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Current technologies for plastic waste treatment: A review

Fan ZHANG, Yuting ZHAO, Dandan WANG, Mengqin YAN, Jing ZHANG, Pengyan
ZHANG, Tonggui DING, Lei CHEN, Chao CHEN

PII: S0959-6526(20)34567-4
DOI: https://doi.org/10.1016/j.jclepro.2020.124523
Reference: JCLP 124523

To appear in: Journal of Cleaner Production

Received Date: 17 June 2020

Revised Date: 24 September 2020
Accepted Date: 3 October 2020

Please cite this article as: ZHANG F, ZHAO Y, WANG D, YAN M, ZHANG J, ZHANG P, DING T, CHEN
L, CHEN C, Current technologies for plastic waste treatment: A review, Journal of Cleaner Production,
https://doi.org/10.1016/j.jclepro.2020.124523.

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Current technologies for plastic waste treatment: A
review
Fan ZHANG a, Yuting ZHAO a, Dandan WANG a, Mengqin YAN a, Jing ZHANG a,
Pengyan ZHANG a, Tonggui DING a, Lei CHEN b, Chao CHEN a, c, d, *
a
Shanghai Key Laboratory for Urban Ecological Processes and Eco-Restoration, School of
Ecological and Environmental Science, East China Normal University, 500 N. Dongchuan Rd.,
Shanghai, 200241, China
b
Shanghai National Engineering Research Center of Urban Water Resources Co., Ltd., Shanghai,
200082, China
c
Institute of Eco-Chongming (IEC), 3663 N. Zhongshan Rd., Shanghai 200062, China

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d
Shanghai Engineering Research Center of Biotransformation of Organic Solid Waste, 500 N.
Dongchuan Rd., Shanghai, 200241, China

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Email: [email protected]

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Current technologies for plastic waste treatment: A review
Fan ZHANG a, Yuting ZHAO a, Dandan WANG a, Mengqin YAN a, Jing ZHANG a, Pengyan ZHANG
a
, Tonggui DING a, Lei CHEN b, Chao CHEN a, c, d, *
a
Shanghai Key Laboratory for Urban Ecological Processes and Eco-Restoration, School of Ecological and
Environmental Sciences, East China Normal University, 500 N. Dongchuan Rd., Shanghai, 200241, China
b
Shanghai National Engineering Research Center of Urban Water Resources Co., Ltd., Shanghai, 200082, China
c
Institute of Eco-Chongming (IEC), 3663 N. Zhongshan Rd., Shanghai 200062, China
d
Shanghai Engineering Research Center of Biotransformation of Organic Solid Waste, 500 N. Dongchuan Rd.,
Shanghai, 200241, China
Email: [email protected]

ABSTRACT

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Conventional nonbiodegradable plastic waste (NPW) treatment technologies include landfill and

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incineration, which face bottlenecks and cannot solve NPW problems effectively. Therefore, many
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advanced NPW treatment technologies have been reported. This review summarize currently
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reported advanced NPW treatment technologies, analyze their mechanisms and development status,

and propose an outlook for their industrial application based on the gap between the current
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development status and industry requirements. The technologies are introduced based on basic
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classification into two strategies: recycling and degradation. Recycling technologies are further
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categorized into three subtypes: physical recycling, energy recovery, and resource recovery.

Degradation technologies are further categorized into two subtypes: biodegradation and

oxo-biodegradation. Oxo-biodegradation is divided into abiotic degradation and biotic degradation.

Abiotic degradation includes photodegradation, thermodegradation, mechanochemical degradation

and other degradation techniques. The mechanisms for pyrolysis and photodegradation are

systematically summarized. The purpose of this review is to provide readers with a comprehensive

introduction to various advanced NPW treatment technologies, which can enable readers to

understand the development status and outlook of the technology.

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Keywords

Plastic waste; Plastic waste recycling; Plastic waste degradation; Disposal methods

1. Introduction

The development of industry results in not only many products for human activities but also a

large amount of wastes to the environment because used products are discharged after human

activities. These wastes include gas wastes, water wastes, and solid wastes (Tang et al., 2020; Zhang

et al., 2018; Zhao et al., 2020). Plastic waste is a representative waste product that originates from

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industrial development, and its discharge to the environment causes severe environmental problems.

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Currently, plastic products are an indispensable part of people's daily lives and are applied in various
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industries, such as construction, healthcare, electronic components, agriculture, automotive, and
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packaging (Anuar Sharuddin et al., 2016). The demand for plastics continues to increase owing to the

excellent advantages of plastics, such as convenience, durability, resistance to erosion, ease of

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processing, and low cost (Wong et al., 2015). As shown in Fig 1, since 1950, global plastic
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production has grown at a compound annual growth rate of 8.4%; the annual plastic production was
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360 million tons in 2018, and plastic production is estimated to reach 500 million tons in 2025 (Bai

et al., 2019; Gibb, 2019; PlasticsEurope, 2019). Approximately 60% of plastic enters the

environment as plastic waste (Geyer et al., 2017). The demand of plastic mainly comprises

polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET),

polyurethane (PUR) and polystyrene (PS) as shown in Fig 2a (Rodrigues et al., 2019).

Correspondingly, the generated plastic waste also originates from the above major plastic products.

For example, the packaging industry consumes the highest proportion of plastics produced and it is

the major plastic waste source because of the widespread application of disposable products

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(PlasticsEurope, 2019). NPW discharged from the packaging area mainly comprises PP, PE, PS, and

PET as shown in Fig 2b (Colantonio et al., 2019) . Plastics undergo slow degradation and can remain

in the environment for at least decades or even hundreds of years; they are thus named

nonbiodegradable plastics and cause ever-increasing levels of global NPW, thus bringing about

various environmental issues (Garcia and Robertson, 2017).

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Fig 1. Growth trend of plastic production. Source: (Bai et al., 2019; Geyer et al., 2017;
PlasticsEurope, 2019)
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Fig 2. a) Proportion of demand of various plastic types. Source: (PlasticsEurope, 2019). b) Major

composition of plastic packaging wastes. Source: (Colantonio et al., 2019).

To date, many techniques have been invented and applied for NPW treatment. These

technologies can be divided into conventional NPW treatment technologies and advanced NPW

treatment technologies. Conventional methods for the disposal of NPW include incineration and

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landfills, which face a specific bottleneck. Incineration of NPW requires a large amount of energy

and discharges hazardous by-products (Ashworth et al., 2014). The by-products such as CO2, acidic

gases (oxides of sulfur), persistent organic compounds (dioxins and furans), heavy metals, and

particulate matters are highly hazardous which can result in global warming and several health

problems including respiratory symptoms, decreased lung function, and high cancer risk (Franchini

et al., 2004; Yang et al., 2012). Landfilling has been used regularly to treat NPW, and even today,

the highest portion of plastics are subjected to landfills (Pramila and Vijaya, 2011). However,

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nonbiodegradable plastics degrade slowly in landfill conditions, taking up increasingly land space

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because of an increasing amount of NPW disposal. In addition, the interaction of plastics with
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groundwater and toxic substances rich in water in landfills can generate toxic leachate, even causing
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deterioration of the surrounding land (Teuten et al., 2009). Therefore, landfilling has been considered

as the most undesirable management strategy and been regulated by many kinds of stipulations
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(Okan et al., 2019). To overcome the problem faced by conventional technologies such as
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incineration and landfills, various advanced plastic treatment technologies have been developed, for
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instance, pyrolysis, photodegradation, thermodegradation, and biodegradation.

Although several research papers on advanced plastic treatment technologies have been

published, current review papers focus on only a certain technique, such as pyrolysis or

photodegradation, or a certain type of polymer waste, such as PE or PS. These review papers cannot

provide a systematic and comprehensive review of the vast and variable currently reported advanced

NPW treatment technologies. Therefore, this review present a variety of treatment technologies for

NPW without specifically focusing on a certain polymer or method. The aim of this review is to

provide a systematic and comprehensive understanding of all currently reported advanced

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technologies for disposing of NPW. This review summarize currently reported advanced NPW

treatment technologies, analyze their mechanisms and development status, and propose an outlook

for their industrial application based on the gap between current development status and industry

requirements.

2. Methods

The main purpose of this review is to introduce the currently reported advanced technologies for

nonbiodegradable NPW treatment. The introduction covers the technology mechanisms and

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development status and the gap between the current development status and industry requirements.

The outlook is proposed based on the introduction.-p

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A literature search was carried out using the most widely used databases, including
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ScienceDirect, Scopus, Web of Science, Wiley, the American Chemical Society and other

commercial websites (PlasticEurope, etc.). To cover most of the reported literature, the keywords
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were selected systematically. The selected keywords included “plastic” AND “recycling OR
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degradation” AND “pyrolysis OR gasification OR hydrocracking OR incineration OR glycolysis OR

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hydrolysis OR methanolysis OR alcoholysis OR microorganisms OR mealworms OR composting

OR photo oxidaiton OR mechanochemical OR thermooxidation”. Afterwards, the abstracts and titles

of relevant papers were screened and analyzed according to this review’s themes. The numbers of

documents obtained for each technology in the two most well-known databases (Web of Science and

Scopus) over 15 years are shown in Table 1. Please note that some papers are counted repeatedly.

The Web of Science database yielded 2666 records in total, while Scopus yielded 2936 records in

total. Among these papers, 217 representative papers have been selected as references because of

their innovativeness, systematic nature or high impact.

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Table 1. The number of documents identified in the Scopus and Web of Science databases over 15

years.
Technique Scopus Web of Science
Pyrolysis 686 480
Gasification 147 80
Hydrocracking 32 20
Incineration 602 218
Glycolysis 101 57
Hydrolysis 152 117
Methanolysis 16 12
Alcoholysis 22 15

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Microorganisms degradation 467 355
Invertebrate degradation 10 10

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Composting 203 154
Photodegradation 403 991
Mechanochemical degradation
Thermodegradation
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79
25
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Total 2936 2666
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To review the technologies systematically, analysis was carried out based on the following
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classification. First, the technologies were classified into recycling and degradation. Second,

recycling technologies were classified into three subtypes: physical recycling, energy recovery, and
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resource recovery. Degradation technologies were classified into two subtypes: biodegradation and
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oxo-biodegradation. Third, energy recovery mainly included incineration; resource recovery

included chemolysis and thermolysis, including pyrolysis, hydrocracking and gasification; and

oxo-biodegradation included abiotic degradation and biotic degradation. Fourth, abiotic degradation

was categorized as photodegradation, thermodegradation, mechanochemical degradation and other

degradation techniques. The detailed mechanisms of pyrolysis and photodegradation were also

systematically summarized.

3. Classification of NPW disposal methods

NPW disposal methods can be classified into two types due to basic strategies used: one is

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recycling, the other is degradation (Schneiderman and Hillmyer, 2017). Recycling disposal methods

can be further classified into various subtypes according to technical characteristics. The American

Society for Testing and Materials (ASTM) standard D5033-(2000) divides recycling into four

categories: primary recycling (mechanical reprocessing of scrap materials with properties similar to

those of virgin plastics, named ASTM I), secondary recycling (mechanical reprocessing of used

materials into products with fewer performance requirements, named ASTM II), tertiary recycling

(recovery of valuable chemical intermediates in the form of gases, liquids, and even solids, named

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ASTM III) and quaternary recycling (recovery of the energy content of plastics by incineration,

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named ASTM IV) (Okan et al., 2019). Primary recycling and secondary recycling involve
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mechanical reprocessing of used materials into products with little or no effects on their physical
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properties, which can also be considered physical recycling. Tertiary recycling involves valuable

chemical intermediate recovery, while quaternary recycling involves energy recovery, which can be
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seen as resource recovery and energy recovery, respectively. Therefore, this article introduces the
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technology of recycling based on physical recycling, resource recovery, and energy recovery which
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covers ASTM I and II, ASTM III and IV, respectively. Physical recycling includes direct reuse,

extrusion, segregation and so on. Resource recovery includes thermolysis (pyrolysis, gasification,

hydrocracking) and chemolysis. Energy recovery usually refers to incineration.

Degradation, as the name implies, in this strategy where NPW undergo a series of degradation

processes eventually converted to carbon dioxide and water, which are released into the environment.

The microbial degradation of plastic has attracted much attention due to its advantages of low energy

consumption, complete degradation, and environmentally friendliness (Ammala et al., 2011).

However, plastics people used are non-biodegradable in most cases. To reverse this adverse situation,

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a large number of advanced technologies have been applied to pretreat nonbiodegradable plastics to

increase their degradability by microorganisms. Mainstream pretreatment technologies can be

classified into four categories: photodegradation, thermodegradation, mechanochemical degradation,

and other degradation. These pretreatment technologies are combined with subsequent

biodegradation treatment to achieve oxo-biodegradation. In this article, NPW degradation will be

classified into the following two categories: biodegradation and oxo-biodegradation.

To illustrate the NPW disposal method clearly and systematically in this article, a scheme for

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currently reported advanced NPW disposal methods are given in Fig 3 based on the NPW

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classification described in this section. The following contents will be organized according to the
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scheme shown in Fig 3.
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Advanced Nonbiodegradable Plastic Waste Disposal Methods

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Recycling Degradation
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ASTM Ⅰ、Ⅱ ASTM Ⅲ、Ⅳ Biodegradation Oxo-Biodegradation

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Energy Resource
Physical
Recovery Recovery Abiotic Degradation
Recycling

Incineration Thermolysis Chemolysis

Reuse Directly Photo Mechanochemical Thermo Other
Degradation Degradation Degradation Degradation
Extrusion

Segregation Pyrolysis Hydrocracking Gasification Biotic Degradation

CO2 H2O

Fig 3. Classification of currently reported advanced NPW disposal methods.

4. Recycling of NPW

Due to the growing environmental problems associated with NPW, recycling methods have

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received widespread attention due to their environmental friendliness and economic benefits

(Howard, 2002). More importantly, recycling methods can recover abundant valuable products such

as fuels and oil. This is consistent with the theme of sustainable development advocated by countries

worldwide. According to a previous report, recycling 1 ton of plastic waste will save up to ~130

million kJ of energy (Garcia and Robertson, 2017). The annual energy savings from recycling all

global plastic waste is equivalent to 3.5 billion barrels of oil, valued at approximately $176 billion

(Geyer et al., 2017). Accordingly, research on recycling technologies is of great significance for

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future development.

