Journal of Polymer Science - 2020 - Thiounn - Advances and Approaches For Chemical Recycling of Plastic Waste

Received: 10 December 2019 Revised: 7 March 2020 Accepted: 13 March 2020
DOI: 10.1002/pol.20190261
REVIEW
Advances and approaches for chemical recycling of plastic

waste
Timmy Thiounn | Rhett C. Smith
Department of Chemistry and Center for

Optical Materials Science and Engineering
Abstract
Technology, Clemson University, The global production and consumption of plastics has increased at an
Clemson, South Carolina
alarming rate over the last few decades. The accumulation of pervasive and
Correspondence persistent waste plastic has concomitantly increased in landfills and the envi-
Rhett C. Smith, Department of Chemistry ronment. The societal, ecological, and economic problems of plastic waste/pol-
and Center for Optical Materials Science
lution demand immediate and decisive action. In 2015, only 9% of plastic
and Engineering Technology, Clemson
University, Clemson, South Carolina, waste was successfully recycled in the United States. The major current
USA. recycling processes focus on the mechanical recycling of plastic waste; how-
Email: [email protected]
ever, even this process is limited by the sorting/pretreatment of plastic waste
Funding information and degradation of plastics during the process. An alternative to mechanical
Directorate for Mathematical and Physical processes is chemical recycling of plastic waste. Efficient chemical recycling
Sciences, Grant/Award Number: CHE-
1708844 would allow for the production of feedstocks for various uses including fuels
and chemical feedstocks to replace petrochemicals. This review focuses on the
most recent advances for the chemical recycling of three major polymers found
in plastic waste: PET, PE, and PP. Commercial processes for recycling
hydrolysable polymers like polyesters or polyamides, polyolefins, or mixed
waste streams are also discussed.
KEYWORDS
plastics, polyethylene, polyethylene terephthalate, polypropylene, recycling
1 | INTRODUCTION dogged environmental persistence in the oceans[6–8] and

on land.[9] The current review aims to highlight contem-
The term “plastics,” in common verbiage, refers to syn- porary academic efforts to develop new methods for
thetic polymers that are ubiquitous in modern society, to recycling some of the most abundantly produced plastics.
the extent that each person consumes 50 kg per year in Specifically, efforts to chemically recycle poly(ethylene
the European Union and 68 kg per year in the United terephthalate) (PET), polyethylene (PE), and polypropyl-
States.[1] Plastics pervade daily life as packaging,[2] cloth- ene (PP), in their various forms, will be discussed. These
ing and sports equipment,[3] biomedical devices,[4] elec- approaches demonstrate some of the chemical methods
tronic components,[5] and in a panoply of other that are effective in recycling hydrolyzable and non-
applications. Unfortunately, the majority of high market- hydrolyzable plastics. Many of these approaches are lev-
share plastics are obtained from the use of nonrenewable eraged by industry to address recycling of mixed plastic
and ecologically devastating petroleum/natural gas feed- waste streams, as will be discussed in the second half of
stocks and processing techniques. The imperative to this review.
access new technologies for recycling and repurposing The Society of the Plastics Industry (SPI) has assigned
plastics is clear given their unsustainable origins and different plastics with Codes 1–6 in order to more easily
J Polym Sci. 2020;58:1347–1364. wileyonlinelibrary.com/journal/pol © 2020 Wiley Periodicals, Inc. 1347

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1348 THIOUNN AND SMITH
identify the polymer used in the production of the mate- plastic waste, however, only 9% was recycled. This com-
rial as well as to expedite the recycling process.[10] pares with 16% that was incinerated and 75% that was
Table 1 summarizes common polymers classified in this landfilled.
way, with some of their most familiar uses highlighted. Contrast these low recycling numbers with the strik-
Organized disposal of vast quantities of plastic waste con- ing fact that an energy saving to society of approximately
sists primarily of landfill techniques, while practices of seven barrels of oils is accrued for every ton of mixed
dumping into waterways still persist, particularly in less plastic waste that is recycled,[13] and it becomes self-
environmentally regulated areas of the world. Beyond evident that oil and energy conservation could be astro-
ecological effects of these behaviors, there are economic nomical if we could implement an effective recycling
and geopolitical concerns of ongoing reliance on the strategy. Should we reach the apex of accomplishment by
dwindling petroleum/natural gas supply available for a recycling all of the plastic waste, consumption of nearly a
growing population. quarter billion barrels of oil could be saved each year
Efforts to recycle plastic waste have grown in mete- from recycling of U.S. plastic alone.
oric fashion over the past two decades, yet the challenges Certainly, not all plastics can be as easily recycled as
associated with harnessing postconsumer plastics as feed- others. In 2015, about 18% of PET was recycled, while
stock for new products are sufficiently severe that the rel- only 10% of high-density polyethylene (HDPE), 6% of
ative amount of plastics recycled remains embarrassingly low-density polyethylene (LDPE)/linear low-density poly-
low.[11] In 2015, approximately 262 Mt of municipal solid ethylene (LLDPE), and < 1% of PP were recycled.[12] A
waste (MSW) was generated in the United States.[12] Of plethora of complexities affect recycling rates, from prac-
the 262 Mt of MSW, a full 13% (34.5 Mt) was constituted tical considerations of collection, sorting, and pre-
of putatively recyclable plastic waste. Of these 34.5 Mt of treatment (e.g., what contaminants, adhesives, colorants,
TABLE 1 The SPI code identification number of polymer resins in plastic products, their structure, and common uses
SPI Polymer Structure Uses

Code
1 Poly(ethylene terephthalate) Soda bottles, water bottles, medicine jars, and
(PET) salad dressing bottles
2 High density polyethylene Soap bottles, detergent and bleach containers,

(HDPE) and trash bags
3 Polyvinyl chloride (PVC) Plumbing pipes, cables, and fencing
4 Low density polyethylene Cling wrap, sandwich bags, and grocery bags
(LDPE)
5 Polypropylene (PP) Reusable food containers, prescription bottles,

and bottle caps
6 Polystyrene (PS) Plastic utensils, packaging peanuts, and

styrofoam
7 Other
Abbreviation: SPI, society of plastics industry.

THIOUNN AND SMITH 1349
F I G U R E 1 Common fates for

current plastic waste [Color figure can
be viewed at wileyonlinelibrary.com]
O O
or residues might be present), to more technical consider-
ations such as chemical reactivity.10 To better understand
the state-of-the-art in addressing these complexities, it is HO OH
instructive to introduce the four classifications of Terephthalic Acid OH

TA HO
recycling: primary recycling, secondary recycling, tertiary PET
OR
recycling, and energy recovery. Primary recycling, also O O
known as closed-loop recycling, is the process of taking
uncontaminated discarded plastics and directly turning
H3CO OCH3
that material into the same “new” product, ideally with- Dimethyl terephthalate
out loss of properties.[14] A familiar example of this DMT
would be to use clean aluminum pipes and use the metal

S C H E M E 1 The synthesis of PET from terephthalic acid or
to make new aluminum pipes. Secondary recycling refers dimethyl terephthalate. PET, poly(ethylene terephthalate)
to mechanical recycling, wherein the chemical identity of
the polymer is unchanged, but the polymer is in some
way physically reprocessed, and thus generally used for a amount of energy is recovered in the form of heat. This is
different purpose than its original use.[15] An example of generally a “last resort” process when no more value-
this is taking waste tires and using the rubber crumb as added application is achievable. Incineration of many
an additive in rubber flooring or park benches. In the plastics also releases hazardous gases and leave behind
context of polymers, the most prevalent problems with toxic residues, presenting undesirable hazardous waste
primary and secondary recycling are related to stability. remediation and collection costs and downstream ecolog-
As the polymers are continually reprocessed, the polymer ical consequences.[14]
may degrade to varying extents, which will have drastic The overall efficiency of recycling plastic waste begins
effects on the mechanical properties of the postrecycled with the sorting and pretreatment process of plastic
product.[15] Additionally, the need for pure/clean plastic waste. Different plastics have different properties and
waste is a significant barrier when postconsumer, mixed- thus have different recycling methods. From the typical
source plastic is targeted for recycling. mixed waste model, each type of plastic must first be
Tertiary recycling, sometimes referred to as chemical sorted. Contaminated plastics in the waste stream can
recycling, uses chemical processes to break down the lead to unwanted decomposition reactions that will
polymer into value-added commodities. Typical processes decrease the efficiency of plastic recycling as well as alter
include hydrolysis[14] and pyrolysis[16] of waste plastics. the end product. While there are many different types of
The product obtained is then used as a feedstock for the sorting processes that have been utilized and are cur-
production of fuels and polymers.[17,18] The last form of rently being studied for optimization,[19,20] this review
recycling is incineration of the polymer for energy recov- will focus on chemical recycling methods of plastic waste
ery. In this process, the polymer is incinerated, and some that occur once sorting is complete.
2 | ACADEMIC ADVANCES IN temperatures and/or with a catalyst).[28] The products

