Chemical Engineering Journal 428 (2022) 131928

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Chemical Engineering Journal

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

Review

Plastic waste upcycling toward a circular economy

Xianhui Zhao a, b, *, Matthew Korey a, Kai Li c, Katie Copenhaver a, Halil Tekinalp a, Serdar Celik d,
Kyriaki Kalaitzidou e, Roger Ruan f, Arthur J. Ragauskas g, h, Soydan Ozcan a, *
a
Manufacturing Science Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37830, United States
b
Environmental Sciences Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37830, United States
c
Buildings and Transportation Science Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37830, United States
d
Department of Mechanical and Mechatronics Engineering, Southern Illinois University, Edwardsville, IL 62026, United States
e
G.W Woodruff School of Mechanical Engineering and School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332, United States
f
Center for Biorefining and Department of Bioproducts and Biosystems Engineering, University of Minnesota, 1390 Eckles Ave, Saint Paul, MN 55108, United States
g
Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996, United States
h
Biosciences Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37830, United States

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

Keywords: Large amounts of plastics are discarded worldwide each year, leading to a significant mass of waste in landfills
Plastic waste and pollution to soil, air, and waterways. Upcycling is an efficient way to transform plastic waste into high-value
Recycle products and can significantly lessen the environmental impact of plastic production/consumption. In this
Upcycle
article, current advances and future directions in plastic waste upcycling technologies are discussed. In partic­
Catalysis
Energy
ular, this review focuses on the production of high-value materials from plastic waste conversion methods,
Compatibilizer including pyrolysis, gasification, photoreforming, and mechanical reprocessing. Plastic waste compositions,
conversion products, reaction mechanisms, catalyst selection, conversion efficiencies, polymer design, and
polymer modification are also explored. The main challenges facing the adoption and scale-up of these tech­
nologies are highlighted. Suggestions are given for focusing future research and development to increase the
efficiency of upcycling practices.

resulting in huge contributions to global waste and environmental

pollution. Recycling is often difficult because post-consumer plastic
1. Introduction
waste often consists of mixed plastics of unknown composition and
frequently contains various contaminants, including organic (e.g., food
There are large amounts of solid wastes in the world, including
remains) and inorganic (e.g., inks) ones. Most of this plastic waste is
plastics, tires, food, animal manure, woody biomass, and their mixtures.
either incinerated in power plants or discarded to landfills or oceans,
Among these solid wastes, plastic receives a great and increasing
resulting in a low or lost value [1]. Single-use multilayer flexible pack­
emphasis because of its production scale and environmental impact [1].
aging is a typical example of such non-recyclable waste that ends up in
Plastics are commonly used for packaging because of their light weight,
landfills and, eventually, in natural habitats. Approximately 8 million
low cost, processability, and high performance [2–4]. Polyethylene (PE)
tons of plastics find their way into oceans annually, and the plastic
and polypropylene (PP) are some of the most commonly used plastics in
pollution in oceans is predicted to outweigh the marine fish by 2050.
multilayer film packaging, among other applications. However, the high
One-third of all plastic produced worldwide is too complex (e.g., com­
durability of plastics causes large amounts of waste accumulation in
plex structures, complex mixture of different polymers) or small to
landfills and oceans because most synthetic polymers are designed for
recover or recycle in a practical and cost-effective manner [6]. Since
longevity and performance rather than recyclability and degradability
plastic waste is largely chemically inert, estimates suggest that existing
[2,5].
material would require around 250–500 years to completely degrade.
The single-use applications of plastics for sterile packaging, storage,
Furthermore, the constituents of plastic waste can enter the human food
transportation, and disposable medical parts play a significant role in its
chain through crops and animals. For example, crops might absorb and
contribution to global waste. Approximately 380 million tons of plastics
accumulate nanoplastics (e.g., dimensions < 6 nm), which can permeate
are produced annually worldwide, and<20% is typically recycled,

* Corresponding authors at: Manufacturing Science Division, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN 37830, United States (X. Zhao).
E-mail addresses: [email protected] (X. Zhao), [email protected] (S. Ozcan).

https://doi.org/10.1016/j.cej.2021.131928
Received 1 June 2021; Received in revised form 5 August 2021; Accepted 16 August 2021
Available online 21 August 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

explored and optimized to mitigate the effects of contamination and

Abbreviations and nomenclature control heating during gasification [13].
To reduce the cost of plastic waste upcycling, new technologies such
Abbreviation or nomenclature Full name as compatibilization have emerged. Compatibilizers are typically
PLA Polylactic acid multicomponent polymers of various architectures, such as graft, block,
ABS Acrylonitrile butadiene styrene and random copolymers, that have tailored thermodynamic interactions
PP Polypropylene with immiscible plastics in a given mixture [14]. The process of com­
PC Polycarbonate patibilization comprises the addition of a substance (the compatibilizer)
iPP Isotactic polypropylene that is tailored to an immiscible blend of plastics or materials to increase
PE Polyethylene their compatibility and stability [10,14]. Compatibilizers have potential
LDPE Low density polyethylene for converting plastics to high-value products with lower costs, and this
HDPE High density polyethylene technique can be used to recycle mixed plastics into equal- or higher-
PET Polyethylene terephthalate value products [10].
PHB Poly(3-hydroxybutyrate) Another new technology for plastic waste upcycling is depolymer­
PS Polystyrene ization. Because the majority of monomers used for plastic production
PVC Polyvinyl chloride are derived from fossil fuels [15], developing selective catalysts to
PUR Polyurethane depolymerize plastics into monomers or building blocks for producing
PTE Polythioester new polymers can be a solution to address plastic waste issues [2].
HHV Higher heating value Depolymerization can aid in reducing plastic waste, but the economic
LHV Lower heating value viability of the pathway should be considered in the long term because
depolymerization has not yet been demonstrated on a large, industrial
scale [2,5].
A final strategy to address the end-of-life issue of packaging plastics
the cell wall of crops (e.g., root). Microplastics in chickens can derive is to use biodegradable polymers such as poly(3-hydroxybutyrate)
from the consumption of earthworms that ingest microplastics. This (PHB), which can result in an environmentally closed circular
poses a serious health threat, the extent of which is unknown [5,7,8]. ecosystem [2]. Some efforts have been made to develop biodegradable
Numerous technologies such as pyrolysis, incineration, and land­ plastics, but the mechanical and other physical properties of these
filling, have been developed to address plastic waste. Additionally, plastics are currently insufficient to completely replace conventional
newer technologies including microwave-assisted conversion, photo­ plastics. For example, PHB has poorer mechanical properties and lower
reforming, compatibilization, and sustainable polymer design are in chemical recyclability (both recycling efficiency and selectivity) than
development [1,2,6,9,10]. Particular technologies are better suited for many commercial polymers such as polyethylene. Therefore, some non-
certain types of polymers or mixtures. The research is ongoing to in­ biodegradable chemically recyclable polymers such as polycarbonates
crease the conversion efficiency (the ratio of the feed consumption (PCs), polyurethanes (PURs), and polyesters are commonly used [2,16].
amount to the total feed amount) and selectivity (the ratio of conversion However, the effect of differing physicochemical properties in plastic
of the feed to a specific product to the overall conversion of the feed). waste streams has not been systematically studied. Overall, the current
Among conventional conversion technologies, landfilling and mechan­ strategies of plastic waste recycling and upcycling have not yet been
ical reprocessing are currently the most common and simplest to thoroughly analyzed to determine the most promising strategies.
implement on a large scale. Landfilling is typically based on anaerobic Considering the complexity of the products to be recycled/upcycled,
degradation of waste (with bottom liner and top soil cover) that can there will not be a single best strategy but rather, a strategy tailored to
generate landfill gas and leachate [11]. However, landfilling has the the specific case.
limitation of space use, emits undesirable gases including CH4 and CO2, This review evaluates current advances and future directions of the
and contaminates the aquifer [12]. Additionally, mechanical reproc­ conversion of plastic waste to high-value products. The novelty and
essing presents a recycling limit issue because the mechanical stability of originality of the present work are a comparison of primary conven­
materials typically decreases with each cycle. Incineration gives rise to tional and emerging conversion strategies, and a concept of designing
environmental issues such as CO2 and toxic pollutant (e.g., dioxin) polymers for subsequent conversion of plastic waste. In particular, this
emissions [9]. work assesses the state-of-the-art of conventional thermochemical
Thermochemical conversion of plastic waste to high-value products upcycling methods such as pyrolysis and gasification, which are of sig­
is a promising technique from environmental and economic perspectives nificant interest with regard to their economic viability, current use in
[9]. Pyrolysis is a type of chemically driven value recovery technique in Europe, and relatively minor environmental impacts. Comparisons
which plastic waste is thermally decomposed at elevated temperatures among various plastic wastes (e.g., PE, PP, polyethylene terephthalate
in an inert atmosphere. Pyrolysis is often combined with in-line catalytic [PET]) and conversion technologies are made. Common reaction
decomposition, in which polymers are thermally decomposed to pro­ mechanisms and catalysts used in the conversion of plastic waste are
duce carbon precursors. This is followed by a chemical vapor deposition examined, as well as their resulting products (i.e., liquid fuel, H2, carbon
pathway, in which a substrate is exposed to volatile precursors that react nanomaterial, lubricant, wax, and composites) and conversion effi­
and/or decompose on the substrate surface, depositing carbon nano­ ciencies. Polymer design and modification for subsequent conversion of
materials. Combining these processes gives the advantages of producing plastic waste are investigated. The main challenges facing the adoption
relatively pure H2 and high value-added carbon nanomaterials [9]. and scale-up of these technologies are discussed. Suggestions for
Gasification is another thermochemical conversion technology in which focusing future research and development are given.
plastic waste is brought to even higher temperatures than those used in
pyrolysis in an oxygen-containing atmosphere. Valuable gas mixtures — 1.1. Plastic waste types and compositions
often referred to as syngas — are produced, which can be used to pro­
duce fuel or can be directly incinerated to produce energy. Gasification Common plastic wastes mainly include PE, polystyrene (PS), poly­
offers wide flexibility in that the composition of the atmosphere or vinyl chloride (PVC), PET, high-density PE (HDPE), and PP. >60% of
gasifying agent can be used to tailor the composition of the product. municipal solid plastic waste is composed of polyolefins, mainly low-
However, it is very sensitive to contaminants. New developments in density PE (LDPE), linear LDPE, HDPE, and PP [15]. Table 1 shows
gasification strategies, such as using utilizing steam or plasma, are being the proximate analysis and properties of different plastic wastes. The