4.1 Physical recycling of NPW -p

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As mentioned above, physical recycling consists of primary and secondary recycling. Primary
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recycling focuses universal attention on factories due to its low recycling cost and simple operation.

To achieve the goal that the products obtained from NPW exhibit performance comparable to that of
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products made from virgin plastics, primary recycling requires a higher quality of waste plastics,
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such as clean, uncontaminated, single-type NPW (Al-Salem et al., 2010). An effective example of
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primary recycling is production of a new PET bottle from a scrap PET bottle, such as Coca-Cola

PET bottles.

Secondary (mechanical) recycling is the process of NPW recovery via mechanical means. In this

type of recycling, the reprocessed products from NPW possess lower performance demands than the

product generated from virgin plastic (Kumar et al., 2011). This is ascribed to peroxidation during

the supply of energy and heat (Al-Salem et al., 2009). The treatment of NPW in this way may

include a series of material recycling methods, such as size reduction by granulators, shredders or

crumblers; segregation; cleaning; drying; palletization; and extrusion. The main disadvantage of this

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type of recycling is the property deterioration of the reprocessed products, mainly due to a decrease

in molecular weight after each cycle caused by chain-scissions (Jagtap, 2015). In addition, the

application scope of this secondary recycling is limited to some kinds of thermoplastics that are not

temperature sensitive and do not possess high melt viscosities (Okan et al., 2019). Generally, PE and

PET are major types of NPW treated via mechanical recycling. Other types of NPW, such as PS, PP,

and PA, account for less than one percent of NPW treated via secondary (mechanical) recycling

(MacArthur, 2017).

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As mentioned above, physical recycling is an environmentally friendly and economically

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beneficial technique. However, due to the constraints faced by primary and secondary recycling
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mentioned above, currently, the physical recovery of NPW is applied narrowly. The application
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prerequisite of this technology is garbage classification, specifically NPW classification; otherwise,

additional labor costs will be needed. Therefore, the widespread application of this technology
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requires corresponding policy support from the government to classify NPW.

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4.2 Energy recovery of NPW

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Energy recovery of NPW usually refers to the process of obtaining energy from nonrecyclable

or economically unprofitable NPW via incineration. This is because some plastic materials possess

calorific values comparable to those of crude oil derivatives (Eriksson and Finnveden, 2009). As

shown in Table 2 that the calorific values of PE, PP and PS are very similar to those of conventional

fuels (for example, the calorific values of gasoline and petroleum are 46 MJ/kg and 42.3 MJ/kg,

respectively), illustrating that polyolefin plastic is the most effective plastic for energy recovery from

a calorific point of view (Costiuc et al., 2015). The main incineration product of carbon dioxide and

water further makes it possible to replace conventional fuels (Thanh et al., 2011). The calorific

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values of PVC, PET, and PA are much lower, and thus, these materials are not suitable for

incineration. PVC can even generate toxic gases such as HCl that corrode equipment.

Table 2. Calorific value of popular plastics and conventional fuels. Source: (Al-Salem et al., 2010)

and (Costiuc et al., 2015)

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Fuel Calorific value (MJ/kg)

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Polyethylene 43.3-47.7

Polypropylene
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Polystyrene 41.6-43.7
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polyvinyl chloride 18.0-19.0

polyethylene terephthalate 21.6-24.2

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polyamide 31.4

polyurethane foam 31.6

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Methane 53
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Gasoline 46

Kerosene 46.5

Petroleum 42.3

Heavy oil 42.5

Household PSWa mixture 31.8

a. Plastic solid wastes.

Incineration equipment is utilized in incineration technology. In general, lab-scale incineration

equipment includes the following parts: detection system, program control system, combustion

charmber, cyclone separator, cooling system, air supply bump, etc. A typical lab-scale fluidized bed

process is shown in Fig 4.

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Fig 4. A lab-scale fluidized bed process for incineration. Source: (Żukowski and Berkowicz, 2019).

1-computer storing FTIR, temperature and acoustic signal data, 2-A/D convertor for thermocouple

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signals, 3-heated probe for sampling the flue gases, 4-exhaust fan, 5-cyclone, 6-ash trap for coarser

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particles, 7-freeboard space, 8-radiation shield, 9-heating sleeve, 10-thermocouples, 11-air supply
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valve, 12-plenum chambers, 13-Ni-Cr perforated plate.
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The conventional incineration process results in a series of problems, e.g., emission of

greenhouse gases (GHGs) such as CO2 and NOX, production of various toxic gases such as dioxin
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and polycyclic aromatic hydrocarbons (PAHs), and formation of a large amount of inhalable
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particulate matter (Antelava et al., 2019; Williamson et al., 2009; Zhu et al., 2017). The release of
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these pollutants into the air will cause a substantial adverse effect on the surrounding environment

and human health. It is estimated that every year, outdoor air pollution causes over 3 million

premature deaths around the world (Lelieveld et al., 2015). Ashworth et al. confirmed that toxic

byproducts produced by incineration are related to certain birth defects in infants (Ashworth et al.,

2014). Astrup et al. discovered that the emission of gases from incineration may exacerbate the

greenhouse effect (Astrup et al., 2009).

To solve the problems caused by conventional incineration, studies on advanced clean plastic

combustion techniques have attracted great interest from scientists. Shimizu et al. proved that porous

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alumina can suppress hazardous substances such as PAHs and CO emission during plastic

combustion in a small-scale fluidized bed combustor (Shimizu et al., 2006). The same experiment

also successfully carried out by Qin et al. in a semi-pilot-scale fluidized bed combustor with porous

and nonporous alumina bed materials (Qin et al., 2016). Introducing nanoparticle such as ceria and

C60 into NPW can not only decrease the emissions of certain toxic PAHs, but polychlorinated

dibenzofurans/dioxins (PCDD/Fs) (Vejerano et al., 2014). Zia et al. added PW such as polyurethane

into municipal solid waste (MSW) to increase the calorific value of the waste without increasing the

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amount of ash formed during incineration (Zia et al., 2007). During incineration of waste containing

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PE and PVC, the addition of goethite can reduce PCDD/Fs and HCB (Jin et al., 2008). An
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approximately 98% combustion efficiency can be got when using a semicontinuously operated
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fluidized bed reactor to combust NPW (Ma et al., 2019). Zukowski et al. also reported that using an

inert cenospheric fluidized bed for polyolefin combustion can achieve a polyolefin conversion of
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97-99% (Żukowski and Berkowicz, 2019). Using Fe2O3 as a catalyst deposited on the cenospheres
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results in a significant reduction in the emission concentrations of CO and NOx (Żukowski and
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Berkowicz, 2019). The examples listed above cover almost all types of plastic incineration, which

help readers have a comprehensive understanding of plastic incineration.

Incineration technology has a long history, and its advantages and disadvantages are obvious.

Incineration of NPW will inevitably produce harmful gases, particulates and other harmful

substances. Although many new incineration technologies have been developed to alleviate the

discharge of hazardous substances from incineration, the technologies are still in a developing stage,

and further study is needed. The large amount of heat energy generated can bring extremely high

economic value. Although the incineration of NPW has many shortcomings at this stage, its

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indispensable advantages endow it with broad prospects and considerable market benefits. It is

estimated that approximately 50% of global plastic waste will be treated via incineration by

approximately 2050 (Geyer et al., 2017). Therefore, it is necessary to further develop advanced clean

plastic combustion techniques to eliminate hazardous discharged gases and particulates to alleviate

or eliminate environmental pollution caused by incineration.

4.3 Resource recovery of NPW

In addition to energy recovery and mechanical recycling, obtaining valuable petrochemicals or

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monomers from NPW is attracting increasing attention. This is deemed resource recovery. NPW can

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be treated to generate a mixture containing a variety of hydrocarbon components for use as fuel. For
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example, polyethylene (PE) has been considered a promising feedstock for fuel (gasoline) and
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value-added products such as synthetic lubricants (Al-Salem et al., 2010).

Currently, resource recovery from NPW is mainly realized via thermolysis. During thermolysis,
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polymers, which are the major component of plastic, undergo chain scission to produce
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low-molecular-weight compounds and monomers (Okan et al., 2019). With the development of
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thermochemical treatment of NPW for fuel recovery, thermolysis technology can be divided into

three types (Brems et al., 2013). Pyrolysis is carried out in an inert atmosphere with or without

catalysts. Gasification is carried out in the presence of substoichiometric amounts of air, usually

leading to CO, CO2 and H2 production. Hydrocracking which is also called hydrogenation is carried

out in the presence of H2.

The goal of all three technologies is to convert large-molecule long-chain polymers into

small-molecule substances such as oil, gas and char at high temperatures. The differences between

these technologies are the operating conditions and products. For example, pyrolysis and

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hydrocracking mainly produce oil, followed by gas while gasification mainly produces gas. This

review focus on a pyrolysis technique because pyrolysis is currently the most widely used technique

in chemical factories. Compared to gasification, pyrolysis does not form dioxins because it is free

from oxygen as a result of the inert atmosphere and a lower temperature requirement which can

decrease operating costs (Al-Salem et al., 2017). In hydrocracking, the cost of producing hydrogen is

relatively high, which limits the development of this technique. Therefore, for practical application

considerations, pyrolysis is the focus of our review, and other technologies are only briefly

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introduced.

4.3.1 Pyrolysis -p
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Pyrolysis is the process by which a long-chain polymer is converted into smaller molecules via
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thermal degradation at a temperature usually ranging from 300-900 ℃ under an inert gas atmosphere

(Chen et al., 2014). During the pyrolysis process, various valuable products are produced mainly in
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the form of gas, liquid oil, and char. Pyrolysis is suitable for treating polymers mainly composed of
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hydrocarbons such as PE, PP, PS, and PET (Wong et al., 2015). Factors that can influence pyrolysis
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include, temperature, retention time, reactor type, catalysts and so on. Therefore, research on the

mechanism of pyrolysis is very helpful in controlling the pyrolysis conditions to realize efficient

resource recovery. In addition, according to whether a catalyst is utilized, pyrolysis can be divided

into thermal pyrolysis and catalytic pyrolysis (Miandad et al., 2016). A schematic of the simple

pyrolysis process is shown in Fig 5.

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 Fig 5. Schematic of the simple pyrolysis process. Source: (Gaurh and Pramanik, 2018).

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4.3.1.1 Pyrolysis Mechanism

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In general, plastic pyrolysis follows a complex route that cannot be described by one or several
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chemical reactions; currently, there is no systematic pyrolysis mechanism reported (Scheirs and
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Kaminsky, 2006). Cullis and Hirschler proposed four main mechanisms in the process of polymer

thermal pyrolysis (Cullis and Hirschler, 1981): (1) end-chain scission/depolymerization, (2)
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random-chain scission/fragmentation, (3) chain-stripping/elimination of the side chain, and (4)

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cross-linking to form a chain network (Buekens and Huang, 1998). However, the plastic
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decomposition route mainly depends on the structure of the polymer. The first two mechanisms can

be expressed by the following formula (Singh and Sharma, 2008).

∗ ∗
→ + (1)

→ + (2)

Thermal chain breakage of polymers follows either chain end decomposition to yield the

corresponding monomers (Eq. (1)) or random decomposition to form fragments of uneven lengths

(Eq. (2)), while the last mechanism often occurs for thermosetting polymers when heated to from

char.

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 Unlike the process of thermal pyrolysis that is carried out only at a high temperature, catalytic

pyrolysis is carried out using various catalysts at lower temperatures than that used for thermal

pyrolysis due to the decreased activation energy for polymer chain breakage caused by the catalysts.

Various catalysts have been successfully applied to decompose many kinds of waste plastics in

catalytic pyrolysis to date, e.g., FCC (fluid cracking catalysts), zeolite-based catalysts(ZSM-5,

HZSM-5, etc.), red mud, silica-alumina, CaO, Ca(OH)2, and MgO (Artetxe et al., 2013; Fan et al.,

2017; Gonzalez et al., 2011; Kumagai et al., 2015; Lee, 2009; Ojha and Vinu, 2015; Stelmachowski,

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2010). Among them, FCC, ZSM-5, HZSM-5, red mud, and silica-alumina are acid catalysts, while

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CaO, Ca(OH)2, and MgO are basic catalysts. Solid acid catalysts are widely used in plastic pyrolysis
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(Liu, R. et al., 2020). Different types of catalysts have different catalytic mechanisms during the
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plastic pyrolysis process, but they also have something in common, namely, both require the

formation of unstable carbenium or carbanion ions and subsequent β-scission to achieve polymer
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chain breakage (Buekens and Huang, 1998). Here, take solid acid catalysts as an example to illustrate
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the mechanism of catalytic pyrolysis of PE, which can be concluded as follows (Singh, 2018).
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(1) Initiation: Initiation of polymer breakage may occur on some defect sites of the polymer chains.

The active site on the solid acid catalyst reacts with the polymer via proton addition, where an

olefinic linkage can be converted into an on-chain carbonium ion:

— CH CH CH=CHCH CH — + HX → — CH CH +CHCH — CH CH — + X (3)

Then, the on-chain carbonium ion undergoes β-scission to break the polymer chain:

— CH CH +CHCH — CH CH — → — CH CH CH=CH + +CH CH — (4)

The on-chain carbonium ion may also undergo random hydride-ion abstraction with the rest of

the polymer chain to form another on-chain carbonium ion (R+). After that, the newly formed

17
 on-chain carbonium ion undergoes β-scission to further break the polymer chain.

— CH CH CH CH — + R → — CH CH +CHCH — + RH (5)

(2) Depropagation: The proton addition of solid acid catalysts, β-scission of carbonium ions and

hydride-ion abstraction of carbonium ions work systematically to decrease the molecular weight

of the main polymer chains, yielding an oligomer fraction (approximately C30–C80). The

oligomer fraction undergoes further chain breakage via β-scission of chain-end carbonium ions

which leads to both gas and liquid formation (approximately C10–C25).

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(3) Isomerization: Carbonium ion intermediates can be rearranged due to hydrogen or carbon atom

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shifting, resulting in double bond isomerization of olefins:
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CH =CHCH CH CH +CHCH CH CH CH=CHCH (6)
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Other important isomerization reactions are methyl-group shift and isomerization of saturated

hydrocarbons (Noh et al., 2018).