P L A S T I C RE C Y C L I N G yielded from this method are TA (or a terephthalate salt)
and EG. There are three different types of hydrolysis that
2.1 | Recycling of poly(ethylene have been studied in greatest detail: acidic, alkaline, or
terephthalate) (SPI Code 1) neutral hydrolysis. While acidic hydrolysis can take place
using concentrated acids, such as phosphoric or nitric,
Poly(ethylene terephthalate), often abbreviated PET or the most common acid used is sulfuric acid.[29–31]
PETE, is a semicrystalline, thermoplastic polymer that is Although the yields obtained from this method are gener-
known for its high strength. Industrially, PET is synthe- ally high, separation of the EG from the highly acidic
sized through a polycondensation reaction between eth- solution is a major drawback of this method. Addition-
ylene glycol (EG) and terephthalic acid (TA) or through a ally, the amount of acid needed to industrialize this pro-
transesterification reaction between dimethyl terephthal- cess pose economic, process, and environmental
ate (DMT) and EG (Scheme 1).[21] Efficient recycling of problems.
PET has reached the most advanced stage of maturity Alkaline hydrolysis generally employs aqueous solu-
among the common plastics, and a variety of methods tions of 4–20 wt% NaOH.[30] This process yields the sodium
have proven utility on a large scale.[21–23] There have terephthalate and EG in relatively good yields, up to 100%
been instances where PET undergoes primary and sec- PET conversion. However, longer reaction times (3–5 hr)
ondary recycling, that is, the recycling of plastic bottles. and high temperatures (>200 C) than needed for acidic
However, a significant remaining problem with recycling hydrolysis techniques are notable drawbacks of this
of PET is that the mechanical properties of the nonvirgin method. Polk et al.[32] have recently improved on the alka-
material are greatly reduced with each reuse. The strain- line hydrolysis process, demonstrating that the addition of a
at-break (the percent of the length that a sample can be phase transfer catalyst (trioctylmethylammonium bromide)
stretched before the sample breaks) for virgin PET, for facilitated the reaction at lower temperatures (70–95 C)
example, is 42%, whereas after only the fifth cycle of while yielding high purity (99.6%) TA in up to 93% yield.
extrusion, the strain-at-break was only 0.7%.[24] This Neutral hydrolysis employs water or steam in the
downcycling process limits the ability to thermo- presence of catalysts.[30] This process uses high tempera-
mechanically recycle PET. For this reason, tertiary tures (200–300 C) and elevated pressures (1–4 MPa).
recycling via chemical processes has been the main focus Neutral hydrolysis, without the need for stoichiometric
of research in the past few years.[21,25] acid or base, would be ideal, but these processes generally
PET can undergo pyrolysis to yield its precursor produce low purity monomers and have relatively slow
monomers, TA, and EG. Kenny et al.[26] have shown that rate of reaction.[30] This process does not take into
the pyrolysis of PET at 450 C yields TA and oligomers account for any mechanical impurities, such as sand and
thereof, which can be further hydrolyzed to obtain the particulates, which can reduce the purity of the monomer
TA monomer. Despite such promising advances, the for further use. Campanelli et al.[33] found that the use of
pyrolysis of PET is seldom used as a method to depoly- large ratios of water:PET (5:1) are needed for the com-
merize PET into its monomeric units on an industrial plete depolymerization of PET.
scale because pyrolysis generally leads to other liquid and Another method to depolymerize PET into its mono-
gaseous side-products, reducing process efficiency, and mers is through methanolysis. In this process, methanol
necessitating costly separation steps.[21] reacts with PET at high temperatures (180–280 C) and
Du et al.[27] used PET from carpet waste as a source pressures (20–40 atm) in the presence of a catalyst, most
and studied the thermal and catalytic decomposition of commonly zinc acetate.[34,35] This reaction leads to the
this waste into oils. The catalytic degradation focused on formation of DMT and EG, which can then be used to
using an aluminosilicate zeolite, ZSM-5, or CaO as the resynthesize PET through a transesterification reaction.
catalyst. They also looked at how steam would affect the A major drawback of this method, outside of the high
final decomposition products. They found that using a temperatures and pressures, is again the purification pro-
catalyst, namely CaO and steam during the pyrolysis process. The crude product contains not only DMT and EG
cess would yield large percentages of benzene in high but also other alcohols and phthalate derivatives.[21] A
purity. These studies foreshadow the promise held by noteworthy advance was developed by Tang et al.,[36]
many decades of plastic waste to serve as the next source who demonstrated that DMT recovered from
of what are typically viewed as petrochemicals. methanolysis of PET could be exploited as a starting
Another chemical process that has shown great prom- material for the synthesis of gasoline and jet fuel.
ise for the depolymerization of PET into its monomeric Aminolysis of PET is an area that has not been widely
units is hydrolysis (reaction with water at elevated exploited, likely because this process requires an amine
(which is often toxic or expensive) to depolymerize PET, sustainably produced organocatalysts such as urea in
yielding diamides of TA. The reaction temperatures gen- place of transition metal catalysts. Urea was quite an
erally range from 20 to 100 C.[21] In a study done by effective catalyst, facilitating 100% conversion of PET
Teotia et al.,[37] four different amines—methylamine, with 74% selectivity of BHET. Additionally, urea could be
ethylenediamine, ethanolamine, and butylamine—were recycled five times without loss of activity or selectivity
reacted with PET. Unprecedented conversion of PET into for BHET.
lower molecular weight oligomers was achieved at ambi- Ionic liquids can also be used as a catalyst for the gly-
ent temperatures and pressures, but this required reac- colysis of PET.[47,48] Despite their high initial cost, ionic
tion times ranging from 10 to 85 days. Soni et al.[38] also liquids have become increasingly attractive tools for
studied aminolysis of PET with a variety of amines and green chemistry because of their low volatility and recy-
achieved complete degradation of the PET to the diamide clability. Consequently, Yue et al.[49] have explored the
after 45 days of reaction. Hoang et al.[39] showed that eth- utility of 1-butyl-3-methylimidazolium hydroxide,
elyenediamine was even more effective and was able to ([Bmim]OH) to serve as a catalyst. A 100% conversion of
depolymerize PET to yield a range of oligomers after only the PET with a selectivity of 72% of BHET was achieved,
17 hr at 100 C. Significantly, longer reaction times were compared to only 11% conversion of PET without the
needed to achieve degradation to small molecules; how- addition of the ionic liquid as a catalyst. In a follow-up
ever, several catalysts, such as dibutyl tin oxide, sodium study,[50] these researchers found that Lewis acidic
acetate, and cetyltrimethylammonium bromide, are ([Bmim]ZnCl3) ionic liquid likewise facilitated a 100%
under development that show promise for shorter reac- PET conversion but with improved selectivity of 84% for
tion times and improved selectivity, but these have not BHET and minimal catalyst loading (0.16 wt%). Liu
yet demonstrated large-scale applicability.[40,41] et al.[51] reported that deep eutectic solvents could also be
Glycolysis of PET is an area that has been widely used to catalyze the glycolysis of PET with EG. They
studied. This is a very versatile process due to the various found that the combination of 1,3-dimethylurea
potential applications of the products obtained. In this (1-3-DMU) with 5 wt% Zn(OAc)2 was able to convert
process, PET is depolymerized by glycols to form mono- 100% of the PET with 82% selectivity for BHET at 190 C
mers, oligomers, and/or polyols, which can then be used in just 10 min. They associated the high selectivity with
for different applications. Some of the glycols that have relatively mild reaction conditions due to the acid–base
drawn particular recent interest for this application synergistic effects between 1-3-DMU and Zn(OAc)2. The
include ethylene glycol, diethylene glycol (DEG), propyl- catalyst was also recycled up to five times without any
ene glycol, butylene glycol, and dipropyleneglycol loss in conversion efficiency. However, the zinc content
(DPG).[42,43] If EG is used to depolymerize PET, the was shown to decrease by 25% after the five cycles, which
major product formed is bis(2-hydroxyethyl) terephthal- limits further recycling ability of the catalyst.
ate (BHET), which can be used to synthesize PET. A Whereas the foregoing discussion highlights efforts
challenge in these promising reactions is the immiscibil- to leverage glycolysis of PET with EG to synthesize
ity of PET with the polyols. Liu et al.[44] sought to address BHET as a monomer feedstock, an emerging area of
this problem by conducting a careful study on the role of interest is the use of the chemically recycled PET prod-
different solvents in the conversion of PET to BHET. ucts as feedstocks for other polymer formulations.
DMSO proved most effective among solvents screened for Mecit and Akar[52] used different glycols to convert
effective cosolvation of EG and PET and thus showed an PET into lower-weight oligomers having hydroxyl end
increase in BHET yield to 82% (when compared to 20% groups that were then reacted with toluene
without the addition of DMSO) with remarkably short diisocyanate to produce urethane oils. The recycled
reaction times of 1 min at 190 C and atmospheric urethane oils showed similar Koenig hardness values
pressure. and touch/hard to dry times to commercially available
Catalyst development has also been an area of active oils. Desai et al.[53] synthesized polyol blends by
research. For many years, zinc acetate was the primary reacting PET waste with plant-derived starch. The olig-
catalyst used in the glycolysis of PET. Troev et al.[45] have omers so formed were then esterified with fatty acids—
recently developed a titanium (IV) phosphate catalyst for themselves primary constituents of low-value, high-
the glycolysis of PET using EG, DEG, or 1,2-propylene volume waste products from other industries.[54–58]
glycol. This catalyst achieved shorter reaction times than The esterified materials were then used to synthesize
previous catalysts, with increased yield and selectivity for polyurethanes. These authors also demonstrated the
BHET formation. Titanium is advantageous because it is facile tunability of adhesion, flexibility, and chemical
nontoxic, though the catalyst could not be efficiently resistance properties of the polyurethanes as a function
recycled. Wang et al.[46] have sought to exploit of PET products present in the formulation.
Amaro et al.[59] used DEG and PET to synthesize oligo-

