Katrina Knauer

Circular Plastics Technologies

Also of interest
Physical Chemistry of Polymers
A Conceptual Introduction
Sebastian Seiffert, 
ISBN ----, e-ISBN ----

Handbook of Biodegradable Polymers

Catia Bastioli (Ed.), 
ISBN ----, e-ISBN ----

Injection Moulding
A Practical Guide
Vannessa Goodship (Ed.), 
ISBN ----, e-ISBN ----

Cellulose Nanocrystals
An Emerging Nanocellulose for Numerous Chemical Processes
Vimal Katiyar, Prodyut Dhar, 
ISBN ----, e-ISBN ----
Katrina Knauer
Circular Plastics
Technologies

Chemical Recycling
Author
Katrina Knauer

ISBN 978-1-5015-2328-1
e-ISBN (PDF) 978-1-5015-1561-3
e-ISBN (EPUB) 978-1-5015-1562-0

Library of Congress Control Number: 2023947821

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the internet at http://dnb.dnb.de.

© 2024 Walter de Gruyter Inc., Boston/Berlin

Cover image: Igor Rupniewski, PhD
Typesetting: TNQ Technologies Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck

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Contents
List of contributing authors VII

Katrina Knauer
1 Circular plastics technologies: introduction 1
1.1 Plastics – the good, the bad, and the ugly 1
1.2 Recycling – why is it so challenging? 3
1.3 A circular economy – Is chemical recycling the answer? 5
References 6

Katrina M. Knauer, Cody Higginson and Minjung Lee

2 Circular plastics technologies: pyrolysis of plastics to fuels and
chemicals 9
2.1 Introduction 9
2.2 Technical scope 11
2.3 Summary and future perspectives 26
References 27

Katrina Knauer, Cody Higginson, Yuanzhe Liang and Minjung Lee

3 Circular plastics technologies: depolymerization of polymers into parent
monomers 33
3.1 Introduction 33
3.2 Technical scope 35
3.2.1 Solvolysis 35
3.2.2 Thermal unzipping into monomers 48
3.3 Summary and future outlooks 52
References 53

Katrina Knauer and Minjung Lee

4 Circular plastics technologies: open loop recycling of waste plastics into new
chemicals 59
4.1 Introduction 59
4.2 Technical scope 62
4.2.1 Solvolysis 62
4.2.2 Polyolefins 65
4.2.3 Oxidation 68
4.3 Summary and future trends 70
References 71

Index 73
List of contributing authors
Cody Higginson Minjung Lee
Menlo Park, CA, USA Golden, CO, USA

Katrina Knauer Yuanzhe Liang

Golden, CO, USA Golden, CO, USA

https://doi.org/10.1515/9781501515613-201
Katrina Knauer*
1 Circular plastics technologies: introduction

1.1 Plastics – the good, the bad, and the ugly

Since their inception in the 1900s, plastics have become a ubiquitous, and integral, aspect
of modern life. When methods and processes to make synthetic polymers, the macro-
molecules that make up plastics, were first introduced to the world they were truly
considered a “wonder material”. You could drop a piece of plastic on the floor, and it
would not shatter like glass. You could make a flexible film with excellent barrier
properties to preserve food significantly longer than paper wrapping. You could replace
heavy metal parts in appliances, automobiles, and electronics. Plastics were incredibly
cheap, lightweight, and versatile and were viewed as entirely disposable when they first
entered the market in the late 1940s. This is evidenced by a now infamous photo in the
1955 Life Magazine issue “Throwaway Living” where a quintessential 1950s family is
happily throwing single-use plastics into the air and boasting that throwing away plastic
utensils and plates saves “forty hours of washing-up time” [1]. This was the beginning of
the plastic linear economy. A linear economy is also referred to as the take-make-waste
model. This is defined by the Ellen Macarthur Foundation (EMF) as a system where
resources are extracted to make products that eventually end up as waste and thrown
away, typically to a landfill. The linear economy model is one in which products are seen
as disposable and replaceable rather than permanent and/or recyclable.
The benefits of plastics are obvious in terms of the impact plastics have had on
quality of life. Plastics are strong yet light-weight and have significantly contributed to
reducing emissions in automobiles and airplanes when used to replace heavier compo-
nents. Plastic packaging preserves food and increases shelf life in a society where food
scarcity is an ever-growing concern as populations across the globe continue to rise.
Plastics like polyethylene (PE) can be sterilized via gamma irradiation and when used in
medical packaging have significantly reduced hospital acquired infectious diseases.
Furthermore, in addition to societal benefits and quality of life improvements, plastics
often have a lower environmental impact factor, when looking at a comprehensive life
cycle assessment (LCA), when compared to non-plastic alternatives such as glass, paper,
metals, and wood. This was demonstrated in a study by Ahamed et al. that summarized
LCA metrics comparing single use high density PE (HDPE) plastic bags and reusable
polypropylene (PP) nonwoven bags to paper and cotton grocery bags [2]. The LCA
concluded that paper or cotton bags demonstrated the highest negative impacts for the

*Corresponding author: Katrina Knauer, Golden, USA, E-mail: [email protected]. https://orcid.org/

0000-0002-0125-7532

As per De Gruyter’s policy this article has previously been published in the journal Physical Sciences Reviews. Please cite as: K. Knauer
“Circular plastics technologies: introduction” Physical Sciences Reviews [Online] 2023. DOI: 10.1515/psr-2023-0020 | https://doi.org/10.
1515/9781501515613-001
2 1 Circular plastics technologies

impact categories including abiotic fossil depletion, freshwater-, marine- and terrestrial-
ecotoxicities, human toxicity, acidification and eutrophication potential when compared
to the single use HDPE bag and reusable nonwoven PP bag [2]. The American Chemistry
Council (ACC) published a study on the potential effects of shifting packaging from
plastics to alternative materials such as aluminum, glass, steel, and paper in the US
and Canadian markets [3]. They summarized that converting from plastic packaging to
alternatives could generate 69 % higher CO2 emissions and 390 % more solid waste by
weight and consume 90 % more energy and 481 % more water to deliver the equivalent
volume of product [3].
The benefits of plastics notwithstanding, the astonishing growth of plastic produc-
tion and the failure to address end-of-life (EOL) issues of today’s plastics has accelerated
the depletion of finite natural resources (i.e., fossil fuels), caused severe worldwide
plastics pollution problems, and led to enormous energy and materials value loss in the
global economy [1, 4]. The vast majority of the chemical building blocks used to make
plastics (i.e., monomers), are derived from fossil fuels and are a major product of the oil
and gas industry. Virgin production of plastics (i.e., converting oil into plastics) can be
reduced by the adoption of a circular economy model for plastics. The EMF defines a
circular economy as a model where products and materials are kept in circulation
through processes like maintenance, reuse, refurbishment, remanufacture, recycling,
and composting. Recycling plastics seems like a no-brainer, yet plastic recycling rates
across the globe remain abysmally low, with the most recent study estimating only 9 % of
all plastic waste is recycled and 22 % is mismanaged (i.e., lost to the natural environment)
[5]. None of the commonly used plastics, presented in Figure 1.1, are biodegradable. Thus,
near-permanent contamination of the natural environment with plastic waste is a
growing concern. Jambeck et al. reported that plastic waste has been found in all major
oceans, with an estimated 4–12 million metric tons of plastic waste entering the marine
environment in 2010 alone [6]. Contamination of freshwater systems and terrestrial
habitats is also increasingly reported, as is the environmental contamination by micro-
fibers that are shed from washing our clothes [7]. There is so much plastic in the

Figure 1.1: A summary of the most used commodity plastics and their associated chemical structures and
recycling numbers.
 1.2 Recycling – why is it so challenging? 3

environment that it is has formed a discernible layer on the earth’s crust that researchers
in the future will be able to use to mark the current epoch, dubbed the Anthropocene, or
maybe more accurately should be called the Plastic-cene [8]. Alan Weisman left a pro-
found impression in his book The World Without Us when he suggested that out of all of
the human activities that have affected the Earth’s natural cycle/environment, plastic
waste is one of the most permanent [9]. The plastic waste problem is obvious but the
solution, however, is not as evident.

1.2 Recycling – why is it so challenging?

The alarming images of plastic waste in our oceans and natural ecosystems has created a
massive spotlight on the recycling industry and sparked a revitalization of an outdated
and inefficient infrastructure. Many consumers, governments, and non-government
organizations (NGOs) are now asking why the recycling rates are so low and what can be
done to improve them. The current state of the art for plastic recycling is a process known
as mechanical recycling (MR). This process involves the sortation of plastics into their
respective chemical families shown in Figure 1.1 followed by grinding/flaking, washing,
extrusion, and pelletization of the sorted plastics. Extrusion is a melt blending technique
that melts down the sorted plastic and blends the various plastic pieces together to yield a
homogenized product that is then pelletized and sold back into the plastic supply chain
for further processing into products. An example of this process in shown in Figure 1.2
and presents the MR of polyethylene terephthalate (PET) bottles into fibers used for

Figure 1.2: An example of the MR process where PET is sorted from other waste streams such as PE and PP,
then flaked, washed, and melt extruded into a polyester fiber for applications in textiles. Adapted from
Ref. [10] with permission from the Royal Society of Chemistry.
4 1 Circular plastics technologies

textiles [10]. While MR is a useful tool for temporarily diverting plastics from the landfill,
the number of re-cycles from an MR process is severely limited due to thermal degra-
dation/oxidation that occurs during multiple heat cycles, contaminations that are not
removed in the washing/sortation cycles, and little to no color control in the final product.
Even before the plastic makes it to a recycling facility, some form of degradation has
already occurred due to exposure to harsh conditions during the virgin plastic processing
and use-life (Figure 1.3) [11]. As a result, very few plastics are recycled back into appli-
cations of their first use-life via MR and are instead usually funneled into a new appli-
cation that is more tolerable to contamination. For example, we often see food/beverage
packaging plastics recycled into something like textiles (Figure 1.2), car bumpers, park
benches, or flowerpots. While this is one may to funnel single use waste into something
more long term, these secondary applications do not have the same volumes as most
single use plastic and thus the dent in waste mitigation is minimal. Furthermore, recy-
cling plastics into new applications is not reducing the virgin production of these ma-
terials. In other words, we are not decreasing our reliance or usage of fossil fuels to
produce plastics by just MR alone.
Another significant challenge with MR processes is that MR requires highly precise
separation/sortation of plastics into their respective chemical families. Even as low as
5 % cross plastic contamination can be detrimental to the recycled material’s perfor-
mance/properties. Some countries, specifically in the EU, require sortation at the
consumer/curbside level and have separate bins for separate kinds of plastics. However,
the U.S. adopted a single stream plastic collection where all plastics are comingled into a
curbside collection bin and sent to a Materials Recovery Facility (MRF) for sortation.
The sortation process has seen tremendous improvements over the last decade with the
implementation of optical and near-infrared (NIR) sortation methods to improve effi-
ciency and purity of the sorted streams. Additionally, some MRFs have even implemented
advanced robotics-based sortation to improve the purity of sorted waste streams
and eliminate human error [12]. However, even with the technological advances made
towards improved sortation, sorting remains a major cost driver for recycling and limits
the feedstocks that can be recycled [13].

Exposure to T, Exposure to T,
UV, chemicals, UV, chemicals, Exposure to high
Exposure to pollutants, pollutants, T’s, water,
high T’s mechanical mechanical chemicals, and
additives stress, etc. stress, etc. additives

Use
Compounder Converter Product Disposal MRF Recycling
Life

Polyolefin Mechanically
Producer Exposure to T, Exposure to T, Recycled
Exposure to
UV, chemicals, UV, chemicals, Polyolefins
high T’s
additives pollutants, pollutants,
mechanical mechanical
stress, etc. stress, etc.

Figure 1.3: Typical lifecycle of a polyolefin pellet from the polymer producer to the recycler and associated
exposure to degradation sources along the supply chain. Adapted from Ref. [11] with permission from Wiley.
 1.3 A circular economy – Is chemical recycling the answer? 5

1.3 A circular economy – Is chemical recycling the

answer?
MR is a relatively low cost and low emissions solution to recycling plastics [14]. However,
the challenges with MR discussed in the previous section have limited the feedstocks
that are useable in MR processes and the MR rates are not enough to mitigate the
enormous flux of plastic waste being produced every day [4]. To truly achieve a circular
economy for plastics, new recycling processes are needed that are more tolerable to
contamination, can yield virgin quality plastic, and can recycle materials infinitely
without a loss in properties. Chemical recycling can be one way to achieve this. This
process differs from MR and is a terminology used broadly to include many kinds of
chemical processes. Depolymerization can break down polymers into their parent
monomers for conversion back into new polymers. Pyrolysis can turn mixed plastic
waste into fuels or naphtha, which can be cracked into petrochemicals to make plastics.
There are even emerging technologies to convert plastics into entirely new chemical
building blocks than what they were in their first use life that can be “upcycled” into
higher value applications. In this text, we will refer to chemical recycling as any pro-
cess that breaks the polymer bonds in plastics and converts the plastic into monomers
or other chemical building blocks. Since the chemical processing of plastic waste allows
for recyclers to build in unit operations to remove additives and contaminants from
the deconstructed liquid products streams, chemical recycling offers a solution to the
contamination problems that limit MR. Furthermore, since chemical recycling is breaking
down the polymer to small molecular building blocks to rebuild into new polymers, the
molecular degradation that plagues mechanically recycled plastics is not a problem.
The plastics industry is placing a big bet on chemical recycling as it comes after
significant pressure from consumers, governments, and NGOs to better mitigate plastic
waste. This is evident by the dozens of startup companies that have emerged over
the last decade that are attempting to scale chemical recycling and demonstrate profit-
able operation. Table 1.1 summarizes some of these companies and the associated
funding/investment made thus far in their respective technologies and is an example of
this expanding field.
This book will provide a high-level overview of emerging circular plastics technol-
ogies through chemical recycling. We break down chemical recycling into three
categories:
1. Pyrolysis of plastics to fuels and chemicals
2. Depolymerization and unzipping of polymers into parent monomers
3. Open loop recycling of waste plastics into new chemicals

Each chapter will highlight notable technological advancements and identify com-
panies that are attempting to commercialize and scale processes within each category.
This is not meant to serve as a comprehensive, in-depth review, but rather act as a guide
6 1 Circular plastics technologies

Table .: Summary of selected chemical recycling startup companies, associated target feedstocks, and
level of investment.

Company Funding/Investment (USD) Target plastic

Purecycle $. M PP
Brightmark $ M PE/PP/PS
Agilyx $ M PE/PP/PS
Nexus $ M PE/PP/PS
Ioniqa $. M PET
Loop Industries $. M PET
Worn Again $. M PET/cotton (textiles)
Circ $. M Pet/cotton (textiles)
Novoloop $ M PE
Grn $. M PET

through the multiple types of chemical recycling being introduced both at pilot
scales and in academic literature. This text will focus primarily on the chemical
deconstruction step of the recycling process and will not discuss the challenges that
remain in the collection of waste plastics. This is an important note to keep in mind as a
reader of this text. Even with the massive growth of chemical recycling startups across
the globe, the plastic waste feedstock volumes and consistency are a significant concern
for recyclers. Most economic models show that chemical recycling is only profitable at
massive, industrial scales [15]. This requires an enormous amount of plastic waste
feedstock, and the current collection infrastructure is not enough to sustain this. As a
result, many governments and NGOs are primarily focused on how to improve plastic
waste collection, make collection for recycling more accessible, and incentivize
consumers to participate [16]. However, this text will only discuss the innovations
associated with the chemical deconstruction step of the cycle. Separate discussions on
improving consumer participation are warranted.