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(4) Aromatization: Some carbonium ion intermediates may undergo a cyclization reaction. An
ur

example is when the hydride ion abstraction first occurs on the olefin, resulting in the formation
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of olefin carbonium ions:

R + R CH=CH— CH CH CH CH CH ↔ R H + R CH=CH— CH CH CH +CHCH (7)

The above mechanisms are based on solid acid catalysts. Woo et al. reported that basic catalyst

MgO initiates carbanion generation through hydrogen abstraction (Woo et al., 2000):

MgO

-H+ + MgO—H

β-scission
+ -
-

18
 (8

The olefin carbonium ion could undergo intramolecular attack on the double bond to cyclize

and form aromatics:

R2
R2CH=CH
CH
+ +
H3CHC CH2 H3CHC CH

CH2CH3

of
H2C CH2

CH2

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(9

) -p
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To improve the quality of the pyrolysis products, the reforming catalyst is usually utilized in
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plastic catalytic pyrolysis. This is because the most promising product of plastic pyrolysis is fuel oil.

For fuel oil, the octane number affects the quality of gasoline and its anti-knock performance.
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Pyrolysis products can improve the octane number through reforming reactions. Reforming catalysts
ur

are considered a kind of catalyst with two different functional active sites, namely, metallic active
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sites and acidic active sites (Buekens and Huang, 1998). Metallic active sites can catalyze

hydrogenation and dehydrogenation reactions, while acidic active sites can catalyze isomerization

reactions. The proper combination of two active sites can facilitate isomerization (isomerization of

linear paraffin into branched molecules), dehydrocyclization (conversion of linear paraffin to

naphthenes), and dehydrogenation (naphthenes are converted to aromatics) in polymer chains (Panda

et al., 2010). After the polymer chain undergoes these reforming processes, the octane number of the

product in the gasoline range is improved without changing the carbon number (Buekens and Huang,

1998). The concise degradation mechanism of the reforming catalyst is illustrated by the

19
isomerization of n-pentane as shown below:

CH CH CH CH CH !!!!!!! H C=CHCH CH CH + H (10)

Pt
$
H C=CHCH CH CH !!!! H C=CHCH%CH & (11)

H C=CHCH%CH & + H !!!!!!! H C—CHCH%CH & (12)

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4.3.1.2 Octane numbers of hydrocarbons

As mentioned above, pyrolysis of NPW can produce gasoline-range hydrocarbons, which are the

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most valuable products. The octane number is an important indicator of the anti-knock performance

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of carburetor engine fuel (Anuar Sharuddin et al., 2016). A high octane number indicates good
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anti-knock performance. The octane numbers of selected hydrocarbons are listed in Table 3. It can be
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seen that the increased amounts of aromatic, naphthene and C6-C12 branched hydrocarbon pyrolysis

products will help to increase the octane number of the pyrolysis oil.
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Table 3. Octane numbers of a number of hydrocarbons. Source: (Buekens and Huang, 1998)
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hydrocarbons Octane numbers

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n-Butane 113

n-Pentane 62

n-Hexane 19

n-Heptane 0

Isooctane 100

2-Methylhexane 41

2,2-Dimethylpentane 89

2,2,3-Trimethylbutane 113

Cyclopentane 141

Methylcyclopentane 107

Cyclohexane 110

20
 2-Methyl-1-hexene 91

3-Methyl-2-pentene 97

Benzene 99

Toluene 124

m-Xylene 145

1,3-Dimethylbenzene 145

1,3,5-Trimethylbenzene 171

Isopropylbenzene 132

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4.3.1.3 Yield of plastic pyrolysis products

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Pyrolysis of plastics generally produces mixed liquid complex compounds, including waxes
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(C19+), diesel-range hydrocarbons (C11-C18) and gasoline-range hydrocarbons (C6-C12) (Ding et al.,
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2019). Gasoline is the most popular pyrolysis product because of its wide application range, and high
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economic value. Most studies try to control pyrolysis parameters to increase the selectivity and yield
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for gasoline-range products. The pyrolysis parameters include feed composition, pyrolysis
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temperature, heating rate, retention time, type of reactors, catalysts, operating pressure and fluidizing
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gases (Chen et al., 2014; Hao et al., 2010). Table 4 lists representative results of NPW pyrolysis

product distribution and yield under various conditions.

Seo et al. reported that replacing the powder zeolite-Y with pellet zeolite-Y can increase the

liquid yield of HDPE pyrolysis from 71.5% to 81% (Seo et al., 2003). Marcilla et al. found that when

the HZMS-5 catalyst is used to pyrolyze LDPE, the distribution of C6-C12 can increase from 23.3%

to 59% (Marcilla et al., 2009b). Ding et al. reported that during the pyrolysis of LDPE, by controlling

the catalytic temperature, the distribution of pyrolysis oil hydrocarbon products can be controlled so

that the main products are monocyclic aromatic hydrocarbons (MAHs) with a high octane number

(Ding et al., 2019). However, in the first example, although the liquid yield is increased, the carbon

21
number distribution of the gasoline-range (C6-C12) is reduced; in the second example, although the

distribution of the gasoline-range is high, the liquid yield is only 18.3%; in the third example,

although the hydrocarbon product distribution is controlled, the liquid yield is reduced. Therefore, it

is impossible to accurately evaluate the actual yield of gasoline-range products obtained by various

pyrolysis methods by considering only the liquid yield and carbon number distribution separately. As

mentioned above, the gasoline-range product is the most valuable pyrolysis product. The actual yield

of gasoline-range products is very important when assessing the pyrolysis technique. The

of
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measurement of actual yield should consider both the yield for liquid products and the carbon

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number distribution of gasoline-range products in liquid products. However, to the best of our
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knowledge, there is no paper reporting the actual yield for gasoline-range products. Most papers
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report liquid yield, components and carbon number distribution in the liquid separately.

To solve this problem, the concept of actual gasoline-range yield (YAGR) is suggested to be used
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to combine the yield for liquid and carbon number distribution of gasoline-range products in a liquid
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to assess the actual gasoline-range product yield. The values of YAGR are calculated as follows:
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'()* % = '- % × /)* % (13)

where YL is the liquid yield of pyrolysis plastics and WGR is the weight distribution of gasoline-range

hydrocarbons in liquid products.

Based on the reported liquid yield and carbon number distribution of gasoline-range products by

weight in published manuscripts, the YAGR values is calculated, and the results are listed in Table 4.

When silica/alumina was used as a catalyst at 450 ℃ at a rate of 5-8 ℃/min, YAGR reached 71.2%

(Seo et al., 2003). Previous examples are evaluated again. When HZSM-5 was used as a catalyst and

the temperature was 550 ℃, although the carbon number distribution of the gasoline-range products

22
is almost 60%, the liquid yield was 18.3%, resulting in a YAGR value of only 10.8% (Marcilla et al.,

2009b). Moreover, when alumina was used as a catalyst, although the carbon number distribution of

gasoline-range is only 53%, the liquid yield can reach 82%, leading to 43.5% of YAGR (Seo et al.,

2003). YAGR comprehensively considers both liquid yield and carbon number distribution, which

may lead to a more precise assessment of the pyrolysis technique.

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23
 1
Table 4. Summary of plastic pyrolysis product yield and carbon number distribution under various conditions.
Temperature Heating rate YAGRc
Feed Reactor Catalyst Gas Retention time Yield (wt%) Distributiond (area%) Ref.
(℃) (℃/min) (%)
Gas Liquid Char C6-C12 C13-C22 C22+
b
Mixed Autoclave 460 H-ZSM5 N2 15 30 min 40 55 5 87 13 - (Marco et al., 2009)
HDPE Two stage batch 450 Y-zeolite - - - 35 58 7 40a 42a 16a
23.2 (Syamsiro et al.,
reactor 2014)

f
PE and Fixed bed reactor 450 HZSM-5 N2 10 40 min 75.1 23.8 1.1 71 28 <1 - (Palza et al., 2017)

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PP
HDPE 2 L batch reactor 440 None - - 2h 9 74 17 73 26.7 <0.5 - (Sharma et al., 2014)

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Mixed Semi-batch reactor 500 None N2 20 30 min 34 65.2 0.8 89 7.3 3.7 - (López et al., 2011a)

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LDPE Microwave oven 500 HY zeolite - 50-60 20 min 41.8 56.5 1.7 94 6 0 - (Ding et al., 2019)
HDPE Fixed bed 550 None N2 5 2h 23 70 7 84 16 0 - (Al-Salem, 2019)

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(batch) reactor
Mixed Semi-batch reactor 500 None N2 10 30 min 10 75.8 14.2 63.4 7 <3.2 - (Singh et al., 2019a)

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Mixed Semi-batch reactor 500 ZSM-5 N2 20 30 min 58.4 39.8 1.8 94 <5 - - (López et al., 2011b)
Red mud 41.3 57 1.7 92 <6 - -
Mixed Semi-batch reactor 500 Red mud N2 ur 20 30 min 42.4 57 0.6 96.2 3.8 0 - (Adrados et al., 2012)
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LDPE Batch reactor 550 HUSY N2 5 - 34.5 61.6 1.9 61a 25.8a <2a 37.6 (Marcilla et al.,
2009b)
HZSM-5 - - - 70.7 18.3 0.5 59 19 0 10.8
PE Steel micro reactor 350 None N2 20 30 min 17.2 80.9 1.9 32.6 45 <23.3 - (Ahmad et al., 2014)
PP 30 67.8 1.6 15.2 46 <33 -
HDPE Batch reactor 450 ZSM-5 N2 5-8 30 min 63.5 35 1.5 99.92a 0.08a 0a 35.0 (Seo et al., 2003)
Zeolite-Y 17.5 81 1.5 86.1 11.6 2.3 69.7
Mordenite 18.5 78.5 3 71.1 28.7 0.2 55.8
Silica/ 21 78 1 91.3 8.7 0 71.2
alumina
Alumina 15.9 82 2.1 53 43.3 3.7 43.5
a. wt% were determined by GC/MS b. mixed means more than three type of plastics c. actual gasoline-range yield
24 d. carbon number distribution in liquid product.
4.3.1.4 Factors influencing plastic pyrolysis

Table 4 shows the parameters that can affect the product yield and carbon number distribution.

The effect of the main parameters is discussed below.

Temperature is considered to be one of the most significant parameters in plastic pyrolysis by

controlling the cracking reaction of plastic (Noh et al., 2018). Temperature obviously affects the

yield of gases and liquid oil but negligibly affects that of chars (López et al., 2011a). In general,

relatively low temperatures favor oil production, while high temperatures favor gas generation

of
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because long chains are broken into short chains (Hernández et al., 2007). Hydrocarbons and

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aromatic compounds are produced at high temperatures due to the triggering of secondary process
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reactions (Miandad et al., 2016). Singh et al. reported the effect of temperature on PP pyrolysis
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product yield and distribution: the gas yield increased from 8.5% to 13.5% when the temperature

increased from 500 to 600 ℃ (Singh et al., 2019b). Onwudili et al. reported that when pyrolyzing PS
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in a closed batch reactor, the maximum liquid oil yield reached 97% at 425 °C (Onwudili et al.,
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2009). However, as the temperature increased to 500 °C, the yield of pyrolysis oil decreased to 68%.
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Marcilla et al. observed that liquid oil formation started at a temperature of 360-385°C while the

maximum liquid oil yield was obtained at 469–494 °C (Marcilla et al., 2009a). Pyrolysis gas and oil

product distributions have an important relationship with temperature. In most previous reports, if

liquid oil is the most desired product, the optimum temperature for pyrolysis is usually below

550 °C.

The residence time is the average amount of time that particles stay in the reactor, which may

influence the distribution and yield of pyrolysis products (Mastral et al., 2002). In most cases,

increasing the residence time is prone to increase the conversion of the primary product to generate

25
to light molecular weight hydrocarbons, noncondensable gas, etc., while decreasing the yield of

liquid oil (Anuar Sharuddin et al., 2016). However, some studies report little effect of residence time

on the yield of liquid oil. Lopez et al. observed that the same yield of liquid oil was achieved at

retention times of 30 min and 120 min (López et al., 2011a). Mastral et al. reported that when the

temperature exceeds 685 ℃, the residence time has little effect on the liquid and gas yield (Mastral et

al., 2003). In addition to liquid oil, retention time also affects wax production. Mastral et al. reported

that a longer residence time resulted in decreased wax yield (Mastral et al., 2002). The effect of

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residence time on pyrolysis product yield at lower temperatures is more obvious than that at higher

temperatures (Anuar Sharuddin et al., 2016). -p

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There have been few reports about the effect of pressure on plastic pyrolysis. Murata et al.
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reported that for PE pyrolysis, when the pressure was increased from 0.1 MPa to 0.8 MPa, the gas

yield increased from 6 wt% to 13 wt% at 410 ℃ but from 4 wt% to 6 wt% at 440 ℃, implying that
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pressure affects the carbon number distribution more obviously at lower temperatures than at higher
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temperatures by decreasing molecular weight (Murata et al., 2004). Schubert et al. also reported
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similar results in LDPE pyrolysis; in addition, at 450 ℃, the liquid yield also increased with

increasing pressure between 2 and 10 bar (Schubert et al., 2019). Pressure also works synergistically

with other parameters, if the similar product distribution and yield are required, then the temperature,

residence time and other parameters should be changed as the pressure changes. Newalkar et al.

reported that the pyrolysis products obtained at a pyrolysis temperature of 600 °C and a pressure of

15 bar are similar to those obtained at a pyrolysis temperature of 800 °C and a pressure of 5 bar

(Newalkar et al., 2014). Therefore, further research into the effects of pressure on pyrolysis plastics

is needed.

26
 The heating rate is another important parameter in plastic pyrolysis. The heating rate can be

classified into two types: nonisothermal (slow pyrolysis) heat and isothermal heat. Nonisothermal

heat corresponds to a heating rate of 5-90 ℃/min, and isothermal heat (rapid pyrolysis) corresponds

to a heating rate of approximately 20 ℃/ms (Singh et al., 2019a). Singh et al. reported that in the

nonisothermal heating range, compared to a heating rate of 20 ℃/min, pyrolysis at a heating rate of

10 ℃/min resulted in a lower oil yield and a higher gas yield. However, if the heating rate was

increased drastically, then the gas yield was much higher. Singh et al. reported that during isothermal

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heating at a rate of 20 ℃/ms, only 7% oil was produced, while 91% gas was generated (Singh et al.,

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2019a). This result is in consistant with Efika’s research results, that is, rapid heating rate break the
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plastics rapidly into low molecular weight hydrocarbons which are primarily gaseous, while slow
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heating rate produce a high liquid yield in pyrolysis (Efika et al., 2015).