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

Table 1
Proximate analysis and properties of different plastic wastes. A low moisture content (≤0.6%) indicates a fast process of plastic waste drying; a high ash content could
negatively impact the pyrolysis performance; a higher fixed carbon content could typically result in a higher biochar yield during thermochemical processes; high
mechanical strength and chemical resistance of plastic cause difficulty for waste upcycling.
Waste type Moisture Ash (%) Volatile Fixed carbon Other Ref.
(%) (%) (%)

PE 0.17 – 99.8 0.02 Favorable impact strength/chemical resistance/ductility; [17,18]

Effective moisture barrier;
Easily heat sealed
PS 0.45 0.04 99.1 0.39 – [17]
PVC 0.16 – 94.8 5.06 Low cost; [17,19]
Good durability/chemical resistance/machinability
PET 0.38 0.09 90.1 9.43 Superior oxygen barrier/mechanical strength; [17,18]
High modulus/thermal stability (up to 350 ◦ C)
Waste electrical and electronic – 1.9 97.0 1.7 LHV: 37.7 MJ/kg; [20]
equipment (mainly ABS and HIPS) Waste composition (wt%): ABS (64), HIPS (33), PBT (3)
Plastics (PS, PE, PVC, PP, or PET) – 0–0.2 90.4–100 0–9.5 HHV: 20.8–46.5 MJ/kg [21]
Municipal plastic waste 0.6 13.3 85.7 0.4 – [22]
Municipal solid waste – 39.9 49.0 11.1 HHV: 13.4 MJ/kg; [23]
MSW composition (wt%): wood (2.9), paper (8.5), textile (3.2),
plastic (11.2), rubber (0.8), food (55.9), other (17.5)
Municipal solid waste – 7.6 77.5 14.9 MSW composition (wt%): food and fruit (46.4), wood (4.7), paper [24]
(18.2), PVC (30.7)
Fiber waste from paper recycling mill – 5.3–10.8 74.5–85.1 7.5–10.8 HHV: 16.3–28.8 MJ/kg [25]
(containing plastic)
HDPE – – 100 – Calorific value: 38.7 MJ/kg [26]
Combustible solid waste (containing – 7.6 77.5 14.9 Combustible solid waste includes 31 wt% PVC [27]
PVC)
PP 0 0.4 99.6 0 – [28]

Notes: acrylonitrile butadiene styrene (ABS); high-impact polystyrene (HIPS); polybutylene terephthalate (PBT); higher heating value (HHV); lower heating value
(LHV).

Fig. 1. Plastic waste conversion to high-value products. (A) The shredded and sieved municipal plastic waste sample (size range: 1–3 cm). Reproduced with
permission from [22]. Copyright © 2016 Elsevier Ltd. (B) Schematic description of pyrolysis and catalytic decomposition of PP for H2 and carbon nanotubes over Fe/
Ni catalysts (MWCNTs: multi-walled carbon nanotubes). Reproduced with permission from [9]. Copyright © 2020 Elsevier Ltd. (C) Schematic illustration for
converting plastic wastes to C2 fuels by a two-step pathway over a photocatalyst under simulated natural environment conditions: plastic degraded into CO2 by a
photooxidative C–C bond cleavage and the produced CO2 reduced into valuable C2 fuels by a photoinduced C–C bond coupling. Reproduced with permission from
[5]. Copyright © 2020 John Wiley and Sons. (D) Scheme for the PET waste upcycling: PET was chemically hydrolyzed to terephthalic acid and ethylene glycol, which
were converted to higher-value products than PET. Reproduced with permission from [31]. Copyright © 2019 American Chemical Society.

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

moisture content of plastic waste is typically < 1%, but this seemingly conversion performance metrics such as composition and overall yield
low level of moisture is problematic for plastic manufacturing since it of products. Mixed plastic waste containing both degradable and non-
can degrade the polymers significantly. The ash content of plastic waste degradable plastic components presents another challenge. A seem­
typically varies between 0% and 39.9%. Excessive ash in plastic waste ingly infinite number of different polymer structures exist, and even
needs to be removed because a high ash content could have a negative similar structures can exhibit vastly different properties. For example,
impact on the pyrolysis performance based on bio-oil yield. The fixed PE contains secondary carbons that are resistant to oxidation from
carbon content (solid carbon in the material that remains in the biochar exposure to ultraviolet radiation or heat [15]. However, PE, as with
after devolatilization) of plastic waste typically varies between 0% and many commodity polymers, can be engineered to display significantly
32%. Biochar is a carbon-rich porous material that is widely used for different properties with an array of applications all the way from plastic
heat generation and soil remediation. Determining the fixed carbon sandwich bags, bottles, and garbage cans to hip implants. More thor­
content often aids the selection of appropriate conversion pathway and oughly understanding the relationships between a polymer’s chemical
conditions, as it can affect the gasification rate and yield. Additionally, structure/composition and its degradability is important in developing
plastic waste usually has a high volatile content, >48%. The volatile tailored recycling processes.
content may be important for thermochemical processing because the
volatile matter can produce tar, which can be detrimental to reactors. 1.2. Plastic waste recycling and upcycling technologies
The variation in composition of plastic wastes underscores the complex
nature of polymer recycling. Plastic waste recycling encompasses any method in which plastic
Plastic waste is typically cut into small pieces and cleaned to remove waste is reused rather than discarded. Plastic waste is said to be
organic and other impurities from the surface of the material prior to downcycled when it is reused, but the recycled material does not retain
conversions. In one study, HDPE waste collected from city landfills in the properties of the original material. Plastic waste is upcycled, on the
Chennai, India was cut into 0.5–1.0 cm2 pieces [29]. The impurities in other hand, when it can be reused without degrading its value or per­
the obtained plastic chips were removed by repeated washing and formance for the next use. Identifying processes for plastic waste recy­
subsequently dried in an oven, which aided in maximizing the pyrolysis cling and upcycling can help reduce waste buildup in landfills and
yield of bio-oil [29]. Furthermore, washing plastic waste can remove oceans, greenhouse gas emissions, and the dependence on non-
organic residue [14]. Fig. 1A shows a shredded and sieved municipal renewable petroleum resources for polymer production, all while
plastic waste sample (size range: 1–3 cm). The municipal solid waste recovering the economic value of the material [14]. Different plastic
(MSW) collected from a landfill in a further study by Liu et al. [30] was waste recycling and upcycling pathways, shown in Fig. 2, need to be
oven dried at 105 ◦ C for 5 h, and milled. Then, MSW was sieved into applied for specific plastic wastes because of their particular advantages
particles under 200 µm in size and placed in a micro rotary mixer for 2 h and disadvantages. Pyrolysis, incineration, landfilling, and other path­
to homogenize the materials before pyrolysis [30]. The final municipal ways were developed to manage all waste streams. However, plastic
plastic waste size selection depends on the conversion type because an waste is the main waste resource discussed in this review.
optimum feedstock size (e.g., approximately 0.3 cm) can minimize the
heat and mass transfer limitation during the thermal-chemical process. 2. Advances in plastic waste conversion technologies
For example, we have previously [4] found that the biomass feedstock
size had an impact on the bio-oil yield during pyrolysis. The smaller 2.1. Pyrolysis
biomass feedstock (e.g., <0.05 cm) may have a higher heat transfer rate,
causing a lower bio-oil yield because of more thorough breakdown of 2.1.1. Conventional pyrolysis
biomass to gases. The larger biomass feedstock (e.g., >0.4 cm) may have Plastic waste pyrolysis is typically carried out in the absence of ox­
a lower heat transfer rate, causing a lower bio-oil yield because of more ygen at 400–800 ◦ C and atmospheric pressure over various catalysts, as
char generation [4]. shown in Table 3. High temperatures are usually required to carry out
The varied elemental content of different plastic wastes presents a the thermochemical reactions. Maintaining these temperatures during
challenge for converting plastics to high value-added products, as the C/ the entire pyrolysis process is a challenge, so catalysts are typically used
H molar ratio in feedstock significantly affects the pyrolysis yields of for completing the process at lower temperatures [29]. The pyrolysis
products [32]. For example, a higher C/H molar ratio could result in a products mainly contain gas, biochar, and bio-oil. The product yields are
higher biochar yield and a lower tar yield. Balancing the elemental typically in the range of 2–47% of gas, 0–16% of biochar, and 31–91% of
contents of plastic waste by adding in biomass or presorting might be a bio-oil. Bio-oil, being upgraded to jet fuel, can be considered as a high-
solution to resolve this issue. Table 2 shows an ultimate analysis of value product, which is worth more to customers and returns a higher
different wastes, indicating that plastic wastes mainly consist of C, H, O, profit to the owner than a commodity product. Pyrolysis gas used for
and N. The C/H ratio of a material affects the thermochemical heat generation can be considered as a relatively low-value product

Table 2
Analysis of different wastes. The C/H ratio of waste is typically in the range of 5–15, and a high C/H ratio could result in a high biochar yield during pyrolysis. A low O
content might be beneficial for producing hydrocarbons with an easy removal of O. The existence of S indicates H2S might be generated during thermochemical
processes.
Waste type C (%) H (%) O (%) N (%) Other (%) Ref.