mers that proved effective as secondary plasticizers in PVC
formulations resulting in improved thermal stability and HDPE
flexibility of the final PVC product. Furthermore, migration

of PET-derived plasticizer migration was greatly decreased
compared to traditional PVC plasticizers such as,
di(2-ethylhexyl)phthalate (DHEP) which leach out over
time. Initial PET oligomerization was achieved in this
instance by action of a Ca/Zn stearate catalyst at 250 C for
LLDPE
only 20 min. Recently, Sirohi et al.[60] have described
alcoholysis of PET to synthesize oligomers that can be used
as a plasticizer in nitrile-PVC rubber blends. They used a
ZnCl2 catalyst and 1-decanol as the alcohol with reaction
temperatures of 190 C for 4 hr. Once resultant
depolymerized products were blended with nitrile-PVC rub-
ber blends, the tensile properties and the aging resistance of
the materials was significantly buttressed.
LDPE
2.2 | Polyethylene (SPI Codes 2 and 4)
Polyethylene is a lightweight and durable thermoplastic

that finds use in films, tubing, packaging, plastic bags
and bottles, and even automobile parts. PE is typically
made by polymerization of ethylene (C2H4), often facili-
tated by a Ziegler–Natta or metallocene catalyst.[28] The F I G U R E 2 The differences between HDPE (no branching),
linear alkyl chains comprising the PE backbone lack LLDPE (short branches), and LDPE (long branches). HDPE, high-
polar functional groups, and are inert to many chemical density poly ethylene; LDPE, low-density poly ethylene; LLDPE,
reactions, including common acids and bases, under linear low-density poly ethylene
standard conditions. To complicate recycling efforts fur-
ther, there are multiple types of PE: HDPE, LDPE,
LLDPE, ultrahigh molecular weight polyethylene, and products.[61] Moreover, the melt flow index (a key figure
many other crosslinked types of PE.[28] Each of these dif- of merit for processability) changes by two orders of mag-
ferent types of PE is used for different purposes nitude, from 2.25 (reasonable flow) for virgin LDPE to a
depending primarily on the mechanical property profile nearly unprocessable melt flow index of 0.02 g/10 min
required. The most-used PEs include HDPE (SPI Code 2) after 100 extrusion cycles.[61] This changing behavior is
and LDPE/LLDPE (together sharing SPI Code 4). HDPE accompanied by drastic, deleterious drift of mechanical
is flexible, translucent, and shows good toughness at low properties of the recycled LDPE, so these approaches do
temperatures. There is little to no branching in HDPE, not provide a long term, sustainable path forward for PE
thus it is said to be a linear polymer. LDPE and LLDPE recycling. When mechanical processing of PE is no lon-
differ from HDPE in that both are branched polymers. ger feasible, depolymerization of PE through pyrolysis to
LDPE is semirigid and has branches that are both short yield hydrocarbons for fuel/energy applications is often
and long throughout the polymer backbone. LLDPE dif- the final stage of use for such materials.
fers from LDPE in that this form of PE features only There are two major processes for the pyrolysis of PE:
shorter branches (Figure 2). thermal or catalytic pyrolysis. Thermal pyrolysis is simply
The structural variability and relative chemical inert- heating PE at high pressure to break down the polymer
ness of PE have relegated most studies on PE recycling to backbone to form smaller organic molecules. Catalytic
variations on pyrolysis. A primary difficulty associated pyrolysis utilizes a catalyst in an effort to reduce the tem-
with efforts to recycle PE by pyrolysis is that the thermal perature and reaction time and thus improve the eco-
degradation of PE usually proceeds via random scissions nomic viability and, in some cases, the selectivity. In a
at C C bonds. This homolytic scission generates two rad- study by Ahmad et al.,[62] the thermal pyrolysis of com-
ical chains that can go on to form a complex mixture of mercially available HDPE pellets at 350 C which yielded
olefinic products and highly crosslinked polymeric a liquid oil product in 81% yield. The oil consisted mainly
of paraffinic hydrocarbons, most of which, contained amounts of aromatic compounds and showed higher
between 6 and 16 carbon atoms. Specificity for a single heating values between 41 and 42 MJ/kg, which is com-
chemical commodity from PE pyrolysis, however, parable to that of commercially available diesel
remains elusive. An intriguing divergent strategy has (43 MJ/kg).
been devised by Palos et al.,[63] who eschewed the selec- The area of catalytic pyrolysis of PE has also achieved
tivity problem and instead sought to take waste HDPE notable advances in the last few years with regard to
and chemically transform it into a complex mixture akin increasing yields and lowering reaction time/tempera-
to “crude” oil. As long as the complex mixture is com- ture. Santos et al.[66] looked at three different zeolites,
prised by molecules similar to those found in petroleum, HZSM-5, USY, and NH4ZSM-5. These catalysts differ
such a complex mixture could hypothetically be based on pore size, acidic sites, and surface area. This
processed by established petroleum refining and cracking study garnered important insight that catalysts with
techniques. This nascent approach used waste HDPE that larger pore sizes led to a greater yield of liquid products
had already been sorted, washed, and shredded. The and that the less acidic catalysts would yield lighter frac-
HDPE samples so prepared were then heated in a batch tions of gas and liquid products, thus affording flexibility
autoclave reactor at 430 C with short reaction times, up in the process based on end use.
to 38 min, to yield what they refer to as “plastic oil,” with An intriguing study by Chattopadhyay et al.[67] exam-
impressive yields of up to 85–90 wt% oil recovered. While ined the effects of catalysts on pyrolysis of an exceedingly
the oil obtained is not clean enough to be used directly in complex and disparate waste stream of HDPE, PP, PET
place of fuel, this plastic oil can be refined by established and paper biomass (consisting primarily of cellulose).
methodologies to yield target products. The main draw- Cobalt complexes were used as catalysts with various
back of this creative approach is the potentially high chelating agent along with Al2O3 and/or CeO2. The cata-
energy required to produce the plastic oil on large scales. lytic pyrolysis of the paper waste by itself yielded mainly
While many researchers focus on pristine or near- gaseous and solid products, whereas pyrolysis of the
ideal PE sources in their proof-of-principle studies, Das paper/PP/HDPE/PET mixture yielded more liquid prod-
and Tiwari[64] examined the important difference ucts that were rich in aromatics and olefins.
between utilizing virgin and waste plastic products. Addi- The potential for pyrolytic approaches to valorize PE
tionally, a mixed waste feedstock mixture of different waste is counterbalanced by the high energy cost. A
polymers was used. The mixture consisted of HDPE, greener avenue that has shown recent promise in the
LDPE, and PP. The virgin polymers were obtained com- decomposition of plastic waste is the use of supercritical
mercially, and the waste plastics were obtained in the water.[68,69] An added benefit of using supercritical water
form primarily of packaging plastics, plastic containers, is that there is no need for a catalyst. Moriya and
and bottles. The thermal pyrolysis of this mixed waste Enomoto[70] undertook one such study on supercritical
was undertaken at 350 or 400 C and the reaction time water as a medium for the thermal cracking of PE for
was 8 hr. Lower temperature reactions yielded lighter comparison to established pyrolysis techniques. A 5:1
hydrocarbons (< C20) while an increase in temperature ratio of H2O:HDPE was used, and the mixture was
yielded heavier hydrocarbons (> C20). This offers the reacted at 425 C for 2 hr, the oil conversion rate was
potential to tune the oil obtained by varying reaction shown to be 90%.
temperature and holds promise for exploiting mixed Encouragingly, the yield of organic oil produced was
waste streams and thereby circumventing some of the higher for supercritical water cracking, while commensu-
challenges associated with waste separation. rately less coke/char was formed in the process. The oil
Miandad et al.[65] likewise recognized the importance product mainly was composed of a majority of alkenes
of developing strategies to deal with mixed waste. In this with the presence of some alkanes with very little pres-
study, the plastic waste was collected in the form of dis- ence of any aromatic moieties.
posable plates, grocery bags, and cups and comprised not While most of the aforementioned approaches to
only linear alkyl polymers (PP and PE) but also aromatic- recycling PE have focused on the pyrolysis to form
bearing polystyrene (PS) and PET. The plastic samples shorter chain molecules that ultimately tend to be used
were crushed into fine powders and used on their own as in fuel applications, the pyrolysis products may also be
well as mixed together in varying ratios (as little as 20 wt leveraged as feedstocks to produce other polymers.
% PE) with reaction conditions of 450 C for 75 min. Recently, Bäckström et al.[71] depolymerized HDPE waste
Depending on the ratios of the plastic waste liquid oil to synthesize a mixture of succinic, glutaric, and adipic
yields ranged from 24 to 54%. The initial feedstock used acid. This was accomplished through a microwave-
was 1 kg, which shows the potential to scale the system assisted hydrothermal process with the addition of
to an industrial level. The oil obtained consisted of large HNO3. Whereas microwave reactions have in the past
and separate each component are major barriers to