Fluidizing gas is also called carrier gas and engages in the transportation and dilution of
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vaporized products (Anuar Sharuddin et al., 2016). Most carrier gases are inert gases such as
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nitrogen, helium, argon, and among inert gases, nitrogen gas is used widely because of its low cost
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and feasibility. In some cases, active gases such as ethylene, propylene, and hydrogen are also used.

Fluidizing gas species can influence product yield. Abadi et al. found that lighter gas results in a

higher liquid oil product yield; e.g., in a H2 atmosphere, the liquid oil yield reached 96.7%, while in

an Ar atmosphere, the liquid oil yield decreased to 84.8%, and this value further decreased to 33.8%

when no carrier gas was used (Abbas-Abadi et al., 2014). Furthermore, when gases had similar

molecular weights, such as ethylene and nitrogen, the reactive gas ethylene resulted in higher liquid

oil yield and lower char yield (Abbas-Abadi et al., 2014).

The composition and structure of the feedstock plastic influence the pyrolysis products and their

27
yield. For example, compared to PE and PP, PS is prone to pyrolysis with a high product yield.

Achilias et al. observed that when HDPE and PP were used for pyrolysis at 450 ℃ in a fixed bed

reactor, the liquid yields were 44.2 wt% and 64.7 wt%, respectively (Achilias et al., 2007). When PS

was pyrolyzed at 410 ℃, the liquid oil yield reached 97 wt% due to its polycyclic nature (Onwudili et

al., 2009). PVC is a kind of plastic that is not suitable for pyrolysis because it contains a high amount

of chlorine, which can be converted to toxic gases such as HCl, causing equipment corrosion and

environmental pollution. Therefore, a dechlorination process for PVC is needed to reduce the

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chlorine content in liquid oil or gas products (Anuar Sharuddin et al., 2016). In addition to the effect

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of the composition and structure of a certain plastic on the pyrolysis products and yield, the plastic
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mixture also affects the products and yield. Lee et al. reported that when PE and PS are mixed
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together as a pyrolysis feedstock, PE radicals attack PS via hydrogen abstraction to form PS radicals,

which in turn facilitate PE radical generation (Lee et al., 2004). PE and PS work synergistically to
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accelerate PE and PS pyrolysis and further increase the octane number. Considering that a polymer
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mixture feedstock is more similar to the actual application situation than a single type of plastic,
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different kinds of plastic may work synergistically to affect pyrolysis products and yield. Therefore,

the feedstock composition of pyrolysis is an important parameter.

Catalysts are widely used in the pyrolysis of NPW because they can change the kinetics and

mechanism of the pyrolysis reaction and in turn affect the optimal parameters, including the

selectivity of the products. In most cases, the use of catalysts increases the cracking reaction rate,

resulting in an increase in gas yield and a decrease in liquid oil yield, but the carbon number

distribution narrows and the octane number increases because some longer-carbon-chain compounds

are either adsorbed on catalysts or further decomposed into shorter-carbon-chain compounds

28
(Miandad et al., 2016). The catalysts used for plastic pyrolysis can usually be classified into two

types: homogeneous catalysts and heterogeneous catalysts (usually solid catalysts). Homogeneous

catalysts are catalysts that can dissolve in reactants or solvents during pyrolysis, such as AlCl3, FeCl3,

and TiCl3 (Moorthy Rajendran et al., 2020). The most commonly used catalysts are heterogeneous

catalysts because the fluid product mixture can be easily separated from the solid catalyst.

Heterogeneous catalysts include nanocrystalline zeolites, conventional acid solids, mesostructured

catalysts, metals supported on carbon and basic oxides, etc. (Anuar Sharuddin et al., 2016). Manos et

of
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al. used the ultrastable Y zeolite to pyrolyze HDPE, which can narrow the component distribution to

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the gasoline range and increase the octane number of the products (Manos et al., 2000). Miskolczi et
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al. found that when the ZSM-5 catalyst was used to pyrolyze HDPE and PP waste from agriculture
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and packaging sectors, the concentration of impurities such as N, S, P, and Ca was considerably

decreased (Miskolczi et al., 2009). López et al. also observed that the ZSM-5 catalyst decreased the
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temperature significantly without affecting the yields and properties of the pyrolysis products (López
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et al., 2011b). The utilization of catalysts in plastic pyrolysis also results in other favorable changes,
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such as decreasing the retention time and affecting gas or char formation. Different catalysts have

different effects on pyrolysis products. Studying the performance and mechanism of the catalyst has

far-reaching significance for plastic pyrolysis, which can greatly improve resource recovery

efficiency and achieve resource sustainability.

The type of reactor is important in pyrolysis because of its obvious impact on the mixing of

plastics and catalysts, residence time, heat transfer and reaction efficiency (Panda et al., 2010). The

most commonly used lab-scale pyrolysis reactors are batch reactors, semibatch reactors, conical

spouted bed reactors (CSBRs), and continuous-flow reactors (CFRs). CFRs include fluidized bed

29
reactors and fixed-bed reactors. Batch reactors and semibatch and semi-batch reactors are the best

reactors for thermal pyrolysis to achieve high liquid yields because the parameters can be easily

controlled. However, it is not recommended to use these reactors for catalytic pyrolysis, due to the

potential coke formation on the outer surface of the catalyst which can decrease the overall product

yields (Anuar Sharuddin et al., 2016). Furthermore, neither reactor is suitable for large-scale

production due to their high operating cost; therefore, these two reactors are limited to

laboratory-scale use. The fluidized bed reactor is recognized as the best reactor for catalytic pyrolysis

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since the catalyst can be reused many times without the need for frequent feedstock charging and

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discharging, thus reducing labor costs (Anuar Sharuddin et al., 2016). Fixed bed reactors have some
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constraints such as the limited available surface area of the catalyst; however, they are usually used
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as secondary pyrolysis reactors. A conical sprayer bed reactor (CSBR) possesses good mixing

capabilities, which can simultaneously treat NPW with broad particle size distributions and different
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particle densities and treat viscous solids that are difficult to degrade in fluidized bed reactors (Fogler,
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2010). The pyrolysis reactor has an important influence on the pyrolysis products. Taking HDPE
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pyrolysis using silica/alumina catalyst as an example. Seo et al. reported that use a batch reactor

under the pyrolysis temperature of 450 ℃, the pyrolysis product of liquid and gas is 78% and 21%,

respectively (Seo et al., 2003), while Luo et al. reported that when using a batch reactor at a pyrolysis

temperature of 450 ℃, the proportions of liquid and gas pyrolysis products were 83% and 4%,

respectively (Luo et al., 2000). The reactor type affects the bed structure, fluid state, heat transfer,

operation mode, operating conditions, and material waste types, which form a comprehensive

problem. Research on this problem can promote the application of NPW pyrolysis recycling

engineering.

30
 Pyrolysis for NPW treatment has been widely used and studied. Pyrolysis treatment can produce

valuable resources, such as gasoline and diesel. The product yield and selectivity are affected by

pyrolysis processes. The effect has been studied systematically, which makes it possible to produce

resources that best meet people's production needs. Among these products, gasoline has received

widespread attention because of its wide application and high economic value. However, in current

scientific research, the performance of pyrolysis technology is assessed by using the product carbon

number distribution or product yield separately, which cannot reflect the actual yield of the most

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valuable gasoline-range product. Therefore, the concept of actual gasoline-range yield (YAGR), which

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comprehensively considers both liquid yield and carbon number distribution, should be used in
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subsequent research for a more precise assessment of the pyrolysis technique.
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The pyrolysis technique has great market value and can lead to excellent economic benefits, and

this technology has been applied in industry. However, the pyrolysis process requires a large amount
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of heat energy, and coke formation will cause certain damage to the equipment, resulting in regular
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maintenance. How to reduce the energy demand of pyrolysis and alleviate coke production should be
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studied to promote the industrial application of pyrolysis technology in the future.

4.3.2 Hydrocracking

Hydrocracking can also be called hydrogenation. It is a process in which long-chain hydrocarbon

molecules are broken into small molecules, such as gasoline and kerosene, by the addition of

hydrogen under high pressure in a hydrogen atmosphere in the presence of catalysts (Al-Salem et al.,

2017). A simple schematic diagram of hydrocracking is shown in Fig 6.

31
 Fig 6. A simple schematic diagram of hydrocracking. Source: (Munir et al., 2020)

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Compared with pyrolysis, this type of technique has the following main advantages:

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First, hydrocracking can convert waste plastics into high-quality liquid fuels and can provide
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highly saturated liquid fuel products (Kasar et al., 2020). The products possess a narrower molecular
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weight distribution. Hydrocracking shows better selectivity for the gasoline range (C6-C12) product
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than pyrolysis (Munir et al., 2018). Moreover, when pyrolyzing plastics containing benzene rings
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such as PS, the oil obtained contains mainly aromatic compounds such as benzene and xylene, thus
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decreasing the quality of the pyrolysis oil, and additional hydrotreatment steps must be used to
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upgrade the pyrolysis oil (Salbidegoitia et al., 2016). Hydrocracking of plastic can effectively reduce

the aromatic product yield and reduce the heteroatom concentration in the products, the improving

the product quality (Fuentes-Ordóñez et al., 2013).

Second, hydrocracking can increase mass and heat transfer efficiencies. The pyrolysis process

has mass and heat transfer limitations due to the large size of polymer molecules and their high

viscosity as they melt to form a liquid phase (Miranda et al., 2013). However, for a plastic in solution,

the mass and heat transfer limitations are reduced, thereby reducing the reaction temperature of the

process (Gupte and Madras, 2004).

Notably, a hydrogen stream is necessary for the hydrocracking process but it is relatively
32
expensive compared with other fluidizing gases in pyrolysis , such as nitrogen. For example,

electrically produced hydrogen costs approximately $2800 per ton, while the cost of nitrogen is less

than $200 per ton (Ragaert et al., 2017). Moreover, hydrocracking is performed at high pressure,

resulting in high equipment requirements. Therefore, hydrocracking is less popular than pyrolysis

because of its high cost. Therefore, hydrocracking is not the key point of this paper, and a systematic

review of hydrocracking can be found in the work of Munir et al (Munir et al., 2018).

The bottleneck for widespread application of hydrocracking is its high cost and harsh operating

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conditions. The study of improving the process and reducing the cost may facilitate the industrial

application of hydrocracking technology. -p

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4.3.3 Gasification
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In addition to pyrolysis and hydrocracking, gasification is also a type of thermolysis technology

and forms a competitive relationship with the other two technologies. Gasification is a process that
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converts feeds to a syngas containing CO2, CO, H2, CH4 and other light hydrocarbons at high
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temperature in the presence of oxygen; this technique dates from the 1970s (Robinson, 2009; Ruiz et
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al., 2013).

There are many gasification processes used in industry or pilot-scale experiments, such as the

Akzo process, Battelle technique, and Texaco gasification process (Al-Salem et al., 2010). Among

these gasification processes, the Texaco gasification process is by far the most common and

well-known technique (Ragaert et al., 2017). As shown in Fig 7, this process consists of two parts: a

liquefaction step and an entrained bed gasifier. In the liquefaction step, NPW is gently

thermocracked (depolymerization) into several products, including a synthetic heavy oil and some

condensable and noncondensable gas fractions. The noncondensable gases are reused as fuel

33
(together with natural gas) in liquefaction. The heavy oil is filtered to remove large inorganic

particles. The resulting oil and condensed gas are injected into the gasifier. Gasification is carried out

with oxygen and steam at a temperature of 1200–1500 ℃. After a number of cleaning processes

(including removal of HCl and HF, etc.), a clean and dry synthesis gas is generated, which is mainly

composed of CO and H2 and also with smaller amounts of CH4, CO2, H2O and some inert gases

(Tukker et al., 1999). For a detailed introduction to gasification, refer to the review by Ruiz et al

(Ruiz et al., 2013).

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Fig 7. Texaco gasification process diagram. Source: (Tukker et al., 1999)

Compared with pyrolysis with gas products mainly comprising C3-C6, syngas is rich in H2 and

CH4 which can serve as a combustible gas. However, the higher gas flow rate during gasification

operation results in lower throughputs, tougher separation, and lower calorific value of products due

to the dilution effect, which negatively impacts the overall economic benefit (Heidenreich and

Foscolo, 2015). Moreover, the gasification process will also cause some environmental problems by

yielding noxious gases such as NOX. Moreover, the produced syngas contains some impurities such

as NH3, H2S, NOx, alkali metals, and large amounts of tars, requiring an additional purification step

that increases the cost (Dudyński et al., 2015; Ragaert et al., 2017). Gasification requires a
34
high-temperature atmosphere, which requires high-quality equipment and increases the cost. The

study of how to overcome the problems mentioned above is necessary to broaden the application of

gasification in NPW thermolysis treatment.

4.3.4 Chemolysis of NPW for raw monomer recovery

In addition to thermolysis, chemolysis is another resource recycling technology. Chemolysis is

called solvolysis or depolymerization in some literature (Kumar et al., 2011; Ragaert et al., 2017).

Chemolysis of plastic is a process in which individual plastics can be chemically treated or

of
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depolymerized into monomers normally at 80-280 ℃ (Payne et al., 2019). Most of the current

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research on this method focuses on unsaturated polyesters and resins possessing C-O, C-N or other
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hydrophilic groups e.g., polyamides, polyesters, nylons, polyethylene terephthalate, polyurethane,
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polycarbonate, and polylactide (Dimitris et al., 2012; Oliveux et al., 2015; Panda et al., 2010; Payne

et al., 2019; Soroudi and Jakubowicz, 2013). Among these plastics, the widely recycled plastics are
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PU and PET. However, for saturated polymers such as PE and PP, which make up approximately 80%
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of plastic waste, few reports can be found. Moreover, in the chemolysis process, monomer recycling
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operating parameters depend highly on the type of plastic, resulting in difficulty in recycling

monomers efficiently from plastic mixtures with various plastic species. Therefore, the application of

chemolysis is relatively narrow. Currently, some countries are trying to sort NPW, which may

facilitate the application of chemolysis in NPW recycling. Since chemolysis is currently not the

mainstream technology for NPW recycling, This review only briefly introduce the method of

chemolysis. The chemolysis reaction routes mainly include glycolysis, hydrolysis, methanolysis, and

alcoholysis (Kumar et al., 2011).