PE 86.0 11.2 2.4 0.2 S: 0.2 [17]

PS 86.1 6.3 1.7 0.3 S: 0.2 [17,33]
PVC 38.3 4.5 – 0.2 S: 0.6, Cl: 56.4 [17]
PET 62.9 4.3 32.6 0.04 S: 0.1 [17]
Waste electrical and electronic equipment (mainly ABS and HIPS) 85.3 7.8 0.98 3.4 Cl: 0.02, Br: 0.13 [20]
Plastics (PS, PE, PVC, PP or PET) 38.3–86.1 4.3–12.7 1.9–57.0 0.04–5.7 S: 0–0.1 [21]
Municipal plastic waste 79.8 15.5 2.0 2.8 – [22]
Municipal solid waste 29.9–45.3 4.6–6.1 22.0–39.5 1.3–2.3 S: 0.2–1.5 [23,24]
Fiber waste from paper recycling mill (containing plastic) 47.5–67.0 6.7–11.2 21.6–45.6 – – [25]
HDPE 85.4 14.2 0.15 0.08 – [26]
Combustible solid waste (containing PVC) 45.3 6.1 39.5 1.28 S: 0.23 [27]
PP 86.9 12.5 0.32 0.28 S: 0.03 [28]

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

Fig. 2. Plastic waste conversion strategies. A comparison of primary conventional and emerging strategies for plastic waste recycling and upcycling.

be considered as an optimum reaction temperature range for the py­

Table 3 rolysis of waste. The catalysts (e.g., HZSM-5) with high surface areas can
The product fraction of the pyrolysis of various wastes. Polycyclic aromatic
promote the waste conversion. For example, the use of the HZSM-5
hydrocarbons generated from the pyrolysis of PE may derive from Diels–Alder
catalyst (surface area of > 300 m2/g) can lead to a significant
type reactions [17]. PS is well suited for pyrolysis because of its high bio-oil
yield. Catalysts can help cracking large molecules during pyrolysis, and decrease (~34%) in the decomposition temperature of plastic waste,
HZSM-5 is a promising catalyst for the pyrolysis of plastic waste. which is likely attributed to the cracking reactions facilitated by the acid
sites on the catalyst surface [36]. Pyrolysis of plastic waste (containing
Waste type Catalyst Conditions Main Ref.
product
ABS) over the HZSM-5 catalyst can likely follow a degradation mecha­
yield (%) nism of thermal cracking via a scission of C–C bonds of polystyrene
chains [20].
PE Without 800 ◦ C, heat rate: ~ Gas: 46 [17]
350 ◦ C/min, carrier gas: Bio-oil: ~43 Many researchers have focused on the production of high-quality
N2, fixed bed reactor Biochar: 0 bio-oil from the pyrolysis of plastic waste. The temperature, feedstock,
PS Gas: 6 [17] heating rate, and reaction time all influence the pyrolysis performance.
Bio-oil: ~84
For example, Kalargaris et al. [37] obtained high-quality bio-oil,
Biochar: ~2
PVC Gas: 44 [17] exhibiting similar properties to diesel fuel, via the pyrolysis of mixed
Bio-oil: ~31 plastic waste (mainly styrene butadiene and polyester) at two different
Biochar: temperatures (700 ◦ C and 900 ◦ C). The bio-oil produced at 700 ◦ C
~16 exhibited higher brake thermal efficiency (break power of a heat engine
PET Gas: 47 [17]
regarding the thermal input from the bio-oil) and lower emissions of CO,
Bio-oil: ~38
Biochar: ~5 CO2, and NOx, compared with that produced at 900 ◦ C [37]. LDPE,
Municipal plastic Without 500 ◦ C, 2 bar, heat rate: Gas: 10 [22] HDPE, and PP were used in another study to produce bio-oil via slow
waste 20 ◦ C/min, carrier gas: Bio-oil: 80.5 pyrolysis at 300–400 ◦ C in a semi-batch reactor. This study also found
N2, batch reactor Biochar: 9.5
that changing the pyrolysis temperature directly affected the composi­
550 ◦ C, 2 bar, heat rate: Gas: ~11 [22]
20 ◦ C/min, carrier gas: Bio-oil: 82
tion and properties of the produced bio-oil [38]. The pyrolysis degra­
N2, batch reactor Biochar: ~6 dation mechanism of plastics likely contributes from three general
600 ◦ C, 2 bar, heat rate: Gas: ~12 [22] polymer chain reactions: polymer chain scission, side group, and
20 ◦ C/min, carrier gas: Bio-oil: 84 recombination reactions [38]. Bio-oil produced from the pyrolysis of the
N2, batch reactor Biochar: ~4
mixed plastic waste (PE, PP, PET, PS, PVC, and others) in a further study
Waste electrical Without 400 ◦ C, carrier gas: N2, Gas: 3 [20]
and electronic semi-batch reactor Bio-oil: 86 by Singh et al. exhibited properties similar to those of diesel, and the bio-
equipment Biochar: 11 oil obtained at higher heating rates (20 ◦ C/min) had higher density than
HUSY Gas: 3 [20] that obtained at lower heating rates (10 ◦ C/min) [39]. Miandad et al.
Bio-oil: 83
found that raising the pyrolysis temperature from 400 ◦ C to 450 ◦ C
Biochar: 13
HZSM-5 Gas: 2 [20]
increased the bio-oil yield from PS waste in a small pilot-scale batch
Bio-oil: 91 pyrolysis reactor, and the optimum reaction time to achieve the highest
Biochar: 7 bio-oil yield at 450 ◦ C was 75 min (compared with 60 or 120 min) [40].
Different types of plastic wastes (PS, PP, and PE) were pyrolyzed at
450 ◦ C and 75 min of reaction time, resulting in different bio-oil yields
because of its modest heating value [34]. The composition of the
and qualities [41].
product is affected by various factors including the operation tempera­
Dealing with pyrolysis byproducts is often challenging, as the
ture, pressure, space velocity (a ratio of the gas flow rate to the reactor
byproducts consist of solid and gas phases that are potential to be useful
volume), heating rate, reactor configuration, catalyst property, and
in other applications. For example, biochar, a common byproduct, could
catalyst bed material, among others. For example, 500–600 ◦ C [35] can

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potentially be used to produce activated carbon or carbon nanotubes. hydrocarbons or volatiles to produce carbon nanotubes is the design of
Oginni et al. [42] used biochar (derived from pyrolysis of switchgrass) to appropriate catalysts [9]. The formation mechanism of carbon nano­
produce activated carbon, which exhibited a high surface area of 698 tubes from polypropylene is shown in Fig. 1B. Designing catalysts with
m2/g and total pore volume of 0.6 cm3/g. Hidalgo et al. [43] utilized a sufficient thermal stability is also difficult, as coke (carbonaceous ma­
microwave irradiation technology to convert a mixture of biochar and terial) deposition and metal sintering occur at high operation tempera­
ferrocene to carbon nanotubes. The produced carbon nanotubes tures [9]. Including appropriate promoters (substances added to a
exhibited a high intensity ratio of 1.4, indicating a high degree of wall catalyst to improve its performance in chemical reactions, such as Mg
graphitization and material quality [43]. The gas product mainly con­ and Mo) in the catalyst could prevent coke deposition because of their
sists of H2, CO, CO2, and CH4, but varies significantly as a function of oxygen storage capability and contribution to improving active metal
pyrolysis conditions. The proposed mechanism includes producing CO dispersion.
via decarbonylation reactions, CO2 via decarboxylation reactions, H2 via Co-pyrolysis of biomass and plastic waste is a promising pathway
dehydrogenation reactions, and CH4 via the intergradation of H radical toward efficient plastic recycling, as a possible synergistic effect be­
with CH3 radical [32]. The gas could potentially be used to produce tween the processes can improve the bio-oil’s property and yield [33].
liquid hydrocarbon fuel, natural gas, ethanol, or ethylene (for PE pro­ Co-feeding with plastic is helpful for the biomass pyrolysis toward bio-
duction). We [44] successfully converted biogas (mainly CH4 and CO2) oil quality. Plastic waste is known to have a high hydrogen content.
to H2 and CO, which were then converted to liquid hydrocarbon fuel via Biomass can be added to the mixture to rebalance its C/H ratio and
a novel technology of combining tri-reforming and Fischer-Tropsch increase the process selectivity and overall value of the conversion
synthesis. A preliminary economic analysis of the process of landfill products [33]. In one study, PVC and soybean protein were co-
gas conversion to liquid fuel on a commercial scale indicated that the pyrolyzed, and their interaction accelerated the reaction (the
breakeven cost of diesel generated was estimated as $2.7 per gal if the maximum reaction rate was 12–16% higher compared with calculation
landfill gas was free of cost. Additional credits (e.g., renewable fuel of linear combination of individual pyrolysis results) [48]. Fang et al.
credits) can make this process more economically attractive. This pro­ [49] investigated the co-pyrolysis of MSW and paper mill sludge, finding
cess has been applied by T2C-Energy, LLC, and the pilot-scale test was a significant interaction between the MSW and paper mill sludge at high
demonstrated to be successful in 2019 [44]. temperatures (e.g., 700 ◦ C) that decreased the initial temperature
Some researchers have focused on other high-value products from (compared with paper mill sludge). This interaction was favorable for
plastic waste pyrolysis beyond high-quality bio-oil by combining py­ the pyrolysis process. The study found that a mass ratio of MSW to paper
rolysis with other conversion techniques. For example, pyrolysis has mill sludge at 9:1 was suitable for the co-pyrolysis [49]. Finding a
been combined with subsequent in-line catalytic steam reforming. The suitable mass ratio of plastic waste to other components is crucial to
performance of this combined process has been assessed in the H2 pro­ optimize the co-pyrolysis process. While scaling-up the co-pyrolysis
duction from various plastic wastes such as PP, PE, PET, PS, and their process, finding alternatives to replace valuable nutrients/food sources
mixtures [45]. Yao and Wang [9] used the pyrolysis and in-line catalytic (e.g., soybean protein) to upcycle plastic waste will be critical.
decomposition technique to convert polypropylene to H2 and carbon Furthermore, precise control or selection of the molecular weight of the
nanomaterials using sol–gel-prepared Ni-Fe bimetallic catalysts. These polymers being upcycled might be helpful to improve the products of
catalysts are highly active because of their uniform mesoporous struc­ their following conversion.
ture, high dispersion of active metals, and high reducibility. The ma­ Catalytic cracking (i.e., thermal reduction of the molecular weight of
jority of the carbon nanomaterials obtained from reacting PP over the molecules by a catalyst) can reduce the energy demand for plastic waste
Ni-Fe catalysts were in the form of carbon nanotubes, a high-value upcycling, compared with the cracking without a catalyst. Various cat­
product. One proposed mechanism for the bamboo-like multi-walled alysts including zeolites and other metal oxides have been recently
carbon nanotube formation was vapor–liquid-solid: first, the hydrocar­ explored and developed to improve pyrolysis performance. For example,
bon adsorption and decomposition on the catalyst surface to generate the effect of Ni-Fe bimetallic catalysts on the pyrolysis of the plastic
elementary carbon atoms; second, the dissolution and diffusion of car­ waste was studied in a two-stage fixed bed reactor system [46]. The
bon as liquid metastable carbides; and last, the carbon precipitation to catalyst with more Fe resulted in more deposited carbon and hydrogen.
grow a nanotube [9]. However, the thermal and thermo-catalytic This was attributed to its higher cracking ability and a relatively lower
methods for producing carbonaceous fuels can limit their practical ap­ interaction between the support and active sites. The presence of Ni on
plications because they usually require high temperatures (e.g., up to the catalyst improved the graphitization degree of the produced carbons
400 ◦ C) and precious metal catalysts to improve the product selectivity and the thermal stability [46]. Ni-Co-Al catalysts used in a further study
and narrow the product distribution [5]. significantly improved the syngas production during the conversion of
In another study, clean H2 and high-value carbon nanotubes were plastic waste via a two-stage reactor: the first stage pyrolyzed the plastic,
produced from the pyrolysis of mixed plastic waste (mainly PE and PP), and the second stage consisted of dry reforming of the produced py­
with other byproducts such as a small amount of biochar (~0.1 wt%) rolysis gases [50].
and bio-oil (<15 wt% obtained over catalysts) [46]. Carbon nanotubes Muhammad et al. used zeolite catalysts to pyrolyze plastic waste
are cylindrical graphene sheets capped with spherical fullerene mole­ collected from waste electrical and electronic equipment to produce
cules [47] that exhibit highly desirable properties such as superior gasoline range aromatic bio-oil in a two-stage reactor system [51].
electrical conductivity, thermal stability, and high tensile strength. The While, Miandad et al. used natural and synthetic zeolite catalysts to
potential for converting plastic waste to carbon nanotubes and other pyrolyze various plastic wastes such as PP, PS, PE, and their mixtures to
high value-added carbon nanomaterials (e.g., porous carbon nano­ high-quality liquid bio-oil at 450 ◦ C and 75 min of reaction time [52]. In
sheets) that can uptake CO2 has made these conversion strategies a very these studies, the zeolite catalysts increased the conversion selectivity,
active area of research. Panahi et al. [47] pyrolyzed different polymers resulting in bio-oil of a higher quality than that obtained without cata­
at 800 ◦ C and passed the gaseous intermediates through catalysts to lysts. Different catalysts such as HZSM-5, BNH4ZSM-5, and USY (ultra-
synthesize carbon nanotubes via chemical vapor deposition. The catalyst stable Y zeolite) were used in another study for the pyrolysis of urban
type (stainless-steel wire cloths, including SS-304, SS-316, and SS-316L), plastic waste (mixture of PE and PP) [53]. BNH4ZSM-5 was an excellent
catalyst pretreatment method (acid wash and heating at 800 ◦ C), and pyrolysis catalyst, as its high specific area and pore volume resulted in ~
polymer type (PET, PE, PS, and PP) all influenced the yield and physical 33 wt% of bio-oil and negligible biochar [53]. These studies suggest that
properties of the carbon nanotubes. The SS-316 catalyst with PP poly­ the addition of catalysts, especially Ni-based catalysts, can help improve
mer achieved the highest yield of carbon nanotubes [47]. the plastic waste conversion selectivity. For example, Shi et al. [54]
One major challenge for efficient decomposition of plastic pyrolysis studied the co-pyrolysis of cellulose and PP over MCM-41 and Ni/MCM-

