
illustrated in Fig. 2b. The mechanism of catalytic cracking is similar to
that of conventional pyrolysis. In catalytic cracking process, thermal-
initiating, chain-breaking and chain-terminating reactions are
included. Notably, thermal-initiating reaction is initiated at 250–450 ◦ C
and the paraffins obtained from β-scission can be converted to short-
chain olefins via catalyst. In comparison with conventional pyrolysis,
catalytic cracking can generate C5-C16 aliphatic and C8-C18 aromatic
hydrocarbons with higher quality.
2.2.2. Hydrothermal liquefaction
Hydrothermal liquefaction refers to the conversion of plastics into
liquid oil in subcritical or supercritical water at 280–450 ◦ C and
7–30 MPa. Hydrothermal liquefaction is influenced by temperature,
reaction time and solvent. The effect of temperature on PP liquefied oil
was studied at 23 MPa. With temperature increasing from 380 ◦ C to
450 ◦ C, the content of C6-C13 aliphatic hydrocarbons decreased while
that of aromatic hydrocarbons increased (Chen et al., 2019). In the
process of PET conversion, benzoic acid changed from minor to major
product due to increase of temperature from 400 ◦ C to 450 ◦ C (Sesha­
sayee and Savage, 2020). Apparently, high temperature promotes the
hydrothermal liquefaction of plastic wastes to aromatic compounds.
LDPE was transformed into liquid oil in an autoclave. The yield of
C13-C19 cycloalkanes and aromatic hydrocarbons increased from 17.2%
to 86.1% with temperature increasing from 250 ◦ C to 300 ◦ C, which
decreased to 76.3% with temperature rising to 325 ◦ C (Ukarde and
Pawar, 2021). As shown in Fig. 3a, hydrothermal liquefaction of mixed
plastic wastes (PP, PS and PET) was conducted at 25 MPa. The liquid oil
yield decreased from 32.0% to 30.1% with temperature increasing from
300 ◦ C to 350 ◦ C (Seshasayee and Savage, 2021). Therefore, it is easier
for hydrothermal liquefaction of plastic wastes to fuels at relatively low
temperature (300 ◦ C).
Reaction time could influence oil production via hydrothermal
liquefaction of plastics. The effect of reaction time on fuel generation
during hydrothermal liquefaction of HDPE was investigated. The con­
centration of n-alkanes and cycloalkanes products increased within
40–60 min and reached a peak (43.0%) in 90–120 min. In the reaction
time range of 120–240 min, the yield of n-alkane was almost constant
while that of aromatic hydrocarbons increased (Jin et al., 2020). Be­
sides, hydrothermal liquefaction of PS was performed at 400 ◦ C and
30 MPa. Styrene and propane were main products within 20 min.
Extending the reaction to 60 min, the main products were toluene and
ethylbenzene, accompanied with the formation of polycyclic aromatic
hydrocarbons (Bai et al., 2019). Therefore, plastic wastes are converted
into fuels by hydrothermal liquefaction, which can be applied in prac­
tical situations after refining. To avoid coking of products, the time of
hydrothermal liquefaction should not be too long. Hydrothermal
liquefaction of LDPE was performed at 425 ◦ C. The yield of C5-C12
aliphatic hydrocarbons increased from 62.3% to 87.2% as reaction time
rising from 30 min to 60 min. However, the product yield decreased to
77.7% with time further prolonging to 120 min (Čolnik et al., 2021).
Also, the production of C5-C12 liquid oil from PE could be realized at
400 ◦ C. The yield of C5-C12 liquid oil was improved by 5.2% in
30–60 min and then declined slightly to 24.5% at 120 min (Song et al.,
2021). Hence, long-term hydrothermal liquefaction is not conducive to
the formation of gasoline fractions. The reaction time needs to be limited

5
N. Li et al.
Fig. 2. (a) Oil composition of HDPE conversion in catalytic pyrolysis; (b)
Mechanism of mixed plastic wastes in catalytic pyrolysis. The Fig. 2(a) is taken
from Ref. (Pan et al., 2018) with copyright permission.
to 1 h approximately.