References
1. Gonen R. The waste-free world: how the circular economy will take less, make more, and save the Planet.
New York: Penguin; 2021.
2. Ahamed A, Vallam P, Iyer NS, Veksha A, Bobacka J, Lisak G. Life cycle assessment of plastic grocery bags and
their alternatives in cities with confined waste management structure: a Singapore case study. J Clean Prod
2021;278:123956.
3. Associates F. Life cycle impacts of plastic packaging compared to substitutes in the United States and
Canada: theoretical substitution analysis; 2018. Available from: https://www.americanchemistry.com/
better-policy-regulation/plastics/resources/life-cycle-impacts-of-plastic-packaging-compared-to-
substitutes-in-the-united-states-and-canada-theoretical-substitution-analysis.
4. Geyer R, Jambeck JR, Law KL. Production, use, and fate of all plastics ever made. Sci Adv 2017;3:e1700782.
 References 7

5. Diggle A, Walker TR. Environmental and economic impacts of mismanaged plastics and measures for
mitigation. Environments 2022;9:15.
6. Jambeck JR, Geyer R, Wilcox C, Siegler TR, Perryman M, Andrady A, et al. Plastic waste inputs from land into
the ocean. Science 2015;347:768–71.
7. Barnes DKA, Galgani F, Thompson RC, Barlaz M. Accumulation and fragmentation of plastic debris in global
environments. Phil Trans Biol Sci 2009;364:1985–98.
8. Martin C. Plastic world. Curr Biol 2019;29:R950–3.
9. Weisman A. The world without us. New York: Macmillan; 2008.
10. Li H, Aguirre-Villegas HA, Allen RD, Bai X, Benson CH, Beckham GT, et al. Expanding plastics recycling
technologies: chemical aspects, technology status and challenges. Green Chem 2022;24:8899–9002.
11. Westlie AH, Chen EYX, Holland CM, Stahl SS, Doyle M, Trenor SR, et al. Polyolefin innovations toward
circularity and sustainable alternatives. Macromol Rapid Commun 2022;43:2200492.
12. AMP robotics launches automated secondary sortation facilities in Atlanta and Cleveland. Available from:
https://www.amprobotics.com/news-articles/amp-robotics-launches-automated-secondary-sortation-
facilities-in-atlanta-and-cleveland.
13. Fogt Jacobsen L, Pedersen S, Thøgersen J. Drivers of and barriers to consumers’ plastic packaging waste
avoidance and recycling – a systematic literature review. Waste Manag 2022;141:63–78.
14. Uekert T, Singh A, DesVeaux JS, Ghosh T, Bhatt A, Yadav G, et al. Technical, economic, and environmental
comparison of closed-loop recycling technologies for common plastics. ACS Sustainable Chem Eng 2023;11:
965–78.
15. Tullo AH. Plastic has a problem; is chemical recycling the solution. Chem Eng News 2019;97:39.
16. March A, Roberts KP, Fletcher S. A new treaty process offers hope to end plastic pollution. Nat Rev Earth
Environ 2022;3:726–7.
Katrina M. Knauer*, Cody Higginson and Minjung Lee
2 Circular plastics technologies: pyrolysis of
plastics to fuels and chemicals
Abstract: Pyrolysis technologies are a staple in plastic chemical recycling because
of the robustness to contamination and existing infrastructure. Pyrolysis is already
considered to be a reasonably mature technology with numerous pilot plants operating
to pyrolyze plastic waste into fuels and chemicals. This chapter will describe the
pyrolysis process and important process parameters, the types of plastics that are
suitable for pyrolysis recycling, the mechanism of pyrolytic degradation of various
plastics, the products derived from different plastics, companies that have successfully
scaled pyrolysis recycling, and recent innovations in the technology.

keywords: circularity; degradation; fuels; plastic; pyrolysis; thermolysis.

2.1 Introduction
One of the fastest scaling and expanding areas in plastic recycling is the conversion of
waste plastics to petrochemicals and refined hydrocarbons via pyrolysis. Pyrolysis of
plastics (also known as thermolysis or polymer cracking) has been a potential route for
plastic waste management since the 1980s but has seen significant growth and
expansion over the last five years [1]. Pyrolysis can be simply defined as the degradation
of polymers at high temperatures in the absence of oxygen to yield oils consisting of
gaseous and liquid hydrocarbon fractions. In other words, plastics can be transformed
back into something like the crude oil that was originally pumped from the ground
and converted into hydrocarbons in an oil refinery. In the three loops of plastic recy-
cling outlined by the Ellen MacArthur Foundation (EMF), pyrolysis would fall in the
molecular loop where the polymer backbone is broken down to a molecular level
disparate from the parent monomers and further chemistry is required before repo-
lymerization back into the original polymer is possible (Figure 2.1) [2].
Pyrolysis is an energy intensive, robust process that can accommodate common
contaminations associated with post-consumer plastic waste such as food, dirt,
aluminum laminates, printing inks, oil residues, and more [3]. Because of the high

*Corresponding author: Katrina M. Knauer, National Renewable Energy Laboratory, 15013 Denver W Pkwy,
80401-3393, Golden, CO, USA, E-mail: [email protected]. https://orcid.org/0000-0002-0125-7532
Cody Higginson, Novoloop, Inc. 3487 Edison Way Ste. Q, Menlo Park, CA 94025, USA
Minjung Lee, National Renewable Energy Laboratory, 15013 Denver W Pkwy, 80401-3393, Golden, CO, USA.
https://orcid.org/0000-0003-1687-897X

As per De Gruyter’s policy this article has previously been published in the journal Physical Sciences Reviews. Please cite as:
K. M. Knauer, C. Higginson and M. Lee “Circular plastics technologies: pyrolysis of plastics to fuels and chemicals” Physical Sciences
Reviews [Online] 2023. DOI: 10.1515/psr-2022-0175 | https://doi.org/10.1515/9781501515613-002
10 2 Pyrolysis of plastics to fuels and chemicals

Figure 2.1: The EMF has broken down plastic recycling into three loops: (1) the polymer loop where the
polymer backbone remains unchanged (i.e., mechanical recycling); (2) the monomer loop where polymer is
broken down (or “unzipped”) back into the parent monomer that can be directly repolymerized back into the
original polymer; and (3) the molecular loop where the polymer backbone is broken down into useful
chemicals that can be further processed into monomers or used as fuel (i.e., pyrolysis or gasification).

temperatures, even highly contaminated plastics can be processed without difficulty

by pyrolysis [3]. Historically, pyrolysis has been employed at the large scale primarily as
either a “waste-to-fuels” process or “waste-to-energy” process when combined with
gasification (discussed later in this chapter). However, the current momentum towards
a circular economy for plastics has shifted the focus to a “waste-to-plastics” pathway
that involves converting the pyrolysis oil into monomers or other chemicals to be used
for plastic remanufacturing [1].
Pyrolytic recycling of plastic waste has already been achieved on a commercial
scale with new developments to improve the process such as microwaves and catalysts
showing great commercial potential. Major polymer producers all around the world
have announced strategies that plan to use the output of pyrolysis processes to utilize
plastic waste as a raw material to remake plastics [4]. These commitments are likely
reactions to the ambitious goals being set by consumer facing companies such as Coca-
Cola, PepsiCo, and Unilever to incorporate up to 50% recycled material in their pack-
aging in the next 5–10 years despite low volume outputs from mechanical recycling [4].
 2.2 Technical scope 11

Plastic films and flexibles that are used in many types of packaging are very difficult to
recycle via conventional mechanical recycling pathways used today as they are not
compatible with existing processing equipment (i.e., easily jams during sorting or in
hoppers, feeders, and extruders). This limitation, coupled with the rising demand for
recycled materials, has led to a rapid growth and expansion of the pyrolysis industry
along with new innovations. This chapter will describe the pyrolysis process and
important process parameters, the types of plastics that are suitable for pyrolysis
recycling, the mechanism of pyrolytic degradation of various plastics, the products
derived from different plastics, companies that have successfully scaled pyrolysis
recycling, and recent innovations in the technology.

2.2 Technical scope

Pyrolysis

Thermal pyrolysis

Process parameters
Thermal degradation of macromolecules via pyrolysis can be accomplished in the
presence of a catalyst (catalytic pyrolysis) or without (thermal pyrolysis) [5]. Thermal
pyrolysis of plastics involves the decomposition of polymeric materials by means
of high temperatures when it is applied in oxygen-free conditions. Since pyrolysis
relies on the endothermic breaking of covalent bonds the supply of heat is essential
to efficiently decompose the material [6]. Other key process parameters that influence
the end products from pyrolysis are temperature, reactor type, pressure, residence
time, and catalyst loading and type [7, 8]. Each of these parameters can be tailored to
optimize the product yield and composition as well as reduce the energy requirements.
However, temperature and reactor type have the most significant impact on product
selectivity [9].

Temperature. Temperature is probably the most significant operating parameter in

pyrolysis recycling since it controls the cracking reaction of the polymer backbone. The
pyrolysis temperature range can be broad, between 300 and 900 °C for most plastics,
and depends on a myriad of factors [10]. When the temperature is high enough, the
energy will overcome the enthalpy of the C–C bond and result in a broken bond [11].
Temperature settings are based on the type of polymer being pyrolyzed and the
preferred product composition/distribution. Typically, the pyrolysis temperature is
dictated by the onset of degradation of the polymer which can be determined by
thermal gravimetric analysis (TGA). Pyrolysis, for most plastics, begins at ∼300 °C or
earlier depending on the polymer structure and types/concentration of heteroatoms [6].
Typically, polymers with robust carbon-carbon bonds, such as polyolefins, require
12 2 Pyrolysis of plastics to fuels and chemicals

Table .: Summary of pyrolysis temperatures, products, and downstream applications for common plastics.

Polymer Structure Pyrolysis tem- Pyrolysis Downstream

perature (°C) product applications

Polyethylene –a Waxes, paraf- Oil refinery feed-

(PE) [, ] fins, olefins stock for conver-
–b sion to diesel fuel
[–] or chemicals
– [, ]
Polypropylene – Waxes, paraf- Oil refinery feed-
(PP) [, ] fins, olefins stock for conver-
sion to diesel fuel
or chemicals
Polystyrene (PS) – Styrene, styrene Monomers
[, , ] oligomers

Nylon- – [] ε-caprolactam Monomers

 []
– []
Polymethyl – Methyl Monomers
methacrylate [–] methacrylate
(PMMA)

Polyethylene – [] Benzoic acid, Upgrading to

terephthalate vinyl tere- chemicals or fuels
(PET) phthalate,
aldehyde
Polyurethane – [] Benzene, Upgrading to
(PUR) – [] methane, chemicals or fuels
ethylene, NH,
HNC
Polyvinyl chlo- – [] HCl, benzene Upgrading to
ride (PVC) chemicals or fuels

a
High density polyethylene (HDPE), blow density polyethylene (LDPE).

higher energy inputs and temperatures than other common plastics. Table 2.1 sum-
marizes reported temperature ranges required for the pyrolysis of the most common
plastics found in municipal solid waste (MSW). The pyrolysis temperature can also be
influenced by the types of plastic additives in the feedstocks. All plastic formulations
contain a complex concoction of additives, such as stabilizers, plasticizers and/or pig-
ments [12]. Most additive types will evaporate during pyrolysis, but certain additives
 2.2 Technical scope 13

can affect the kinetics and mechanism of degradation and require additional tuning to
the temperature [6]. Furthermore, additives that contain inorganic molecules can
result in char formation and reactor fouling over time.
The selected operating temperature also depends on the target products and
distribution. In general, when the pyrolysis temperature is high, there is increased
production of noncondensable gaseous fractions and lower liquid yields, such as diesel.
Higher temperatures increase the yield of hydrogen, methane, acetylene, aromatics,
and soot, whereas lower temperatures favor generation of aliphatic compounds and
liquid products [13]. Therefore, if a gaseous or char product (e.g., carbon black) is
preferred, higher temperatures >500 °C are suggested. If a liquid, fuel-like product is
preferred instead, lower temperatures in the range of 300–500 °C are recommended,
and this condition is applicable for all plastics [8]. When targeting diesel-like products,
the optimal operating range for most common plastics is 390–425 °C according to the
review by Sheirs et al. [3]. The high temperature requirements associated with pyrolytic
recycling are one of the major limitations considered when scaling the technology as
higher temperatures mean higher costs and greenhouse gas (GHG) emissions. Current
innovations in pyrolysis focus on strategies to lower the required temperatures for
plastic recycling and will be discussed in a later section.

Reactor type. After temperature, the second most important parameter to consider when
designing a pyrolysis process is the reactor type. A pyrolysis process design typically
consists of a feeding section, reactor unit, and product collection vessels that contain
downstream separation lines for product recovery and purification (Figure 2.2) [30–32].
Reactor type directly affects mixing of the plastics, quality of heat transfer, and final
product yield in the pyrolysis process and requires configurations that have excellent
mass and heat transfer characteristics. The type of catalyst that can be used in the process
also depends on the reactor type applied. Several kinds of reactors can be used for
pyrolysis including those involving high heat and mass transfer rates such as fluidized
beds (bubbling and catalytic), autoclaves, melting vessels, plasma reactors, and unique
designs to enable vacuum pyrolysis [33]. Similarly, it is also possible to find rotating cone
[34], cyclonic reactors [35], and ablative process reactors [36] used in pyrolysis processes.
At the commercial scale, the most common types of reactors used are fluidized bed
reactors (FBRs), fluid catalytic cracking reactors (FCCRs), and screw/Auger kiln reactors
(Figure 2.3) [5, 37, 38]. Emerging technologies are also exploring microwave assisted
reactor designs and continuous extrusion designs for pyrolysis processes to lower energy
inputs and increase throughput. The various reactors/configurations listed thus far have
advantages and disadvantages in terms of technical and economic parameters. The
literature contains many reports comparing the operation and performance of pyrolysis
reactors [39–46]. Each configuration comes with benefits and trade-offs, as to be expected.
Some known advantages and disadvantages of pyrolysis reactors identified in the liter-
ature are summarized in Table 2.2. The remainder of this section will focus on the most
common reactor types used at the commercial scale.
14 2 Pyrolysis of plastics to fuels and chemicals

Figure 2.2: Schematic of a small-scale pyrolysis pilot plant. The configuration includes (1) transportation of
the waste to the facility; (2) selective collection and sortation of target feedstocks for pyrolysis; (3) shredding
of the plastic; (4) washing; (5) drying; (6) waste storage; (7) catalyst storage; (8) reactor unit; (9) heating gas
storage; (10) separation unit; and (11) catalyst filter. Reprinted with permission from miskolczi et al. (Source:
Miskolczi 2009) [32].

Figure 2.3: Common reactors used for pyrolytic recycling of plastics: (A) fluidized bed reactor; (B) fluid
catalytic cracking reactor; and (C) screw/Auger kiln reactor.