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

41 catalysts. The loading of 25 wt% of Ni effectively modulated the any contaminants in the plastic or mixed plastics can deactivate the
properties of MCM-41, which led to a 36% increase in the relative total catalysts or interfere with their activity. The catalytic activity depends
amount of olefins and aromatics. The high catalytic performance of the on several factors including catalyst characteristics, plastic physico­
Ni/MCM-41 catalyst can be attributed to its proper physical structural chemical properties, and operating conditions. Conversion of plastic
property, high metal dispersion, and strong metal-carrier interaction waste to high-value products will benefit greatly from the development
[54]. of efficient methods to remove contaminants. Additionally, the devel­
Other parameters have also been studied to evaluate the catalyst opment of low-temperature catalysts (e.g., NiFe2O4#SiO2 and Pt-NiMg/
efficiency, such as the feedstock-catalyst contact mode (e.g., in-situ and Ce0.6Zr0.4O2 catalysts) [12] could reduce the high energy consumption
ex-situ) and gas atmosphere (e.g., He and H2). In an in-situ catalytic caused by high operation temperatures. So far, one promising catalyst
pyrolysis, the catalyst is mixed with the feedstock in one reactor; how­ used for plastic waste conversion could be a promoter-added, ZSM-5-
ever, the catalyst is placed in a secondary reactor in an ex-situ catalytic based catalyst; its high specific area and pore volume lead to a high
pyrolysis. A study by Xue et al. [55] found the contact mode and at­ reactivity and efficiency. Of all common commodity plastics, PS is
mosphere to influence the catalytic pyrolysis performance of plastic particularly well suited for pyrolysis because of its high bio-oil yield of
wastes (PET, PE, PS, and PP) as such: the in-situ and ex-situ catalytic 84 wt% [17], as compared with the 43 wt% bio-oil yield of PE.
pyrolysis occurred via different reaction mechanisms, and the H2 carrier Additives are almost inevitable in plastic waste, and researchers have
gas reduced solid residue in comparison to He carrier gas. One proposed investigated their effect on downstream recycling. For example, Yuan
mechanism for catalytic pyrolysis of PS consisted of the steps of primary et al. [61] found that the additive (in the form of ash, 10% in PVC) in the
cracking, chain attack, and cyclization. The free radical mechanism PVC had a minor effect on the final dechlorination efficiency. The
dominated the thermal decomposition of PS [55]. Lee et al. used CO2 as chlorine-containing PVC poses a threat to pyrolysis because highly
a carrier gas for the pyrolysis of PET, which provided a novel pathway to corrosive HCl can be generated under the thermal degradation process
enhance the energy recovery and reduce the acidic byproducts (e.g., [61]. Song et al. [62] investigated that the additive (in the form of iron
benzoic acid) produced in typical pyrolysis in N2 or He carrier gas [56]. oxide) increased H2, CO and CO2 production for the pyrolysis of MSW.
In thermochemical plastic upcycling processes (e.g., pyrolysis and However, more studies on the impact of additives on the downstream
gasification), fixed-bed, batch, and fluidized reactors are most typically upcycling are lacking. Some attempts at commercial plastic waste
used. A fixed-bed reactor is typically a cylindrical tube filled with solid upcycling have not been successful because of the presence of additives.
catalysts with reactants flowing through the bed; a batch reactor is The mechanism on whether some additives deactivate the downstream
typically a closed vessel with an agitator and heating system. A fluidized process catalysts or corrode the process equipment is not clear.
bed reactor is typically a device in which a fluid flows through solid
catalysts at high enough speeds to suspend the catalysts. These reactors 2.1.2. Microwave-assisted pyrolysis
are designed to minimize operational problems such as coke formation Microwaves are usually referred to as electromagnetic waves [63].
and defluidization by incorporating features such as conical spouted or Microwave-assisted heating has some advantages over conventional
fluidized beds [45]. Fixed-bed reactors are easy to assemble and low- heating, such as the capability of non-contact volumetric heating and a
cost. However, coke can deposit inside the rector tube, which may higher energy efficiency [64]. Using microwave absorbents, known as
damage the reactor with time. Pyrolysis of plastic waste is typically susceptors, along with the feedstock during microwave-assisted pyrol­
investigated in a lab scale. For example, pyrolysis of hospital plastic ysis can help reduce the feedstock processing time and improve the
waste (its minority is infectious, different from the plastic waste heating rate. The absorbents need to be high-loss tangent materials that
generated at home) was investigated using different fixed bed reactor convert microwave to heat energy [64]. Microwave-assisted heating can
scales (the sample mass increased from 0.05 g in a thermogravimetric lead to a uniform heat distribution in some specific configurations and
analyzer to 600 g in a bench-scale reactor). Changing the reactor scale with specific feedstocks. For example, Zhu et al. [65] used a microwave
did not cause significant differences in the pyrolysis product distribution cavity structure with a sliding base based on a phase-shifting heating
(lab scale: 70% of bio-oil and 17% of gas produced; bench scale: 83% of strategy to heat a potato with dimensions approximately 60 × 40 × 9
bio-oil and 17% of gas produced) [57]. mm3 (length × width × thickness). The phase-shifting heating strategy
To scale up the pyrolysis process in the future, some researchers have (moving the sliding base) was helpful to solve the problem of non-
conducted the techno-economic assessments. For example, Fivga and uniform heating during microwave-assisted heating. The coefficient of
Dimitriou [58] studied the pyrolysis of plastic waste for heavy fuel variation of the temperature for the potato was calculated as 0.5. When
substitute production. They estimated that for the 10,000 kg/h plant the phase-shifting heating strategy was applied to NaCl, the coefficient
capacity case, the facility needs to operate approximately one year to of variation of the temperature decreased to ~ 0.2 (~60% increase in
recover the capital investment. The fuel production cost can be reduced the uniformity of heat distribution) [65]. Microwave-assisted pyrolysis
when the plastic waste cost decreases [58]. Bora et al. [59] calculated is a new pyrolysis technique, in which microwave energy is transformed
that pyrolysis has a better economic performance than gasification in into heat inside the feedstock particle. Bio-oil is one common product of
terms of total net present value. Pyrolysis has the potential to reduce the microwave-assisted pyrolysis of plastic waste. Fan et al. [66] studied the
environmental impact of plastic waste. The environmental impact cat­ microwave-assisted pyrolysis of LDPE, finding that the obtained bio-oil
egories mainly include climate change, human toxicity, water depletion, contained 96% of gasoline. Rosi et al. [67] observed a rapid increase of
particulate matter formation, natural land transformation, and marine temperature during the microwave-assisted pyrolysis of halogenated
ecotoxicity. Pyrolysis has a lower overall greenhouse gas emission and plastics. The obtained bio-oil had a higher heating value of 41 MJ/kg
better overall environmental performance than incineration and land­ and was suitable for use as a fuel [67].
filling [59]. Gracida-Alvarez et al. [60] investigated that the pyrolysis- Microwave-assisted co-pyrolysis is often used to promote the syner­
based refinery for the conversion of 500 t/day of waste HDPE can gistic effects between plastic components and the other materials or
generate a net present value of $367 million. The low taxes, low discount fillers. For example, researchers [68] found a synergistic effect between
rates, and other positive incentives can help narrow the gap between the bamboo and PP during the microwave-assisted co-pyrolysis process, as
basic research and commercial applications. the resulting mass of bio-oil exceeded the theoretical production mass.
Research carried out on catalytic degradation of PE by Jia et al. [15] Suriapparao et al. [64] also found that the higher heating value of bio-oil
determined that catalytic pyrolysis has disadvantages including a lack of obtained from microwave-assisted co-pyrolysis of PP and rice husk (42
product control and low energy efficiency. Pyrolysis temperatures MJ/kg) was much higher than that of the bio-oil (20 MJ/kg) obtained
typically range from 400 to 800 ◦ C, and the products are complex, from the microwave-assisted pyrolysis of individual biomass sources. In
consisting of bio-oil, hydrocarbon gas, biochar, and wax. Additionally, addition, microwave-assisted co-pyrolysis has been shown to produce