Currently, water is widely utilized as a solvent in hydrothermal
liquefaction studies. Comparatively, ethanol with low critical point
achieves the mild liquefaction more easily. The effect of solvent type on
the conversion of PS to fuels was studied. The yield of liquid oil reached
84.7% in the presence of ethanol while that obtained with water was
74.2% (Ahmad et al., 2020). Moreover, taking ethanol as a solvent,
LDPE was converted to C5-C10 aromatic and >C13 non-aromatic fuels
with high heat value (29.6 MJ/kg) (Baloch et al., 2020b). Therefore,
ethanol is conducive to improving the output and quality of oil product
derived from hydrothermal liquefaction of plastics. In addition,
co-liquefaction of plastics with biomass has been reported. The yield of
liquid oil achieved 9.1% in the co-liquefaction mode with mass ratio of
Jingou lignite (JG), WS and PET (5:4:1). Compared with the hydro­
thermal liquefaction of single PET, the yield of liquid oil via
co-liquefaction was 4.8% higher under same conditions (Wang et al.,
2014). The co-liquefaction of PE with bagasse at 280 ◦ C was conducted.
The percentage of bio-oil was 31.5%, of which the calorific value
reached 34.9 MJ/kg (Baloch et al., 2020a). In conclusion,
co-liquefaction of plastic wastes and biomass can produce high-value
fuels, but the yield of liquid oil remains to be enhanced. Plastic con­
version via novel heat treatment (250–450 ◦ C) can decrease carbon
number distribution of products, forming gasoline and diesel fractions
(C5-C16 aliphatic hydrocarbons) in the scale-up application.
The mechanism of hydrothermal liquefaction is shown in Fig. 3b,
which is similar to that of conventional pyrolysis. Taking PE and PP
mixture as an example, depolymerization is triggered by dissociation of
free radicals at 280–450 ◦ C and 7–30 MPa. Noticeably, paraffin gener­
ated by saturated aliphatics could be transformed into C2-C4 combus­
tible gases via further cracking. Besides, cyclization and aromatization
6
Journal of Hazardous Materials 424 (2022) 127460
Fig. 3. (a) Effect of temperature on oil yield obtained by mixture of PP, PS and
PET at 25 MPa; (b) Mechanism of hydrothermal liquefaction. The Fig. 3(a) is
taken from Ref. (Seshasayee and Savage, 2021) with copyright permission.
occurred in unsaturated aliphatics, forming C8-C18 cycloalkanes and C6-
C9 aromatic hydrocarbons. The process of hydrothermal liquefaction of
plastic wastes can be summarized as follows: (1) depolymerization, (2)
monomers degradation via fracture, dehydration, decarboxylation and
deamidation, (3) fragments repolymerization.
2.3. Advanced oxidation process
2.3.1. Photocatalytic oxidation
Photocatalytic oxidation refers to oxidative decomposition of plastics
into lower molecular substances via oxidants such as cavities and⋅OH
under photocatalysis. The photocatalyst dominates in the conversion
process. LDPE could be converted to C2 fuel by polyacrylamide (PAM)/
TiO2 and PAM/ZnO under UV light respectively (Kamalian et al., 2020;
Liang et al., 2013). Evidently, oxidative species are formed via PAM/­
TiO2 or PAM/ZnO photocatalysis, producing low molecular fuels. Con­
version of polylactic acid (PLA), PET and polyurethane (PUR) to fuels by
CdS/CdOx photocatalysis under solar light was examined. The H2
product accounted for 38.8%, 16.6% and 22.5% respectively (Uekert
et al., 2018). Additionally, a two-step conversion route of C–C bond
cleavage and coupling was designed via Nb2O5 photocatalysis. PE, PP
and PVC were degraded to CO2, which was further photo-reduced to
CH3COOH (<40.0%) (Jiao et al., 2020). The current photocatalysts
possess poor capability of CO2 reduction, leading to low yield of C2 fuels.