4.3.4.1 Alcoholysis

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 Depolymerization of polymers in alcohol to form monomers is called alcoholysis (Pardal and

Tersac, 2006). Chemical degradation of polyurethane can be achieved by alcoholysis, resulting in

polyhydroxy alcohols and small carbamate fragments formed by transesterification reactions. No

CO2 is formed in this reaction. If a diol is used as the alcohol, the urethane fragment also contains a

terminal hydroxyl group. The obtained monomers can be reused to form polyurethane foam directly

after adding isocyanates and different proportions of fresh polyhydroxy alcohols (Ullmann, 2003b).

Guo et al. first used alcoholysis under mild and solvent-free conditions to convert polycarbonate into

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bisphenol A with an excellent yield of 97.2% (Guo et al., 2018).

4.3.4.2 Hydrolysis -p
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The depolymerization of polymers in aqueous solution (acidic, alkaline, neutral) is known as
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hydrolysis (Raheem et al., 2019). Hydrolysis can directly recover raw materials by a targeted

reaction of water molecules at the linkage points of the starting materials (Kumar et al., 2011). For
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polyurethane foam hydrolysis, the product yield is very high with the recovery of almost 100% of the
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polyether and 90% of the amine. Moreover, the recycled monomer materials can be reused directly
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with fresh raw materials for the same foam after the hydrolysis reaction. This will improve the

economic benefits while reducing environmental pollution. Under high pressure and temperature, in

acidic, alkaline or neutral (aqueous) media, water hydrolyzes the functional ester groups in PET

bottles or waste to break the polymer chains to form monomers (Raheem et al., 2019). Sinha et al.

reported that PET can be hydrolyzed to terephthalic acid and ethylene glycol at 200-300 ℃ and 1-4

MN/m2 in the presence of esterification catalysts such as alkali metal acetates with water or steam

(Sinha et al., 2008).

4.3.4.3 Methanolysis

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 When a polymer is depolymerized in the presence of methanol, it is called methanolysis (Kim et

al., 2009). The methanolysis of PET leads to the formation of dimethyl terephthalate and ethylene

glycol monomers. These two monomers are potentially valuable for the production of other materials,

such as synthetic resins and epoxy resins. Genta et al. reported that PET can be depolymerized into

dimethyl terephthalate and ethylene glycol through the intermediate methyl-(2-hydroxyethyl)

terephthalate in supercritical methanol at temperatures between 543 and 573 K under estimated

pressures of 0.1-15 MPa (Genta et al., 2005). Kim et al. found that through the methanolysis

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technique, polycarbonate can be depolymerized into bisphenol A (BPA) and dimethyl carbonate

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(DMC) monomers at 160-220 °C without using a catalyst or toxic solvents (Kim et al., 2009).
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4.3.4.4 Glycolysis
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The depolymerization of polymers in the presence of glycol, such as ethylene glycols or

diethylene glycol is known as glycolysis (Kumar et al., 2011). Glycolysis is a commercial PET
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recovery method that has been adopted by well-known companies around the world (such as DuPont
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and DOW) (Ragaert et al., 2017). This chemolysis process is best suited for the recovery of
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polyimide wastes (Scheirs, 1998). Moreover, glycolysis is also the most widely used chemical

recycling process for PU (Simón et al., 2015). Glycolysis is a universal recovery method because, in

addition to the formation of monomers, specialized oligomeric products such as α, ω-dihydroxy

substances (polyols) can also be produced. The latter can be further used in the synthesis of polymers

such as unsaturated polyesters, polyurethanes, vinyl esters, epoxy resins and so on (Ragaert et al.,

2017).

As mentioned above, chemolysis technologies can recover monomers from NPW. The recovered

monomers can be reused to form new polymers via polymerization. In addition, the decomposed

37
monomers can also be repolymerized to form a new target polymer or oligomer by different

chemolysis techniques, which is convenient for manual control. However, the current study only

focuses on unsaturated polyesters and resins possessing C-O, C-N or other hydrophilic groups, such

as PU and PET, which make up only approximately 20% of NPW. Moreover, different types of

plastic require different operating parameters. Therefore, the application scope of chemolysis is

relatively narrow, and classification of NPW is needed in advance. Implementation of the garbage

classification policy will facilitate this industrial application. If chemolysis can be applied to

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saturated polymers such as PE and PP, it will be more attractive to industry.

5. Degradation technology for NPW -p

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As mentioned above, NPW recycling can recover plastic, resources and energy, which is the
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main advantage of recycling technology. Physical recycling can yield plastics with performance

similar to or lower than that of virgin plastics; however, it is known that after several cycles, the
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properties of plastics will gradually decrease, resulting in plastics that are not suitable for reuse and
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that eventually require degradation treatment. Furthermore, the technologies for resource and energy
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recovery possess properties of high energy consumption and high equipment requirements. Moreover,

most resource and energy recovery technologies produce extra byproducts that are toxic or

nonrecyclable and exist in the environment for a long time. Because of these problems, different

technologies for the degradation of NPW reveal their own unique advantages. Ideally, the

degradation products of plastics are CO2 and H2O. Compared with the recycling of plastics, the

degradation of plastics does not require harsh conditions, such as high temperature and high pressure.

Therefore, the degradation of NPW is an environmentally friendly and nonhazardous management

method (Moharir and Kumar, 2019). Most importantly, research on using degradation technology to

38
regenerate other useful chemicals or polymer materials such as C2 fuels during polymer degradation

is emerging, which is more conducive to the utilization of plastic resources (Jiao et al., 2020). Based

on these findings, the degradation of NPW is a promising treatment mode for environmental

sustainability and has attracted the attention of scientists as well as enterprises.

Degradation technologies can be classified into two types: biotic and abiotic technology. The

degradation rate of biotic technology is slow, and the degradation rate of abiotic technology is fast,

but if using abiotic technology only to degrade plastics, the high energy consumption is unfavorable

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for application to plastic pollution. Therefore, research combining the two technologies has received

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extensive attention. Most of the research on abiotic technology focuses on the influence of abiotic
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technology on the physical and chemical properties of plastics rather than the mineralization rate in
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an effort to promote the biodegradability of plastics by changing the physical and chemical

properties of plastics. In this review, Degradation technology is divided into biodegradation

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technology and oxo-biodegradation technology. The former uses microorganisms or other organisms
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to degrade plastics into carbon dioxide and water. In the latter, the polymer first undergoes various
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abiotic predegradation processes, such as photodegradation and thermal degradation, to be degraded

into small-molecule substances that can be easily degraded by microorganisms or other organisms to

carbon dioxide and water.

5.1 Biodegradation of plastic

The biodegradation of plastic is an environmentally friendly treatment that does not generate any

by-products (Moharir and Kumar, 2019). Biodegradation of plastic is a process in which plastics or

polymers are broken down by living organisms or microorganisms, e.g., invertebrates, bacteria, fungi

and even algae (Shah et al., 2008; Yang, S.-S. et al., 2018). The end products of this process are CO2,

39
H2O or other nonhazardous biomass. Biodegradation technology can be divided into two modes. One

is to use invertebrates such as waxworms and mealworms to eat plastic and degrade plastic in their

guts. The other is to use microorganisms to degrade plastic and eventually convert plastic into

nonhazardous substances.

5.1.1 Degradation of plastic with invertebrates

In the 1950s, researchers observed that certain beetles and larvae in the Tenebrionidae,

Anobiidae and Dermestidae families exhibit an interesting ability to eat and damage plastic

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packaging materials (Gerhardt and Lindgren, 1954). However, there has been no effort to study the

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mechanism, and since then only a few reports have described the plastic-eating behavior of
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mealworms. In 2014, Yang et al. first reported the bacterial species in the guts of waxworms that can
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degrade PE films (Yang et al., 2014). This discovery sparked widespread interest among scientists in

the use of insects to degrade plastics. Recently, superworms were used to degrade PS, and it was
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found that almost half of the ingested PS was converted to CO2 via the mealworm gut microbe (Yang
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et al., 2020). Moreover, C-carbon isotope tracer experiments were performed, showing that the
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mineralization of ingested PS was greater than 95%. This report proves again that certain

invertebrates in nature have a positive effect on plastic degradation and that these invertebrate guts

can produce specific bacteria that degrade plastic. Brandon et al. used mealworms to degrade PE and

PS and found that the biodegradation rate of PE is comparable to that of PS (Brandon et al., 2018).

Moreover, they found that Citrobacter sp. and Kosakonia sp. are both related to the biodegradation

of PE and PS, which indicates that the adaptability of the mealworm gut microbiome enables the

degradation of chemically dissimilar plastics (Brandon et al., 2018). An example of mealworms

eating plastic is shown in Fig 8.

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 Fig 8. Mealworms eating Styrofoam. Source: (Yang et al., 2015a)

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The biodegradation of plastics by different invertebrates is listed in Table 5. As shown in Table 5,

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current research on invertebrate-degradable plastics mainly focuses on the degradation of
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polyethylene or polystyrene, because these two plastics are representative and widely used in the
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market (Peng et al., 2020). In addition, the invertebrates used in these studies are generally
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mealworms or waxworms. The dominant microorganisms for degrading PE in the gut are
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Enterobacter asburiae YT1, Bacillus sp. YP1. The dominant microorganisms for degrading PS are
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Exiguobacterium sp. strain YT2, Spiroplasmataceae, Enterococcaceae, Erwinia, Brevibacterium,

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Aeromonas sp. and Klebsiella pneumoniae. Additionally, the microorganisms that degrade both PE

and PS are Citrobacter sp. and Kosakonia sp. Although some authors indicate that Citrobacter sp.

and Kosakonia sp. can degrade different plastics, the current research only focuses on the

degradation of PE and PS. In the future, the sample species should be expanded to include plastics

such as PVC, PET, and PP to test whether strains such as Citrobacter sp. and Kosakonia sp. can

degrade other types of plastics in addition to PE and PS.

As mentioned above, plastic can be degraded by certain bacteria in the gut after being ingested

by invertebrates. Currently reported invertebrates for this function are various mealworms and

waxworms. The greatest advantages of using invertebrates to degrade plastics is that invertebrates
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are easily available in nature and that the degradation products are pollution-free. However, the

degradation rate is slow. Because this technology is currently relatively new, only PS and PE have

been studied, and whether some specific types of microorganisms in specific invertebrates can

degrade most types of NPW should be systematically studied. In the future, research on this

technology should expand the types of plastics studied and expand the types of invertebrates used to

improve this technology’s industrial applicability.

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Table 5. Degradation of plastics by invertebrates.
Dominant microorganisms for Weight loss wt% and
Plastic substrates Invertebrates Time Ref
plastic degradation in guts amount of worms
Mealworms (the larvae of
PS or styrofoam Exiguobacterium sp. strain YT2 31/500 30d (Yang et al., 2015a, b)
Tenebrio molitor Linnaeus)
Indian mealmoths (the larvae Enterobacter asburiae YT1 and
PE 6.1 and 10.7/200 28d (Yang et al., 2014)

f
of Plodia interpunctella) Bacillus sp. YP1

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superworm (the larvae of

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PS foam - 65/300 28d (Yang et al., 2020)
Zophobas atratus)

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PE, PS Mealworms Citrobacter sp. and Kosakonia sp. 48.3 and 31.7/120 32d (Brandon et al., 2018)

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Lesser waxworm (Achroia
HDPE - 43.3/100 28d (Kundungal et al.,

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grisella)

2019)

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3.15 and 1.79/250
SBR and tire crumb Mealworms
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2019)

Dark mealworms (larvae Spiroplasmataceae,

PS 55.4/410 31d (Peng et al., 2019)
of Tenebrio obscurus) Enterococcaceae, and
Enterobacteriaceae
Larvae of the wax
PE - 3.37/100 12h (Bombelli et al., 2017)
moth( Galleria mellonella )
Lesser wax moth (Achroia
PE - - - (Chalup et al., 2018)
grisella)

PS Yellow mealworms Erwinia and Brevibacterium. 35.1/120 32d (Yang, S.S. et al., 2018)

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 Mealworms (Tenebrio Aeromonas sp. and Klebsiella
PS -/20 21d (Tang et al., 2017)
molitor) and superworms pneumoniae
(Zophobas morio)

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5.1.2 Degradation of plastic with microorganisms
According to “BS CEN/TR 15351-2006”, biodegradable materials are required that then can be

mineralized into carbon dioxide, water and biomass during the biodegradation process

(CEN/TR15351-2006). In general, the biodegradation process of polymers can be divided into four

steps (Lucas et al., 2008): (1) biodeterioration, in which microbial biofilms form on the surface,

leading to polymer surface degradation that breaks polymer material into smaller particles; (2)

depolymerization, in which biofilm microorganisms secrete extracellular enzymes, which then

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catalyze the depolymerization of polymer chains into oligomers, dimers or monomers; (3)

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bioassimilation, in which the small molecules produced in the disaggregation process are absorbed
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into microbial cells to generate primary and secondary metabolites; (4) mineralization, in which the
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metabolites generated in the bioassimilation step are mineralized to final products such as CO2, CH4,
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H2O and other metabolites or gases, which are released into the environment. A simple schematic of
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the polymer biodegradation process is shown in Fig 9. It is worth noting that, generally,
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microorganisms mineralize organic compounds into water and carbon dioxide under aerobic
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conditions, while under anaerobic conditions, carbon dioxide, water and methane are produced (Shah

et al., 2008).

H2O
Polymer a. Biodeterioration
CO2

b. Depolymerisation
c. Assimilation CH4

d. mineralisation

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 Fig 9. Simple schematic of polymer degradation. a) Polymers are broken down into small pieces

via various microbial communities. b) Microorganisms secrete catalytic agents to cleave polymer

chains. c) Small molecules are specifically absorbed into microbial cells and produce metabolites. d)

Metabolites are mineralized and produce H2O, CO2, CH4, etc.