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

bio-oil with a lower acidity and moisture content than those of bio-oil Gasification typically occurs at higher temperatures (≥800 ◦ C) with a
obtained from the microwave-assisted pyrolysis of individual biomass gas carrier containing O2 in partial combustion conditions, resulting in
sources [64]. Microwave-assisted co-pyrolysis of biomass with plastic is gas as the main product. Table 4 shows the conversion performance of
a promising thermochemical pathway to convert mixed waste to bio-oil, various wastes via gasification and other thermo-chemical technologies.
but biomasses and plastics vary significantly regarding their elemental The gasification of plastic waste is typically carried out at the temper­
composition. Fodah et al. [63] also found that the yields of microwave- ature of approximately 850 ◦ C and atmospheric pressure over various
assisted pyrolysis products varied largely, depending on the feedstock catalysts. Gasification of MSW has a high overall efficiency and produces
type and pyrolysis conditions (e.g., heating rate and microwave power). less particulate matter [72]. Different reactors, such as single-staged and
One challenge is the further improvement of the microwave-assisted multi-staged, have been developed for gasification. The multi-staged
conversion process for easy acceptability and affordability. For the mi­
crowave heating mechanism, the electromagnetic energy is converted to
thermal energy. The microwave penetrates into the material and is Table 4
stored as energy, which is then converted to heat inside the material core The conversion of various wastes via gasification and other thermo-chemical
[63]. A broader screening of biomasses and plastics (with different conversion technologies. 800–900 ◦ C is typically used for gasification, and the
physicochemical properties) will contribute to building a database and produced gas mainly contains H2, CO, and CH4.
optimize the microwave-assisted co-pyrolysis process. Waste type Catalyst Conditions Main Ref.
The heating characteristics of microwave-assisted pyrolysis may lead product
yield
to a narrower product distribution. Fan et al. [66] studied the ex-situ
catalytic cracking of vapors from microwave-assisted pyrolysis of Municipal solid Without 850 ◦ C, MSW feed of 4.4 Gas: 1.1 [75]
LDPE. Compared with in-situ catalytic cracking, ex-situ catalytic waste g/min, downdraft fixed- Nm3/kg
bed gasifier
cracking has some advantages: the pyrolysis and catalytic cracking
Municipal solid Without 750 ◦ C, MSW feed of 25 Gas: ~1.5 [76]
temperatures can be individually regulated, the vapors likely have more waste kg/h, steam gasification, Nm3/kg
contact with the catalyst, and there is no need to separate the catalyst fluidized bed reactor
from the biochar produced (the catalyst can be regenerated for reuse). Plastic waste Without 900 ◦ C, in-situ gasification CO2: 97% [77]
chemical looping
LDPE has poor dielectric properties, which makes it a poor absorber of
combustion
microwave. Microwave absorbents can be added (mixed with LDPE) to MSW with Without Plasma gasification, H2: 61% [78]
increase the efficiency of microwave pyrolysis. In theory, bio-oil from plastic solid plasma gasifier CO: 32%
pyrolysis of LDPE should exhibit no acid, no water, and a high calorific waste CO2: 7%
value owing to the absence of oxygen during the pyrolysis conversion Pinewood with Without 900 ◦ C, steam gasification, Gas: ~51 g [79]
PP semi-batch reactor
process. The crude bio-oil is typically further upgraded via a catalytic
Pinewood with Without 900 ◦ C, steam gasification, Gas: ~46 g [79]
process to enhance its selectivity and narrow the resulting product dis­ PET semi-batch reactor
tribution for valuable chemical products. Fan et al. investigated the ef­ Artificial waste Without 900 ◦ C, fluidized-bed Gas: 0.7 [80]
fects of the pyrolysis temperature (350–550 ◦ C), catalytic reaction gasifier Nm3/kg
Waste electric Without 429 ◦ C, carrier gas: N2, Gas: 10% [67]
temperature (350–550 ◦ C), and catalyst to reactant ratio (0–0.1) on the
and 2.45 GHz, absorber: Bio-oil:
yield and chemical profile of products. A higher catalyst to reactant electronic carbon, microwave 64%
ratio, pyrolysis temperature, and catalytic reaction temperature favored equipment multimode reactor Biochar:
gas production. The coke yield ranged from 0.1 to 1.9 wt% based on the 26%
reactant mass [66]. This indicates that catalysts need further exploration Mixed wood Without Biomass/polymer mass Gas: 28% [64]
sawdust and ratio of 1:1, 450 W, Bio-oil:
(e.g., adding promoter Mg to reduce the carbon deposition due to oxy­
PS microwave-assisted co- 59%
gen storage capability) [69] to minimize coke generation to further pyrolysis Biochar:
improve the catalytic performance during microwave-assisted pyrolysis 13%
or co-pyrolysis. Rice husk and Without Biomass/polymer mass Gas: 35% [64]
PP ratio of 1:1, 450 W, Bio-oil:
Along with bio-oil, other products are produced from the microwave-
microwave-assisted co- 41%
assisted conversion of plastic waste as well. For example, porous sulfo­ pyrolysis Biochar:
nated carbon has been produced from LDPE plastic via sulfuric acid 24%
soaking through the microwave process [70]. Lithium-sulfur batteries MSW with coal Coal char 550 ◦ C (pyrolysis), 800 ◦ C Gas: 1.6 [81]
have high energy density and have been explored as next-generation (oxidation), 800 ◦ C Nm3/kg
(reduction), waste feed of
batteries. A porous sulfonated carbon layer can be used as an inter­
1.3 g/min, three-stage co-
layer in lithium-sulfur batteries to improve the sulfur cathode capacity. gasification, tubular
This technique of functionalizing the LDPE plastic via microwave reactor
treatment can be extended to other polymers, unlike the pyrolysis of PE CaO 800 ◦ C, air gasification, H2: 38% [82]
biomass waste to produce carbon materials [70]. In another study, ter­ bench-scale fixed reactor CO: 34%
CH4: 4%
ephthalic acid was produced from the depolymerization of PET waste CO2: 24%
via microwave-assisted neutral hydrolysis, a chemical process of Coconut shell Nickel and 870 ◦ C, steam gasification, Gas: 571 [83]
decomposition performed under neutral conditions (not alkaline or mixed with dolomite fluidized and fixed bed g/kg
acidic conditions). 2-pyrone-4, 6-dicarboxylic acid, a valuable monomer HDPE waste gasifiers
LDPE MgO 2.45 GHz, microwave- Gas: [66]
used to synthesize biodegradable polymers, was then produced from
assisted pyrolysis 25–73%
terephthalic acid via a comprehensive chemo-microbial hybrid process Bio-oil:
[71]. These studies prove microwaves can be utilized not only in py­ 24–39%
rolysis, but also in neutral hydrolysis, based on the desired products such Biochar:
as bio-oil, porous carbon, and monomers. 1–50%
Bamboo and PP HZSM-5 250 ◦ C, feedstock/catalyst Gas: [68]
ratio of 2:1, bamboo/PP ~34%
2.2. Gasification ratio of 1:2, 1,000 W, 2.45 Bio-oil:
GHz, microwave-assisted 62%
2.2.1. Conventional gasification co-pyrolysis Biochar:
3%
A second conversion technology, gasification, differs from pyrolysis.