recycling efforts.[73]
isotactic PP
In cases where separation is effective and practical,
there are still drawbacks to melt reprocessing of PP. As
with the other polymers discussed herein, recursive
heating cycles rapidly degrade the PP backbone. Thermal
syndiotactic PP
degradation of PP is more severe than in PE because the
tertiary carbon atom present in the PP backbone is sus-
ceptible to thermo-oxidative and photo-oxidative degra-
dation.[73] While some PP plastics include stabilizer to
atactic PP prevent degradation from occurring, if the PP polymer
has been successfully recycled into a new material, this
F I G U R E 3 The differences between isotactic, syndiotactic, material must then include additional stabilizers to
and atactic PP. PP, polypropylene imbue the “newly” made material the same oxidative sta-
bility, while the buildup of stabilizer and sacrificial stabi-
lizer degradation products contributes commensurately
been dismissed as impractical for large-scale operations, to the deterioration of PP properties. The elongation-at-
recent advances and implementation on a commercial break for a virgin, unstabilized sample of PP is 65%; how-
scale have begun to dispel these preconceptions.[72] The ever, after just 10 recycling cycles the elongation-at-break
products of the microwave reaction were carried forward has decreased to 45%.[74] When PP can no longer be
as plasticizers in a poly(lactic acid) formulation. Incorpo- mechanically recycled through either shredding or melt
rating these PE-derivative plasticizers into the PLA for- reprocessing, there are some emerging strategies to con-
mulation increased the strain at break to 144% as vert PP into value-added feedstocks.
compared to 6% for PLA without the use of any plasti- Interest in tertiary recycling of PP has been growing
cizer. This study illuminates a creative path forward to rapidly. The depolymerization of PP into propylene has
exploit postconsumer petrochemical waste for improved even been accomplished by Guddeti et al.[75] In this pro-
performance of sustainably sourced polymers. cess, PP was depolymerized in an induction-coupled
plasma reactor. Under these conditions, PP was
converted to gaseous products (up to 78 wt%) and of the
2.3 | Polypropylene (SPI Code 5) gaseous product formed 94% was identified as propylene.
Other studies have used plasma as a media to depolymer-
Polypropylene (PP) has a similar backbone to PE, but the ize PP into other value added commodities.[76] One major
presence of an additional methyl group as a sidechain on advantage of using a plasma reactor is that reaction times
each repeat unit has a significant impact on the proper- are very short; however, the cost to setup and operate
ties. PP is a light weight, tough, crystalline thermoplastic plasma reactors on an industrial scale detracts from the
polymer that finds use in reusable food containers, the practical viability of these approaches. Another drawback
automotive industry, and even the furniture market.[73] of using such high temperatures is that any contaminants
PP is synthesized from the propylene (C3H6) using either present, as would be expected in a waste stream, tend to
a Ziegler–Natta or metallocene catalyst. PP can have yield many side reactions and have profound impact on
three different types of structures, atactic, isotactic, and product yields.
syndiotactic,[28] depending on the relative disposition of As for PE recycling strategies, supercritical water is a
the methyl side chains with respect to one another along privileged media for contemporary PP recycling as well.
the backbone (Figure 3). Chen et al.[77] used supercritical water to convert PP into
The configuration of the methyl groups has an effect oil. Optimal reaction conditions were found to be at
on the crystallinity of the PP and consequently on bulk 425 C for 2–4 hr or 450 C for 0.5–1 hr, in which case up
properties. The tacticity of PP generally has little effect to 91 wt% of the PP was converted into oil. The composi-
on recycling techniques and consequently will not be dis- tion of the oil was found to be olefins, paraffins, cyclo-
cussed further here. Very little of the PP that enters the alkanes, and aromatics. The analysis of the oil showed
marketplace—less than 1%—ends up being recycled, that it had similar properties to that of naphtha, which
largely due to the fact that PP is generally found in mixed can be further purified to make gasoline. The use of
waste streams[12] such as cable coverings, electronic supercritical water to depolymerize PP is a largely sus-
appliances, and rugs. In each of those materials, PP is not tainable step toward upgrading waste PP into value-
the only polymer that is present, thus, having to wash added feedstocks.
The decomposition of PP can also yield solid carbona- 2.4 | Current industrial efforts in plastic
ceous products that can be used for various applications. recycling
Liu et al.[78] described a two-stage reactor. In the first step
of the process, PP is catalytically pyrolyzed to yield gas- Given the contemporary importance of plastics recycling,
eous and liquid products. These products are then taken there are significant industrial efforts to commercialize
to the second stage of the process in which the products processes based on the previously discussed strategies to
are thermally decomposed to make either carbon nan- chemically recycle mixed waste streams comprising both
otubes or gaseous products, which mainly consisted of H2 hydrolysable plastics (primarily PET) and non-
or CH4. This process allows for the collection of gaseous hydrolyzable plastics (such as PE, PP, and PS).
and solid products that can be used in different applica-
tions. In a similar vein, Mishra et al.[79] successfully syn-
thesized carbon nanotubes and hydrogen gas from waste 2.4.1 | Industrial approaches to recycling
PP using a chemical vapor deposition method with a PET and mixed polyester waste
nickel-based catalyst. The carbon nanotubes synthesized
by this process showed high transmittance (85%) of light There are many different companies active in the chemi-
at 550 nm, which can be exploited as transparent elec- cal recycling of PET and other polyesters on an industrial
trodes for optoelectronic devices. The gas evolved was scale from real-world waste streams. Most of their
mostly aliphatic molecules, with very little to no presence recycling methods of PET employ variations of the depo-
of aromatics. lymerization approaches discussed in the previous
Given the difficulties associated with obtaining section with the aim of producing various monomers.
near-pure PP from waste, the incorporation of PP into Chemical recycling of PET has reached a more mature
other waste streams for recycling has drawn interest as state due to the relative ease of its depolymerization as
well (some of the PE recycling strategies have already compared to polyolefins.
illustrated this approach; vide infra). The annual avail- Depolymerization of polyesters to several different
ability of gigaton quantities of biomass (primarily lig- monomer feedstocks has been successfully commercial-
nocellulosic) make this an attractive waste stream for ized. Carbios focuses on enzymatic hydrolysis of polyes-
valorization.[80–82] Simple pyrolysis of biomass waste ters such as PET (Scheme 2) to yield TA. While the
alone generally leads to low-value final products. The optimal enzyme varies depending on the particular poly-
addition of PP to biomass waste, however, can enhance ester to be hydrolyzed, the enzymes employed by Carbios
the properties of the final products. Zhao et al.,[83] for are all hydrolase enzymes produced by Thermobifida alba
example, mixed bamboo waste with PP and the or Fusarium solana pisis. The use of T. alba, a
copyrolysis of the two yielded bio oils that have poten-
tial as fuels. To accomplish this transformation, a zeo-
lite catalyst (HZSM-5) was used while the bamboo:PP
ratio and catalyst loading were varied. Even under
optimal conditions, bamboo alone still gives quite a
poor oil yield (30 wt%) and low oil quality. The
bamboo-derived oil consisted primarily of aliphatic
hydrocarbons.
When a 2:1 ratio of bamboo:PP was employed, they
found that oil production could be more than doubled
to 62 wt% with attendant improvement in oil quality.
The bamboo/PP-derived oil consisted of more aromatic
and naphthenic compounds. Such compositions are
ideal feedstocks for jet fuel production due to the large
amounts of heavier hydrocarbons produced. Lee
et al.[84] further demonstrated the broader scope of
such processes by showing that PP addition to high cel-
lulose content agricultural waste from sources other
than bamboo can likewise improve the production of S C H E M E 2 General reactions for the hydrolysis,
oils in high yields and of more desirable composition methanolysis, and aminolysis of PET to synthesize terephthalic acid
than can be accomplished by pyrolysis of cellulose (TA), dimethyl terephthalate (DMT), and diamines of TA. PET,
alone. poly(ethylene terephthalate)
thermophilic bacterial species, allows the hydrolysis to be temperature of 150–350 C with a pressure between 1 and
carried out at higher temperatures and is a key to the suc- 20 atm. After this treatment, the reaction mixture is fil-
cess of this process. tered and the EG is distilled to be reused in the process.
Following enzyme-catalyzed hydrolysis, the product When PET waste is treated by the DEMETO process, TA
TA is purified and used to prepare virgin PET. The pat- is the major product and is readily obtained in pure form
ented Carbios process accomplished depolymerization at by simple precipitation, filtration, washing and drying.
20–80 C and is operable over a wide pH range from 4 to DEMETO also works as a method to recycle polyamides.
10.[85] The specific pH values are selected on the basis of In this case, the hydrolysis of amides is analogous to the
the particular polyester to be depolymerized. The enzyme hydrolysis of esters discussed in detail in the previous sec-
loading varies from 0.005 to 15 wt% and reaction times tion. Amides, however, are somewhat less reactive to
can vary from 5 to 72 hr. hydrolysis. For this reason, acidic media, such as HCl,
Another company focusing on depolymerization of H3PO4, or H2SO4, is used in the DEMETO processing of
PET and polyesters is Gr3n. Their process focuses on less- polyamides. Although DEMETO is a more energy-