Microbial degradation of plastics is affected by many factors, such as the chemical structure,

molecular weight, thickness, and additives of the plastic (Haider et al., 2019). Bovey et al. found that

polymers containing more amorphous areas are more likely to be degraded because of their high

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permeability to oxygen, making them more susceptible to thermal oxidative degradation which is

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beneficial to subsequent microbial degradation (Bovey and Winslow, 1979). Haider et al. reported
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that the thickness of a plastic film affects the efficiency of biodegradation (Haider et al., 2019). The
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thicker the film is, the stronger the polymer is, and the more difficult it is to be degraded. Among the

parameters, molecular weight is the determinant parameter affecting polymer degradation by

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microorganisms (Moharir and Kumar, 2019). In general, an increase in molecular weight results in a
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decreased rate of polymer degradation by the microorganism. In contrast, low-molecular-weight

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polymers such as polymer monomers, dimers, and oligomers are easily degraded and mineralized by

microorganisms. It has been reported that biodegradation can be completed within a reasonable time

when the polyolefin is degraded by microorganisms to an average molecular weight of less than

5000 Da (Reddy et al., 2009).

For different plastics, the suitable types of microorganisms that can degrade plastics are different

(Table 6). As can be seen from Table 6 that the current study focuses on specific plastic degradation

by using specific microorganisms. The time required for microbial degradation of plastics is

generally long. Currently, only a few studies report the final mineralization of plastic after microbial

46
degradation, which is an important index to evaluate the efficiency of plastic degradation. In the

future, research should focus on cultivating microorganisms with the ability to rapidly degrade

plastics and systematically studying microbial degradation of a plastic mixture of different plastic

types considering the total mineralization to increase their industrial feasibility.

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Table 6. Degradation of plastic by microorganisms without abiotic pretreatment.
Plastic
Microorganisms Weight loss wt% Time Mineralization% products Ref.
substrates
MHET,TPA, (Yoshida et al., 2016)
PET Ideonella sakaiensis 201-F6 12 15d 75
CO2, H2O
Penicillium oxalicum NS4 and 55.3, 36.6 and - alcohols,phenols, (Ojha et al., 2017)
HDPE, LDPE 90d
Penicillium chrysogenum NS10 58.6, 34.4a alkanes, alkenes

f
(Giacomucci et al., 2019)

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PVC P. citronellolis and B. flexus 14/- 30d - -

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LDPE Aspergillus niger and terreus 35.3 and 22.1 77d - CO2, H2O, acid (Sáenz et al., 2019)

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Bacillus sp. DG22 and Paenibacillus (Liu, Y. et al., 2019)

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PVA 54.5 and 46.6 8d - -
sp. DG14

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PU Aspergillus tubingensis - 20d - - (Khan et al., 2017)

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Polylactide Laccaria laccata, Clitocybe sp, 20, 15, 12 and 10 (Janczak et al., 2018)
180d - CO2, H2O
(PLA) Arthrobacter sulfonivorans and
Serratia plymuthica
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Carboxylate, (Hung et al., 2019)
PES Papiliotrema laurentii 5307AH 32 8d -
alcohol, CO2

PS Pseudomonas spp. and Bacillus spp. 10 and 23.7 30d - - (Mohan et al., 2016)

LDPE Bacillus subtilis H1584 1.75 30d - - (Harshvardhan and Jha, 2013)

a. These numbers refer to the weight loss rate of HDPE, LDPE under Penicillium oxalicum NS4, respectively, and the weight loss rate of HDPE, LDPE degradation under Penicillium
chrysogenum NS10, respectively.

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5.1.3 Treatment of plastic with composting

Plastic composting is a method that controls plastic biodegradation and transforms plastic into a

substance similar to humus (Shah et al., 2008). In this process, a certain weight of dry plastic is

placed in a definite amount of mature compost mixture and treated with existing microorganisms in

the compost mixture at an intermediate temperature (up to 40 ℃) or a high temperature(over 50 ℃)

(Semitela et al., 2019). One actual example is shown in Fig 10. The microorganisms (mesophilic and

thermophilic) include bacteria, fungi, and actinomycetes (Singh and Sharma, 2008). During

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composting, the water content (usually 60-80%) is maintained, and after a specific time, plastic is

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converted to biomass, minerals, CO2, H2O, CH4, etc. (Unmar and Mohee, 2008). Furthermore, during
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composting, a large amount of eat will be generated, which can destroy some pathogens in the waste
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(Shah et al., 2008). The composting degradation technique is mainly applied to biodegradable

plastics. The currently reported satisfactory efficiency for plastic compositing is from lab-scale
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composting; the dry weight of plastic debris collected after composting is not more than 10% of the
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original plastic dry weight (Korner et al., 2005).

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Fig 10. Practical examples of composting techniques. Source: (Liu, Z. et al., 2020)

Composting plastics is a resource-based treatment technique. Plastic composting can not only

improve the soil performance with generated humus but also obviously reduce the amount of and

harm caused by NPW. Therefore, with the shortage of land resources, NPW composting has great
49
potential for the treatment of plastics in the future. The widespread application of NPW composting

requires the widespread application of compostable plastics. How to produce sufficient compostable

plastics or convert noncompostable plastics into compostable plastics is an issue requiring

collaboration among industry, research, government and citizens to fix.

5.2 Oxo-biodegradation of plastic

As mentioned above, plastic can be degraded by microorganisms or invertebrates. However, it is

difficult for microorganisms to degrade plastic completely in a short time due to the structure of the

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polymer, the long polymer chains, and the presence of additives such as antioxidants in the plastic.

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Therefore, pretreatment of the plastic is needed to predecompose the polymer into products that are
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easy for microorganisms to degrade. Oxo-biodegradation has been studied widely, treating plastic
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with a two-stage process: abiotic oxidation and biotic degradation (Ammala et al., 2011). The first

stage uses photodegradation, thermal degradation and other techniques to oxidize the plastic. The
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second stage uses microorganisms to biodegrade plastic products generated in the first stage. It has
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been reported that the efficiency of the abiotic degradation stage affects the total efficiency of
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oxo-biodegradation (Wiles and Scott, 2006). The unique property of the oxo-biodegradation process,

which combines abiotic and biotic technology, can not only greatly reduce the time required for

plastic microbial degradation but also facilitate the conversion of plastics into harmless products.

This is one of the important NPW treatment technologies studied today.

5.2.1 Photodegradation of plastic

Photodegradation is a process in which polymers can be decomposed by absorbing energy from

light to generate free radicals. In the presence of oxygen, it is also called photooxidative degradation.

In general, near-UV-range light (290-400 nm) is the main light source causing photodegradation

50
(Singh and Sharma, 2008). Fig 11 shows a lab-scale photodegradation reactor. Near-UV-range light

can cleave the C-C bond of the polymer chain because of its high energy (Ravelli et al., 2016).

Compared to other degradation technologies, the photodegradation technique has a unique advantage

since light can be spatiotemporally localized, and controlled in a facile, green and independent way

(Chatani et al., 2014). Photodegradation not only makes use of sunlight in nature to degrade plastics

but also reduces the time required for subsequent biodegradation and provides the possibility for

complete degradation of plastics.

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Fig 11. A lab-scale photodegradation reactor.

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5.2.1.1 Types of mechanisms for plastic photodegradation

Photodegradation of polymers includes several processes such as chain scission, crosslinking and

secondary oxidative reactions, which take place via the generation and transfer of free radicals

(Bracco et al., 2018). There are two main methods to generate free radicals. The first is to irradiate

plastic with UV light without adding chromophores or other additives or catalysts. The second is to

add photoactive species into polymers to facilitate free radical generation. Currently, photoactive

species include photosensitive groups introduced onto polymer chains, such as carbonyl groups and

photoactive fillers mixed into polymers. Photoactive additives can be classified into two types:

additives that undergo decomposition reactions to generate free radicals upon UV light irradiation
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and are then sacrificed during the photodegradation process and additives that continuously generate

free radicals without sacrificing themselves (Grassie and Scott, 1985). To better differentiate these

two additives, the former is named the additive photosensitizer, and the latter is named the additive

photocatalyst. In other words, photoactive species in polymers can be classified into three types:

photosensitive groups in chains, additive photosensitizers, and additive photocatalysts.

5.2.1.1.1 Plastic degradation mechanism via UV light irradiation

UV light in the wavelength range of 280-420 nm can initiate the bond cleavage of polymer C-C

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bonds or C-H bonds directly (Pospisil and Nespurek, 2006). This is because UV wavelengths of 320

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nm and 290 nm correspond to the bond dissociation energies of the C-C bond (375 kJ/mol) and C-H
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bond (420 kJ/mol), respectively, making it possible to break the C-C bond and C-H bond to form
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free radicals (Pospisil and Nespurek, 2006). This process is illustrated in Scheme 1 (initiation part).

Upon UV light irradiation at a wavelength shorter than 320 nm, the C-C bond is broken forming
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alkyl radical R·. This is the initiation step. Then, R· reacts with oxygen to form ROO·. ROO· further
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reacts with the polymer to form hydroperoxide ROOH and R·. This is called propagation, meaning
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that autooxidation starts. R· and ROO· can also react with each other via radical coupling and

disproportionation reactions to result in the termination step.

Initiation:

01 . .
P— R ! P + R (1)
01 . .
R— H ! R + H (2)

Propagation:

. .
R + O2 → ROO (3)
. .
ROO + RH → ROOH + R (4)

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 Termination:

. .
R + R → R—R (5)
. .
R + ROO → ROOR Radical coupling or disproportionation reactions

(6)

. .
ROO + ROO → ROOR + O2

(7)

Scheme 1. Direct photodegradation of polymer by UV irradiation via initiation, propagation and

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termination.

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The hydroperoxide groups ROOH are deemed the most important intermediates in the
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photooxidative process, which is extremely photolabile. The bond dissociation energy of the most
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stable hydroperoxide (H2O2) is 211 kJ/mol, equivalent to the energy of light with a wavelength of

550 nm (visible light) (Wang et al., 2019). The weak O-O bond is prone to breakage, generating
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alkoxy and hydroxyl radicals and accelerating autooxidation (Carlsson and Wiles, 1976). The alkoxy
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radicals can further undergo β-scission, which ultimately leads to the degradation of the polymer
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chain as shown in Scheme 2.

OH
·
O hυ O
+ · OH (8)

·
O β-scission H ·
+
(9)
O
·
O
H-abstraction
(10)
O
Scheme 2. The mechanism of O-O bond cleavage of hydroperoxides, subsequent β-scission and

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 H-abstraction.

The termination reaction of photodegradation usually involves a combination of alkyl radicals or

peroxyl radicals to generate stable products as described in Scheme 1. In general, macroalkyl radicals

can be combined to form crosslinked, branched, or disproportionated products, while peroxyl

radicals are eventually terminated by reacting with other free radicals to form dialkyl peroxides,

carbonyl species or alcohol (Mark et al., 1986). Moreover, the type of termination step is also related

to oxygen pressure (Yousif and Haddad, 2013). Because the propagation and termination reactions

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are similar to all types of plastic photodegradation, these two reactions will not be described later.

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If the polymer is irradiated with light with a wavelength shorter than 320 nm, then the polymer
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should be degraded. However, the higher-energy portion of UV light (280-315 nm) with an energy
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between 426-389 kJ/mol is mostly filtered by the stratosphere, and less than 2% of this light reaches

the Earth’s surface; only the lower-energy portion of UV light (315-400 nm) with an energy of
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389-300 kJ/mol reaches the Earth’s surface (Yousif and Haddad, 2013). Therefore, for polymers
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such as PE and PP, which are mainly composed of C-C and C-H bonds, the degradation rate is very
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slow under sunlight irradiation (Wang et al., 2019). If the polymer possesses other kinds of chemical

bonds in addition to C-C and C-H bonds, then the initiation reaction can occur in a different way to

accelerate polymer degradation. Taking unsaturated polymers as an example, singlet oxygen 1O2

produced by light and oxygen reacts with the unsaturated site through the "Alder-ene" reaction to

generate hydroperoxide group, the important intermediate for the photooxidative process (Scheme 3)

(Mark et al., 1986).

1 01
R − HC = CH − CH − R + O2 !!! R − CH − CH = CH − R (11

) OOH

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 Scheme 3. Photodegradation of unsaturated polymers with singlet oxygen.

5.2.1.1.2 Plastic degradation mechanism via photoactive species

As mentioned above, photoactive species in polymers can be classified into three types:

photosensitive groups in chains, additive photosensitizers, and additive photocatalysts. For the first

type, photosensitive groups in chains and photosensitive groups are introduced to the polymer chains

of
ro
to form chromophores, which can be excited by UV light and participate in subsequent degradation

-p
reactions. One of the most successful examples of this type is the E-CO polymer where carbonyl
re
groups have been introduced into the polymer backbone by copolymerization of ethylene with
lP

carbon monoxide (Roy et al., 2011). The carbonyl groups can also be introduced into the side chains

by copolymerization of vinyl monomers with vinyl ketone (Kirillov et al., 2020). Polymers
na

containing carbonyl or ketone groups can undergo Norrish types I and II and hydrogen atom
ur

abstraction reactions under UV radiation (Scheme 4). The products produced by the Norrish type I
Jo

reaction can react with hydroxyl radicals to form acids (Coffman et al., 1958).
O O
Norrish Ⅰtype (12)
· +·
O O
· + · OH
OH
(13)

O O (14)
Norrish Ⅱ
+

O OH
RH (15)
· + R·
H abstraction

Scheme 4. The photodegradation process of polymers containing carbonyl groups.

55
 In addition to the reactions listed in Scheme 4, the triplet excited carbonyl or ketone groups

caused by light radiation can also transfer their energy to oxygen molecules, resulting in singlet

oxygen (1O2) generation, as shown in Scheme 5. 1O2 can react with unsaturated sites through the

"Alder-ene" reaction, as shown in Scheme 3.

3
%P = O& + O → %P = O& + 1
O2 (16)

Scheme 5. Reaction of triplet excited sensitizer with oxygen.

Another type of photosensitive chromophore in polymer chains is metal-metal bonds in the

of
ro
polymer backbone (Tyler, 2015). The metal-metal bonds can be cleaved by visible light to result in

-p
polymer degradation (Tyler and Chen, 2004). The formed metal radicals are captured by free radical
re
traps, which are usually organic halides or molecular oxygen (Scheme 6) (Tyler, 2003).
lP

01
−R − M − M − R − M − M − R − M − M − R − ! −R − M − M − R − M · + · M − R − M − M − R − (17)
01/7 $ 89 :
−R − M − M − R − M · + · M − R − M − M − R − !!!!!!!!!!!! − R − M − Trap + Trap − M − R −
na

(18)

Scheme 6. Photo-degradation initiation of polymers with metal-metal bonds.

ur

The second type of photoactive species is the additive sensitizer, which is added to and mixed
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with polymers. They can be excited by irradiation to generate radicals to cause initiation. Then, the

additive photosensitizers undergo decomposition. An example of a mechanism for an additive

photosensitizer is illustrated in Scheme 7. These additives include metal chlorides (e.g., cobalt(II),

lithium, titanium, iron(III), nickel(II), copper(II)), M(stearate)n complexes, metal carboxylate and

pigments (Daglen and Tyler, 2010; Parejo et al., 2006; Roy et al., 2008; Singh and Sharma, 2008).