Fluidized bed reactors. FBRs (Figure 2.3A) are the most widely used reactor type for
plastic pyrolysis [8, 46]. In this type of reactor configuration the plastic waste is melted
(i.e., converted to a “fluid”) and passed through a solid granular material (sand or solid
 2.2 Technical scope 15

Table .: Comparing advantages and disadvantages of common pyrolysis reactors (red = poor;
yellow = satisfactory; green = good) [, –]

catalyst) at high enough speeds to suspend the solid and yield fluid-like properties [47].
This process, known as fluidization, imparts many important advantages to an FBR over
other pyrolysis reactors. FBRs are characterized by excellent heat and mass transfer
rates, resulting in consistent temperature control throughout the reactor and highly
uniform products [31]. In a catalytic FBR, the catalyst sits on a distributor plate and is well
mixed with the fluid in the bed providing a large surface area for reaction to occur [48].
From an economic point of view, FBRs are very attractive as they have low operating
costs, can be operated in continuous mode, and the catalysts (when used) can be
recovered and recycled in the process several times [8, 10]. Some disadvantages to using
FBRs can be the complexity in the reactor design, solid fraction attrition, and bed
defluidization which can lead to frequent shutdowns [49]. Solid fraction attrition is
attributed to the solid/solid collisions in the hot solid media leading to attrition phe-
nomena and producing fine particles in the resulting solid fraction [50]. These small
particles hinder the separation process resulting in higher solids concentrations in the
liquid fraction. This promotes aging, erosion, blockage, and combustion problems in the
FBR design [41].
Regardless of the challenges associated with FBRs, they are considered robust and
scalable reactors that are widely employed in demonstration and commercial pyrolysis
plants [46]. An example of a successful commercial pyrolysis operation using an FBR is
Recycling Technologies in the United Kingdom (UK). Recycling Technologies claim they
can process up to 20 tons per day (TPD) of plastic waste into Plaxx™, a low sulfur heavy
fuel oil, via their FBR pyrolysis configuration. Another example is the BP process that
used an FBR to pyrolyze up to one TPD of plastic waste into light and heavy waxes,
although this plant is no longer operational.
16 2 Pyrolysis of plastics to fuels and chemicals

A variant of the FBR is the conical spouted bed reactor (CSBR) that is designed
with more intense mixing in the bed to prevent defluidization events and reduce
shutdowns. While CSBRs have not been demonstrated on a large scale, this type of
reactor has been applied for the thermal pyrolysis of polyolefins on a laboratory scale,
reporting very high yields of wax up to 80 wt% [51]. Other studies have reported
successful conversion of polyolefin feedstocks to gasoline and diesel range products
[52–54].
Fluid catalytic cracking reactors. FCCRs are common reactors found in conventional
refineries and have historically been applied to convert vacuum gas oil (VGO) to gas-
oline. A primary challenge in achieving a continuous process for plastic pyrolysis is the
continuous feeding of the feedstock in solid form into the reactor [55]. Fluid catalytic
cracking reactors (FCCR) offers a solution to this problem by dissolving the plastic feed
in a suitable solvent, followed by pyrolysis of the solution [55–57]. A common FCCR
configuration is outlined in Figure 2.3B. First, a hot particulate catalyst is contacted with
the dissolved plastic feedstock, creating cracking products and a coked catalyst. The
plastic is cracked into gaseous components and separated to fuel gas [31]. The coked
catalyst is separated, stripped of residual oil products, and regenerated by burning the
coke. The hot catalyst is then recycled to the riser for additional cracking [58]. FCCRs are
characterized by good solid polymer mixing, but some disadvantages associated with
this type of reactor are high energy requirements (compared to other pyrolysis re-
actors), the costs associated with use of solvent, and very dilute feed streams [59]. One
example of a large-scale operation using an FCCR is Reentech in South Korea. This
process applies an FCCR pyrolysis configuration cracking of plastic wastes [3].
Screw/auger reactor. Screw/Auger Kiln reactors are a relatively simple design that
overcome some of the problems of conveying heat for pyrolyzing plastics. Auger re-
actors are typically made up of a tubular reactor and a screw conveyer as shown in
Figure 2.3C. The screw is used to convey a single feedstock or a blend with solid heat
carriers down the length of a reactor tube. This is a continuous process where the
residence time can by varied by the varying the speed of the screw and length of the
reactor [60]. Typically, metal or ceramic spheres are added to the conveyer line that
help avoid coke build-up and improve the heat transfer during the pyrolysis process.
Some key benefits to using an Auger reactor for pyrolysis is the continuous operation,
ability to purge through the length of the reactor (i.e., efficient chlorine removal), and
selective zone heating [60]. Auger reactors have been historically used to pyrolyze tires
and thermoset based waste electrical and electronic equipment (WEEE). Two well-
known examples of commercial scale use of screw/Auger reactors to pyrolyze plastic
waste are Agilyx and Renewlogy. Agilyx is currently operating a pilot facility using a
continuous, dual screw reactor design to process 10 TPD of plastic waste. Renewlogy is
also operating a pilot plant facility at 10 TPD using an Auger/kiln reactor design.
Brassard et al. recently reviewed auger reactor designs and the effect of various
operational parameters on their performance [61].
 2.2 Technical scope 17

Pressure and residence time. Pressure and residence time are both temperature depen-
dent factors that can influence product distribution and yield from plastic pyrolysis.
Typically, in a pyrolysis process, applying higher pressures can shift the molecular weight
of the product distribution and shifts the product yields to more gaseous products.
However, this trend is only apparent at high temperatures and shows less impact at lower
temperatures. The residence time can be defined as the average amount of time that the
molten or dissolved plastic spends in the reactor [62]. Shorter residence times will yield
longer carbon products and longer residence times will increase the overall yield of
lighter hydrocarbons and noncondensable gases [63]. Studies applying auger reactors in
pyrolysis processes have highlighted the importance of short residence time for
obtaining a high yield of light olefins [3]. However, this affect is also temperature
dependent as seen by Mastral et al. who studied the effect of residence time and tem-
perature on product distribution of HDPE thermal cracking in an FBR. It was found that a
higher liquid yield was obtained at longer residence times when the temperature was less
than 685 °C. However, at higher temperatures, the residence time had less influence on
the liquid and gaseous yield [62].

Degradation mechanisms and products

The pyrolytic degradation mechanisms of plastics depend on the parent polymer. There
are four types of degradation mechanisms that can occur: random-chain scission, end-
chain scission, chain-stripping, and crosslinking. These different mechanisms are related
to the bond dissociation energies, the chain defects of the polymers, the aromaticity, and
the presence of halogen and other hetero-atoms in the polymer chains. The products
obtained from pyrolysis vary based on the parent polymer and are summarized for
common plastics in Table 2.1. This section will discuss the different types of plastics that
can be recycled by pyrolysis and their respective products. Additionally, companies that
have demonstrated pilot scale pyrolysis recycling operations are summarized in Table 2.3
along with the respective primary feedstocks and products.

Polyolefins. Of the most common waste plastics, polyolefins are probably the most ideal
feedstocks for pyrolysis recycling due to their lack of hetero-atoms. Polyolefins include
high density polyethylene (HDPE), low density polyethylene (LDPE), linear low-density
polyethylene (LLDPE), and polypropylene (PP). In high temperature environments,
polyolefins degrade via random chain scission of carbon-carbon bonds where the
polymer is broken randomly along the backbone into smaller molecules of varying
chain lengths. As an example, the pyrolytic degradation mechanism of HDPE is outlined
in Figure 2.4. Initiation consists of homolytic breaking of the carbon–carbon bonds by
random chain scission, resulting in the formation of two radicals. This is followed by
depropagation and the release of olefinic monomeric fragments from primary radicals.
This mechanism perpetuates with hydrogen chain transfer occurs leading to the for-
mation of olefinic species and polymeric fragments. Moreover, secondary radicals can
also be formed from hydrogen abstraction through an intermolecular transfer reaction
18 2 Pyrolysis of plastics to fuels and chemicals

Table .: Select pyrolysis companies, primary feedstocks, and primary products as listed on company
websites.

Company Primary feedstock Primary product

Brightmark Energy (formerly RES HDPE Diesel, naphtha, wax

Polyflow) LDPE
PP
PS
VadXX HDPE Diesel, naphtha, syngas, carbon black
LDPE
PP
PS
Agilyx (formerly PlasFuel) HDPE Light synthetic crude oil; styrene
LDPE monomers
PP
PS
Pyrowave PS Styrene monomer and oligomers
Nexus Fuels LLC HDPE Light crude, diesel, gasoline, kerosene,
LDPE wax
PP
PS
Renewlogy HDPE Crude oil and kerosene
LDPE
PP
PS
Recycling Technologies UK NAa Low sulphur hydrocarbon Plaxx™
New Hope Energy HDPE Synthetic fuels
LDPE
PP
PS
Plastic Energy HDPE Diesel, naphtha
LDPE
PP
PS
Quantafuel HDPE Purified diesel
LDPE
PP
Fuenix Ecology NAa Naphtha, paraffin and LPG
Blest HDPE
LDPE
PP
PS
Climax Global Energy NAa Crude oil, diesel
EcoFuel Technology HDPE Purified diesel and kerosene
LDPE
PP
PS
Enval Plastic Aluminum Aluminum, crude oil
Laminates
 2.2 Technical scope 19

Table .: (continued)

Company Primary feedstock Primary product

Braven (formerly Golden Renewable PET Braven PyChem (Naphtha)

Energy) HDPE
LDPE
PP
PS
Reentech PE Diesel, kerosene, gasoline
PP
PS

Figure 2.4: HDPE pyrolysis degradation steps and corresponding mechanisms.

between a primary radical and a polymeric fragment. β-cleavage of secondary radicals

leads to an end-chain olefinic group and a primary radical which can ultimately lead to
chain branching. Termination occurs in bimolecular mode with the coupling of two
primary radicals or by disproportion of the primary macroradicals. The final pyrolysis
product from polyolefins consists of a mixture of waxes, paraffins, and olefins that can
be converted to diesel fuel or sold to an oil refinery as feedstock. The pyrolysis oil can be
20 2 Pyrolysis of plastics to fuels and chemicals

further refined to via hydrotreatment to produce olefins and other polymer precursors
for remanufacturing of plastics similar to the process for purifying naphtha for plastic
production [64].
The pyrolysis of polyolefins is not a trivial process and requires a considerable
amount of energy. It has been reported that at temperatures above 250 °C, the activation
energies required for depolymerization of polyolefins range from 150 to 300 kJ/mol [1, 65].
This clearly demonstrates the energy intensiveness of these processes. As a result, many
efforts focus on lowering the temperatures required for pyrolyzing polyolefins (as dis-
cussed in later sections) and improving the value of the pyrolysis product.

Unzipping polymers. Some common plastics undergo an “unzipping” mechanism in a

pyrolysis process in which the polymer depolymerizes directly into parent monomers
under pyrolysis conditions. These plastics include polystyrene (PS), polymethyl meth-
acrylate (PMMA), and polyamide-6 (PA-6 or Nylon-6). The unzipping mechanism occurs
by end-chain scission where the polymer is broken up from the end groups yielding the
corresponding monomers (Scheme 2.1). Since the resulting pyrolysis oil is made up of
mostly the original monomers, these types of plastic pyrolysis fall into the monomer loop
(Figure 2.1) and will be discussed in more detail in Chapter 2 of this book.

Polymers containing hetero-atoms. Ideal conditions for pyrolyzing plastics require the
absence of oxygen. As a result, polymers containing hetero-atoms in the backbone are
not ideal feedstocks for pyrolysis recycling. Common plastics that contain hetero-atoms
are polyethylene terephthalate (PET), polyurethanes (PURs), polyamides, and polyvinyl
chloride (PVC). Other hetero-atoms found in common plastics include bromine and
fluorine. Under pyrolysis conditions hetero-atom containing plastics can yield haz-
ardous and corrosive products such as ammonia, hydrogen cyanide, hydrogen chloride,
hydrogen bromide, bromine, hydrogen fluoride, and others [3]. If these types of plastics
are used as feedstocks for pyrolysis then careful selection of methods to neutralize or
inhibit the effects of hazardous compounds formed are required. This imparts high
costs and energy input for the overall recycling process and has significantly limited the
widespread adoption of pyrolysis considering the large volumes of PET and PVC found
in MSW.
If pyrolyzed, the degradation of mechanism of PET, which contains oxygen and
aromatic groups, degrades by random scission of the ester links in the main chain that
form carboxylic acid and olefinic end groups [66]. The carboxylic acid end groups

Scheme 2.1: Schematic of end-chain scission of PA-6 producing ε-caprolactam

 2.2 Technical scope 21

undergo decarboxylation to yield phenyl end group compounds. Subsequently, benzoic

acid and vinyl benzoate are formed by scission of the phenyl end group compounds.
During pyrolysis, other volatile products are formed from vinyl benzoate and benzoic
acids including benzene, toluene, styrene, and ethyl benzene. The final pyrolysis oil
consists mostly of benzoic acid and vinyl terephthalate which can be upgraded to useful
chemicals or fuel [10].
PURs are an incredibly complex group of plastics in that are either thermoplastics
or thermosets (i.e., crosslinked) and can be synthesized from numerous types of
monomers. PURs are classified based on a urethane linkage in the backbone, but in
reality, this makes up a small percentage of the actual polymer structure. As a result of
this complexity, several different types of degradation mechanisms can occur during
pyrolysis such as random chain scission, chain stripping, and crosslinking. Overall,
studies show that pyrolyzing PURs results in a complex mixture of compounds in the
pyrolysis oil such as benzene, methane, ethylene, amines, and hydrogen cyanide [3].
PVC breaks down via chain stripping under pyrolysis conditions. In this mecha-
nism, the reactive substituents or side groups on the polymer chain are eliminated,
leaving an unsaturated chain. This polyene then undergoes further reaction, including
β-scission, aromatization, and coke formation. This results in very little monomer
recovery and the pyrolysis oil consists mostly of benzene and hydrochloric acid (HCl).
The presence of HCl leads to corrosion of the reactor and formation of organochlorine
compounds [67]. Additionally, the presence of chlorine limits the application of the
pyrolysis oil as fuel. As a result, pyrolysis plants typically avoid PVC feedstock unless it
has undergone a dichlorination pretreatment [7].
The presence of halogens is a particular problem in pyrolytic recycling as they can
lead to the formation of highly toxic and dangerous compounds. Halogens can be present
on the polymer backbone, such as the case with PVC, or in the additives such as bromi-
nated flame retardants used in many plastic formulations (present in some cases as high
as 60% by mass of the polymer). As a result, dehalogenation has been a major focus in
pyrolysis innovations. Dehalogenation technologies have been developed as a pretreat-
ment step, using solvents or thermal treatment to remove halogens. Dehalogenation of
liquid products using catalysts or antimony has also been studied. Scrubbing gas effluents
from the pyrolysis process to remove HCl and HBr is also employed. Additionally, some
efforts have even focused on capturing the bromine released during pyrolysis for reuse in
flame retardants [68, 69].

Mixed plastic feedstocks. Pyrolysis is often presented as a solution for recycling of highly
mixed, heterogeneous waste. Pyrolysis recycling of mixed waste plastics may be one
avenue for recovering value from unwashed, commingled plastics and lowering the costs
and logistics of plastic sortation typically required for recycling [3]. However, as
demonstrated in the previous section, pyrolyzing different plastics can lead to varying
compositions, yields, and quality of pyrolysis oil products. As a result, most commercial
facilities have focused on single stream feedstocks. Several researchers have studied the
22 2 Pyrolysis of plastics to fuels and chemicals

resulting pyrolysis oil from mixed plastic waste streams [13, 20, 23, 48, 70]. These studies
have focused primarily on mixtures of PE, PP, and PS, with low levels of PVC contami-
nations. Overall, the pyrolysis of mixed plastics produces lower liquid yields of target
products liquid when compared to the pyrolysis of single plastic waste streams. Despite
the lower liquid yield the quality of pyrolysis oil produced is typically comparable to the
single plastic feedstocks. These studies have shown that the oil composition is still
acceptable for further processing in petrochemical refineries. The challenge then be-
comes the techno-economics. Pyrolyzing mixed plastic streams will save on costs in the
sorting steps. However, there is still the question on whether these cost savings justify the
high energy and costs of pyrolysis when only 50% of the pyrolysis oil can be recovered.

Assisted pyrolysis technologies

Microwave assisted technology

As noted, one of the major drawbacks to pyrolysis is the high energy inputs required to
break the robust bonds in common plastics. Additionally, plastic feedstock has very low
thermal conductivity which leads to a low rate of heat transfer through the materials
and thus requires long residence times to achieve target yields [71]. In electric-heated
pyrolysis, the plastic waste is heated by an external heating source which heats
everything in the pyrolysis reactor, including the evolved volatiles. This results in
significant energy losses and can also promote undesired side reactions that can lead to
the formation of toxic compounds, increased production of char, and fouling of the
reactor [72, 73]. Microwave heating can be applied as a more efficient means of heating
the reactor. Microwave-assisted pyrolysis offers a lower energy pathway for breaking
carbon bonds and recovering high quality pyrolysis oil. Microwave-assisted pyrolysis
uses microwave heating to thermally crack the plastic waste. In this process, the waste
material is mixed with a microwave-absorbent substance such as particulate-carbon.
This substance absorbs microwave energy which then generates sufficient thermal
energy to achieve the temperatures required for pyrolysis to occur [71]. Microwave
radiation offers several advantages over conventional pyrolysis methods such as rapid
heating, lower residence times, and lower production costs [8]. Unlike conventional
methods, microwave energy is supplied directly to the material through the molecular
interaction with the electromagnetic field, thus no energy is wasted to heat up the
surrounding area of the pyrolysis chamber. One limitation to microwave-assisted py-
rolysis is the lack of sufficient data to quantify the dielectric properties of various
plastic waste streams [8]. The efficiency of microwave heating significantly depends on
the dielectric properties of the material, which can vary depending on the plastic
feedstock [71]. Therefore, most studies focus on single waste streams. Nevertheless,
microwave-assisted pyrolysis continues to be explored, with some companies demon-
strating the process at the pilot-scale such as Pyrowave, a startup company that uses
microwave-assisted technologies to pyrolyze PS into styrene monomer. In-depth
 2.2 Technical scope 23

reviews of microwave-assisted pyrolysis have been presented by Lam and Chase [71]
and Undri et al. [74].