easily processed polyester waste streams that include col- intensive process than the low-temperature Carbios pro-
ored PET bottles and polyester textiles. The process they cess, the time required is much shorter.
employ is their patented DEMETO (depolymerization by Whereas Carbios and Gr3n focus on production of TA
microwave technology) technology, which is able to cut from PET (Scheme 2), companies such as Ioniqa Tech-
reaction times down to 10 min. nologies and Jeplan have developed commercial varia-
In the first step of the patented process, the plastic tions of the depolymerization of PET into BHET
waste is ground up and mixed with a solvent.[86] The sol- (Scheme 3). In Ioniqa's patented process, an ionic catalyst
vent is typically ethylene glycol (Scheme 3) and an alkali complex is able to degrade PET into BHET.[87] This ionic
base, such as NaOH, KOH, or LiOH. This heterogeneous catalyst complex generally consists of a nanoparticle,
mixture is then transferred to a reaction chamber where such as magnetite or maghemite, that is magnetic in
microwaves are used to heat the chamber to a nature, a bridging group, such as triethoxysilylpropyl,
and an ionic catalyst, such as (bmim)+ and FeCl4−. This
catalyst is able to depolymerize PET waste at tempera-
tures of 200 C with only a catalyst loading of 2 wt%.
Yields for this process can be up to 93% with near quanti-
tative conversion of the PET waste.
It is notable that Ioniqa's magnetic metal particles
serve a dual role of catalyst and pigment adsorbent. Mag-
netic particles are also easily removed by magnetic
catchers in the process line to prevent their incorporation
in end products. In contrast, Jeplan uses separate catalyst
and activated carbon to remove inks and dyes. This
approach simplifies catalyst preparation but makes sepa-
ration of the catalyst and adsorbent less straightforward
that in Ioniqa's approach. Jeplan' process is successful for
recycling mixed colored and clear PET bottles and fibers
by heated the waste materials with BHET at 220 C for
1 hr.[88] This achieves what they term as a
predecomposition product in which the PET is broken
down into oligomers. Ethylene glycol and sodium meth-
ylate catalyst are added to the predecomposition solution
and are heated at 200 C for 2 hr to completely decom-
pose the PET to form BHET. The solution is cleaned with
activated carbon in order to remove dyes and impurities.
The BHET solution is then purified and obtained as a
S C H E M E 3 The glycolysis of PET using ethylene glycol, in pure monomer in 98% yield, which is used to synthesize
the first part of the reaction PET is broken down into oligomers/ virgin PET.
polyols of PET, which then are further broken down into bis Both the processed developed by Ioniqa Technologies
(2-hydroxyethyl) terephthalate (BHET). PET, poly(ethylene and Jeplan demonstrate the additional considerations
terephthalate) one must keep in mind when converting the knowledge
learned from academic studies to practical handling of focuses on the dissolution of the dyes in the textile waste
mixed waste streams. In the case of mixed PET waste pro- followed by dissolution of the polyester. The solvents used
cesses, these considerations include recovering catalyst in this process can vary, but 1,3-dimethyl-2-imidazolidinone
and removal of pigments and dyes, considerations men- (DMI) is a suitable solvent to dissolve both the dyes and the
tioned much less frequently in academic investigations. polyester resin.[91] In the first step of this process, the textile
waste is mixed with DMI at a temperature between 90 and
100 C for 10 min. This process selectively dissolves the
2.4.2 | Industrial approaches to recycling dyes and not the polyester resin. The polyester resin is sepa-
mixed-composition textile waste rated from the DMI by filtration, and the dye and DMI are
separated from each other. The dye-free polyester resin is
Mixed textile waste is a challenge for the recycling process then dissolved in DMI at a temperature of 120–130 C for
because it most typically consists of hydrolysable synthetics 2 hr. This mixture is then filtered to remove any solid impu-
such as polyesters and polyamides as well as cotton and rities and the polyester resin is isolated by evaporation of
other fibers. Commercially viable primary or secondary the DMI solution. This allows for the recycling of the DMI
recycling of textiles is not developed due to the complexity solvent and the polyester resin.
of the constituents present in the material. Additionally, Another company, Aquafil, focuses on reusing nylon
with such a high content of biomass, generally pyrolysis to 6, a polyamide that can undergo hydrolysis analogous to the
form liquid fuels in unfavored due to the high oxygen con- processes used to hydrolyze PETs. The recovered nylon can
tent of biomass. Most recycling of textiles thus requires be respun into their ECONYL yarn, which can then be fed
costly separation of the synthetic polymer from the natural back into textiles. Their patented process employs initial
fiber. Trash-2-Cash, Tyton, and Worn Again are three com- thermal decomposition of any polyurethane present in the
panies seeking to recycle textile waste. material.[92] This is achieved by heating the waste at a tem-
Tyton focuses on recycling wasted textiles to regener- perature of 150–200 C for up to 24 hr. Temperature control
ate the cellulose portion (from the cotton textiles) and allows selective decomposition of less thermally stable fibers
convert the PET into TA and EG. They focus on the use while leaving the polyamide fibers intact. The next step of
of subcritical water as a media to break down the textile this process is to separate the polyamide fibers from the
waste. In an exemplary application, they took mixed tex- decomposed polyurethanes by washing in a polar solvent,
tile waste and placed it in a hydrothermal reactor at a such as ethanol, at a temperature of 5–78 C for up to 10 hr.
temperature of 155 C and pressure of 120–150 psi with At this point, the polyamide fibers are dried and purified
5% (w/v) sodium hydroxide and 0.5% (w/v) of a phase and can be readily reused. The solvent is separated and puri-
transfer catalyst for 60 min.[89] The resulting mixture was fied from the degraded components and is reintroduced into
taken and the TA was recrystallized, thus allowing it to the process.
be separated from the cellulosic pulp. The TA is used for The commercial processes described here for the treat-
making virgin PET, while the cellulosic pulp product is ment of mixed textile waste again demonstrate the addi-
further washed and processed to decrease the molecular tional strategies that must be implemented to deal with
weight of constituent cellulose, thus allowing it to be practically available waste streams. In the case of mixed tex-
used to make new textiles as well. tile streams, removal of dyes and pigments by either their
Trash-2-Cash focuses on cellulose regeneration by differential solubility or thermal stability is one consider-
using an ionic liquid in which the cotton is dissolved and ation. Another consideration is the separation of different
can be separated from the polyester. They focus on using types of material to produce one or more chemically distinct
their patented ionic liquid, Ioncell F, to selectively dis- products. For textiles, this comes down to the separation of
solve the cellulose portion in mixed textiles.[90] The ionic cellulose (cotton) and polyurethanes from polyesters. The
liquid generally consists of 1,5-diazabicyclo[4.3.0]non- foregoing examples illustrate methods to accomplish such
5-enium acetate (DBNH-OAc), which is mixed with the separation by selective crystallization, variable solubility, or
textile waste for 1 hr at 80 C. The cellulose solution is differential thermal stability.
then taken to a dry-jet wet spinning step in which cellu-
losic fibers are spun directly from the extractant. The
undissolved polyester is taken and washed with the ionic 2.4.3 | Industrial approaches to recycling
liquid two more times to yield essentially pure PET resin. polyolefins
The ionic liquid and water are separated and fed back
into the recycling process. In a recent report by Closed Loop Partners, only one
Worn again focuses on separating the PET resin from example of successful commercial recycling of PE was
the cotton using a solvent-based system. This process noted.[93] This may not be surprising given the lower
reactivity and higher-temperature pyrolytic pathways further applications. Throughout the entire process, the
that academic studies have revealed thus far for maximum temperature reached is approximately 550 C,
degrading PE, as discussed in the previous section. so it is rather energy intensive.
Despite these inherent challenges, BioCellection, Inc. has Pyrowave employs industrial microwave reactors to
successfully recycled HDPE and LDPE through a pat- depolymerize PS to form monomers. Their process uses a
ented process referred to as accelerated thermal oxidative pyrolysis reactor and a proprietary catalyst loaded
decomposition (ATOD).[94] In ATOD, the polymer is bro- 0.5–50% w/w. Using the catalyst allows them to affect
ken down into oxygenated organic compounds to include transformation of the PS to monomers at a lower temper-
succinic, glutaric, adipic, pimelic, suberic, and azelaic ature (350–500 C) than in the Agilyx process.[97] The
acid. To accomplish the oxidation, ATOD utilizes an oxi- Pyrowave process then employs two sequential con-
dizing acid, such as HNO3, to treat mixed PE waste at densers, the first with a working temperature of 55–90 C,
60–200 C for 30 min–30 hr. The resulting mixture is puri- and the second with a working temperature of 2–10 C,
fied to yield the various organic acid compounds. facilitating efficient separation of target styrene monomer
There is only one major company focused solely on from other impurities. Yields for styrene monomer recov-
utilizing PP as a feedstock. PureCycle Technologies has ery can be up to 95% in purity needed for synthesis of
been successful in recycling PP to give a recycled PP virgin PS.
product, whose mechanical properties are equivalent to Whereas both Agilyx and Pyrowave processes rely pri-
those of virgin PP. The process is a purification method marily on thermal depolymerization techniques, Poly-
that can remove color, odor, and impurities from waste styvert has developed a process to purify PS. This