Therefore, it is critical for rational design of photocatalyst and optimi­
zation of C–C bond breaking and coupling to achieve efficient con­
version of plastic wastes into multi-carbon fuels at room temperature
and pressure. Furthermore, Uekert et al. (2019) conducted PET and PLA
conversion via carbon nitride/nickel phosphide (CNX=Ni2P) photo­
catalysis under alkaline conditions. As a result, acetate and formate
N. Li et al. Journal of Hazardous Materials 424 (2022) 127460

⋅COOH +⋅COOH → HOOC− COOH (13)

generated, which could be applied as fuels after updating in Table 3. In
comparison with two-step conversion, direct generation of low carbon
organics improves the sustainability and value of photocatalytic system.
The photocatalytic process for plastic conversion is controllable with
no extra oxidant, avoiding secondary contamination. In scale-up appli­
cations, plastics could induce depolymerization by conventional heat
treatment. Provided by thermal energy, the plastics could be trans­
formed into gas and liquid fuels. According to Eq. (9), the pyrolysis
process requires 314.4–658.1 RMB per ton plastic for obtaining thermal
energy (Fivga and Dimitriou, 2018). However, the primary energy
source for plastic photocatalysis is solar light, which triggers plastic
decomposition and sustains photocatalytic conversion of plastic wastes
into fuels. Therefore, plastic conversion via photocatalysis can save
operating cost due to no thermal energy consumption compared to
pyrolysis.
S=(1000×q)/3600×K (9)
Where S is pyrolysis cost per ton of dry plastics, q is the energy
requirement for dry plastic pyrolysis (1316.1 kJ/kg), K is the electricity
price for industrial consumption in China (0.86–1.80 RMB/kWh).
However, solar energy utilization for plastic conversion is insuffi­
cient due to the low proportion of UV light. More visible-light-driven
photocatalyts needs to be developed for fuel conversion from plastics.
The mechanism of plastics conversion via photocatalysis is shown in
Fig. 4a. Semiconductor photocatalysts usually have a band structure and
narrow width of band gap. The photocatalytic conversion process of PE
is described in Eqs. (10–14). When the photon energy acquired by
semiconductor is larger than its band gap, the electrons can be stimu­
lated from valence band to conduction band, leaving photo-induced
holes on the valence band. Also, holes can oxidize water to ⋅OH,
which further oxidizes PE to CO2. Moreover, CO2 is converted to acetic
acid via the reduction of electrons on conduction band. The equations of
photocatalytic conversion of PE are listed below:
H2O + h+ →⋅OH + H+ (10)
(11)
∙OHOH
− (CH2 − CH2)n ̅→2nCO2
− ̅̅̅
CO2 + e− + H+ →⋅COOH (12)
HOOC− COOH + 6e− + 6 H+ → CH3COOH + 2 H2O (14)
where h+ and e- denote photo-induced holes and photo-generated
electrons respectively.
2.3.2. Fenton oxidation
Fenton oxidation refers to polymer oxidation to small molecular
substances via⋅OH generated by Fe2+ activated H2O2. Fenton oxidation
of sulfonated LDPE and HDPE was conducted at 65 ◦ C. LDPE and HDPE
were converted to carboxylic acids with yields of 87.5% and 88.8%
respectively (Chow et al., 2016). Also, the sulfonated PVC was decom­
posed to carboxylic acids (75.5%) via Fenton oxidation at 65 ◦ C (Chow
et al., 2017). Obviously, PE can be converted into carboxylic acids more
efficiently than PVC. Generally, PE and PVC can be fragmented by
Fenton oxidation, while PS requires UV light to promote the trans­
formation process. PS could be converted into fuels after sulfonation by
Fenton or light-assisted Fenton process at 75 ◦ C. However, no reaction
was found by direct Fenton oxidation of PS within 5 h. Noticeably, the
conversion of PS to CO2 by photo-Fenton oxidation exceeded 89.0% at
300 min under UV light (Feng et al., 2011). Therefore, the rapid
oxidation of PS cannot be achieved with⋅OH in Fenton process. Several
oxidants react together in light-assisted Fenton oxidation system.