Hydrothermal liquefaction
Another method for improving the energy efficiency and yield in plastic pyrolysis is
by incorporating subcritical or supercritical water and is known as hydrothermal
liquefaction (HTL) [75]. When under subcritical or supercritical conditions water
contains enough energy to break carbon-carbon bonds making it a useful solvent for
advanced oxidation processes, including degradation and thermochemical conversion
of plastic waste [76]. Super critical water (SCW) exists at a temperature above 374 °C and
pressure higher than 22.1 MPa, and the physical and chemical properties are dramat-
ically different compared to water at ambient/atmospheric conditions [77]. The high
density and ionic product of SCW promotes the solvation of compounds, while the high
diffusivity and low viscosity promotes faster mass transfer during pyrolysis [75, 78, 79].
The HTL pyrolysis process contains a series of reactions including hydrothermal
cracking, hydrolysis, free radical, nucleophilic substitutions, and cyclization that con-
verts plastics into monomers or chemical feedstock [80]. The SCW can serve as a solvent,
catalyst, or reactant [81, 82]. Hydrocarbon yields and distributions are highly dependent
on the residence time, but unlike conventional pyrolysis, the heating rate in HTL was
reported to have an insignificant effect on product distribution [75]. HTL is not as
heavily studied as conventional pyrolysis, but has started to attract more interest in
recent years. Some challenges associated with using SCW-assisted pyrolysis are the high
costs of equipment and operation and the corrosive effects of SCW on the reactor [5, 83].
One industrial scale example of an HTL process is the ReNew ELP technology that uses
SCW to process plastic waste. ReNew ELP’s catalytic hydrocracking (Cat-HTR) tech-
nology uses SCW to break down plastic feedstocks and harvest hydrogen from the water
for use in the creation of new, stable hydrocarbons.

Catalytic cracking
Over the years, various types of pyrolysis have been developed based on the kinetics of
the degradation and are categorized as fast, catalytic fast, intermediate, slow, and
vacuum pyrolysis [37]. Adding catalysts to the pyrolysis process can facilitate lower
temperatures and shorter residence times [51, 67, 84, 85], increase the yield and
selectivity of the pyrolysis oil [85, 86], and limit side reactions and the formations of
undesired products [51]. Catalysts will impart better control over the product selec-
tivity, but the reactor choice and operating conditions still have a significant effect on
the product distribution and yields. Additionally, catalyst properties such as the acidity
and pore structure also play a major role in the product distribution obtained [55–57].
Multiple studies have revealed that using catalysts can modify the selectivity towards
the production of light olefins, gasoline, or diesel based on the type of catalyst used [31,
51–53, 56, 87]. Homogeneous and heterogeneous catalysts have been investigated with
heterogenous catalysts being the most common in industrial practice due to the ease of
24 2 Pyrolysis of plastics to fuels and chemicals

separation and recovery associated with these kinds of catalysts [88]. Homogenous
catalysts include Lewis acids and fused metal tetracloroaluminates (M(AlCl4)n), where
the metal can be lithium, sodium, potassium, magnesium, calcium, or barium [88, 89]. A
wide variety of heterogeneous catalysts can be used including conventional solid acids
(such as zeolites, silica–alumina, alumina, and other FCC catalysts), mesostructured
catalysts, nanocrystalline zeolites (such as n-HZSM-5), and several others [88, 90]. FCC
catalysts are the best choice for maximizing liquid oil production from plastics as they
have the highest catalytic activity [8]. Additionally, FCCs can be recovered and reused
and are economically attractive. FCC catalysts are typically made of zeolite crystals and
a non-zeolite acid matrix known as silica–alumina. FCC catalysts are normally used in
the petroleum refining industry to crack heavy oil fractions from crude petroleum into
gasoline and liquid petroleum gas (LPG) fractions where aromatic and naphthenic
compounds are selectively formed [6].
Catalysts are primarily used to reduce the overall costs of the process while also
improving the value and selectivity of the products. Several reports show that the use of
an acid catalyst may reduce the pyrolysis temperature, overall energy consumption,
and total operating cost of the process [67, 91–95]. Catalysts can improve the hydro-
carbon distribution to yield pyrolysis oil that resembles conventional fuel such as
gasoline and diesel (e.g., C2–C4 olefins) without requiring further refining [8]. Schirmer
et al. showed that the catalytic cracking of PE increases the gasoline yield when
compared to conventional pyrolysis [96].
Catalytic cracking also involves several drawbacks. Catalysts can be easily deac-
tivated by carbonaceous deposits, inorganic materials, and chloride and nitrogen-
containing species making the process highly sensitive to contamination typically
associated with plastic waste streams [55–57, 97]. Finally, many chemical recyclers
have struggled to find an optimum catalyst that is ideal for cracking multiple types of
plastic waste streams [57]. As a result, intensive pre-treatment steps are often required
to limit deactivation of the catalyst. Furthermore, the required catalyst regeneration
increases the process complexity and total operating cost [5].

Gasification

Gasification is another important plastic recycling process that is typically classified in

the same category as pyrolysis recycling and is the preferred route for heavily
contaminated and otherwise unusable, waste streams [5]. Gasification applies high
temperatures to convert organic solid material (coal, biomass, plastics, and organic
waste) into a gaseous mixture (syngas) of carbon monoxide (CO), hydrogen (H2), carbon
dioxide (CO2), and methane (CH4). Gasification consists of heating plastics with a sub-
stoichiometric amount of oxygen or air, and steam at temperatures of 700–1500 °C and
atmospheric pressure [98, 99]. Process parameters such as temperature, O2/H2O ratio,
and residence time can be tailored to target a specific H2/CO ratio in the resulting
 2.2 Technical scope 25

syngas. For example, more steam yields more H2 in the syngas when compared to pure
oxygen or pure air gasification. The syngas produced from gasification can be used in
Fischer–Tropsch processes (FTS) to produce fuels and chemicals or converted to
methanol via catalytic hydrogenation [100]. Methanol can be further converted to
olefins via downstream catalytic processes and used to produce new polymers from
chemically recycled intermediates [5].
Gasification can be done in air which decreases the costs of gas separation
compared to steam gasification, however, the presence of N2 in such a high-temperature
environment triggers the production of harmful nitrogen oxides (NOx) which are 300X
more damaging GHGs than CO2. Air gasification also requires higher volumes than
steam processes, thus negatively impacting investment costs. Additional challenges
associated with the gasification of plastic waste are the high amount of energy required
and high production of char that occurs during the process. Typically, dual-stage
gasification reactors are required to mitigate char production and reactor fouling,
increasing the overall investment costs of the process [101]. Another key challenge is the
high yields of toxins and aromatics that limit the direct use of the syngas in
downstream processes.
Overall, gasification is a well-established technology and the recent momentum
towards a circular economy has led to the development of increasingly viable and
sustainable solutions, such as the combination of gasification with pyrolysis or com-
bustion and the cogeneration of different products (e.g., syngas, heat, and power) as
summarized by Heidenreich and Foscolo [102]. Eastman has pioneered gasification as
recycling technology for carpet waste feedstocks. Eastman’s gasification plant in
Kingsport, TN uses plastic waste and coal feedstocks to generate syngas which they then
feed into other processes at the Kingsport site in a completely integrated design. On a
pilot scale, Texaco Inc. and Shell developed a proprietary gasification process, in which
petroleum feedstocks were replaced by plastics (Figure 2.5) [6]. Ube Industries in Japan
gasifies plastics in a pressurized FBR, developed jointly by Ube and Ebara Co.

Plasma pyrolysis/gasification

Plasma assisted pyrolysis combines pyrolysis with the thermochemical properties of

plasma. The process is similar to gasification and uses extremely high temperatures,
ranging between 1730 and 9730 °C, to convert plastic waste into syngas. Plasma assisted

Figure 2.5: Basic schematic of Texaco gasification process [6].

26 2 Pyrolysis of plastics to fuels and chemicals

pyrolysis is extremely fast, lasting between 0.01 and 0.5 s, depending on the process
temperature and type of waste feedstock [103]. The resulting syngas is composed mainly
of CO, H2, and small amounts of higher hydrocarbons. Plasma pyrolysis has several
advantages over conventional pyrolysis and gasification. Plasma pyrolysis is very fast
leading to lower emissions and is suitable for mixed plastic feedstocks [97, 103]. The
high temperatures decompose any toxic compounds in the syngas and limit the for-
mation of HCl from PVC. The produced gas has a low tar content and high heating value
which makes it suitable for electricity generation in turbines or hydrogen production in
an integrated process.
There are still several technical challenges to be addressed before the technology
can meet plastic waste management requirements and become commercially available.
The challenges differ depending on the specific plasma technology [104]. Thermal
plasma technology is a well-established technology in metallurgy processing or mate-
rial synthesis, but not in waste management [103]. For now, due to economic and legal
aspects, the most important application of the technology is the destruction of haz-
ardous waste rather than recycling, but some stakeholders predict that plasma assisted
gasification of plastics may soon be commercialized [97].

2.3 Summary and future perspectives

Pyrolysis technologies are leading the way in chemical recycling because of the
robustness to contamination and existing infrastructure. Pyrolysis is already consid-
ered to be a reasonably mature technology with numerous commercial plants oper-
ating to pyrolyze plastic waste (Table 2.3). However, current energy requirements,
variability of the waste streams, poor life cycle assessment metrics, and techno-
economics have presented limitations to implementation of pyrolysis as a major
recycling route for plastic waste. At large scales (e.g., tons per day), using pyrolysis and/
or gasification technologies to produce fuels and/or chemicals from plastic can address
the challenges of waste management and increasing global energy demand simulta-
neously. Overall, pyrolysis is considered a relatively simple, flexible, and suitable
process for recycling plastic waste streams that are difficult to depolymerize. However,
many still agree that an improved understanding of the chemistry and more innovative
reactor designs are required to realize the full potential of pyrolysis and to achieve
lower GHG emissions. Additionally, the absence of an optimum reactor technology to
employ catalytic fast pyrolysis is another major bottleneck in industrial applications.
Despite the drawbacks, consumer product companies are making big commitments
to use recycled content in their packaging. Governments are also pushing companies to
use more recycled plastic. California wants plastic packaging to contain 50% recycled
content by 2030. The European Union is pushing for 30% by the same date. Shifting the
endgame of pyrolysis to a waste-to-plastics model can help companies and governments
achieve these goals. This will require collaborative efforts between the recyclers and oil
 References 27

refineries that are willing to purchase the pyrolysis oil for conversion into chemical
feedstocks for plastics. The feed flexibility of thermal processes supports the potential
of pyrolysis and gasification; however, the strong variability in plastic waste streams
calls for further assessments through fundamental experiments and models. Addi-
tionally, innovations to lower the energy requirements and costs are needed to mini-
mize the environmental footprint and provide an economically viable pathway to a
circular plastics economy via pyrolysis recycling.

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Katrina Knauer*, Cody Higginson, Yuanzhe Liang and Minjung Lee
3 Circular plastics technologies:
depolymerization of polymers into parent
monomers
Abstract: While most commodity plastics were not designed to easily depolymerize, some
common plastics can be broken down into their parent monomers in the presence of heat,
pressure, catalysts, and/or solvent. Here, we provide a high-level overview of the depoly-
merization technologies that have been studied and/or scaled as promising monomer-loop
recycling processes for selective plastic waste streams. Namely, commodity plastics that are
considered unzippable/depolymerizable include polyethylene terephthalate, polyamides,
polymethyl methacrylate, and polystyrene. Monomer-loop recycling technologies are one
of several pathways toward a circular economy for plastics.

Keywords: Depolymerization; recycling; solvolysis; unzipping; circularity; plastics.

3.1 Introduction
In contrast to the pyrolysis of plastic waste to produce fuel, naphtha, and other chemicals
(Section 3.1) along the molecular recycling loop, some plastics can be depolymerized or
“unzipped” to recover monomers directly in the so-called monomer recycling loop [1].
These monomers can be purified to remove additives, fillers, and pigments present in the
plastic waste and used to resynthesize the parent polymer. In a sense, this is an idealized
representation of a circular material – one that can be cycled through monomer and
polymer repeatedly (Figure 3.1).
Not all plastics are amenable to this kind of depolymerization. Most plastics manu-
factured today were designed for the “take-make-waste” model, based on a linear
economy framework that does not adequately address materials’ end-of-life issues. In
principle, any polymer could be rendered “depolymerizable” by manipulating the
thermodynamic equilibrium of the polymerization and depolymerization by modifying
temperature, pressure, concentration, state, etc. [3]. A thermodynamic measure of
depolymerizability, or how easily a polymer can unzip to its parent monomers, can be

*Corresponding author: Katrina Knauer, National Renewable Energy Laboratory, 15013 Denver W Pkwy,
Golden, CO, 80401-3393, USA, E-mail: [email protected]. https://orcid.org/0000-0002-0125-7532
Cody Higginson, Menlo Park, CA, USA
Yuanzhe Liang, National Renewable Energy Laboratory, Golden, CO, USA
Minjung Lee, Bioenergy Science and Technology, National Renewable Energy Laboratory, 15013 Denver W
Pkwy, Golden, CO, 80401, USA. https://orcid.org/0000-0003-1687-897X

As per De Gruyter’s policy this article has previously been published in the journal Physical Sciences Reviews. Please cite as:
K. Knauer, C. Higginson, Y. Liang and M. Lee “Circular plastics technologies: depolymerization of polymers into parent monomers”
Physical Sciences Reviews [Online] 2023. DOI: 10.1515/psr-2023-0014 | https://doi.org/10.1515/9781501515613-003
34 3 Circular plastics technologies

Figure 3.1: Simplified schematic of the monomer loop for plastics recycling as defined by the Ellen McArthur
Foundation (EMF), figure adapted from Ellis et al. [2].

measured by the ceiling temperature (Tc) of the polymer [4]. The Tc is defined as the
temperature at which the polymerization and depolymerization reactions reach an
equilibrium state. In other words, depolymerization will occur at temperatures above the
Tc of the polymer. However, most commodity plastics have a Tc at or near the carbon
degradation temperature and undergo random chain scission and crosslinking rather
than an “unzipping” mechanism to monomer. Unzipping occurs when the bonds break at
the polymer chain end (i.e., chain-end scission) to release the monomer in a systematic
mechanism rather than random fragmentation along the backbone (Figure 3.2).
Some commodity plastics can be broken down into one or more of their constituent
monomers in sufficiently high yield and purity to be used to produce new polymers with
properties comparable to the original material. For some condensation polymers like
polyethylene terephthalate (PET), this depolymerization process requires the input of
stoichiometric reactants and catalysts, while other materials, such as polystyrene (PS) or
polymethyl methacrylate (PMMA), can be coaxed under appropriate conditions to unzip

Figure 3.2: Simplified representation of Tc and

random chain scission verses chain-end unzipping
mechanisms in polymer depolymerization.
 3.2 Technical scope 35

predominantly into their component monomers (styrene and methyl methacrylate,

respectively). We categorize these depolymerization routes into two general branches:
solvolysis and pyrolytic depolymerization (“unzipping”). Selected examples of plastics for
which depolymerization is being explored as a means of chemical recycling, and the
methods used to accomplish this are surveyed in this chapter. The conditions and pro-
cesses described are not exhaustive, but are intended to be representative of chemical
recycling strategies for the various classes of materials discussed herein [5].

3.2 Technical scope

3.2.1 Solvolysis

Solvolysis is the depolymerization of a polymer by reaction with the chosen solvent, such
as water, methanol, or ethylene glycol. Solvolysis is particularly suited for the breakdown
of condensation polymers containing functional groups cleaved by hydrolysis and
alcoholysis, and to some extent phosphorolysis and aminolysis, including polyesters,
polyamides, polyurethanes, and polyethers. The primary goal behind the solvolysis
chemistries discussed in this section is to collect monomers that can be purified and
re-polymerized into their parent materials in an infinite cyclic process.