PP rather than relying on total chemical disintegration of approach is conceptually similar to that employed by
the polymer. Their patented process focuses on using PureCycle Technologies for reclaiming PP. The Poly-
mixed postconsumer and postindustrial PP waste.[95] The styvert process[98] employs p-cymene to dissolve the PS
PP waste is heated with a fluid solvent to a temperature waste. PS is quite soluble (up to 33% w/w) in p-cymene,
of 80–220 C and at a pressure of 150–15,000 psig to pro- minimizing the amount of solvent needed. Furthermore,
duce reclaimed PP. The fluid solvent used does not dis- p-cymene is a primary component of some naturally
solve the PP, but rather dissolves dyes, pigments, occurring essential oils, and so could conceivably be sus-
fragrance compounds, and other impurities that may be tainably sourced. After dissolution of PS, insoluble mate-
present in the waste PP. The resultant pure PP is dis- rials are filtered out. The PS solution is then washed with
solved in another solution and is then separated and pre- a solvent in which PS is insoluble, typically heptane, hex-
cipitated out for use in any process typically requiring ane, or octane. This allows for the selective precipitation
virgin PP. of PS, while other low molecular organics, including pig-
Although the methods for chemical recycling of PS ments and dyes, remain in solution. This process can be
are not explicitly delineated in the previous section, the repeated with different precipitation solvents multiple
problems of low reactivity facing efforts to recycle PE and times followed by drying at 120 C to give PS pellets
PP also affect PS, so the methods for its recycling are sim- appropriate for use in manufacturing new expanded PS
ilar to those discussed for PE and PP. One unique practi- and high-impact PS products. The p-cymene used in the
cal barrier to PS recycling that is not faced in efforts to process is recovered and continually used in the process.
recycle other plastics is that much of the PS waste is in While each of the aforementioned companies in this
the form of Styrofoam. Styrofoam has a high volume for section has focused on one specific polyolefin, there are
a given mass, making it considerably more costly to companies that have successfully commercialized pro-
transport a given mass to a central recycling facility for cesses for recycling mixed plastic waste. Given the com-
processing. plexity of separating organic compounds or purified
Companies that focus on recycling PS include Pyro- polymers for even a single-component polyolefin waste
wave, Polystyert, and Agilyx. Agilyx converts PS into liq- stream, it is perhaps unsurprising that successful pro-
uid styrene monomer using a pyrolysis technique similar cesses for valorizing mixed polyolefin waste streams to
to those discussed for pyrolysis of PE or PP. Their process convert them into liquid oils that can be used as fuels or
involves initial melting and compacting of PS waste, other commodity chemicals. This approach is in contrast
which is then fed into the pyrolysis reactor.[96] The waste to the focus on the regeneration of monomers or poly-
is then heated and gaseous products are released and mers to be fed back into PET or polyolefin production
condensed. Heavier hydrocarbons and oligomers can be that typifies most of the efforts in commercial plastic
fed back into the pyrolysis reactor for further cracking. recycling discussed so far.
The lighter hydrocarbon fractions and the styrene mono- Resynergi focuses on pyrolysis of variously comprised
mer are separated and isolated and can be used for mixed plastic waste streams. Their process uses
microwave energy to induce “fast pyrolysis” in which the GreenMantra Technologies is a company that utilizes
plastic waste is heated to temperatures between 650 and proprietary catalysts to transform PE, PP, and PS into
700 C and broken down into liquid fuel. Their patented either liquid fuels or polymer additives. GreenMantra
process feeds waste into their pyrolysis chamber under Technologies currently focuses on producing Ceranovus,
an inert atmosphere of nitrogen or argon, with low pres- an additive for PE or PP. The GreenMantra process
sures of 1–2 psig.[99] The pyrolysis chamber contains sili- involves a thermochemical process in which the plastic
con carbide spheres and a screw-type mixer to ensure waste can consist of a mixture of PE and PP with some
uniform heating during the pyrolysis process. The pyroly- capabilities of handling small quantities of PS.[102] The
sis gases are then sent through a catalyst-filled cracking plastic waste is pretreated by extrusion and then
chamber to further decompose the plastic waste. The preheated through a proprietary cycle and then placed in
gases are then sent through subsequent condensers, the pyrolysis reactor in which the plastic waste undergoes
which first condense heavy gases and waxes, then diesel depolymerization. This step can include catalysts such as
gases and then lighter gases such as gasoline fuels. These zeolites or alumina based catalysts, in order to target spe-
fractions can then be used as fuels for a variety of cific end products. The gases are then sent to a cooling
applications. stage where the gases are condensed and then sent for
Plastic2Oil employs a process similar to that purification. The purified products can be commercially
employed by Resynergi. The Plastic2Oil process specifies viable without any further purification.
that direct use of unsorted and unwashed plastic waste is Cadel Deinking targets mixed waste comprising both
achieved in their facility. The waste is first premelted at a polyolefins and PET. Rather than relying on thermal
temperature of 250–340 C, a temperature at which some decomposition of these plastics, Cadel Deinking focuses
of the lower molecular weight impurities are burned off on their purification and co-processing into processable
or volatilized as well.[100] The premelted waste is then fed pellets. The process consists of first washing the postcon-
into a pyrolysis reactor held at 340–445 C, with residence sumer and postindustrial plastic.[103] The separated poly-
times as short as 10 min. The pyrolysis gases are then mer residue is then ground and placed into a tank that
taken to catalyst towers. These catalyst towers feature dif- contains a mixture of surfactants (between 0.1 and 5 wt
ferent temperature/catalyst zones to facilitate sequential %) and has a pH of 11–13. The surfactant tank stage pro-
reaction of target gases at each stage. The overall process cess is repeated a total of three times to ensure complete
yields approximately 87% liquid fuel products with the removal of inks and dyes. The material is then dried and
balance consisting of unspecified residue and syngas can be processed into pellets for further use.
(a mixture of hydrogen and carbon monoxide gas that is
an industrially important feedstock) in a ratio that is
dependent on the particular nature of the mixed plastic 2.4.4 | Industrial approaches to recycling
waste used. mixed waste including SPI Code 3–7
Plastic Energy is an emerging company employing a plastics or other materials
patented pyrolysis technique termed Thermal Anaerobic
Conversion (TAC) in which plastic waste can be ther- Multilayer films and materials tend to include a more
mally decomposed into a mixture of various hydrocarbon than just one polymer, precluding their recyclability by
oils that is referred to as TACOIL. TACOIL can then be methods that rely on manual separation. For this reason,
used to make other plastics, or be used as a fuel. In the multilayer films tend to be difficult to recycle through
TAC process,[101] pellets or flakes of waste plastic are first primary and secondary recycling methods. Thus, most of
extruded at ~300 C and then transferred into an oxygen- the waste is thermally converted into other commodity
free pyrolysis chamber at 390–410 C, where they are agi- chemicals. Companies such as Recycling Technologies
tated with a stirrer. The pyrolysis gases are sent through and Enval focus on recycling mixed plastic waste 3–7 and
a condenser, in which heavier, long chain hydrocarbons multilayer films.
are condensed and sent back into the pyrolysis reactor. Recycling Technologies focuses on thermally cracking
This design feature eliminates the need for a catalytic complex mixed plastic waste into gaseous and liquid
reactor used in the Resynergi or Plastic2Oil processes to products. This process involves initial separation of PET
break down the larger/heavier hydrocarbons. The pyroly- and HDPE from the mixed plastic waste components, in
sis gases now consist of diesel, kerosene, light oil, and order to recycle them in a different process.[104] The rest
waxy components that are separated by distillation. Waxy of the mixed waste is shredded. The shredded waste is
components are fed back into the pyrolysis reactor and then dried until a water content of < 5 wt% is achieved.
the diesel, kerosene, and light oil products can be sold as Dried waste is fed into a fluidized pyrolysis reactor at
fuels. 400–600 C. Pyrolysis produces fuels comprising C5 to
C100 hydrocarbons, with roughly 80% of the hydrocar- into the reactor, Zone 4, where it is heated at 300–365 C
bons consisting of C5 to C40. A fraction of the fuel from for up to 2 hr. This burns off most of the heteroatoms
the pyrolysis is used to power the reactor. such as chlorine from PVC. The products from this stage
Renewlogy has focused on commoditizing mixed plas- are either gases, waxy solids, or char. The waxy solids are
tics with SPI Code 3–7. One major benefit of their sent to zone five of this process, where pyrolysis occurs.
method is that it is a continuous process into which plas- At this point, the waxy solids are heated to 365–488 C for
tic waste is fed without ever having to cool and reheat 30–90 min. The resulting gases are then taken to con-
the chamber, as is the case in batch reactors used by most densers where liquid fuels are purified. The solid char is
recycling companies.[105] After some manual separation, taken to Zone 6 and heated to temperatures of 454–982 C
the plastic waste consisting primarily of SPI Code 3–7 in order to further crack this solid into gases. The gases
plastics is heated to 120–315 C to melt the material. Mol- can then be taken and sent to fractionation columns and