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

gasification allows the reactions to be optimized individually under gaseous molecules or atoms are in the ionized form [86]. Plasma can
appropriate operating conditions [73]. The primary challenge facing enable charged particles to interact with neighboring particles. A plasma
gasification of waste is that it is intrinsically related to the physico­ gasification facility can be based on a gasification reactor with a plasma
chemical properties of the input material, making it very sensitive to torch and plasma cupola [86]. Compared with conventional gasifica­
impurities or contaminants [74]. The oxidizing agent used in gasifica­ tion, thermal plasma gasification has some advantages such as higher
tion is usually oxygen, air, or steam [59]. Using air as an agent can cause syngas yield, lower tar content, and more efficient energy use [87].
a high N2 content in the gas product, which dilutes the energy content Plasma processing can lead to high energy density and high reaction
and limits the application of the gas product. When steam is used as an temperature (e.g., >1,000 ◦ C), which can promote the interactions be­
agent, the reactions during gasification can include steam reforming, tween excited ions and particles [87].
water–gas shift, and Boudouard reactions [59]. Different approaches Yayalik et al. [88] studied the plasma gasification of MSW and pro­
such as steam and plasma have been developed to aid gasification by posed some reaction pathways. For example, the decomposition of MSW
providing control of moisture content and a more efficient method of generates CO, H2, CO2, H2O, and C. The formation reactions mainly
heating, respectively. The gasification product mainly contains gas in include: C reacting with H2O to produce CO and H2, and C reacting with
the form of H2, CO, and CH4. However, the gas yield can vary largely CO2 to produce CO [88]. A two-stage fluid bed gasification-plasma
from 10 to 73% (other products are biochar and bio-oil) depending on process was used for the gasification of refuse derived fuel (containing
the gasification conditions (e.g., reaction temperature, reactor configu­ plastic), finding that plasma is helpful to remove tar and purify syngas
ration) and waste feed types. [74]. Tar can block reactor pipes and can be considered as a relatively
Syngas, a valuable product, is a mixture of H2 and CO that is used for low-value product. In another study, air and steam plasma gasification
liquid fuels and chemicals. When syngas is desired as a primary product of household waste containing approximately 5 wt% of plastic was
from gasification, its yield and composition are crucial and can be performed in a plasma reactor [13]. Calculations showed that the air and
adjusted through different process parameters. The effect of changing steam plasma gasification of household waste can produce a high-
the equivalence ratio (ratio of the actual to stoichiometric fuel/air ratio; calorific syngas with concentrations of 82 and 95 vol%, respectively.
0.2–0.8), reaction temperature (550–850 ◦ C), and moisture content Household waste often contains toxic substances, which are difficult to
(9–52%) during MSW gasification was investigated in a fluidized bed treat. However, plasma gasification reliably destroys highly toxic furans,
reactor [84]. The syngas yield increased with an increase in the equiv­ dioxins, and benzo(a)pyrene, all substances that cannot be destroyed
alence ratio, and a higher temperature broadened the syngas mass dis­ through conventional incineration [13].
tribution. The H2 production yield was promoted, but the energy Supercritical water has also emerged as a candidate for converting
conversion efficiency was inhibited with an increase in moisture content plastic waste through gasification. For the supercritical water gasifica­
at 650 ◦ C. The appropriate MSW moisture content for gasification was tion, supercritical water serves as a solvent to facilitate a homogeneous
found to be < 20% [84]. In another study, the presence of NiO modified reaction [89]. In addition, supercritical water serves as a catalyst to
dolomite catalysts increased the gas yield dramatically, and the H2 improve the reaction rate, attributed to the H-radicals at high temper­
content increased up to 40% during the gasification of MSW [72]. To atures and high ion production near critical points. Furthermore, su­
assist the gasification technology development, mathematical models percritical water can tolerate wet plastic waste without a drying
such as computational fluid dynamics simulations can be developed, pretreatment, and can reduce the coking in the reaction. In a quartz tube
which could aid in linking the gasification process and related param­ reactor, the amount of water added is determined by the reaction
eters with its resulting products [72]. pressure, reaction temperature, and tube volume [89]. One proposed
For the techno-economic assessments of the gasification process, Ng mechanism for H2 formation is mainly from the CO formation, followed
and Phan [85] reported that using gasification (producing H2) can by the water–gas shift reaction [90]. In one study, the supercritical
potentially save $2.26 million per year on waste disposal cost while water gasification of refuse derived fuel was performed in a batch
diverting it from landfills. A large gasification system (e.g., >100 dry t/h reactor at 450 ◦ C with RuO2/r-Al2O3 catalysts, finding that the carbon
of waste) is ideal to be competitive with the production cost of H2 gasification efficiency was ~ 98% (compared with the non-catalytic test,
generated from conventional fossil-based systems [85]. Bora et al. [59] ~42%). When other components of MSW such as waste textile and waste
found that the fast pyrolysis and gasification of PP waste can generate wood were gasified, the reactivity of the feedstock depended on its
total net present values of $149 million and $96 million, respectively. composition because the produced gas composition varied largely [90].
The waste price, discount rate, and plant life are the most critical factors Peng et al. [91] proposed a supercritical water gasification mechanism
for the economic performance of the thermochemical systems. For of polymer-containing oily sludge. The reaction pathways included py­
example, when the discount rate increases from 10% to 15%, the total rolytic reaction of polymer-containing oily sludge, steam reforming re­
net present value of gasification decreases from $96 million to ~$9 action, coking reaction, water–gas shift reaction, and methanation
million [59]. reaction [91].
Catalyst deactivation is a concern during gasification of plastic
waste, which is largely a result of contamination of the feedstock sour­ 2.3. Other conventional conversion technologies
ces. Developing methods (e.g., presorting and cleaning) to effectively
remove the contamination from plastic waste before gasification will be Compared with pyrolysis and gasification, incineration of MSW has a
important to preserve the catalyst activity. Additionally, utilizing the greater environmental impact resulting from CO2 and particulate matter
gaseous products of gasification such as H2 and CO for liquid fuel pro­ emissions [92]. Incineration is an exothermic process that involves the
duction via Fischer-Tropsch synthesis, while utilizing solid products combustion of waste. The discharge of the flue gas and ash can cause
such as biochar for carbon nanotube production (previously discussed) heat loss [92]. However, the incineration of MSW can be improved by
at the same time can be a promising pathway to augment the value and more sufficient utilization of the byproducts [93]. Modern incineration
implementation of gasification strategies for upcycling plastic waste. equipment, designed with effective flue gas cleaning, ash recycling, and
use of combined power and heat cycles, can benefit in the area of
2.2.2. Plasma- and supercritical water-assisted gasification environmental sustainability [92]. Improving the energy efficiency,
In addition to microwaves, plasma and supercritical water have been efficiently managing the residues, enhancing the plastic waste quality (e.
used to assist existing technologies to upcycle plastic waste. In plasma g., presorting and cleaning) [92], and developing new plastic waste
gasification, the heat is provided from thermal plasma that typically collection technologies are promising pathways for future expansion
derives from direct current non-transferred arc plasma torches [78]. and adoption of incineration as a plastic recycling technique.
Plasma is known as the fourth state of matter, in which part of the Mechanical reprocessing, including precleaning sorting and melt

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

extrusion, can be used to remanufacture plastic waste [47]. Mechanical future.

reprocessing mainly consists of shredding, melting, and remolding
plastic [14]. However, there are some limitations to mechanical 2.4. Emerging conversion technologies
reprocessing. For example, thermosets cannot be reprocessed via con­
ventional mechanical reprocessing methods [14]. Additionally, me­ 2.4.1. Photoreforming
chanical reprocessing of plastic waste typically produces lower-value Another promising recycling technology is photoreforming, a simple
products with degraded properties [1]. Physical presorting of compo­ and low-energy method to convert plastic waste to H2 or other chemicals
nents for mixed plastic waste streams prior to mechanical reprocessing is such as acetic acid (CH3COOH) using sunlight, water, and a photo­
necessary but comes at a high cost [18]. Contamination from unwanted catalyst [6]. Photoreforming of plastic waste under mild conditions (e.
polymers and fillers is another challenge in mechanical reprocessing [1]. g., ambient temperature and pressure) typically results in a low selec­
The development of decontamination technologies for fast cleaning of tivity and product yield, but recent research has begun to address this
the plastic waste and efficient presorting of the plastic mixtures will issue. In one study, plastic waste (e.g., PET, polylactic acid [PLA], and
significantly increase the yield of high-purity polymers [14]. A potential polyester microfibers) was successfully photo-reformed to H2 and other
pathway being explored by some researchers for plastic presorting uses chemicals at ambient temperature over CNx/Ni2P catalysts, which are
the melting points of plastics to presort thermosets and thermoplastics. inexpensive and nontoxic [99]. Ambient-temperature photoreforming is
This concept and other improvements to mechanical recycling warrant a simple and low-energy technology, but it has only been performed on
future study. very small scales. Uekert et al. were able to upscale the process from 2 to
Conventional incineration of plastic waste has higher CO2 emissions 120 mL, but were unable to produce larger yields [99]. In another study,
than mechanical recycling [94]. Incineration of plastic waste emits CO2, visible light–driven oxygenation of C–C bonds of PE (which is non-
but some of the embodied energy of the MSW can be recovered. As with biodegradable) was conducted to produce fuels and chemicals over a
other recycling methods, high costs are involved in collection, separa­ vanadium photocatalyst under mild conditions. This methodology could
tion, sorting and recycling for mechanical melting recycling [94]. be used to recycle a broader range of polymers as well [100]. PE has also
Different polymer molecular weights and phase separation can inhibit been completely photodegraded via C–C cleavage into CO2, which can
the interfacial adhesion of plastic mixtures, which is detrimental to their be further photo-reduced to C2 fuel such as acetic acid via C–C coupling
mechanical performance. Incineration is inexpensive and convenient for over Nb2O5 photocatalysts at the conditions of natural environ­
mixed plastic waste since it can avoid the need for presorting. However, ments—atmospheric pressure, room temperature, water, air, and
starting components cannot be recovered and reused once burned [14]. simulated one-sun irradiation—as shown in Fig. 1C [5]. Based on the
Incineration can be utilized when the mixed plastic waste cannot be above proposed photoconversion mechanism, this technology can
sorted or other recycling methods are too expensive. highly selectively convert various plastic wastes (PE, PVC, and PP) to C2
Landfilling has been widely utilized as a method to store plastic fuels. However, the current acetic acid yield from this process is rela­
wastes. The waste degradation process in a bioreactor landfill is tively low, at ~ 0.1 mg/gcat (gcat refers to grams of catalyst). Designing
microbially accomplished to achieve an extensive and fast stabilization two-component photocatalysts (one for C–C cleavage and the other one
of waste [11]. The recirculation of the collected leachate mainly con­ for C–C coupling) could increase the yield [5]. In addition, other new
tributes to this process [11]. Large amounts of plastic waste go to technologies such as 3D printing can be applied to synthesize custom­
landfills globally, but space availability and environmental pollution are ized photocatalysts (with better heat/mass transfer) to improve the CO2
significant issues in landfilling [47]. Most plastics are chemically stable reduction efficiency. The photoreforming system needs to be upscaled
and durable, and as previously discussed will not fully degrade for further (e.g., much>120 mL) to be a viable conversion technology for
hundreds of years. However, some plastics do have components that global plastic waste. 3D printing technology is a class of computer-aided
break down quickly which can lead to air, soil and aquifer pollution manufacturing, facilitating the production of parts with complicated
from placing their waste in a landfill [47]; microplastics become a huge geometries [4,101]. For example, Thakkar et al. [102] 3D-printed
issue because they end up in human food chain. The landfill gas for­ zeolite monolith catalysts (outside diameter ~ 8 mm) for CO2 removal
mation involves a variety of reactions such as hydrolysis, aerobic and from an enclosed environment.
anaerobic digestion, fermentation, and methanogenesis [95]. To reduce >50 million tons of H2 are produced worldwide each year for use in
harmful gas emissions, we [12,44] demonstrated conversion of landfill pharmaceutical, chemical, and agricultural industries. 96% of the H2
gas from landfills to liquid fuels. This conversion of landfill gas to liquid supply in the world is generated through the reforming of fossil fuels [6].
fuels is a highly promising technology (integration of tri-reforming and Plastic waste pyrolysis into H2 requires a high energy input and releases
Fischer-Tropsch synthesis) for expansion and commercialization. large amounts of greenhouse gases (approximately 12 g CO2 per 1 g H2)
Biochemical conversion such as anaerobic digestion of biodegrad­ [6]. Therefore, photoreforming has become a potential alternative to
able plastic waste via micro-organisms has emerged as another prom­ convert plastic waste to H2 for industrial use. In one study, three
ising technology for upcycling [47]. For example, researchers [96] commonly used polymers – PLA, PET, and PUR – were successfully
reported that wax-worm caterpillars may degrade PE into ethylene photo-reformed to produce H2 over inexpensive CdS/CdOx quantum
glycol, a chemical which could be upcycled into the supply chains for dots catalysts at ambient pressure and temperature [6]. Other polymers,
producing polyester fibers and antifreeze, although the exact degrada­ such as polyethylene glycol, PVC, polyvinyl pyrrolidone, PS, PE, poly­
tion mechanism and products are still being uncovered. Other re­ methyl methacrylate and PC, have also been photo-reformed to produce
searchers [97] indicated that the gut bacterium of mealworms can H2. Furthermore, PET water bottles were photo-reformed into H2.
consume polystyrene to produce CO2 and other products. Researchers Plastic waste is a freely available substrate, but challenges for its pho­
[98] have also developed bacteria that degrades low- or high- toreforming include its low water solubility, complex structure, and
crystallinity PET into CO2 or even into its monomers. The PET hydro­ general non-biodegradability [6].
lysis reaction took place in this process [98]. Although biochemical
conversion is an exciting upcycling technology with high potential, this 2.4.2. Other emerging conversion technologies
type of polymer degradation has significant limitations. The process is Numerous other technologies have been developed to convert plastic
currently very costly and time-consuming. Additionally, biochemical wastes. For example, hydrogenolysis (a chemical reaction in which a
conversion can produce small-chain polymers or microplastics which carbon–carbon or carbon–heteroatom single bond is cleaved by H2) has
can cause significant harm to aquatic life. Limiting or reducing the cost, been used to convert plastic waste (such as polyesters and PCs) to value-
speed, and harmful byproducts of biochemical conversion of plastic added diols over a molecular ruthenium catalyst [103]. Glycolysis (a
waste is crucial to make it a viable technology for widespread use in the process that degrades polymers by glycols) has been used to convert PET