3.2.1.1 Polyethylene terephthalate

PET, the condensation polymer of terephthalic acid (TA) and ethylene glycol (EG), is the
third most produced thermoplastic (following polyethylene and polypropylene, respec-
tively), and the most common thermoplastic polyester produced today. It is used in a wide
range of applications such as textile fibers, thermoforming in manufacturing, and food,
drink, and storage containers. Most of the demand for PET is for textile fibers, while
beverage bottles constitute the second largest source of demand for PET. While me-
chanical recycling of PET is currently widespread, the mechanical, thermal, and rheo-
logical properties of the recycled plastic weaken over repeated processing cycles
compared to virgin resin [6]. Furthermore, most mechanical recyclers will only take rigid,
clear PET bottle flake as feedstock and other PET form factors (textiles, clam shells, film,
etc.) are landfilled. It is perhaps for this reason that significant research efforts have
focused on the chemical recycling of PET to recover virgin-like quality monomers, and
headway has been made in the commercialization of several PET depolymerization
strategies [7, 8]. Multiple reagents exists that can cleave ester bonds in PET backbones, but
the primary strategies that enable recovery of chemicals useful for the synthesis of
virgin-grade PET are hydrolysis, methanolysis, and glycolysis (Figure 3.3).
36 3 Circular plastics technologies

Figure 3.3: Solvolytic routes for chemical depolymerization of PET into monomers TA, DMT, BHET, and EG.

3.2.1.1.1 Hydrolysis
Hydrolysis of PET involves reacting the polymer with water at elevated temperatures to
cleave the ester bonds, usually in the presence of a catalyst [8], the products of which are
TPA and EG, and has been reviewed extensively in the academic literature [8–14]. The
reaction can take place under acidic, alkaline, or neutral conditions, and research related
to enzymatic hydrolysis of PET has also gained considerable momentum in recent years,
as outlined below [8, 11, 15–18].

3.2.1.1.1.1 Acidic hydrolysis. Acidic hydrolysis of PET can be carried out with concentrated
mineral acids serving as catalyst, including nitric acid and phosphoric acid [11, 19].
However, the most common acid used in this process is sulfuric acid, as outlined in the
following examples [8, 11, 20–22]. Brown and O’Brien described a process in 1976
employing at least 87 % sulfuric acid for the hydrolysis of PET [23]. In this case, the
depolymerization was carried out at 100 °C for 5 min at atmospheric pressure, after
which near-theoretical yields of TPA and EG were obtained in crude form. Thereafter, the
crude hydrolysate was treated with sodium hydroxide to neutralize the sulfuric acid and
TA (pH 7.5–9.0), forming soluble sodium terephthalate. The mixture was filtered to
remove insoluble residues and passed through an ion exchange decolorizing column. The
solution containing ethylene glycol, sodium sulfate, sodium hydroxide, and sodium
terephthalate was acidified to pH 2.5–3.0 by addition of sulfuric acid to precipitate ter-
ephthalic acid, which was collected by centrifugation and found to be of 99+% purity after
washing with water. The ethylene glycol in the aqueous centrifuge mother liquor was
extracted with trichloroethylene and recovered at 99+% purity by distillation.
In 1982, Pusztaszeri described a lower temperature process employing concentrated
sulfuric acid to depolymerize PET scrap [21]. In the process, PET solid is stirred with water
and concentrated sulfuric acid (volume ratio of 2:13 to 8.5:13) at room temperature for 5–
30 min at atmospheric pressure to produce a fully liquified crude product. Crude TPA,
having solubility in water of 0.0017 g/100 g of solvent, is precipitated by the addition of an
equivalent volume of cold water and collected by filtration [23]. In this case, the filtrate
 3.2 Technical scope 37

containing aqueous ethylene glycol, excess sulfuric acid, and other impurities is dis-
carded as waste. The use of less concentrated sulfuric acid to depolymerize PET for
recovery of TA and EG has been described by Yoshioka, et al. [22] However, the process
requires higher temperatures (150–190 °C) and pressures than the preceding two ex-
amples to obtain comparable yields of TA, and reaction times of up to 12 h were reported.
While the reaction efficiency and yield of TA and EG from acidic hydrolysis of PET are
typically high, there are several shortcomings of this method that make it somewhat
unattractive for industrialization. These include the use of large volumes of strong acids
and the generation of copious aqueous and inorganic salt waste [11].

3.2.1.1.1.2 Alkaline hydrolysis. The hydrolysis of PET in basic media is usually performed
with aqueous sodium hydroxide solutions of 4–20 weight percent (wt%) to produce so-
dium terephthalate and ethylene glycol in good yield [11]. Furthermore, nearly complete
conversion of PET is possible. On the other hand, alkaline hydrolysis is typically slower
than acidic hydrolysis with conventional heating methods, and is often performed at high
temperatures (in some cases greater than 200 °C) and elevated pressure (1.4–2 MPa) [11].
The process can be carried out in aqueous solution, or in non-aqueous co-solvents
employing a phase transfer catalyst [11, 24, 25]. TA monomer can be recovered by
neutralization of the hyrolysate with strong mineral acids (typically sulfuric acid or
hydrochloric acid) and precipitation, while the EG product generated can be recovered by
distillation or “salting out” from the filtrate. Such a process was patented as early as 1959;
Pitat and colleagues reported the alkaline hydrolysis of PET in 18 wt% aqueous sodium
hydroxide solution at 100 °C for 2 h, at which point the majority of the sodium tere-
phthalate product formed precipitates from the reaction mixture [26]. The terephthalate
salt is collected by filtration and redissolved to form a nearly saturated solution to which
sulfuric acid is added to provide TPA as a filterable precipitate in 94 % yield. The filtrate
containing EG hydrolysis product is recharged with NaOH and recycled into subsequent
rounds of hydrolysis to accumulate EG, which is later recovered by distillation. Overall,
the process requires approximately 0.8 kg of solid sodium hydroxide per kilogram of
terephthalic acid recovered.
In a more recent example of alkaline hydrolysis, Loop Industries patented their first-
generation process in 2017 wherein an organic co-solvent, preferably dichloromethane
(DCM), is used to swell the PET and accelerate depolymerization in a solution of C1–C4
alcohol and potassium or sodium hydroxide [27]. The organic solvent is present at 3–
5 volume percent relative to the alcohol (preferably methanol) containing dissolved po-
tassium or sodium hydroxide. In contrast to the other examples of alkaline hydrolysis
presented above, the exothermic depolymerization occurs at atmospheric pressure
without additional external heating. The process enables recovery of TA and other TA
derivatives such as 4-(methoxycarbonyl)benzoic acid) after dissolution of salts formed in
the depolymerization with water, followed by acidification with sulfuric acid and
collection of the precipitated TA. Ethylene glycol, in addition to dichloromethane and
methanol used in the depolymerization, are recovered by a distillation process.
38 3 Circular plastics technologies

Alkaline hydrolysis is not without drawbacks; as in acidic hydrolysis, separation

processes required to obtain pure monomers can be energy intensive, and these methods
still generate large amounts of inorganic salt wastes. One apparatus and method pro-
posed in a 2013 patent application by Parravicini and colleagues from the Swiss recycling
company Gr3n aims to increase the depolymerization efficiency and reduce the waste
generated in the process [28]. The DEMETO method (depolymerization by microwave
technology) utilizes a continuous reactor to carry out hydroglycolysis of PET, described as
hydrolysis by alkaline hydroxide salts in an ethylene glycol solvolytic mixture, and is
purportedly tolerant of contaminants present in the PET feedstock. The approach may
also be applicable to polyamides (vide infra). The method involves co-feeding ground PET
via an Archimedean screw system and solvolytic reagents (sodium or potassium hy-
droxide salts in ethylene glycol) via a separate feed line into an elongated horizontal
microwave reaction chamber (Figure 3.4, upper left). The heterogeneous reaction
mixture is carried through the reaction chamber and into a separation unit consisting of
filtration and distillation modules. EG is distilled from terephthalate salts and can be
reused in the solvolytic mixture and for synthesis of new PET resin. The terephthalate
salts are acidified with hydrochloric acid to yield TA precipitate for new PET synthesis
(Figure 3.4, right). The proposed handling of waste salts in the DEMETO process differs
from other examples presented in this section. Namely the sodium or potassium chloride
salts from the TA precipitation step are electrolyzed to regenerate NaOH (or KOH) re-
agents, and hydrogen and chlorine gas (Figure 3.4, bottom left). Hydrogen and chlorine
are photochemically recombined to regenerate the hydrochloric acid used in precipita-
tion of TA. While the Gr3n process has yet to be demonstrated at commercial scale, the
consideration in the process design for addressing common waste streams in PET hy-
drolysis is noteworthy.

Figure 3.4: Hydroglycolysis unit proposed by Gr3n for scalable chemical recycling of PET [29].
 3.2 Technical scope 39

3.2.1.1.1.3 Neutral hydrolysis. PET hydrolysis under neutral conditions is performed with
water or steam, typically at elevated pressures (1–4 MPa) and temperatures in the range
of 200–300 °C, with a ratio of PET to water from 1:2 to 1:12 [11]. The neutral hydrolysis
process occurs substantially faster when performed with a PET melt rather than the solid,
leading to a preference for conditions above 245 °C [30]. While neutral hydrolysis can be
conducted without additional catalysts, common transesterification catalysts can also be
employed, including alkali-metal acetates, as well as acetates of zinc, calcium, and
manganese [11]. Campanelli and colleagues report that addition of zinc acetate to neutral
depolymerization reactions at 250–265 °C increases the rate constant by approximately
20 % compared to the uncatalyzed system [31]. Key benefits of performing PET hydrolysis
under neutral conditions as described above compared to acidic and alkaline conditions
are the avoidance of highly corrosive reaction conditions, simplifying apparatus main-
tenance, and the lack of large quantities of waste inorganic salts formed as process
byproducts. Despite these advantages, a key drawback is the typically lower purity of the
TA product due to contamination by other insoluble impurities and fillers that may be
present in the parent polymer, thus requiring more complex purification approaches that
negate some of the benefits of neutral hydrolysis. Furthermore, neutral hydrolysis of PET
is typically slower than either acidic or basic hydrolysis processes. A strategy for the
neutral hydrolysis of PET was described by Tustin and colleagues in a now-expired patent
issued to Eastman Chemical Company [32]. In the process, PET is first heated with water at
200–280 °C and pressures greater than 1.7 MPa for 2 h to provide a crude TA precipitate
upon cooling. EG could be isolated by a two-stage distillation of the filtrate. The crude TA
was purified by heating in the presence of a flow of steam to produce a vapor composed of
water and TA. The TA was collected as a solid deposit after cooling and was found to be
95.7 wt% pure by HPLC. The isolated TA could be used to resynthesize PET, but this was
only demonstrated after diluting with virgin-grade TA such that the TA recovered from
the neutral hydrolysis was only 36 wt% of the total TA feed. Few major industrial
chemical recycling efforts for PET today seem to rely on the neutral hydrolysis strategy,
likely because of the challenges associated with the lower purity of TA obtained from the
method.

3.2.1.1.1.4 Enzymatic hydrolysis. An approach for PET hydrolysis that is gaining momentum
is the use of esterase enzymes to facilitate depolymerization into TPA, EG, as well as
bis(2-hydroxylethyl) terephthalate (BHET), and mono(2-hydroxyethyl) terephthalate
(MHET) [5, 16–18]. Ester degrading enzymes (i.e., esterase) have been identified and studied
in nature for decades. PET is an excellent candidate for esterase degradation given the high
concentration of ester bonds in the polymer backbone. As a result, PET biodegradation via
enzymatic hydrolysis has been studied for nearly two decades [33–40]. One of the most
notable findings were those reported by Yoshida et al. in 2016 where they characterized the
soil bacterium, Ideonella sakaiensis 201-F6, which employs a two-enzyme system to depo-
lymerize PET to TPA and EG [41]. The first enzyme was named PETase which performs the
initial attack on the PET backbone cleaving the ester bonds to form BHET, MHET, and TPA
40 3 Circular plastics technologies

Figure 3.5: Scheme demonstrating PETase depolymerization of PET to BHET, MHET, and TPA. MHETase
converts MHET to TPA and EG, adapted from Austin et al. [46].

(Figure 3.5). The PETase activity will also cleave the resulting BHET to yield MHET and EG.
The second enzyme is called MHETase which further hydrolyzes the MHET to produce TPA
and EG [41]. The structure, mechanism of hydrolysis, the evolution products, and engi-
neering of the two-enzyme system for PET depolymerization have been reported in detail by
Knott et al. [42]. The enzymatic recycling of actual PET waste was modeled and analyzed
based on techno-economic analysis (TEA) and life cycle impacts by Singh et al. (Figure 3.6)
[5]. The process involves first pretreating post-consumer polyester flakes to reduce the
crystallinity. This is required since PETase does not demonstrate significant activity on
crystalline substrates and will only attack amorphous domains. Most PET waste is ∼30–40 %
crystalline, thus an amorphization step is required prior to enzymatic recycling. This is done
by extruding the PET flake and cryo-grinding the extruded material into an amorphous
powder. Following pre-treatment, the PET is enzymatically depolymerized in a bioreactor
containing both PETase and MHETase. The gradual addition of sodium hydroxide (or a
neutralizing base) is required to maintain the pH. Most enzymes are only active within a
specific pH window and as PET is depolymerized, the pH gradually decreases due to the
formation of TPA. To maintain the activity of the PETase and MHETase, the reaction requires
pH control. Following depolymerization, the recycled TPA and EG are recovered via
downstream processes. Costs and energy inputs of this process are dominated by the cost of
the PET feedstock and the energy requirements for the PET flake pretreatment (i.e., cryo-
grinding). Uekert et al. conducted a life cycle assessment (LCA) of this process and reported
that enzymatic hydrolysis currently performs 1.2 to 17 times worse than virgin TPA and PET
production across most impact categories, excepting ecotoxicity and fossil fuel depletion
 3.2 Technical scope 41

Figure 3.6: Simplified process flow diagram of the PET enzymatic depolymerization process from Singh et al. [5].

[43]. The top contributors to these impacts include post-consumer PET collection and the
required pretreatment, sodium hydroxide usage for pH control, and electricity inputs [43].
As a result, current studies are focused on discovering and engineering enzymes that are
active on crystalline substrates and in wider pH windows [44, 45].
Carbios is a France based startup company founded in 2011 that is actively scaling a
PETase based recycling technology for PET waste. The Carbios technology was published
by Tournier et al. in 2020 [18]. The Carbios enzyme is only effective on amorphous PET and
requires a amorphization pretreatment as well as the pH control reported previously in
this text. Carbios claims 90 % amorphous PET depolymerization into target monomers in
under 10 h [18]. In 2021, Carbios launched an industrial demonstration plant in Clermont-
Ferrand, France to validate the efficiency of their enzymatic process. The demonstration
plant includes a 20-cubic-meter depolymerization reactor capable of processing two
metric tons of PET per cycle. Carbios intends to scale this process to a fully industrial scale
in 2023 [47].

3.2.1.1.2 Methanolysis into DMT and EG

In the methanolysis of PET, methanol (MeOH) deconstructs the PET backbone via a
transesterification reaction at the ester bond resulting in the methyl-ester analogue of
TPA, DMT, and EG. Methanolysis has several advantages over other solvolysis processes
such as higher robustness to contamination [48], existing infrastructure [49], and the
insolubility of DMT in water allowing for easier separations and purification than TPA.
Additionally, conventional PET manufacturing processes require the conversion of TPA
to DMT for transesterification with EG to produce high molecular weight PET products.
Thus, methanolysis products are ideal for immediate reuse in PET manufacturing.
However, new trends for PET production processes are using TPA instead of DMT as the
raw material [50]. This creates vulnerability in the economic model for methanolysis as
the conversion of the DMT to TPA by hydrolysis adds considerable costs to the
42 3 Circular plastics technologies

methanolysis process [51]. The methanolysis of PET waste has been studied for decades
and several types of methanolysis processes have been explored with the primary
pathways falling under liquid methanolysis, vapor methanolysis, and super critical
methanolysis.