ten material is fed into the pyrolysis reactor with an purified. Zone 7 then cleans and purifies the char so that
auger. Preheating the material is another energy-saving it can be used as a solid fuel source.
aspect of this process that also helps maintain the reactor ReNew ELP focuses on using supercritical water as a
temperature so it does not fluctuate as it would by put- medium to convert mixed plastic waste into chemical feed-
ting in colder plastic waste. Additionally, the auger is stocks for various applications. Cat-HTR (Catalytic Hydro-
maintained at a steady rate in order to continuously feed thermal Reactor) is a patented hydrothermal process in
the plastic into the reactor. All of these subtleties contrib- which the breakdown of mixed plastic waste is achieved in
ute to producing consistent products. The reactor temper- up to 85% conversion to liquid oil. The process involves ini-
ature is maintained at 400–550 C, where gases are tial grinding of waste feedstock to produce slurry with water
formed and sent through four condensers of varying tem- and oil.[108] The oil used can be paraffinic oil, crude oil, bio-
peratures. The first condenser removes heavy hydrocar- oil, and so on. Depending on the initial feedstock, catalysts
bons and waxes that are fed back into the pyrolysis such as sodium hydroxide can be added. The slurry of waste
system. Up to 80% of the plastic is converted into fuels is then fed into a reactor with a temperature of 250–350 C
that can be used as feedstocks for other materials. and a pressure of 100–350 psi for 10–25 min. After the allot-
RES Polyflow also uses a continuous system and can ted time the products are cooled to a temperature of
recycle mixed plastics of SPI Codes 1–7 without the use of 50–180 C followed by reducing the pressure to atmospheric
a catalyst. As this process can make use of all types of plas- pressure. The liquid oil obtained can be used for various fuel
tic, no manual separation is needed prior to feeding mate- applications. One of the main reasons for the addition of oil
rial into the reactor. Their patented process relies on to the process is that the use of sub/super-critical water gen-
multiple reactor zones for the sequential separation of com- erally restricts the concentration of organic matter that can
modities.[106] At each reactor zone, there is an exit source be put into the slurry. Additionally, water requires more
where the pyrolysis gases can be captured. The plastic energy per unit volume to heat and can lead to charring of
waste is fed through each zone by either a conveyer belt or the feedstock waste. The addition of oil mitigates these
an auger with a fixed speed. Yields for this process can be issues.
up to 93% with the finished product having characteristics Most of the companies that have demonstrated com-
similar to that of crude oil. This material can then be mercial processes for recycling mixed plastic waste have
processed in typical petroleum cracking systems. focused on the pyrolysis of waste plastics to give fuels.
Vadxx is another company that uses a continuous The temperature, feed rate, and residence time are all fac-
flow process. The products obtained are classified into tors that can be adjusted to optimize the liquid products
four different types of fuel, EcoFuel-I, EcoFuel-II, depending on the input of the waste plastic.
EcoFuel-SNG, and EcoFuel-S. EcoFuel-I is used as diesel Some waste materials are composed of plastic lami-
oil, whereas EcoFuel-II is used for gasoline, EcoFuel-S is nated or otherwise integrated into metal housings. Enval
a solid carbon-based fuel, and EcoFuel-SNG is the syn- has made inroads to recycling such materials with a par-
thetic natural gas that is used by Vadxx to power the pro- ticular focus on using microwaves to induce pyrolysis of
cess. To separate these fuels from one another, seven aluminum laminates. In their patented process, they use
different zones are employed.[107] The first zone is the a dual chamber reactor in order to sustain a continuous
feed, in this part of the process; the plastic waste is gener- process.[109] Both chambers are interconnected and con-
ally shredded and fed into the second zone. The second tain a bed of carbon black conduction source and a stirrer
zone compresses the plastic waste and reducing the vol- to fluidize the chamber. The chamber is heated at
ume, this is most typically achieved by extrusion of the 500–600 C and the laminate is fed into Chamber 1. Gas-
waste at ~100 C. Zone 3 melts the polymer waste at eous products from the pyrolysis of the organic material
100–300 C. At this point, the polymer waste melt is sent leave both chambers, and the aluminum metal is fed out
of an exit at the top of chamber 2. This process yields oil undergo various scrubbing and purification steps in order
and aluminum metal in 98% purity that can be resmelted to be further used in other processes in a separate facility.
into virgin materials.
APK is another company that that is able to selec-
tively purify polymers in mixed plastic waste from non- 4 | CONCLUSIONS
plastic components. Their Newcycling technology
involves milling waste through a dry mechanical separa- With many plastic recycling processes focusing on primary
tion process to facilitate separation of plastic from tex- and secondary recycling, there is still a great disparity
tiles, sand, metal particles, and so forth.[110] The material between the amount of plastic waste and how much is
is then taken and split into light and heavy fractions recycled. We must now turn to other processes that can be
through air sifting. The lighter fractions typically consist used in conjunction with current processes in order to allevi-
of film particles, fibers, corks, and so forth. The heavy ate the problems associated with the massive amounts of
fraction mainly consists of hard plastics and heavy impu- plastic waste being produced. As outlined here, there have
rities. The heavy fraction is then placed into sink or float been many academic studies that delineate general strategies
separation tanks in which the density of the media is for the chemical recycling of hydrolysable polymers like PET
altered to separate specific plastic resins. Impressively, and nonhydrolyzable polymers like polyolefins. These studies
this conceptually simple process can yield plastic resins suggest that chemical transformation of waste plastics into
with a yield and purity of > 97%. The plastic resins are value-added chemicals can be a convenient avenue to supple-
then taken and dried through extrusion processes to form ment current recycling processes. Industrial efforts to com-
granulates, which can be used for further applications. mercialize chemical recycling processes for plastic waste
illuminate more complex issues of separation and purifica-
tion associated with real-world waste streams, from mixed
3 | INDUSTRIAL ADVANCEMENTS plastic waste to multicomponent metal–plastic components
I N M I X E D SO L I D M U N I C I P A L to full spectrum municipal waste. Despite the complexity of
WASTE the problem, by intelligently tailoring catalysts, solvents, tem-
perature stages, residence times, and initial feedstock,
Pilot-scale facilities have begun to make headway in impressive yields of desired products (monomers, gases, oils,
recycling full-spectrum MSW comprising plastic, textile, and solids) have been achieved.
food, and other waste components. The complex nature Continued efforts need to be focused on catalysts to
of MSW has led companies that focus on this set of waste improve the overall efficiency and lower the temperature to
material to rely on thermal gasification. bring down energy demands of recycling processes. The cur-
Sierra Energy focuses on using MSW, biomass, construc- rent state of chemical recycling of plastic waste shows prom-
tion, demolition, and industrial waste as feedstocks for gasifi- ise to become one of the main processes in which we can
cation. In their patented FastOx gasification strategy, the efficiently reduce the amount of waste in landfills.[113–121]
waste material is converted into syngas. The MSW is shred-
ded and dried to less than 50 wt% moisture and is fed into ACKNOWLEDGMENTS
the reactor, which can have temperatures up to 2200 C. At This work was supported by the National Science Foun-
this point, the waste is devolatilized and a stream of steam dation (CHE-1708844).
and oxygen is injected,[111] facilitating the high temperature
conversion into syngas. From here, the crude syngas is sent ORCID
to a cleaning chamber to be conditioned to meet require- Rhett C. Smith https://orcid.org/0000-0001-6087-8032
ments for its downstream use in other industries.
Enerkem strategically targets otherwise nonre- RE FER EN CES
cyclable, noncompostable MSW as a feedstock for its pro- [1] Plastics Insight, World Per-Capita Consumption Of PE, PP &
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WO2019204687A1, 2019. AUTHOR BIOGRAPHIES
[95] J. M. Layman, M. Gunnerson, H. Schonemann, K. Williams
(The Procter & Gamble Company, USA.) Patent Timmy Thiounn earned his B.S. from
WO2017003796A1, 2017.
the University of South Florida. He is
[96] B. Cavinaw, S. Crawford, S. Lamaze, D. Allen,
E. Christenson, M. Rumford (Agilyx Corporation, USA.) Pat-
currently a Ph.D. candidate in the
ent US10301235B1, 2019. research group of professor Rhett
[97] J. Doucet, J.-P. Laviolette (Pyrowave Inc., Can.) Patent C. Smith at Clemson University. His
WO2018018153A1, 2018. research interests include sustainable
[98] R. Cote (Polystyvert Inc., Can.) Patent WO2016049782A1, and environmentally friendly poly-
2016. mers for durable applications.
[99] B. Bauer, J. Tanne, T. Spott, F. Mayhew, A. J. McInnis,
M. Leis, C. Cardinal, T. Greer (Resynergi, Inc., USA.) Patent
WO2020006512A1, 2020.
Rhett C. Smith earned his B.S. from organo-main group polymers for sustainable energy
the University of Toledo and his Ph. generation and construction applications.
D. from Case Western Reserve Uni-
versity, where he worked for John
D. Protasiewicz. After that, he was a
National Institute of Health Postdoc- How to cite this article: Thiounn T, Smith RC.
toral Fellow at Massachusetts Insti- Advances and approaches for chemical recycling of
tute of Technology. In 2006, he joined the faculty at plastic waste. J Polym Sci. 2020;58:1347–1364.
Clemson University, where his interests include https://doi.org/10.1002/pol.20190261