However, the exact oxidation mechanism is not yet clarified and re­
quires further investigation. Moreover, photo-Fenton oxidation of sul­
fonated PE, PP and PVC was reported. The main product was CO2, which
could be converted to acetic acid after photo-reduction (Chow et al.,
2018).
Plastic conversion via Fenton oxidation usually occurs at mild re­
action conditions. The conversion process is efficient owing to rapid
decomposition of hydrogen peroxide, benefiting for large-scale appli­
cations. Nevertheless, the process requires large amounts of hydrogen
peroxide, resulting in high operating costs.
Fig. 4b shows the Fenton oxidation process for plastic (PE as an
example) conversion to fuels. The addition of Fenton reagent to PE
generates a large amount of ⋅OH, which could break the C–C bond. PE is
decomposed into adipic acid, glutaric acid and succinic acid by α-break,
β-break and γ-break, respectively. As described in Eqs. (15–18), Fe2+
reacts with H2O2 to form Fe3+ and ⋅OH. Besides, H2O2 is converted to
⋅HO2 with Fe3+ catalysis, which can react with H2O2 to form more ⋅OH.

Table 3
Fuel conversion from plastics via advanced oxidation process.
Type of Technology System Conditions Products Yield Refs.
plastics

LDPE Photocatalysis polyacrylamide grafted UV light CO2 / (Liang et al.,

TiO2 2013)
PET Photocatalysis Carbon Nitride/Nickel Solar light, T = 25 ◦ C H2 77.2 μmol/g (Uekert et al.,
Phosphide 2019)
PET Photocatalysis CdS/CdOx Visible light H2 278.2 mmol/ (Uekert et al.,
g 2018)
LDPE Photocatalysis ZnO UV light CO2 / (Kamalian et al.,
2020)
PVC Fenton FeCl3, H2O2 T = 50 ◦ C, C/S Ratio = 8.0 C1-C2 acids 82.5% (Chow et al.,
2017)
LDPE Fenton FeCl3, H2O2 Chlorosulfuric acid = 2.5%, No light C1-C4 acids 62.4% (Chow et al.,
2016)
PE Fenton FeCl3, H2O2 UV-Vis light, pH = 2.5, Time = 2 h CO2 > 99% (Chow et al.,
2018)
PS Photo-Fenton FeCl3, H2O2 UV light, Time = 300 min CO2 89.0% (Feng et al.,
2011)
PVA Electrocatalysis H3PO4 T = 100 ◦ C, External voltage = 0.55 V H2 9.5 µmol/min (Hori et al.,
2020)
PVC Electrocatalysis TiO2/graphite cathode, T = 100 ◦ C, pH = 3.0, Oxygen flow = 40 mL/min, Carboxylic 75.0% (Miao et al.,
Time = 6 h, Applied potentia = − 0.7 V acid 2020)
PP Solar Thermo-coupled NaOH, KOH T = 350 ◦ C, Time = 60 min, External voltage Gas 33.1% (Jiang et al.,
electrocatalysis = 1.5 V 2020)

LDPE: Low density polyethylene; PET: Polyethylene terephthalate; PVC: Polyvinyl chloride; PE: Polyethylene; PS: Polystyrene; PVA: Polyvinyl alcohol. PP: Poly­
propylene; T: Temperature

7
N. Li et al. Journal of Hazardous Materials 424 (2022) 127460

Fig. 4. Mechanism of plastic conversion to fuels (a) Photocatalytic oxidation; (b) Fenton oxidation; (c) Electro-catalytic oxidation; (d) advanced oxidation. The Fig. 4
(a) is taken from Ref. (Jiao et al., 2020) with copyright permission. The Fig. 4(b) is taken from Ref. (Chow et al., 2016) with copyright permission. The Fig. 4(c) is
taken from Ref. (Miao et al., 2020) with copyright permission.