3.2.1.1.2.1 Liquid methanolysis. Liquid methanolysis is a catalytic process that involves

high temperature (180–280 °C) and pressure (20–40 atm) to fully depolymerize the PET
backbone. High temperatures are required to fully melt the PET and allow for full
penetration of the methanol into the bulk of the polymer and high pressure is required to
keep the MeOH in the liquid state at temperatures above the boiling point. Typical
transesterification catalysts used for PET polymerization can also be used for liquid
methanolysis such as zinc acetate (the most commonly used catalyst for methanolysis)
[50], magnesium acetate, cobalt acetate, or titanium-based transesterification catalyst.
Liquid methanolysis can be operated as a batch or continuous process. However, the
high-pressure operation renders continuous mode challenging and expensive to operate
and most processes at pilot or industrial scale are done in batch mode.
Several efforts have been made to reduce the temperature and pressure required for
complete methanolysis of PET to DMT and EG and improve the LCA metrics. These efforts
typically include the addition of co-solvents (to better solubilize the PET and improve
contact with the methanol), novel catalysts, or both. For example, Liu et al. reported that
aromatic solvents assisted in the dissolution of PET due to intermolecular interactions
and improved the depolymerization efficiency of PET in solvolysis processes [52]. Ionic
liquids have also been explored as cosolvents to improve the yields and energy re-
quirements for methanolysis [53], but have significant cost limitations when applied to
PET recycling and the value of the DMT products are not sufficient to justify the use of
ionic liquids. Pham et al. recently reported a low-energy catalytic PET methanolysis
process using potassium carbonate. This study reported yields of DMT of 93.1 % at 25 °C in
24 h [54]. Yang et al. recently reported a study applying liquid methanolysis, with a
toluene cosolvent, with zinc bis[bis(trimethylsilyl)amide] as the catalyst to depolymerize
a mixture of polyesters including PET at temperatures below 120 °C and DMT yields >80 %
(Figure 3.7) [55]. These results are particularly impactful as this demonstrates that other
relatively common polyesters can be depolymerized into their parent monomers in the
same pot as PET such as polylactic acid (PLA) and polybutylene adipate terephthalate
(PBAT).
Recently, Loop Industries pivoted from hydrolysis of PET to liquid methanolysis and
filed a patent for a low-temperature, liquid methanolysis process to depolymerize PET
(Figure 3.8) [56]. In the Loop process, stoichiometric (or sub-stoichiometric) amounts of
alkali methoxides and co-solvents are used as active ingredients to depolymerize PET at
temperatures less than 60 °C.

3.2.1.1.2.2 Vapor methanolysis. Vapor methanolysis is another method to depolymerize

PET which uses super-heated vapor instead of liquid methanol. Vapor methanolysis is
 3.2 Technical scope 43

Figure 3.7: Graphical results from Yang et al. applying liquid methanolysis on mixed polyester substrates.
Substrates in this study were (a) BPA-PC/PET mask, (b) PLA/PBS straw, and (c) PLA/PBAT bag [55].

Figure 3.8: Depiction of the Loop Industry methanolysis process to yield DMT and monoethylene glycol
(MEG), taken from the Loop website [56].
44 3 Circular plastics technologies

usually conducted at temperatures above 250 °C. Since it is not required to keep the
methanol in a liquid state, vapor methanolysis does not need the high pressures used in
liquid methanolysis. In the vapor methanolysis reactor, the PET exists in a melt phase and
the methanol gas is passed through the PET melt. The influence of temperature on the
gas–liquid interactions in vapor methanolysis is more complex than liquid methanolysis
and high agitation is required to ensure good contact between the gas bubbles and the
PET melt [48]. Some benefits of vapor methanolysis, when compared to liquid meth-
anolysis, are the lower pressure which allow for easier removal of the DMT product as a
vapor. Since products can be removed in-situ via vapor removal, the reaction equilibrium
is also shifted promoting higher conversions. Thus, vapor methanolysis typically results
in higher yields than liquid methanolysis [57], but the reaction rate is much slower.
In the 1990s, Eastman-Kodak developed and patented an integrated methanolysis pro-
cess with their plant in Kingsport, TN to produce high purity DMT from PET [58]. Since then,
the company, now only Eastman, has revitalized the technology and is currently performing
feasibility tests to commercialize a methanolysis facility to recycle PET waste [49].

3.2.1.1.2.3 Supercritical methanolysis. Efforts have been made to improve product yields
and economics for methanolysis of PET via the use of supercritical methanol. As dis-
cussed in Section 3.1, the high density and ionic product of supercritical fluids (SCFs)
promotes the solvation of compounds. Depolymerization under a supercritical state of
methanol allows for high conversion of PET and an improved DMT yield (up to 95 %)
within 1 h under optimal reaction conditions (260–270 °C, 9–11 MPa) [59, 60]. Additionally,
Sako et al. reported up to 100 % yields of DMT from PET in 30 min under super critical
methanol conditions [61]. While the conversion rates in supercritical methanolysis are
significantly faster than liquid or vapor methanolysis, the reaction must be conducted at
a higher temperatures and pressure, and thus, high capital and operating costs are the
primary disadvantages. Additionally, the high pressures render continuous processing of
PET very difficult as noted for liquid methanolysis. Nevertheless, reports of successfully
applying supercritical methanolysis, or other SCFs, to deconstruct PET are released
regularly [57, 62].

3.2.1.1.3 Glycolysis into BHET

Glycolysis of PET involves transesterification with excessive glycol to generate BHET and
EG as products. The reaction can take place with or without catalysts. Chen et al. reported
in 1991 that PET was depolymerized at high temperature (200–240 °C) and pressure (2–
6 bar) in the absence of a catalyst, but the monomer yield remained low [63]. The
glycolysis product was quenched to room temperature in the protection of nitrogen gas at
the end of the reaction. Next, a large amount of water was used to wash the solid contents
to remove the unreacted EG, followed by filtration to obtain the insoluble products. The
final products were then transferred to boiling water, where BHETwas extracted from
the suspension.
 3.2 Technical scope 45

Factors that influence the non-catalytic PET glycolysis include the reaction temper-
ature, pressure and concentration ratio of EG to PET. Increasing pressure or temperature
can accelerate the reaction rates. At a constant temperature, pressure and PET concen-
tration, the glycolysis rate of PET is proportional to the square of EG concentration. It
indicates that EG acts as both a reactant and catalyst in glycolysis. Furthermore, the
system quickly reaches an equilibrium between BHET and PET oligomers (e.g., dimer and
trimer) at a higher ratio of EG/PET, whereas the depolymerization ends incompletely with
higher molecular weight oligomers at a lower ratio of EG/PET.
Various types of catalysts were discovered to improve the PET glycolysis kinetics,
conversion, and reaction conditions. Güçlü et al. reported the first employment of metal
acetates as a PET glycolysis catalyst in 1989. In their experiment, xylene was used to form
a multiphase reaction in zinc-acetate-catalyzed glycolysis of PET with EG at 170–245 °C.
BHET was extracted constantly from the xylene layer to shift the equilibrium of the PET
depolymerization, yielding ∼80 % monomer conversion [64]. Chen et al. found that
manganese acetate could depolymerize ∼100 % PET into BHET and dimers at 190 °C after
1.5 h [65]. Light metal salts were reported to catalyze PET glycolysis by Troev et al. In their
reaction, titanium phosphate successfully depolymerized PET into BHET up to 97 %
selectivity at 190 °C after 2.5 h [66]. Fang et al. reported that polyoxometalates could
achieve 85 % yield of BHET at 190 °C for 40 min [67]. Ionic liquids (ILs) were first used as
PET glycolysis catalysts in 2009 by Wang et al., who found the ILs could achieve full
conversion of PET to BHET at 180 °C at ambient pressure after 8 h [68]. Another attempt
was made by Yue et al. to use basic ILs to catalyze glycolysis of PET into BHET with a yield
of 71 % at 190 °C for 2 h [69]. Similar to ILs, deep eutectic solvents (DESs) were chosen for
PET glycolysis-catalysts because of low cost, low toxicity and simple chemistry. In 2015,
Wang et al. reported the first employment of DESs to catalyze PET glycolysis. Their
optimal reaction condition took place at 170 °C for 30 min, achieving 83 % yield of BHET
[70]. Sert et al. discovered that an effective DES made from potassium carbonate and EG
was able to achieve BHET yield of ∼88 % at 180 °C after 2 h [71]. Organocatalytic PET
glycolysis was discovered as the catalyst using the amine base 1,5,7-triazabicyclo[4.4.0]
dec-5-ene (TBD) by Fukushima et al. in 2011. In this case, BHET yield reached 78 % at 190 °C
and 1 atmospheric pressure after 3.5 h [72]. Jehanno et al. utilized a methanesulfonic acid
and salt derived from TBD as a PET glycolysis catalyst, yielding 91 % BHET conversion at
180 °C after 2 h [73]. Emerging techniques, such as, microwave-assisted PET glycolysis can
reduce energy consumption in conventional heating reaction conditions. Pingale et al.
reported the first microwave irradiation study on PET glycolysis in 2008. In their reaction,
microwave heating shortened the depolymerization timespan by 16 times, while
providing the same yield of BHET [74]. Recently, Parrott patented a microwave-assisted
PET glycolysis technique, which can achieve 94 % BHET yield with 0.1 wt% zinc acetate as
a catalyst in 5 min of irradiation at 250 °C [75]. Last but not least, a variety of heteroge-
neous catalysts have been found to assist PET glycolysis. For example, 3 nm cobalt
nanoparticles were reported as reusable catalysts for PET glycolysis by Veregue et al. The
46 3 Circular plastics technologies

conversion of BHET reached 77 % at 180 °C after 3 h [76]. Wang et al. used a colloidal
catalyst based on graphitic carbon nitride to catalyze PET glycolysis, achieving 80 % BHET
yield in 30 min at 196 °C [77].
In addition to various lab practices, glycolysis is one of the most widely used in-
dustrial PET chemical recycling methods. Eastman Chemical Company patented their
glycolysis process for recycling post-consumer or scrap polyester in 1995. In the first stage
of the process, the polyesters are mixed with EG in a ratio of EG to dicarboxylic acid
component in the polyester between 2 to 6 [78]. Then the reaction takes place between
180 °C to 240 °C for up to 4 h to produce an oligomeric material with salts of metals (e.g.,
Zn, Sb, Ti, Sn, Mn, or Ge) as catalysts. The second stage of the process involves dissolving
the glycolysis products in a hot solvent (e.g., water, alcohols, ethers, nitriles, chlorinated
hydrocarbons, aromatic hydrocarbons, or ketones). The hot stream is then treated with
adsorbents (e.g., activated carbon, activated clay, silica, and alumina), followed by hot
microfiltration to remove insoluble impurities, such as pigments and trace metals. The
product will precipitate out when cooling the hot permeate to room temperature, and
then the product is extracted through filtration or centrifugation.
Ioniqa’s technology offers a closed-loop solution for PET recycling via a patented
glycolysis process [79]. Their process involves using a combination of a catalyst complex,
heat, and pressure to break down PET under the glycolysis condition using ethanediol.
The catalyst comprises butylmethylimidazolim (bmim+) and FeCl4−, the bridging moiety
is triethoxysilylpropyl, and the nanoparticle is magnetite/maghemite. The preferred
combination of catalyst loading, temperature, pressure and reaction time is 2–5 wt%,
180 °C, 60 kPa and 1.5 h. The process also involves recovering the catalyst and retrieving
trimers, dimers and/or monomers. In the first step of retrieving, water is added to
dissolve monomers and solvent, whereas catalyst complex can be recovered in a separate
phase under influence of an external electro-magnetic field gradient (e.g., 1T). The second
step of retrieving involves crystallization of monomers. As Ioniqa stated in their patent,
the degradation product is ready to be used without further need of purification.
Jeplan’s glycolysis technology can break down PET plastic that has been contami-
nated with other materials, e.g., food residue or labels [80]. In the first step of the
glycolysis process, PET is heated together with bis(β-hydroxylethyl) terephthalate (BHET)
to pre-decompose the PET at 200–245 °C, under normal or increase pressure for up to
1.5 h. Then a reaction between pre-decomposition products with EG (3–5 wt%) takes place
at 200–220 °C under normal or increase pressure for up to 2.5 h for BHET conversation. An
ester exchange reaction catalyst (e.g., sodium and magnesium methylates, fatty acid salts
and carbonates of Zn, Cd, Mn, Co, Ca, and Ba such as zinc borate and zinc acetate, metal Na
and Mg, and oxides) can be added to the depolymerization reaction to facilitate smooth
reaction. In the second step, the glycolysis product is brought into contact with activated
carbon for decoloring treatment and then cation and/or anion exchange resins at 30–70 °
C for deionization treatment. In the third step, BHET is recovered by distillation or
evaporation to distill off the compounds with a boiling point lower than that of BHET. The
 3.2 Technical scope 47

temperature and pressure in this step are selected to be 100–150 °C at 70–300 Pa. The
BHET obtained from Jeplan’s glycolysis process can be used to produce high-quality PET
fibers, films, and bottles.
IBM-VolCat developed a glycolysis method of depolymerizing polyesters from post-
consumer products, e.g., beverage bottles, to produce a high purity BHET [81]. The
depolymerization reaction takes place with an alcohol of 25 carbons and an amine
organocatalyst at 150–250 °C. The selection of an organocatalyst with a boiling point
significantly lower than the boiling point of the alcohol allows for the easy recycling of the
amine catalyst. Increasing the reaction temperature and pressure above the boiling point
of alcohols can accelerate depolymerization rates and catalyst recovery. Upon comple-
tion of the depolymerization reaction, the product undergoes direct filtration to remove
insoluble contaminations and unreacted polymers, then treatment with activated carbon
to remove additional impurities including dyes, and treatment with ion exchange resins
to remove catalyst residues. Lastly, a combination of crystallization and distillation is
used to recover BHET and EG. In an exemplar application, VolCat demonstrated that the
proposed glycolytic depolymerization of PET can close the loop in the PET bottle industry,
i.e., depolymerization of post-consumer beverage bottles to product high purity BHET
and then production of high-quality bottle grade PET from the recovered BHET.

3.2.1.2 Polyamides

Polyamides are another class of polymers that contain cleavable heteroatoms in the
backbone and are suitable for chemical depolymerization routes. The most common
polyamide plastics found in municipal solid waste (MSW) are polyamide 6 (PA6) and
polyamide 66 (PA66). The amide groups are stable enough to render PAs as highly useful
materials in many high-performance applications such as fibers in carpets and textiles,
automotive and aerospace applications, electronics, and building and construction ma-
terials. The amide bonds in PAs offer a point of attack for various degradation agents that
can depolymerize the polymer to parent monomers via pyrolysis, hydrolysis, ammo-
nolysis, or by applying supercritical fluids or ionic liquids. In Section 3.1, we discussed the
thermal unzipping of PA6 (also known as Nylon 6) to its parent monomer, cyclic
ε-caprolactam (CPL), under pyrolysis conditions. Studies have shown that PA6 will
depolymerize to CPL in >80 % yields at temperatures 330–400 °C [82]. BASF patented a
catalytic pyrolysis technology for depolymerizing PA6 (from carpet waste) into CPL in
1991 but is not practicing the technology today [83].
The amide bonds in PAs offer a point of attack for various degradation agents that can
depolymerize the polymer to parent monomers using similar solvolytic approaches
applied to PET such as hydrolysis, aminolysis, and methanolysis, albeit under different
conditions [84]. PAs are associated with high glass transition temperatures (Tg), high melt
temperatures (Tm), and high concentrations of hydrogen bonding. Thus, for complete
depolymerization of these materials, more extreme conditions are often required then
for PET. Most studies have focused on depolymerization of PA6. This is likely due to the
48 3 Circular plastics technologies

lower crystallinity, lower Tm, and lower resistance to chemicals and acids than PA66
which makes it easier to break down chemo-catalytically. However, high operational
temperatures (>250 °C), 13, 16 high pressures 16 and strong acidic or basic conditions often
entail high energy input and operational difficulties that limit the applicability.
Chemical recycling of PA66, on the other hand, is even more challenging, because
PA66 polymer chains interact more strongly with one another since each secondary
amide bond participates in two strong hydrogen bonds [85]. As a result, PA66 possesses a
rigid semi-crystalline polymer structure, which translates into a higher tensile strength
and higher melting point compared to PA6 on a macroscopic scale [86]. Both the intrinsic
strength of the secondary amide bond and the resulting semi-crystalline polymer matrix
pose severe challenges for the chemical recycling of PA66, which is typically tackled by
applying high temperatures (>275 °C) [87–90], high pressures [91–93], supercritical fluids
[94, 95], and/or strong acidic [84] or alkaline conditions [90, 96].
A process for depolymerizing PA6 scrap using high pressure steam was patented by
AlliedSignal [97]. In the AlliedSignal process, PA6 was dissolved in high-pressure steam at
125–130 psi and 175–180 °C for 0.5 h in a batch process and then continuously hydrolyzed
with super-heated steam at 35 °C and 100 psi (790 kPa) to yield 98 % CPT. The recovered
monomer could be repolymerized without additional purification. Braun et al. 1999
reported the depolymerization of nylon 6 carpet in a small laboratory apparatus with
steam at 3400 °C and 1500 kPa for 3 h to obtain a 95 % yield of CPT [98]. Aquafil Econyl and
gr3n are two other companies that are commercially operating technologies for depo-
lymerizing PA 6 and PA 66 via solvolysis. These technologies focus mostly on recycling of
used carpets or fishing gear.