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Received: 10 December 2019 Revised: 7 March 2020 Accepted: 13 March 2020

Advances and approaches for chemical recycling of plastic

Timmy Thiounn | Rhett C. Smith

Department of Chemistry and Center for

1 | INTRODUCTION dogged environmental persistence in the oceans[6–8] and

J Polym Sci. 2020;58:1347–1364. wileyonlinelibrary.com/journal/pol © 2020 Wiley Periodicals, Inc. 1347

SPI Polymer Structure Uses

2 High density polyethylene Soap bottles, detergent and bleach containers,

3 Polyvinyl chloride (PVC) Plumbing pipes, cables, and fencing

5 Polypropylene (PP) Reusable food containers, prescription bottles,

6 Polystyrene (PS) Plastic utensils, packaging peanuts, and

Abbreviation: SPI, society of plastics industry.

F I G U R E 1 Common fates for

instructive to introduce the four classifications of Terephthalic Acid OH

would be to use clean aluminum pipes and use the metal

2 | ACADEMIC ADVANCES IN temperatures and/or with a catalyst).[28] The products

Amaro et al.[59] used DEG and PET to synthesize oligo-

flexibility of the final PVC product. Furthermore, migration

2.2 | Polyethylene (SPI Codes 2 and 4)

Polyethylene is a lightweight and durable thermoplastic

and separate each component are major barriers to

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