8
N. Li et al.
Besides, the interaction between ⋅OH and RH generates R⋅(Eq. 19).
Eventually, the polymer is transformed into CO2 and H2O with breakage
of C–C bond (Eq. 20). The equations about Fenton oxidation of plastics
to fuels are listed below:
Fe2+ + H2O2 →Fe3+ +⋅OH + OH− (15)
Fe 2+ 3+
+⋅OH →Fe + OH −
(16)
Fe3+ + H2O2 →Fe2+ +⋅HO2 + H+ (17)
⋅HO2 + H2O2 → O2 + H2O +⋅OH (18)
RH +⋅OH → R⋅+ Fe2+ (19)
+ +
R + O2 → ROO →⋅⋅⋅→ CO2 + H2O (20)
2.3.3. Electrocatalytic oxidation
Electrocatalytic conversion of plastics contains two routes of direct
and indirect oxidation. Direct oxidation route refers to the electrophilic
attack of polymer by ⋅OH generated via water discharge on the surface of
anode. Indirect oxidation means strong oxidizing intermediates domi­
nate in the plastic conversion process. Polyvinyl alcohol (PVA) was
converted to H2 (9.5 µmol/min) successfully with an external voltage
(0.55 V) applied in H3PO4 solution at 200 ◦ C (Hori et al., 2020). Also,
electrocatalytic degradation of PVC was conducted for carboxylic acid
(75%) formation on TiO2/C cathode (− 0.7 V) at 100 ◦ C (Miao et al.,
2020). Obviously, electrocatalytic degradation of plastic wastes could
generate single product, which can be converted into fuels without
post-treatment. In contrast to single electrolysis, the combination of
pyrolysis and electrolysis can produce abundant fuel components. The
PP conversion to H2 and C1-C5 fuels was realized through solar
thermo-coupled electrolysis. Furthermore, the PP depolymerization was
enhanced with rising temperature (350–390 ◦ C) and electrolysis current
(0–400 mA) (Jiang et al., 2020). Therefore, by considering fuel yield
with temperature and electrolysis current, it is prospective to design an
electrochemical system with high-efficiency under low temperature and
current. In this way, the industrial utilization of plastic wastes can be
achieved with electrocatalysis.
The electrocatalytic oxidation is controllable for plastic conversion
at room temperature and pressure. The voltage and electrode could
affact plastic oxidation directly. High purity fuels will be formed at
appropriate conditions (e.g., voltage). However, the electrode life is
short and the electrocatalytic power consumption is high.
Electrocatalytic conversion route of plastics (e.g., PVC) is described
in Fig. 4c. After receiving electrons from the cathode (TiO2/C), PVC is
reduced, triggering dechlorination at high temperature. Also, PVC oxi­
dization occurs with⋅OH to form carbonyl and hydroxyl groups, which
are further converted into small molecules (e.g., alcohols, carboxylic
acids and esters). At last, these substances are mineralized to CO2 and
H2O partially. The mechanism of electrocatalytic oxidation of plastic
wastes is proposed. Initially, H2O in the acidic solution is adsorbed on
the surface of metal oxide anode. As shown in Eq. (21), H2O loses
electrons under the electric field, forming MOx(⋅OH) (MOx represents
anode).
MOx + H2O → MOx(⋅OH) + H+ + e− (21)
Furthermore, metal peroxide (MOx+1) generated due to the invasion
of oxygen atoms to MOx lattice (Eq. (22)).
MOx(⋅OH) → MOx+1 + H+ + e− (22)
Selective oxidation of polymer was conducted via MOx(⋅OH)z and
MOx+1 in solution (Eqs. (23) and (24)).
R + MOx(⋅OH)z → CO2 + MOx + ZH+ + Ze− (23)
R + MOx+1 → RO + MOx (24)
9
Journal of Hazardous Materials 424 (2022) 127460
Overall, plastic conversion via Fenton, photocatalysis and electro­
catalysis can generate⋅OH, converting plastic wastes into long-chain free
radicals (Fig. 4d). Furthermore, C2-C4 carboxylic acid (e.g., HCOOH,
CH3COOH and C₂H₂O₄) and H2 are formed with further oxidation.