3.2.2 Thermal unzipping into monomers

3.2.2.1 Polymethyl methacrylate

Polymethyl methacrylate (PMMA) is a widely used thermoplastic in various electronics,

automotive, and building and construction applications. Notable products and tradenames
for PMMA are Perspex®, Plexiglas® and Lucite® [99]. PMMA is one of the few commodity
plastics that undergoes chain unzipping into the parent monomer, methyl methacrylate
(MMA), using thermal of photochemical approaches [100, 101]. In a pyrolysis process, the
liquid product from PMMA is comprised mostly of MMA that can be used to resynthesize
PMMA products. Thermal pyrolysis of PMMA has been studied extensively [99, 100, 102,
103]. The effects of temperature, additives, fillers, and solids loading on the distribution of
pyrolytic products were have been investigated [104, 105]. Studies have shown that PMMA
thermal pyrolysis results in nearly 97 % recovery of MMA at relatively low temperatures at
temperatures between 400 and 500 °C. In several papers it was reported that the liquid
pyrolysis product was so pure that it could be polymerized again without any further
 3.2 Technical scope 49

treatment [105–107]. As outlined in Section 3.1, this process can be aided/assisted by the use
of microwaves or plasma to improve monomer yields and reduce energy inputs and
residence time [108–111].
Even though PMMA depolymerization via pyrolysis is more facile than other com-
modities such as polyolefins (Figure 3.9), we have not seen widespread adoption of this
recycling process. One significant limitation is likely feedstock reliability. Unlike PET and
polyolefins, PMMA is not collected in curbside recycling bins since it is not a common
household plastic. As a result, there is no widespread collection system for PMMA and this
requires special collections or drop-offs. Some companies, such as CompuPoint USA, are
collecting used electronics and separating PMMA components. In 2022, Sumitomo
Chemical announced that they were piloting a pyrolysis technology for PMMA recycling
[112]. The Japan Steelworks Co. developed a continuous, twin-screw extruder technology
to pyrolyze PMMA to MMA and improve the economics and energy inputs for the process.
A schematic of The Japan Steelworks Co. is presented in Figure 3.10 [113].

Figure 3.9: Comparison of unzipping mechanism of PMMA and PS to polyolefins from Vollmer et al. [8].
50 3 Circular plastics technologies

Figure 3.10: Schematic of twin-screw reactive extrusion design to depolymerize PMMA [113].

3.2.2.2 Polystyrene

Polystyrene (PS) is another important commodity plastic used in packaging applications.

General-purpose PS is a transparent, hard, and somewhat brittle plastic. PS can also be
easily foamed (i.e., Styrofoam), to yield a lightweight, waterproof packaging material.
Expanded polystyrene (EPS) is another similar foam material, which has been used as
insulation, life vests and rafts, and food containers. PS foam is notoriously challenging
from a recycling perspective due to the low density and porosity (i.e., uptake of con-
taminants) of the foam waste. Additionally, PS foam has been identified as a major
contributor to ocean plastic debris and easily breaks apart in the natural world yielding a
formidable amount of microplastics. As a result, researchers, companies, and NGOs have
focused significant effort towards the effective recovery and recycling of PS. Thermal or
thermo-catalytic pyrolysis of PS to styrene monomer has been studied extensively
[114–119]. However, unlike PMMA, PS will undergo random chain scission at mid-
temperatures in pyrolysis (i.e., 300–400 °C) generating a liquid oil, consisting mainly of
C6-C12 aromatic hydrocarbons, gasses, and solid residues. At higher temperatures (400–
500 °C) chain-end scission becomes the primary mechanism and the pyrolysis product
consists primarily of styrene monomer. However, this process is not perfect. Styrene and
α-methylstyrene have poor thermal-oxidative stability, resulting in the formation on
undesired side products in the pyrolysis process (Figure 3.11). This increases the costs and
energy for downstream separations to recover the styrene monomer in high yields. The
oil product is not suitable for automotive fuels due to the high content of aromatic
hydrocarbons that can cause carbon formation problems in the engine. Several factors
inhibit the formation of styrene: heat transfer problems due to the difficulty of estab-
lishing contact between PS and the heat transfer material causing uneven heat supply,
and intensified side reactions at high temperatures and long contact times.
One approach to overcome the issues mentioned above is depolymerization with a
temperature of less than 550 °C and a vapor resident time of less than 10 s in a uniform
heat distributed fluidized bed reactor. Liu et al. have reported styrene yields of 72–79 %
using this method [115]. Another approach is depolymerization in a hydrocarbon me-
dium, which can avoid the heat transfer problem and side reactions mentioned above
and achieve high styrene selectivity.
 3.2 Technical scope 51

Figure 3.11: Scheme of pyrolysis reaction for PS and undesired side reactions. (A) Hemolytic cleavage of
backbone C–C bond in PS, (B) beta-cleavage of the backbone C–C bond and formation of styrene monomer,
(C) hydrogen transfer and formation of trimer, and (D) thermal cracking of the trimer.

Several companies have emerged in the last decade that are piloting thermal py-
rolysis of PS to recover styrene monomer. Most notably is Agilyx, a startup company that
has pioneered a pyrolysis technology to depolymerize PS waste (Figure 3.12), with an
emphasis on PS foam [120]. Agilyx has demonstrated a pyrolysis technology at their
facility in Tigard, Oregon, which has a capacity of 10 tons per day of PS waste, according
the to the Agilyx website. Agilyx claims their core differentiator from other pyrolysis
technologies is their novel styrene purification process using Technip Energies’ process
for purifying styrene monomer. The technology for the purification of Agilyx Styrene Oil
has been pilot tested in Technip Energies’ Research Center in Weymouth, MA, USA.
Pyrowave is another company attempting to optimize and scale the pyrolysis of PS waste
52 3 Circular plastics technologies

Figure 3.12: Schematic of Agilyx pyrolysis process for PS waste as shown on the Agilyx website [120].

to recover styrene monomer. Pyrowave is pioneering a microwave assisted pyrolysis

process and claim their process is less energy intensive and polluting than conventional
PS pyrolysis.

3.3 Summary and future outlooks

Monomer-loop recycling technologies are one of several pathways toward a circular
economy for plastics. While most commodity plastics were not designed to easily depo-
lymerize, some common plastics can be broken down into their parent monomers in the
presence of heat, pressure, catalysts, and/or solvent. Here, we provided a high-level
overview of the depolymerization technologies that have been studied and/or scaled as
promising monomer-loop recycling processes for selective plastic waste streams.
Namely, commodity plastics that are considered unzippable/depolymerizable include
PET, PA6, PMMA, and PS. While several reports have demonstrated that these polymers
 References 53

can be depolymerized to recover high monomer yields, many gaps and challenges still
exist before these technologies can achieve industrial reality. In a recent study by Uekert
et al., the technical, economic, and environmental metrics of emerging closed-loop
recycling processes were analyzed and compared against mechanical recycling [121].
Regardless of the high monomer yields and purity that can be achieved through these
chemical depolymerization routes, mechanical recycling outperformed all other tech-
nologies, as well as virgin plastic production across economic and environmental con-
siderations, but it exhibited lower material qualities and other technical metrics. Thus,
chemists have their work cut out for them to continue to optimize and improve chemical
depolymerization technologies and reduce the environmental impact of the proposed
routes. However, the future is bright. In a recent Strategy for Plastics Innovation repot
from the U.S. Department of Energy, chemical recycling was identified as a promising
technology for mitigating plastic waste and highlighted as key area for innovation and
optimization [122].

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Katrina Knauer* and Minjung Lee
4 Circular plastics technologies: open loop
recycling of waste plastics into new
chemicals
Abstract: Open-loop recycling is any recycling process where the recycled materials
are converted into new raw materials, often of higher value than the parent monomers.
Typically, materials recycled through open-loop recycling go on to be used for purposes
different from their former, pre-recycled purpose. This means that the input into the
recycling process is converted to a new chemical building block, which can be used as
an input into another manufacturing process. Open-loop recycling processes usually
involve processing various types of products of similar material makeup and change
the properties of the material itself (through heat, chemical reactions, or physical
crushing). This chapter will highlight promising pathways for upcycling of various
plastic waste streams into new applications via open loop chemical and biological
recycling processes.

Keywords: circular economy; plastics; recycling

4.1 Introduction
One concept that many in the field of plastics agree on is that to sustainably manage the
staggering amounts of plastic waste production that is projected in the next several
decades, we need to shift from a linear “take-make-dispose” economy to a circular
economy. Simply put, a circular economy is an economic system that aims to eliminate
waste and establish continual use of resources and carbons (Figure 4.1). According to a
2020 report by Closed Loop Partners, a circular plastic economy is projected to be worth
$4.5 trillion dollars by 2030 [1]. Some argue that a true circular economy for plastics in
one in which plastics are cycled into the original application an infinite number of
times. In chemical recycling, this means the polymer is decomposed to the original
monomers and subsequently repolymerized into the parent polymer [2]. However,
some researchers are challenging the definition of circularity by exploring chemical
processes that can convert polymer chains into new chemical building blocks that can
be used to create entirely different materials from the parent polymer. This concept has

*Corresponding author: Katrina Knauer, E-mail: [email protected]. https://orcid.org/0000-0002-

0125-7532
Minjung Lee, https://orcid.org/0000-0003-1687-897X

As per De Gruyter’s policy this article has previously been published in the journal Physical Sciences Reviews. Please cite as: K. Knauer
and M. Lee “Circular plastics technologies: open loop recycling of waste plastics into new chemicals” Physical Sciences Reviews
[Online] 2023. DOI: 10.1515/psr-2022-0178 | https://doi.org/10.1515/9781501515613-004
60 4 Circular plastics technologies: open loop recycling

Figure 4.1: Model depicting a circular economy for plastics where raw materials are only used once for initial
design and then supplemented with recycled feedstocks.

recently been popularly referred to as “upcycling” [2]. This type of recycling aligns with
the concepts of a circular economy which is restorative and regenerative by design.
This means materials constantly flow around a ‘closed loop’ system, rather than being
used once and then discarded, but do not necessarily have to stay in their own circle. In
the case of plastic, circularity can also be defined as simultaneously keeping the value of
plastics in the economy, without leakage into the natural environment. Upcycling of
plastic via chemical processes offers another kind of route to valorize recycling and
create value added intermediates from plastic waste (Figure 4.2) [2]. This type of

Figure 4.2: Open loop recycling of plastic waste

where plastics are deconstructed into chemical
building blocks disparate from the parent
monomers that are used to create new, higher
value materials. Adapted from Ref. [2].
 4.1 Introduction 61

recycling falls into the “Molecular Loop” that is outlined and defined in Chapter 1 of this
text, also known as closed-loop recycling. Unlike pyrolysis, the goal is not to use the new
chemicals derived from the decomposed plastic as fuel, but to further process them into
useful monomers and/or chemical building blocks that can re-enter the chemical supply
chain. Many of the chemical recycling methods discussed in this chapter will overlap
with those covered in Chapter 2, but instead of unzipping the polymer into the original
monomers, these techniques are applied to yield new chemicals and impact new
functionality.
Most upcycling processes have focused on using specialty and engineering ther-
moplastics or thermosets such as polyurethanes (PURs), polyamides (PAs), poly-
carbonates (PCs), polyesters, and epoxies as the primary source of feedstock. These
plastics fall into the number 7 category for recycling. The reason for this is that these
types of plastics are complex in design and vary significantly in structure across ap-
plications. For example, PURs can be manufactured using several different types of
monomers for varying applications but are still collectively referred to as PURs. As a
result, it is challenging to identify an “unzipping” mechanism for these waste streams
and pyrolysis of such polymers can yield highly variable oil. Large scale recycling
efforts have mainly focused on the 1–6 plastics, as these materials are typically designed
for single-use applications and make up most of the plastic waste stream. Number 7
plastics are usually used in applications where higher performance and longer life-
times are required. However, these materials are starting to build up a substantial
waste as consumerism and obsolescence continues to grow. For example, polyesters
and PURs are a substantial component of most textiles and footwear. According to
World Footwear, 24.2 billion pairs of show were manufactured in 2018, but 90 % of all
shoes enters a landfill once disposed [3]. PAs make up a large portion of the fishnet
industry, and in one clean-up alone 24 tons of PA fishnets were collected from the shores
of Antarctica [4]. PCs are also starting to pile up with the rise of discarded and outdated
electronics [5].
Polyolefins such as polyethylene (PE) and polypropylene (PP) are also often used in
upcycling applications. In contrast with polymers linked by heteroatoms (as discussed
below), C–C-linked polymers, exemplified by PE and PP, present opportunities for ad-
vances in catalysis science, considering their abundance and the technical challenges
associated with cleaving C–C bonds. The resilience of C–C-linked polymers to the
unzipping mechanism described in Chapter 2 has led to the emergence of new, catalytic
technologies to break C–C bonds while also imparting new functionality to the polymer.
In Chapter 1, the pyrolysis of polyolefins to fuels and chemicals was discussed in detail.
This chapter will focus on emerging catalytic technologies such as metathesis, hydro-
genolysis, oxidation, and other catalytic processes that can convert polyolefins into new
chemical building blocks.
The remainder of this chapter will cover other open loop recycling methods that fall
in the molecular loop, outside of pyrolysis and gasification, that have been applied to
break down plastic waste and which types of plastics are best suited for each method.
62 4 Circular plastics technologies: open loop recycling

4.2 Technical scope

4.2.1 Solvolysis

In Chapter 2, the unzipping of polymers into parent monomers via solvolysis was dis-
cussed in detail. Solvolysis processes can also be applied and tuned to yield new chemical
building blocks from plastic waste. Many of the processes described in this section will
resemble those described in Chapter 2. This section will outline how solvolysis of plastics
can be used to convert waste carbons into valuable chemical building blocks, disparate
from parent monomers, to be funneled back into the chemical supply chain.

4.2.1.1 Glycolysis

Glycolysis processes can effectively break ester, carbonate, and amide bonds in mul-
tiple types of plastics. In Chapter 2, the glycolysis of PET into bis(hydroxy ethylene)
terephthalate (BHET) and a mixture of its oligomers was discussed in detail. This
technology has been applied at the pilot scale as an effective means of “unzipping” PET
into the starting monomers followed by purification and subsequent re-polymerization
into PET. However, glycolysis has also been applied as a means of upcycling PET waste
into aromatic polyester polyols which are key starting materials in the synthesis of rigid
polyurethanes (Scheme 4.1) [6]. The best studied glycolysis reaction of PET is the one
with an excess of 1,2-ethanediol (ethylene glycol, EG) or 2,2′-oxydietha-nol (diethylene
glycol, DEG) resulting in polyols of high crystallinity [6]. Polyols are primary building
blocks for PURs. The preparation of polyester polyols usually includes two stages. In the
first stage, depolymerization of PET takes place, resulting in a glycolyzed product (GP)
that consists of a mixture of BHET, oligomers, and unreacted glycols. In the second
stage, GP is reacted with dicarboxylic acids, glycols and other additives resulting in
polyester polyols (Scheme 4.1). The motivation to convert PET waste into polyols is that
PURs are typically much higher value polymers than PET and thus provide an economic
incentive to PET recycling. A basic schematic of this process is outlined in Figure 4.3.
This technology has been scaled and commercialized by Resinate Materials Group
(RMG) based in Plymouth, MI. RMG developed a one-step process to convert post-
consumer PET into aromatic polyester polyols. RMG claims that the resulting aromatic
polyols have desirable properties and attributes for formulating PUR products and are
especially useful for PUR dispersions for coatings applications [7]. Huntsman has also
announced that its polyols production facility in Kuan Yin, Taiwan, will begin to utilize

Scheme 4.1: Glycolysis of PET to aromatic polyols.