AB
CoCl !! CoCl + Cl · (19)
AB
%RCOO& M !! %RCOO& M + RCOO · (20)

RCOO· /Cl · (21)

PH ·
56
 Scheme 7. Photodegradation initiation of polymers by additive photosensitizer.

The last category of photoactive species is additive photocatalysts which are mixed into polymers

and can be excited by light irradiation to radicals that participate in initiation reactions. They are

stable and do not sacrifice themselves during a reaction. Among additive photocatalysts, TiO2 is a

well-known photocatalyst that can catalyze polymer degradation reactions. The detailed procedure is

shown in Fig 12. In this process, TiO2 can be excited by UV light where electrons from the valence

band (VB) of TiO2 are excited to the conduction band (CB) forming holes (h+) in the valence band

of
and free electrons (e-) in the conduction band (García-Montelongo et al., 2014). In the presence of

ro
-p
water and oxygen, photogenerated electrons can reduce oxygen molecules to form superoxide ion
re
radicals, and holes can oxidize water molecules to form hydroxyl radicals. These are extremely
lP

important reactive oxygen species for the photocatalytic degradation process and can participate in

further radical degradation steps (Liang et al., 2013). Ultimately, the generated reactive oxygen
na

radicals and generated holes can degrade the surrounding polymer molecular chains and trigger
ur

subsequent autooxidation processes. An example of subsequent degradation steps can be seen in

Jo

Scheme 8. Take PE as an example, the reactive species attack adjacent polymer chains to form

carbon-centered radicals resulting in initiation reactions, as shown in Scheme 8 (29) and (30)

(Thomas et al., 2013). Carbon-centered radicals then undergo an autooxidation process to form

peroxy radicals in the presence of O2. The peroxy radicals further react to produce substances

containing carboxyl and carbonyl substances (Shang et al., 2003). In this way, polymers can

eventually be further oxidized to carbon dioxide and water (Scheme 8).

-
·O2
hυ AB
O2
e
-
TiO → TiO De + h G (22)
-
CB e
-
e+
Energy
57
O + e → ·O (23)
h
+
VB h
h
+ H O+ h → · OH + H (24)
H2O
+
H ·OH H O+ ·O → HOO·+ OH (25)
 Fig 12. Mechanism by which TiO2 generates active oxygen species under UV light.

AB
photocatalysts !! · OH + HO· + · O (28)

· OH/HO· · (29)
+ H O/H O

of
+
h ·O
+ HO·

ro
· (30)
O
· O
-p
hυ
O (31)
re
·
O
O O O
O
hυ hυ
+ + O2 CO2 + H O
lP

+ O2 C + C 2
(32)
HO H

Scheme 8. The mechanism of photodegradation of polyethylene in the presence of photocatalysts.

na

Here, a concept must be developed to prevent readers from confusing the photosensitizers and
ur

photocatalysts used in plastic photodegradation. According to the mechanism discussed above,

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photocatalysts do not experience changes in their structural properties during the process of polymer

degradation. That is, under suitable conditions, the photocatalyst will always generate electrons and

holes to further generate active radicals. However, the structure and properties of photosensitizers

will change and even disappear with the progress of the degradation reaction and eventually,

photosensitizers cannot be used. Some reported papers classified photocatalysts and photosensitizers

as a single type of material and named them photosensitizers, which may cause confusion for future

study in the plastic photo-degradation field. Therefore, the photocatalyst is separated from the

photosensitizer category in this review.

58
 Based on the mechanisms of plastic photodegradation mentioned above, this review summarize

the main mechanisms to give a systematic view of the mechanisms, which is shown in Fig 13.

O2
R-CH=CH-CH2-R
1
O2 “ene” reaction (P is represent for polymer chains, different numbers
represent for different lengths of polymer chains)
3
(P=O) R-CH-CH=CH-R O ·
(P3·)
(RCOO)3M / MCln(M is metal like Co(2), Fe(3), Cu(2), etc.) OOH
· H P2
Propagation P

of
O2 PH (P·)
Initiation RCOO·/Cl· PH P1-C-O· P1-C-OH

UV
UV ·

ro
P-R / P-H P POO· POOH OH
O PH
H abstraction ·
·OH
POOP + O2
·OH
P-P
Termination -p
Radical coupling or disproportionation reactions
re
+ H2O2
h O O (P4·)
HOO·

+ · +
·
lP

HOO·
UV

Photocatalyst
· O
- P C
·O2
na

- HO
e
O2
+
h +
P P
ur

Acid, aldehyde, ketone, etc.

Jo

UV
O2

CO2 + H2O

Fig 13. Summary for plastic photo-degradation mechanisms.

5.2.1.2 Controllability of the photodegradation process

As mentioned above, plastic has good durability and can be used for a long time in daily life. The

good durability of plastic meets customers’ requirements during its usage; however, plastic cannot be

easily degraded after disposal, causing severe environmental problems. The photodegradation

process has been studied to increase plastic degradability. The photodegradation process relates to

changes in the polymer chain or additives in polymers, which exist during the service life of plastic

59
and may degrade plastics during their usage before disposal. Therefore, how to control the

photodegradation process is very important to achieve the good stability of plastic during usage and

good degradability after disposal. Daglen et al. reported the gap in controllability between ideal and

real photodegradable plastics (Fig 14) (Daglen and Tyler, 2010). For the ideal photodegradable

plastic, the photodegradation process is suppressed initially for a tunable period to achieve good

stability of the plastic during usage, which results in a stabilization period (Daglen and Tyler, 2010).

After a tunable period, the photodegradation process begins, and the plastic is degraded completely

of
ro
and quickly within a short period of time (Tyler, 2003). For real photodegradable plastics, the

-p
photodegradation process cannot be suppressed initially, affecting the stability of plastic during its
re
service life without a stabilization period, and the photodegradation rate is not high enough to realize
lP

complete and fast plastic degradation in a short time. Therefore, controlling the photodegradation

process for photodegradable plastics is a key point affecting the widespread application of
na

photodegradable plastics.
ur
Jo

100
Ideal Reality
Degradation (%)

0
Tunable
Irradiation time

Fig 14. Comparison between ideal and real photodegradable plastics. Source: (Daglen and Tyler,

2010)

60
 To date, two methods have been applied to suppress the photodegradation process to induce a

stabilization period. One is to add antioxidants to the plastic, which can react with the active radicals

and stop the degradation process, and the other is to use stabilizing agents to screen or absorb UV

irradiation, which can prevent the UV from reaching the bulk of the polymer (Yousif and Haddad,

2013). Ahmed et al. observed that when using sulfadiazine tin complexes to dope PVC, sulfadiazine

tin complexes can react with peroxide radicals to produce nonharmful by-products, preventing the

autooxidation degradation of PVC upon irradiation with UV light (Ahmed et al., 2019). Rabie et al.

of
ro
found that maleic diamides can act as photoabsorbers to effectively alleviate photodegradation of PS

-p
(Rabie et al., 2013). Controlling the ratio of antioxidants in plastic can effectively control the start
re
time of plastic degradation. Malaiaka et al. reported the Scott-Gilead system, in which metal
lP

dithiocarbamates are used as the antioxidants to react with hydroperoxides to form metal carboxylate

complexes and prevent plastic degradation initially. After a long period of UV irradiation, the
na

increasingly generated metal carboxylate complexes can, in turn, accelerate the photodegradation
ur

rate of the polymer chains (Al-Malaiaka et al., 1987).

Jo

Although some technical methods have been applied to suppress the photodegradation process to

achieve stability of plastics during usage, the boundary between the stabilization period and the

degradation period of plastics cannot be clearly identified by users. Plastics may experience

long-term light irradiation during manufacturing, storage, sales, and usage, which makes it difficult

for users to determine whether the plastic is in the stabilization period or the degradation period. This

problem hinders the widespread application of photodegradable plastics. Therefore, it is imminent to

develop a technique to not only tune the stabilization period and degradation period but also clearly

distinguish the nodes between the stabilization period and the degradation period via some changes

61
that can be observed by users, such as color change. Based on the ideal photodegradable plastic

mentioned by Daglen et al (2010), the color change node is suggested to add between the

stabilization period and degradation period to indicate the status of the plastic, as shown in Fig 15.

of
100

ro
Ideal
Degradation (%)

-p
re
Color change node
lP

Color
Color Ⅱ
na

0
Tunable
Irradiation time
ur

Fig 15. Proposed ideal photodegradable plastic with a color change function to indicate the status of
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the plastic.

Studies on the photodegradation of plastics are summarized in Table 7. As can be seen in Table 7,

a few studies have reported the degradation of polymers by using solar light or UV light without any

photocatalysts or photosensitizers. Most of the existing literature studies the photodegradation of

plastics with photocatalysts or photosensitizers without considering the stabilization period, some

studies investigate the effect of stabilizers on the photodegradation rate of plastics, and a few studies

investigate the stabilization period of plastic. Therefore, to facilitate the industrial application of the

photodegradation technique in plastic treatment, more studies on tuning the stabilization period and

62
degradation period should be conducted.

In 2020, Jiao et al. reported using the photodegradation technique to not only degrade plastics

into carbon dioxide and water but also convert CO2 to C2 fuels (Jiao et al., 2020). They used Nb2O5

as a photocatalyst to successfully convert plastic into C2 fuels during the photodegradation process.

This study provides a way to not only alleviate the white pollution problems but also recycle

resources from plastic by using the photodegradation technique.

Among various abiotic degradation techniques, photodegradation is the most widely studied and

of
ro
used technique. To facilitate photodegradation technology development, the following issues should

-p
be considered in future studies. As mentioned above, plastic can undergo photodegradation via direct
re
light irradiation and photoactive species. The photoactive species contain photosensitive groups in
lP

chains, additive photosensitizers, and additive photocatalysts. The photodegradation efficiency is

different for different photoactive species. However, currently, most studies classify photocatalysts
na

as photosensitizers, the two of which are different in terms of whether they are sacrificed during a
ur

reaction, thus affecting the photodegradation efficiency of plastic. This may cause confusion and
Jo

dispute in scientific studies in this area. Separating photocatalysts and photosensitizers into different

categories at the same level is suggested to facilitate further development in the field of plastic

photodegradation. To facilitate the industrial application of photodegradation technology, studies on

balancing the stabilization period and degradation period and how to distinguish the nodes between

the stabilization period and degradation period via color change are necessary. Although only a few

papers report the conversion of plastic to fuels via photodegradation technology, this suggests

promising application of photodegradation to not only degrade NPW but also recycle resources from

NPW.

63
Table 7. Photodegradation of plastics by using various techniques.
Plastic types method Reaction time Weight loss Carbonyl index products dosage wt% Stable time Ref.
and light wt%
source
PS photocatalyst 288h UV 22 - - 1 - (Fa et al., 2013)

PS photocatalyst 150h UV 22.5 - CO2, VSa 2 - (Shang et al., 2003)

f
PP photocatalyst 126h sunlight - 1.5 - 0.2 - (Verma et al., 2017)

o
ro
PP photocatalyst 144h UV 6 2.4 CO2, H2O 1 96h (García-Montelongo
et al., 2014)

-p
LLDPE photocatalyst 33d Solar light - 3 CO2, H2O 8 - (Zenteno et al.,

re
2017)
(Liu et al., 2013)

lP
PE/starch photosensitizer 500h UV - 0.17 - 0.32 -

LDPE photosensitizer 520h UV 40 0.55(230h) CO2, H2O 1 - (Liang et al., 2013)

na
LLDPE photocatalyst 26d Solar light - 1.49 - 5 - (Zapata et al., 2014)

PVC photosensitizer 216h UV ur 71 - CO2, VSa 3 - (Yang et al., 2010)

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PE photosensitizer 63d Solar light - 0.6 - 0.2 - (Pablos et al., 2010)

PE/PP/PS directly chain 90d UV - - - - - (Cai et al., 2018)

cleavage
PE photosensitizer 160h sunlight 37 - CO2, H2O 1.5 - (Zhao et al., 2008)

PS photosensitizer 180h visible 12 - CO2, H2O - - (Nakatani et al.,

2015)
light

PE/PP/PVC photocatalyst 90h visible 100 - CH3COOH, 2 - (Jiao et al., 2020)

64
 light CO2

PVC photosensitizer 30h UV 2.6 - - 2 - (Ahmed et al.,

2019)
PS photosensitizer 300h UV 0.35 - - 0.5 - (Rabie et al., 2013)

PS photocatalyst 600h sunlight 20 -- CO2 2 250h (Lei et al., 2015)

LDPE photosensitizer 180h UV 35 - - 60h (Xu et al., 2018)

f
a. VO is volatile species

o
ro
-p
re
lP
na
ur
Jo

65
5.2.2 Thermodegradation of plastic

It is worth noting that thermodegradation is not equivalent to the pyrolysis where introduced in

section 3.3.1. The main difference between these two methods is their different purpose: pyrolysis

aims to recover fuel such as gasoline, while thermodegradation aims to facilitate the subsequent

microbial degradation by degrading macromolecular polymers into small-molecule products.

Thermodegradation is usually carried out in the presence of oxygen, and the reaction temperature is

lower than the pyrolysis temperature. A simple example of a thermooxidation experiment is shown

of
ro
in Fig 16. Therefore, in this section, thermal-degradation is equivalent to thermo-oxidation

-p
degradation. The mechanism of thermo-oxidation degradation is similar to that of photooxidation
re
degradation, as shown in Scheme 2 (8). In the presence of oxygen, polyolefins can form a
lP

hydroperoxide group under the conditions of heating and shear stress. The O-O bond in this group is

easily broken to form alkoxy groups and hydroxyl radicals, and then degradation continues to form
na

esters and lactone during the autooxidation process via classical free radical chain reactions
ur

(Chiellini et al., 2006). However, one difference between thermo and photooxidation is that ketone
Jo

products are thermally stable but not stable to light (Wiles and Scott, 2006).

Fig 16. Thermooxidation experiment of rubber. Source: (Li et al., 2020).