3. Conclusion and perspective
In recent decades, fuel conversion from plastic wastes has received
extensive attentions in order to alleviate environmental pollution and
energy crisis. This review summarizes the available technologies for
plastic wastes conversion into fuels comprehensively. Some conclusions
are put forward below:
(1) The fuels, obtained from plastic wastes conversion via traditional
thermal treatment, possess high calorific value and superior
performance approaching gasoline and diesel. However, the
plastic pyrolysis process needs high temperature and long reac­
tion time, producing liquid oil with low yield, octane value and
wide range of carbon number distribution. Besides, the pipeline is
clogged easily due to the formation of olefins and paraffins during
reactions. What’s worse, volatile compounds generate in the
pyrolysis process, resulting in environmental pollution.
(2) Efficient conversion of plastic wastes can be realized at relatively
low temperature via novel heat treatment. The obtained fuel is
highly selective, among which isomerization and aromatization
products account for a large proportion. Nevertheless, catalysts
with high demand in plastics conversion are difficult to recover.
The catalyst deactivation occurs owing to impurity deposition in
cokes and plastic wastes. Besides, the reaction equipment re­
quires strict resistance to high pressure and corrosion.
(3) Advanced oxidation can achieve target fuel conversion from
plastic wastes under room temperature and pressure, reducing
energy consumption considerably compared to heat treatment.
Furthermore, the advanced oxidation process is controllable with
efficient plastic conversion and high product purity. However,
the reaction process requires highly-efficient catalysts, and the
liquid products have relatively low calorific value. Interestingly,
active sites on catalyst surface can be adjusted by appropriate
design, realizing oxidative species regulation and high-quality-
fuels production. Overall, fuel conversion from plastic wastes
via advanced oxidation is promising for future applications.
Although certain progress has been obtained in the fuel conversion
from plastic wastes, the following challenges still remain to be overcome
in future research:
(1) The addition of biomass in conventional thermal treatment of
plastic wastes decreases microwave energy, heat energy and
thermal conductivity losses, improving fuel yield by synergistic
effect. However, few studies have been focused on the influential
parameters (e.g., temperature, feed ratio of plastics to biomass
and reaction time) and related mechanism of plastics/biomass co-
pyrolysis. The optimization of reaction parameters based on
mechanism deserves further investigations to achieve higher fuel
yield. The maximization of economic benefit can be realized by
considering process parameters and product quality
simultaneously.
(2) Catalyst plays a crucial role in the novel heat treatment of plastic
wastes. Many kinds of plastic wastes exist, but a majority of
catalysts are efficient for single polymer decomposition merely.
The catalyst presents the drawbacks of easy deactivation and high
cost. Therefore, it is essential to develop catalysts with excellent
adaptability, high activity and recyclability. In order to avoid
clogging, the reactor design should be optimized to separate the
concentrated brine in time and deter salt deposition. Moreover,
N. Li et al.
the equipment performance can be enhanced via the develop­
ment of novel pressure and corrosion resistant materials.
(3) The liquid products, obtained by advanced oxidation of plastics
have low calorific value. The species and density of oxidants in
the system can be regulated via appropriate modulation of active
sites on catalyst surface. Accordingly, selective rupture of
chemical bonds in polymers and directional conversion of target
fuels can be realized. Furthermore, the photocatalysts should be
designed rationally via energy band modulation, heterojunctions
construction and co-catalysts loading. The separation of photo­
generated carriers is desired to be accelerated, prolonging the
service time of photocatalysts. Besides, optimization of C–C
bond breakage and coupling process of intermediates may realize
efficient transformation of multi-carbon fuel from plastic wastes
under natural illumination.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This research was financially supported by the National Natural
Science Foundation of China (52100156 and 521176197) and Shenzhen
Science and Technology Program (GJHZ20200731095801005 and
JCYJ20200109150210400).
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