 4.2 Technical scope 63

Figure 4.3: Schematic of resinate process to upcycle PET into aromatic polyester polyols.

the company’s Terol polyols technology to recycle PET scrap into polyols to satisfy the
growing demand from the regional PUR foam insulation market. Converting PET into
polyol building blocks allows for the inclusion of post-consumer recycled content in PUR
materials. PURs are not readily collected in curb side recycling programs. As a result, the
PUR market has limited access to post-consumer recycled feedstocks. PET, on the other
hand, is readily collected (globally) in curbside/home recycling and provides high vol-
umes of potential recycled building blocks for the PUR market. Additionally, PET is sold at
∼$1.50/kg while PUR products can range from $4 to $15/kg depending on the grade and
target application. Funneling PET waste into PUR products is a clear example of upcycling
plastic waste into higher value products (Figure 4.3).
Rorrer et al. also applied moderate glycolysis of PET to incentivize both higher extents of
waste plastics reclamation and use of bio-based chemicals with waste-based intermediates
[8]. Partially glycolyzed PET can be effectively upcycled into unsaturated polyesters that can
be crosslinked and filled with glass or carbon fibers to yields a high-performance composite
material for automotive and aerospace applications (Figure 4.4). Life cycle assessment (LCA)
showed that this approach results in reductions in energy input and greenhouse gas emis-
sions (GHGs) relative to standard composites manufacturing today [8].
Glycolysis has also been applied in deconstructing PCs [9], PAs [10], and PURs [11] into
upcyclable chemical building blocks. Chemical deconstruction of the number 7 plastics
via glycolysis becomes more complicated by the multiple types of polymer backbones that
are associated each plastic. For example, in the PUR industry, the combinations of diols,
diacids, ethers, polyols, diisocyanates, and chain extenders are endless. While glycolysis
can effectively break bonds in PUR backbones, the significant diversity in these materials
makes even open loop recycling very challenging.
64 4 Circular plastics technologies: open loop recycling

Figure 4.4: Schematic of conversion of waste PET to high performance composites. Adapted from Ref. [8].

4.2.1.2 Hydrolysis

Any polymers that contain hydrolysable groups are susceptible to hydrolysis as in the
reaction with water or steam. In terms of performance, hydrolysis is typically seen as an
undesirable event leading to a loss in mechanical properties. However, in some cases,
hydrolysis can be applied as a useful means of decomposing plastic waste once it is
reached the end of its use-life. In Chapter 2, the hydrolysis of PET to yield terephthalic acid
(TPA) and EG. However, hydrolysis as also been applied as a recycling method for other
types of plastics as well such as PURs [12], PAs [13], and PCs [14].
The hydrolysis of PURs under elevated conditions, was the first type of recycling used
explored for PURs by the Ford Motor Co. in the late sixties. Hydrolyzing a urethane bond
results in the formation of an amine, alcohol, and carbon dioxide (CO2) as shown in
Scheme 4.2. Hydrolytic decomposition of PURs results in the formation of diamines, diols,
 4.2 Technical scope 65

Scheme 4.2: Hydrolysis of urethane bond to yield an amine, alcohol, and CO2.

and polyols (typically either polyether diols or polyester diols depending on the type of
PUR). This process requires a high amount of energy input and is typically carried out at
temperatures between 300 and 500 °C. The energy consumption is further increased by
the necessity to separate the amines from the polyols. The diols and polyols can be reused
to manufacture PURs and the diamines can be used in the synthesis of other high per-
forming materials such as PAs. The diamines can also be further converted into the
original monomers, diisocyanates, via a phosgenation reaction. Phosgenation requires
highly pure diamines and is considered a highly dangerous and toxic process [15]. Thus,
applying the diamines in new polymers is the preferred upcycling route. Hydrolytic
recycling of PURs is usually carried out on aliphatic PUR structures. The hydrolysis of
aromatic PURs based on either methylene diisocyanate (MDI) or toluene diisocyanate
(TDI) will yield aromatic diamines such as 4,4-diaminodiphenylmethane (MDA) or 2,4-
and 2,6-toluylene diamines. These are not only cancerogenic substances but also increase
the viscosity of the recycled mixture making separation more difficult.
Beyond glycolysis and hydrolysis, studies have been conducted applying meth-
anolysis, acid hydrolysis, and other solvolysis methods as open loop recycling processing
for polyesters, polyamides, polycarbonates, and polyurethanes.

4.2.2 Polyolefins

4.2.2.1 Olefin intermediate

The C–C bond cleavage of PE is an energy intensive process that is industrially accom-
plished through pyrolysis or gasification at very high temperatures as outlined in Chapter 1.
These technologies are often associated with an uncontrolled distribution of products. A
more controllable and tailorable approach to upcycle polyolefins is through the installation
of cleavable linkages along the polymer backbone that allow selective deconstruction as
outlined in Figure 4.5. Incorporating cleavable linkages into polyolefins can be achieved by
introducing tunable amounts of unsaturation. Subsequent C=C bond cleavage via oxida-
tion, metathesis, and other approaches would produce telechelic polymers and/or upcyc-
lable intermediates (Figure 4.5). This technology is still in early-stage development and has
not been demonstrated at scale but shows promise as potential low energy pathways for
upcycling polyolefin waste into higher value applications and reducing the overall envi-
ronmental impact of polyolefin waste.
66 4 Circular plastics technologies: open loop recycling

Figure 4.5: Opportunities in polyolefin upcycling via open loop recycling via the olefin intermediate. Adapted
from Ref. [16].

4.2.2.2 Hydrogenolysis

Hydrogenolysis is an open loop recycling pathway that converts polyolefins into hy-
drocarbons that can be used as fuel or useful chemical building blocks (Scheme 4.3). The
mechanism involves aliphatic molecules adsorbing to the surface of a noble metal
catalyst followed by dehydrogenation (through C–H activation of the backbone, resulting in
two carbon atoms adsorbed to a metal surface in a reactive state), C–C bond cleavage, and
ultimately desorption [17]. A series of catalysts, including carbon-supported ruthenium (Ru),
porous silica supported platinum (Pt), and a complex atomic layer deposition Pt on a
perovskite support, have all been leveraged as hydrogenolysis catalysts capable of converting

Scheme 4.3: Basic schematic of hydrogenolysis of

PE to alkanes. Adapted from Ref. [20].
 4.2 Technical scope 67

Figure 4.6: Schematic of hydrogenolysis of LDPE into liquid alkanes, adapted from Ref. [19].

polyolefins into alkane and iso-alkane mixtures in a solvent-free system [16]. Celik et al.
obtained high yields of liquid hydrocarbons via hydrogenolysis of PE using well-dispersed Pt
nanoparticles supported on SrTiO3 nanocuboids at 300 °C for 96 h [18]. Rorrer et al. was able
to achieve depolymerization of both PE and PP substrates at even milder conditions (225 °C,
24 h) using a Ru nanoparticles supported on carbon (Figure 4.6) [19].
Deconstructing polyolefins via hydrogenolysis is in early phase development and has
not been demonstrated at the pilot scale. Further studies are needed to better understand
the effects of branching, feedstock variations, additives, and contaminants on the
hydrogenolysis products from actual post-consumer polyolefin waste. Regardless,
hydrogenolysis shows some promise as a viable, potentially lower-energy platform for
deconstructing polyolefin waste into fuels or petrochemicals. While pyrolysis requires
high temperatures (>600 °C) and offers very little control over the product selectivity,
C–C bond cleavage via hydrogenolysis allows for selective depolymerization of poly-
olefins into liquid alkanes with targeted molecular weight ranges at lower tempera-
tures (<250 °C) [19]. This selectivity may eliminate the need for downstream refining
that is required to convert pyrolysis oil into diesel fuel. However, since hydrogenolysis is
not operating at the same pilot scale as matured pyrolysis technologies, it is difficult to
compare the energy usage and GHG emissions of the two deconstruction platforms. In a
2021 perspective, Kot et al. summarized the energy demand reported from several PE
hydrogenolysis studies and found that there is a large (an order of magnitude) variation
in energy demand among studies. Furthermore, it becomes evident that lower reaction
temperatures are not necessarily less energy-intensive than higher temperatures
because mild processes require longer times to convert the polymer completely [21].
68 4 Circular plastics technologies: open loop recycling

The selected catalysts may also impart economic challenges and catalysts recovery/
recyclability will be imperative to maintain a cost-effective process. Furthermore, the use
of hydrogen will also likely be unfavorable from an LCA point. Much is still unknown
regarding the economics of hydrogenolysis, and more extensive TEA and LCA exami-
nations should be conducted. Nevertheless, researchers are continuing to pursue
hydrogenolysis and explore ways to improve the product selectivity and lower energy
requirements via catalyst optimization, reactor optimization, and supplementing with
“green hydrogen”.

4.2.3 Oxidation

Polyolefins readily undergo autoxidative deconstruction, especially when exposed to

high temperatures, UV irradiation, or other energy inputs, and this reactivity leads to the
polymer degradation and formation of microplastics over several years when present in
the natural environment. Ideally, this degradation mechanism could be controlled and
used to support oxidative conversion of polyolefin waste into useful chemical products.
Autoxidation of polyolefins has been studied extensively. The introduction of oxygen into
the polymer backbone competes with undesirable reactivity that results in polymer chain
crosslinking and β-scission reactions, both of which can adversely affect physical and
mechanical polymer properties. Early studies of polyolefin autoxidation showed that
nitric acid- and metal-catalyzed autoxidation conditions modify the morphology and/or
led to the break down PE and PP into oxygenated small molecules (Figure 4.7) [20]. These
efforts provided a foundation for subsequent studies exploring autoxidation methods to
convert polyolefin feedstocks into useful products. Nitric acid is a precursor to NOx-based
radical initiators/catalysts that support oxidative deconstruction of HDPE, LDPE, and PP
into lower molecular weight products. For example, PE feedstocks produce mixtures of
dicarboxylic acids with a range of molecular weights. These conditions have been
adapted by a start-up company, Novoloop Inc., using post-consumer PE as a feedstock.
Their process prioritizes C4-18 dicarboxylic acids, some of which contain NO2 function-
ality in the hydrocarbon chain, which provide building blocks for a PUR material,

Figure 4.7: Catalytic oxidative deconstruction of polyolefins into chemical feedstocks, adapted from Ref. [20].
 4.2 Technical scope 69

Figure 4.8: Novoloop oxidation process for polyethylene.

Oistre™, in addition to 3D-printable materials. The Novoloop oxidation process is outlined

in Figure 4.8.
In 2003, Partenheimer showed that autoxidation conditions similar to the “Mid-
Century process”, used for industrial oxidation of p-xylene to TPA, support C–C cleavage
and oxidative deconstruction of multiple classes of polymers into oxidized products.
Sullivan et al. demonstrated the biological funneling of this product mixture into a
microbial conversion process to convert the mixture into a single bioproduct [22]
(Figure 4.9). These precedents show how industrial autoxidation methods, currently
applied to small molecule hydrocarbon feedstocks, could be leveraged to design new
routes for polyolefin conversion and utilization.
Another potential strategy for upcycling of polyolefins involves the chemical modi-
fication of the polymer backbone by the introduction of oxygen into the backbone to
provide desirable material properties, such as improved surface wetting and adhesive

Figure 4.9: Schematic of oxidation integrated with microbial funneling to convert mixed plastic waste into
valuable and tunable bioproducts, adapted from Ref. [22].
70 4 Circular plastics technologies: open loop recycling

Figure 4.10: Radical pathways

associated with polymer reactions,
including MA functionalization, adapted
from Ref. [20].

behavior, while maintaining other physical and mechanical properties. Oxy-

functionalized polyolefins are also privileged with respect to their end of life (EoL)
possibilities. Oxidized PEs show increased rates of biological and photochemical degra-
dation. These considerations have motivated efforts to incorporate oxygen-based func-
tional groups into post-consumer polyolefins as an open loop recycling pathway.
Peroxide-initiated radical functionalization of polymers with maleic anhydride (MA)
is an important industrial application of post-polymerization functionalization of poly-
olefins (Figure 4.10). This process incorporates polar functional groups along the back-
bone of commodity PE and PP, and the resulting polymer exhibits improves barrier
properties and enables the synthesis of composite materials (e.g., via grafting) to access
improved thermal and mechanical properties. The commercial MA functionalization
method provides valuable context for research efforts to functionalize of the C–H bonds
in polymer backbones with polar functional groups. Thermal or Copper-catalyzed acti-
vation of ethyl diazoacetate enables carbene insertion into aliphatic C–H bonds in the
polyolefin backbone, installing ester groups that resemble MA fragments.
Many of these fundamental concepts would require substantial development to find
their way to the marketplace. For example, air- and moisture-sensitive catalysts may not
tolerate impurities likely to be present in waste plastics, and the costly reagents or
catalysts will likely limit large-scale realization. Nevertheless, post-consumer function-
alization offers a potential pathway to create materials with entirely new, higher-value
applications that could valorize polyolefin waste and support additional life-cycles for
polyolefin waste.

4.3 Summary and future trends

Open loop recycling technologies show promise for utilizing waste carbons in multiple
applications and life cycles. While polymer scientists work to develop more inherently
recyclable-by-design (i.e., more easily depolymerized) plastics for the future, open loop
 References 71

recycling offer low energy pathways to convert waste plastics today into new chemical
building blocks. Most of these processes apply know deconstruction technologies such as
solvolysis, hydrogenolysis, or oxidation. However, emerging processing also demonstrate
combinations of chemical and biological processes to convert waste carbons into high
value products.

References
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Index
acetylene 13 hydrogenolysis 61, 66, 71
acidic hydrolysis 36 hydrolysis 36, 38, 39, 64, 65
additives 12 hydrothermal Liquefaction 23
Agilyx 51 Ioniqa 46
alkaline hydrolysis 37 Jeplan 46
alkane 67 LCA 68
aromatics 13 life cycle assessment 1, 40, 63
auger kiln 13, 16 liquid methanolysis 42
autoxidation 68, 69 loop industries 37, 42
benzoic acid 21 maleic anhydride 70
caprolactam 47 materials recovery facility 4
carbios 41 mechanical recycling 3, 11
carbon fibers 63 metathesis 61
catalysts 10, 13, 15, 23 methane 13
catalytic cracking 23, 24 methanolysis 41
catalytic hydrocracking 23 MHETase 40
ceiling temperature 34 microbial conversion 69
chemical recycling 5, 59 microwave radiation 22
circular economy 10, 25, 59 Molecular Loop 61
closed-loop recycling 61 naphtha 33
conical spouted bed reactor 16 neutral hydrolysis 39
cyclonic reactors 13 nitrogen oxides 25
defluidization 15 olefin intermediate 65
degradation mechanisms 17 open loop recycling 63, 65, 70
depolymerization 33 oxidation 61, 68, 71
diamines 64 oxyfunctionalized polyolefins 70
dicarboxylic acids 62, 68 peroxide 70
dielectric 22 PETase 40
diesel 13, 16, 19, 23, 24 plasma 25
enzymatic hydrolysis 39 polyamide-6 20
epoxies 61 polyamides 38, 47, 61
esterase 39 polycarbonates 61
ethylene glycol 35 polyesters 61
fischer–tropsch processes 25 polyethylene 17, 61
fluid catalytic cracking 13, 16 polyethylene terephthalate 20, 34
fluidized bed reactors 13, 14, 50 polymethyl methacrylate 20, 48
gasification 10, 24 Polyolefins 17, 20, 61, 65
glycolysis 44, 62, 63, 65 polyols 62, 65
Gr3n 38 polypropylene 17, 61
greenhouse gas 13 polystyrene 20, 50
greenhouse gas emissions 63 polyurethanes 20, 61
halogens 21 polyvinyl chloride 20
heterogeneous catalysts 24 pressure 17
homogenous catalysts 24 process design 13
hydrogen 13 pyrolysis 9, 33, 49, 50, 67

https://doi.org/10.1515/9781501515613-005
74 Index

reactor 13 terephthalic acid 35

residence time 17 transesterification 41
rotating cone 13 unsaturated polyesters 63
ruthenium 66 unsaturation 65
silica 66 unzipping 20, 34, 48, 61, 62
solvent 16 upcycling 60, 61, 63, 65
solvolysis 35, 48, 62, 71 vapor methanolysis 42
supercritical methanolysis 44 vinyl benzoate 21
supercritical water 23 VolCat 47
syngas 24, 26 waste-to-energy 10
TEA 68 waste-to-fuels 10
techno-economics 22 waste-to-plastics 10
temperature 11