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

to bis(2-hydroxyethyl)terephthalate over the Fe3O4@SiO2@(mim) high temperatures (2,200–2,500 ◦ C). In addition, graphene foil can act
[FeCl4] catalyst, which provided nearly 100% yield and selectivity as various flexible components in a lithium-ion battery, which opens
[104]. Chemical hydrolysis was utilized in one study to convert PET new application possibilities for graphene in a variety of fields [112].
waste to two monomers (terephthalic acid and ethylene glycol), which This technology has also shown the ability to produce carbon nanotubes
were then converted to higher-value products than PET, as shown in from plastic wastes, as discussed previously.
Fig. 1D [31]. A two-step method (methanolysis and hydro­ The treatment of PVC waste is particularly challenging [19]. In
deoxygenation) was used in a further study to convert PC waste to jet thermal treatments such as pyrolysis and gasification, the chlorine in
fuel range high density polycycloalkanes under mild conditions [105]. PVC is converted to large quantities of HCl that can cause serious
The gasoline and jet fuel range C7–C8 aromatics and cycloalkanes were corrosion to process equipment at a wide range of temperatures. Based
produced by the alcoholysis of the PET waste (methanol is highly on these issues, PVC was used as a hydrogen source by Lu et al. to reduce
reactive for the alcoholysis of PET), followed by solvent-free hydroge­ hydrogen carbonate to formate under hydrothermal conditions via a
nation and hydrodeoxygenation [106]. green approach. The authors found that PVC could be completely
A catalytic processing of polyoxymethylene polymer waste com­ dechlorinated at 300 ◦ C [19]. This research suggests that PVC is not
bined with biomass-derived diols was conducted at low temperatures (e. suitable for pyrolysis but can be utilized via other processes such as
g., 100 ◦ C) by Beydoun and Klankermayer to produce value-added cyclic dichlorination.
acetals, as shown in Fig. 3A. Cyclic acetals can be applied as fuel addi­ The chemical inertness of PE owing to its strong single C–H and C–C
tives, solvents, pharmaceutical intermediates, and monomers for poly­ bonds makes it difficult to degrade through low-energy processes [15].
merization reactions [107]. PET was upcycled by researchers in Therefore, researchers developed a tandem catalytic cross alkane
combination with a bio-based monomer into higher-value and long- metathesis method to efficiently degrade PE to liquid fuels and waxes
lifetime composites (e.g., fiber reinforced plastic) [108]. The growing under mild conditions, as shown in Fig. 3B with a proposed degradation
market size and high selling price of fiber reinforced plastics make them mechanism. Alkane metathesis is a technology in which alkanes are
ideal applications in which to use bio-based, sustainably sourced rearranged covalently to create products with a new distribution of al­
monomers [108]. Additionally, commodity polymer waste, bisphenol A kanes. Readily available and inexpensive light alkanes (e.g., petroleum
based polycarbonate, has been upcycled via an organocatalytic depo­ ether) were used as the reagents in this study. This method exhibited
lymerization procedure into high-value added functionalized cyclic superior selectivity for linear alkane formation and allowed for different
carbonate. Cyclic carbonate is an attractive monomer also used to syn­ types of PEs with a variety of molecular weights to be completely con­
thesize PURs or PCs for various applications [109]. A proposed mech­ verted to liquid fuels and waxes. The distribution of these products can
anism for this depolymerization is the ring-closure of the carbonate be controlled by the reaction time and catalyst structure. The catalyst is
[109]. These emerging technologies showcase researchers’ great inter­ compatible with various polyolefin additives, indicating common plastic
est in the upcycling of plastic wastes. waste, such as PE bags, bottles, and films, can be converted to high-value
Recently, researchers from Rice University [111] has developed a chemicals without any pretreatment [15]. In the future, the governing
flash graphene technology to convert plastic waste to graphene that process mechanism needs further study to apply it to the degradation of
exhibited turbostratic arrangement between the stacked graphene other polymers such as PVC and polyoxymethylene.
layers. Flash graphene technology is a flash Joule heating process in
which amorphous conductive carbon powders are compressed inside a
ceramic or quartz tube between two electrodes. High-voltage electric 2.5. Summary of conventional and emerging conversion technology
discharge can bring the carbon source to temperatures higher than
2,500 ◦ C in<100 ms, converting the amorphous carbon to flash gra­ Based on all the discussed plastic waste conversion technologies
phene [111]. In another study, a solid-state chemical vapor deposition (conventional and emerging), co-pyrolysis of plastic waste and biomass
method was used to convert plastic waste (PET, PVC, PE, PS, PP, and is a promising technology to achieve products with high quality and
polymethylmethacrylate) to graphene foil at a large scale [112]. The yield. Photoreforming is currently an emerging technology that can
obtained graphene foil exhibited a much higher electrical conductivity convert plastic waste to H2 and chemicals under mild conditions, but the
than conventional free-standing graphene film obtained at extremely process should be scaled up. Designing polymers that can easily be
modified and recycled in the future is also critical to recover value from

Fig. 3. Some emerging technologies for

plastic waste conversion. (A) An efficient
pathway for upcycling the polyoxymethylene
plastic in combination with biomass-derived
diols into versatile cyclic acetals. Repro­
duced with permission from [107]. Copy­
right © 2020 John Wiley and Sons. (B)
Proposed degradation of PE through cross-
alkane metathesis with light alkanes (e.g.,
n-hexane). Dehydrogenation of PE and light
alkane generates unsaturated olefins. Cross
olefin metathesis followed by hydrogenation
results in breakdown of PE chain into shorter
chains. Repeating the tandem reaction in
multiple cycles degrades PE into short al­
kanes appropriate for transportation fuel use.
Reproduced with permission from [15].
Copyright © 2016 American Association for
the Advancement of Science. https://doi.org/10.1126/sciadv.1501591. Further permission related to the material excerpted should be directed to the American
Association for the Advancement of Science. (C) Strategies for reprocessing and increasing the molecular weight of PLA, which provide a route toward closed-loop
recycling of liquid crystalline polymer-reinforced composites. The PLA phase can be chemically recycled for many times without loss of mechanical properties.
Reproduced with permission from [110]. Copyright © 2019 American Chemical Society. https://pubs.acs.org/doi/10.1021/acssuschemeng.9b06305. Further
permission related to the material excerpted should be directed to the American Chemical Society.