Jakubowicz studied the thermooxidation degradation of PE and estimated that the average

66
molecular weight of PE is 5000 Da after 2 weeks of treatment at 70 ℃ and after 8 weeks of treatment

at 60 ℃, which indicates that temperature is an important factor affecting the degradation process

(Jakubowicz, 2003). This article also shows that temperature, rather than the oxygen concentration

(in the range of 5-20% oxygen), is the main factor affecting the degradation rate. Khabbaz et al. also

recognized that thermooxidation degradation of plastic, such as PE, can enhance the degradation

efficiency (Khabbaz et al., 1999). They degraded PE at 60 ℃ and 100 ℃ for 14 days and found that

the degradation rate was higher at the higher temperature and that when some pro-oxidants were

of
ro
added to PE, the degradation degree of PE was better.

-p
As mentioned above, compared with the temperature required by the pyrolysis technology, that
re
required by the thermo-oxidation technique is greatly reduced, so the requirements for equipment are
lP

also lower. The decomposed oligomers can be more easily degraded by microorganisms. However,

thermooxidation degradation of plastics takes a long time, which consumes more energy than
na

photodegradation. Follow-up research should be devoted to accelerating the rate of thermooxidation

ur

degradation and reducing energy consumption.

Jo

5.2.3 Mechanochemical degradation of plastic

Mechanochemical degradation of polymers involves degradation under mechanical stress caused

by strong ultrasonic irradiation (Li, J. et al., 2005). In this process, the polymer is subjected to very

high vibrations, which is simply a mechanical force. When ultrasonic waves pass through the

solution, polymer chains are broken down via sheer and mechanical forces with the assistance of

chemical reactions induced by radicals, resulting in reduced molecular weight (Gowariker et al.,

2000). A schematic example of the mechanochemical technique is shown in Fig 17. Moreover, when

the mechanical degradation of the polymer is conducted in the presence of oxygen instead of other

67
inert gases, such as nitrogen, the polymer is degraded rapidly. This is because oxygen can react with

radicals generated by sheer force and facilitate the autooxidation process, while nitrogen or other

inert gases cannot react with radicals resulting in radical recombination (Singh and Sharma, 2008).

of
ro
-p
re
Fig 17. Schematic of the reactor for polymer melt mechanochemical degradation (1-ultrasonic
lP

generator; 2-piezoelectric transducer; 3-horn; 4-die; 5-electric heaters; 6-thermocouple; 7-melt).

na

Source: (Li, Y. et al., 2005)

ur

Li et al. studied the degradation process as well as the molecular weight distribution of the HDPE
Jo

melt during ultrasonic degradation (Li, Y. et al., 2005). In the initial stage, the ultrasonic degradation

of the HDPE melt was a random process, and the molecular weight distribution was broad. After that,

the ultrasonic degradation of the HDPE melt was a nonrandom process, and the molecular weight

distribution became narrower. Finally, the molecular weight approached the limit. This study also

confirms that the mechanochemical method can have a positive effect on the degradation of plastic.

Inoue et al found that the mechanochemical technique is beneficial for dechlorination of polyvinyl

chloride with oxide powders such as CaO, Fe2O3, SiO2 and Al2O3, leading to a reduction in the

molecular weight of PVC (Inoue et al., 2004).

The mechanochemical degradation technique uses ultrasound waves to shear polymer molecules
68
and degrade macromolecules into small molecules. Due to the high energy of ultrasounds, the

degradation of polymers into small molecules is fast. Therefore, the mechanochemical degradation

technique is a promising plastic degradation technique. However, the high requirements for

ultrasonic devices result in high costs. Moreover, a large part of the ultrasound energy is converted

into heat energy, so the energy utilization rate is low, and the energy consumption is high (Ahmadi et

al., 2012). Therefore, in the future, people should focus on reducing ultrasonic energy loss and the

cost of ultrasound equipment.

of
ro
5.2.4 Other degradation techniques for NPW treatment

-p
Other techniques that can generate reactive oxygen species (ROS) can also be used to degrade
re
NPW. These techniques involve reagents such as ozone, the Fenton reagent and other strong oxidant
lP

agents such as persulfate, and thus, ROS can be easily produced.

Zhu et al. observed that when polyvinyl alcohol (PVA) was exposed to ozone in aqueous
na

solutions at 20 ℃, pH=9, and an ozone penetration rate of 18 g/h, the molecular weight of PVA is
ur

reduced from 130191 to 2300, and the degradation rate was as high as 98% (Zhu et al., 2020). Liu et
Jo

al. studied the degradation of PS and HDPE using the Fenton reagent and persulfate in a simulated

microplastic environment (Liu, P. et al., 2019). The results showed that both kinds of techniques can

accelerate the aging of plastics and that it is a promising option for the degradation of microplastics

in aquatic environments.

ROS can facilitate plastic degradation because of their high activity. Although only a few studies

currently use other techniques that can generate ROS to degrade plastics, many techniques can be

involved; therefore, other degradation techniques that can generate ROS are a promising research

direction in plastic degradation.

69
5.2.5 Toxicity of products for NPW after abiotic treatment

As mentioned before, during plastic processing, various additives will be added due to their

different end applications. After abiotic treatment of NPW, various small fragments generated by

degradation and additives will be released. Studying the toxicity of these degradation products and

additives is very important for subsequent biotic treatment of plastics. Wiles et al. reported that some

metal ion additives (such as nickel dialkyldithiocarbamate) have no toxicity effect on the subsequent

biotic treatment of PE mulching film due to their low concentration in plastics (Wiles and Scott,

of
ro
2006). Rojas et al. found no evidence to indicate that oxo-degradation additives have toxic effects on

-p
certain plants (Rojas and Greene, 2007). There is no evidence to show that oxo-degradation plastic
re
fragments undergo harmful bioaccumulation, although there is also no evidence indicating that they
lP

do not (Sen and Raut, 2015). The toxicity of the fragments produced by abiotic oxidative degradation

of plastics has not been studied in-depth and is unpredictable. The problem of biotoxicity of plastic
na

degradation products after abiotic treatment should be paid attention because this can provide
ur

assistance for subsequent biotic treatment.

Jo

5.2.6 Biodegradation of NPW after abiotic treatment

This review have already introduced several abiotic methods for plastic degradation, such as

photodegradation and thermodegradation. Abiotic degradation can predecompose polymers into

products that are easily degraded by microorganisms to decrease the NPW degradation time. It is

also possible to use abiotic technology alone to convert NPW to carbon dioxide and water. However,

the energy cost will be high resulting in low economic efficiency. Therefore, a combination of

abiotic technology and biotic technology can make use of the high reaction rate of abiotic technology

and the low cost and harmless products of biotic technology. The representative reported

70
oxo-biodegradation of NPW is shown in Table 8. Hadad et al. reported that upon degradation by

Brevibaccillus borstelensis, the weight loss for LDPE pretreated with the photodegradation technique

is 6.2% which is higher than that of nonpretreated LDPE (2.5%) (Hadad et al., 2005). When using

photodegradation as a pretreatment technique and then Brevibacillus borstelensis to biodegrade PE,

mineralization can reach 11.5% after 90 days (Abrusci et al., 2011). Jeyakumar et al. also reported

that when PE is pretreated with thermooxidation and then with Engyodontium album MTP091 (F2),

the weight loss is 7.5%, while the weight loss of unpretreated PE is only 6% (Jeyakumar et al., 2013).

of
ro
PS pretreated with ozone exhibits a mineralization rate 16 times that of unpretreated PS when biotic

-p
treatment with Penicillium variabile CCF3219 (Tian et al., 2017). Jakubowicz observed that the
re
thermooxidation products of PE can be further biodegraded, and the degree of bioassimilation after
lP

180 days is approximately 60% which continues to increase (Jakubowicz, 2003). These results fully

illustrates the positive impact of abiotic treatment on subsequent microbial treatment.

na

Most of the current research studies the biodegradation of NPW under specific pretreatment
ur

conditions to generate plastic products with some type of properties. The properties of abiotic
Jo

products are not systematically tuned; therefore, currently, there is no systematic study on the effect

of the properties of abiotically treated plastic products on biotic degradation efficiency, which is a

very important factor to design abiotic technology operating parameters for future industrial

application of oxo-biodegradation technology. Therefore, it is necessary to systematically study the

effect of the properties of abiotically treated plastics on biodegradation efficiency.

71
 Table 8. Oxo-biodegradation of types of NPW.
Plastic Weight
Abiotic pretreatment Microorganisms Time Mineralization% products Ref.
substrates loss wt%
HNO3 treatment, 20 min Aspergillus terreus MANGF1/WL (Sangale et al., 2019)
PE 58.5 60d - -
UV treatment and Aspergillus sydowii PNPF15/TS
R. rhodochrous, N. asteroids and C.
PE Thermooxidation - 180d >60 CO2, H2O (Ashworth et al., 2014)
cladosporoides

f
o
PE Photodegradation Brevibacillus borstelensis - 90d 11.5 CO2, H2O (Abrusci et al., 2011)

ro
PE Nature weathering a year Aspergillus and Penicillium - 90d 12.4 CO2, H2O (Ojeda et al., 2009)

-p
Gamma rays irradiation

re
LLDPE Bacillus amyloliquefaciens 3.2 60d - CO2, H2O (Novotný et al., 2018)
and thermooxidation

lP
LDPE, PP Gamma rays irradiation Aspergillus sp., Paecilomyces
1.5 90d - CO2, H2O (Sheik et al., 2015)
lilacinus, Lasiodiplodia theobromae

na
PE Photodegradation Brevibaccillus borstelensis 14 90d - - (Hadad et al., 2005)

PS Ozone ur
Penicillium variabile CCF3219 - 112d 0.16 CO2, methanol (Tian et al., 2017)
Jo
PE Thermodegradation - - 180d 60 CO2, H2O (Jakubowicz, 2003)

Photodegradation or Phanerochaete chrysosporium NCIM CO2, alcohols,

PP 18.8, 9.42 365d - (Jeyakumar et al., 2013)
Thermodegradation 1170 (F1) and Engyodontium album acids, H2O
MTP091
HDPE, PP, Burkholderia sp., Nitrosomonas sp. 15-20 alkanes,
Photodegradation 90d - (Muenmee et al., 2016)
PS AL212, Nitrobacter, winogradkyi, 5-9 alkenes,
Methylobactor sp., Methylococcus 2-4 alcohols,
capsulatus, Methylocystic sp. and acids, ketones,
Methylocella sp. CO2, H2O
72
6. Conclusion and outlook

This review covers the currently reported advanced NPW treatment methods. Each technique has

its own characteristics and limitations. Traditional incineration and landfills will cause serious

secondary pollution of the environment and have been abandoned by an increasing number of

countries.

Physical recycling methods (ASTM ℃ and ℃) are the most sustainable technologies. However,

the decrease in the performance of plastics after several cycles of physical recycling should be

of
ro
considered, which will result in plastics ending in energy recovery, resource recovery or degradation.

-p
Among energy recovery and resource recovery technologies (ASTM III and IV), pyrolysis is the
re
most widely used technique. Based on the development status of pyrolysis, A combination of the
lP

parameters of liquid yield and product distribution has been proposed, named actual gasoline-range

yield (YAGR). The YAGR can reflect the actual valuable yield of liquid oil and pyrolysis selectivity
na

toward gasoline-range products, facilitating evaluation on industrial applicability of a specific

ur

pyrolysis technique. Hydrocracking and gasification are also excellent energy recovery technologies
Jo

that can recover valuable oil and gas, but the high equipment and operating costs and toxic

by-products should be considered. Chemolysis can recover monomers of polymers. However,

polymers such as polyethylene and polypropylene that contain only C-C bonds and C-H bonds are

difficult to recover with this technique.

Degradation is another promising technology to treat NPW. In biodegradation, some kinds of

invertebrates are used to degrade NPW, and the active microorganisms in the invertebrates have been

reported. However, most of the studies focus on PE and PS, and the degradation efficiency of

invertebrates on other kinds of plastic should also be studied in the future to facilitate their industrial

73
application. Microbial degradation has also been studied widely; however, currently, most studies

focus on using one specific kind of microorganism to degrade a certain type of polymer, so research

on microorganisms to degrade mixtures of various plastics should be considered for future industrial

applications.

In most situations, plastic biodegradation will take a long time. Abiotic plastic pretreatment is

necessary to accelerate plastic biodegradation. The combination of abiotic and biotic technology is

called oxo-biodegradation. Abiotic degradation technology can reduce the degradation time of

of
ro
plastics in the biodegradation stage. The abiotic degradation mechanism is summarized

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systematically based on photodegradation. Combined with specific initiation mechanisms of
re
thermodegradation, mechanochemical degradation and other techniques, the summarized mechanism
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can also be used for other abiotic technologies. Most plastic photodegradation studies classify

photocatalysts as photosensitizers, although the two are different in terms of whether they are
na

sacrificed during a reaction, thus affecting the photodegradation efficiency of plastic. To avoid
ur

confusion in future studies, photocatalysts and photosensitizers are suggested to separate into
Jo

different categories at the same level. The controllability of photodegradation performance is

important for photodegradable plastics. Ideal photodegradable plastics are suggested to not only tune

the stabilization period and degradation rate, but also clearly distinguish the nodes between the

stabilization period and the degradation period via an observable color change. Although many

studies have reported oxo-biodegradation of plastics, there has been no systematic study on the effect

of plastic product properties after abiotic treatment on biotic degradation efficiency, which is a very

important factor in the selection of abiotic technology operating parameters for future industrial

applications of oxo-biodegradation technology. Moreover, only a few studies have systematically

74
reported the toxicity of abiotic products and their effect on subsequent biodegradation. In subsequent

studies, these aspects of the work should be paied attention to. Recently, the conversion of plastics

into useful resources by controlling the degree of plastic degradation has emerged, which combines

plastic recycling with degradation and sheds new light on NPW treatment.

Acknowledgements

This work was financially supported by Science and Technology Commission of Shanghai

of
Municipality (No. 19ZR1415500), Fundamental Research Funds for the Central Universities and

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Shanghai Engineering Research Center of Biotransformation of Organic Solid Waste
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(SERC2020B01).
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Highlights

Plastic waste disposal technologies are reviewed based on recycling and degradation.

The mechanisms for pyrolysis and photo-degradation are systematically summarized.

Actual gasoline-range yield is proposed to assess the actual pyrolysis performance.

Ideal photodegradable plastic model with indicating color change node is proposed.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

None.

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