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

plastic wastes. Strategies for simplifying processing and integrating molecular weight of polymer PLA, as shown in Fig. 3C. Christensen et al.
upcycled products into existing supply chains for industries, as well as [115] found that plastics polymerized via dynamic (reversible) covalent
the potential demand for upcycled products, all warrant further study. diketoenamine bonds can be used to recover the monomers from com­
Additionally, the cost involved in energy consumption, presorting of mon additives, even in mixed plastic waste streams. Recovered mono­
plastic mixtures, chemical additives, and product separation should be mers can subsequently be used to produce the same polymer
considered and analyzed in future studies. For example, phenolic com­ formulation with the same performance as well as other polymer for­
pounds are valuable chemicals, but separating them from bio-oil is an mulations with differentiated properties. This poly(diketoenamine)
expensive process [113]. A gas purification process is typically used plastic can be produced, used, recycled, and re-used without a loss of
after the gasification to clean the syngas generated. AlMohamadi [114] value. Such a closed-loop polymer life cycle is crucial to sustainability
studied the steam gasification of MSW for gasoline production. The efforts. These dynamic covalent polymers have the potential to replace
plant’s capital investment was largely affected by the MSW pretreat­ non-recyclable thermoset materials [115].
ment, gas purification ($26 million cost), and steam cycle. A vitrimerization approach [117] has also been used to reprocess
All the described technologies are highly beneficial for the envi­ thermoset waste such as polyurethanes via dynamic chemistry. In vit­
ronment because they can reduce plastic waste, but the environmental rimerization, permanent networks are changed to dynamic ones over an
impact (e.g., gas product emission and compatibilizer synthesis) appropriate catalyst solution, which turns them into vitrimers. This
involved in those processes also needs to be controlled and minimized. process has two requirements: a solvent for swelling the thermoset waste
The distributed nature of plastic waste presents a major challenge as and a catalyst that is either miscible or soluble in the solvent for facili­
well, as it has led to small-scale, sparse conversion infrastructure. tating the dynamic reactions. Transesterification reactions allow dy­
Finally, various states in the United States having different balances namic bond exchange between hydroxyl and ester groups within the
between sustainable and fossil fuel energy can influence the decision thermoset network. Yue et al. found that even though the mechanical
making in funding research and the construction or expansion of recy­ performance of the reprocessed PUR was diminished, adding carbon
cling facilities. Regarding future plastic waste management, the inte­ nanostructures to the newly formed vitrimer (vitrimerized PUR) allowed
gration of multiple technologies is promising. For example, co-pyrolysis it to resemble or even exceed the properties of the original material. By
of plastic waste and biomass residue can be applied to produce bio-oil, optimizing parameters of the vitrimerization process such as the catalyst
biochar, and gas. Fossil fuel-based plastics can be replaced with bio- species, catalyst concentration, and temperature, this methodology
based ones for contributing to the environmental sustainability. Bio-oil could be very promising for the upcycling of thermoset waste [117]. The
can be upgraded to transportation fuel over Ni-based zeolite catalysts. described research indicates that polymer properties can be maintained
Biochar can be used to generate carbon nanotube via microwave irra­ during mechanical reprocessing when combined with chemical strate­
diation technology. Gas can be converted to syngas via a methane gies such as vitrimerization and maintenance of a polymer’s molecular
reforming technology, which is then converted via Fischer-Tropsch weight (via solid state post condensation or depolymerization/
synthesis to liquid hydrocarbon fuel. polymerization).
Ring-opening polymerization/depolymerization of biosourced poly­
3. Polymer design and modification for subsequent conversion thioesters (PTEs) has the potential to produce high-value materials, such
of plastic waste as self-immolative polymers, optical/photochemical plastics, and
degradable biomaterials, which can be easily reused [118]. The design
Chemically recyclable polymers have been designed and developed of sustainable or “green” polymers has received much attention in recent
in recent years as a method to manage plastic at the end of its usable life. years, particularly because of their renewable feedstock/monomers,
Mechanical reprocessing, as described previously, can degrade the high recyclability, material durability, and/or cost-effective synthesis
polymer’s quality and cause residual impurities after multiple cycles of under environmental-friendly conditions. However, manifesting all
reuse [115]. However, chemical recycling can recover the precursor these qualities in a single polymer is difficult. Extreme conditions and
building blocks via depolymerization [116]. Nevertheless, polymers that expensive catalysts are usually required in the monomer-polymer-
can be selectively and easily depolymerized back to monomers usually monomer processing cycle, which can cause a low depolymerization
require low-temperature (e.g., –40 ◦ C) polymerization pathways and selectivity. Ring-opening polymerization and depolymerization of PTEs
lack the mechanical/physical properties required for practical use. under mild conditions has been a recent breakthrough in this field so far.
Additionally, the depolymerization of chemically recyclable polymers PTEs can be easily polymerized and recycled because of their suscepti­
typically has low selectivity, meaning depolymerization can produce a bility to nucleophiles. However, further improvement to optimize
mixture of many products which require substantial separation and thermolysis and reduce cost (e.g., developing renewable bio-based cat­
purification. This low selectivity makes it difficult to attain a circular alysts) is needed for the commercialization of PTEs [118].
monomer-polymer-monomer cycle in which a polymer can be depoly­ Another major challenge for upcycling mixed plastic waste is that
merized and subsequently polymerized to the original product. There many plastics are immiscible with each other, leading to phase sepa­
are also often trade-offs between a polymer’s ability to depolymerize rated materials with degraded properties [14]. Even a small amount of
and its properties. This means that chemically recyclable polymers often contamination of another type of plastic can drastically change the
suffer poor performance and are not as widely useful as many virgin (or properties of the recycled materials. The compatibilization of mixed
chemically non-recyclable) polymers [116]. Furthermore, monomer plastics can prevent the need for presorting, and a compatibilizer can
recovery is usually costly, energy-intensive, and incompatible with control the phase behavior of the polymer mixture. A compatibilizer is
complex mixtures. Depolymerizing plastics in a short reaction time at similar to surfactants developed for stabilizing immiscible water/oil
low temperatures and with high tolerance to additives is challenging mixtures. Compatibilizers can also be tailored to a given plastic waste
[115]. However, these challenges have inspired researchers to look for composition. In the future, advanced computational modeling and data
possible solutions. analysis for developing novel compatibilizers, catalysts, and polymers
To overcome some of the obstacles in the development of chemically will be helpful for upcycling polymer mixtures [14]. Particularly,
recyclable polymers, Zhu et al. [116] designed a polymer system based developing a few common compatibilizers for a wide range of plastic
on γ-butyrolactone via a trans-ring fusion with repeatable chemical mixtures would be of significant interest, as mixed plastic waste with
recyclability, and the polymer can be synthesized at room temperature different compositions currently requires different compatibilizers.
under solvent-free conditions. Kort et al. [110] developed liquid crys­ Finally, providing more education to the public on the importance of
talline polymer-PLA composites that can be recycled several times waste sorting and good recycling practices will help tremendously in
without a decrease in mechanical properties via maintaining the addressing mixed plastic waste in the future.

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X. Zhao et al. Chemical Engineering Journal 428 (2022) 131928

Numerous different multiblock copolymers have been developed appropriately to reduce the interfacial energy and improve the interfa­
recently for use in compatibilization of mixed plastic waste. For cial adhesion between immiscible polymer blends [18]. Some multi­
example, a multiblock copolymer was synthesized by Eagan et al. [10] block copolymers such as PE-PLA and PE-PP copolymers have been
for compatibilization of PE and isotactic polypropylene (iPP). The commercialized but at high prices, indicating the processing cost of
copolymer was added to improve the performance of a mixture of multiblock copolymer compatibilizers needs to be further reduced
recycled PE and iPP, two of the most common plastics in the world. before they are widely implemented.
These blends are shown in Fig. 4A–C. PE and iPP have similar hydro­ The use of renewable resources as feedstock typically does not
carbon makeup, but they do not blend or adhere, leading to fragile in­ resolve all the end-of-use issues that plastics currently face. Biochemical
terfaces and phase separation. Recycling of polyethylene and iPP recycling of biodegradable polymers can fail to recover valuable build­
traditionally results in lower-value products due to degraded properties ing block chemicals and cause potential environmental pollution [116].
and sorting expenses, and approximately 95% of the material value (or However, developing the biodegradable polymers to have higher
economic value) is lost while recycling these commodity plastics. selectivity can be one potential method for the future plastic waste
However, combining polyethylene and iPP using a multiblock copol­ upcycling. For example, mulch films are produced for single-use agri­
ymer as a compatibilizer has significant potential to affect the economic cultural applications to secure crops and suppress weed growth, but they
viability (e.g., eliminating the sorting expenses) and sustainability of are typically composed of nonbiodegradable PE [119]. The accumula­
recycling their waste [10]. Multilayer films consisting of two or more tions of these plastic wastes have negative economic and ecological
polymers are typically produced to combine the advantages of each impacts, as previously discussed. Biodegradable polymers such as poly
component and improve the overall performance in food packaging (butylene adipate-co-terephthalate) could replace the nonbiodegradable
application [18]. PET and PE are recyclable in the neat form, but a PET/ PE because poly(butylene adipate-co-terephthalate) can degrade into
PE multilayer film is difficult to recycle because one component cannot soil, producing CO2 and microbial biomass [119]. The generated CO2
be physically separated from the other component due to the adhesion can be captured for methane tri-reforming use to produce syngas [69]. In
promoted by the tie layer. Therefore, the PET − PE multiblock co­ addition, a strategy to replace fossil fuel-based plastics with bio-based
polymers were synthesized by Nomura et al. and introduced to PET/PE plastics (e.g., making PLA from biomass such as corn) [120] can help
blends as an adhesive layer and compatibilizer additive. Then, the the reduction of greenhouse gas emissions from plastics.
mixture was melt-reprocessed and exhibited superior mechanical
properties compared with the blends processed without compatibilizers. 4. Conclusions
This same strategy can be used for mixed waste combinations, such as
PET/PP. However, the compatibilizer needs to be designed 4.1. Summary

Upcycling of plastic waste has recently gained increased attention.

The state of the art in polymer design for end-of-use, waste conversion
technologies, reaction mechanisms, resulting product types/value, and
efficiencies was systematically studied in this review. Plastic waste has
great potential for conversion to high-value products such as liquid fuel,
H2, carbon nanotubes, and monomers. Each existing conversion tech­
nology has specific applications and types of plastic waste with which it
can be optimally applied. The integration and scale-up of multiple
technologies should be developed to address the enormous amount of
plastic waste around the world.
The ability to convert plastic waste to an equal- or higher-value
product is affected by several factors, including the plastic composi­
tion, processing history, reaction temperature, catalyst activity, and
many other factors depending on the target application. For example,
raising the reaction temperature from 400 ◦ C to 450 ◦ C can increase the
bio-oil yield for PS pyrolysis, and raising the temperature from 550 ◦ C to
850 ◦ C can expand the syngas mass distribution for MSW gasification.
Co-pyrolysis of plastic waste and biomass was found to be a promising
technology because of the processes’ synergism, resulting in a high
product yield and quality. A promoter-added zeolite-based catalyst was
identified as a promising catalyst in plastic waste pyrolysis because of its
high specific area, pore volume, and metal dispersion.
The design and modification of virgin polymers play a crucial role in
their upcycling after their end of use. Designing polymers with recycling
or upcycling in mind can help reduce plastic waste considerably.
Chemically recyclable polymers that can be depolymerized back to
monomers after their typical end of use have been developed. Two such
systems identified in this review were a polymer system based on
γ-butyrolactone and a polymer system that was polymerized via dy­
namic covalent diketoenamine bonds. Finally, multiblock copolymers
Fig. 4. Tensile properties of PE/iPP materials and blends. (A) transmission
were used as an adhesive layer and compatibilizer additive for immis­
electron microscopy (TEM) images of PE/iPP blends without block copolymer
cible plastic mixtures such as PE/iPP and PE/PET.
showing droplet morphology; (B) TEM images of PE/iPP blends with 5 wt%
tetrablock copolymers showing droplet morphology; (C) materials were melt-
blended without block copolymer or with 1 wt% diblock (green), 1 wt% tet­ 4.2. Challenges and future directions
rablock (orange), or 5 wt% tetrablock copolymers. Reproduced with permission
from [10]. Copyright © 2017 American Association for the Advancement The primary challenges facing wide-scale implementation of plastic
of Science. waste conversion include high cost (e.g., because of high energy

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