Chemical Recycling PET

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Current Developments in Chemical Recycling of Post-Consumer Polyethylene

Terephthalate Wastes for New Materials Production: A Review
Article in Journal of Cleaner Production · April 2019

DOI: 10.1016/j.jclepro.2019.04.019
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Journal of Cleaner Production 225 (2019) 1052e1064
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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro
Review
Current developments in chemical recycling of post-consumer

polyethylene terephthalate wastes for new materials production:
A review
Ademola Bolanle Raheem a, c, Zainura Zainon Noor a, b, Azman Hassan a, *,
Mohd Kamaruddin Abd Hamid a, Sani Amril Samsudin a, Ali Hussein Sabeen a
a
School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310, Skudai, JohorBahru, Malaysia
b
Centre of Environmental Sustainability and Water Security, Universiti Teknologi Malaysia, 81310, Skudai, Johor, Malaysia
c
Chemical Engineering Department, Faculty of Engineering, University of Port-Harcourt, Port-Harcourt, Nigeria
a r t i c l e i n f o a b s t r a c t
Article history: This paper appraised divergent chemical depolymerization routes for reprocessing chemically synthesis
Received 23 October 2018 polyethylene terephthalate (PET) plastics bottle waste and offer resolutions to control the environmental
Received in revised form complications emanating attributable to its utilize and disposal to the habitat. The consciousness to prune
30 March 2019
environs contaminants and make it “green” demand for the reclaim and reprocessing it back to PET bottles,
Accepted 1 April 2019
Available online 4 April 2019
precursor products like glycolyzate, and other inventions such as unsaturated polyester resins, epoxy
resins, composites etc. Controlling this necessitates assorted reprocessing methods of which chemical
recycling that transform PET into monomer/oligomer is the most prosperous one. This review explored in
Keywords:
Polyethylene terephthalate
detail current events in the PET chemical recycling using glycolysis method. The study was based on their
Recycling kinetics of reactions current evolution concerning their depolymerization agents, reaction conditions, kinetics of reactions,
Chemical recycling catalysts used, products of reprocessing, and their prospective use. Benefits of PET recycling and glycolysis
Catalytic depolymerization as well as criteria and necessitation factors that used to adjudge them as the best method and sub-method
respectively were highlighted. The prospect for the conversion of glycolyzate into other PET recycling
methods products were shown. PET recycling was concluded to be a partial resolution to wastes man-
agement, and also grants the conservation of natural petrochemical resources and energy.
© 2019 Published by Elsevier Ltd.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053
2. Chemical recycling of PET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
2.1. Alcoholysis method of PET recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056
2.2. Hydrolysis method of PET recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1057
2.3. Aminolysis method of PET recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1057
2.4. Ammonolysis method of PET recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
2.5. Glycolysis method of PET recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059
2.5.1. Kinetics of waste PET glycolytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059
2.5.2. Theoretical and simulation research on PET glycolysis depolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
2.5.3. Microwave glycolysis depolymerization of PET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
2.5.4. PET glycolysis depolymerization catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1060
2.6. Merits and limitations of glycolysis PET depolymerization method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
3. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1062
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1063
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1063
* Corresponding author.
E-mail address: [email protected] (A. Hassan).
https://doi.org/10.1016/j.jclepro.2019.04.019
0959-6526/© 2019 Published by Elsevier Ltd.
A.B. Raheem et al. / Journal of Cleaner Production 225 (2019) 1052e1064 1053
List of acronyms AD Azo-dyestuffs

TEG Triethylene glycol
PET Polyethylene terephthalate Co3O4 Cobalt(II,III) oxide
TPA Terephthalic acid Mn3O4 Manganese(II,III) oxide
BHET Bis (2- hydroxyethyl) terephthalate UPP Unsaturated polyester polyurethane
DMT Dimethyl terephthalate CoMn2O4 Manganese(III)-cobalt oxide
EU European Union ZnCo2O4 Cobalt(III)-zinc oxide
GAIA Global Alliance for Incineration Alternatives Bmim 1-Butyl-3-methylimidazolium
EPA Environmental Protection Agency ILs Ionic liquids
USA United Sates of America SO24 Sulfate ion
EG Ethylene glycol TiO2 Titanium dioxide
CoCl4 TetrachloroCobaltate (or Cobalt tetrachloride) B3LYP Functional theory model for trans-esterification and
ERD Epoxy resins and its hardeners amidation with catalyst
VER Vinyl ester resins TBD 1,5,7-triazabicyclododecene
AR Alkyd resins DBU 1,8-diazabiocyclo [5.4.0] undec-7-ene
H2O Water MB Methyl benzoate
PG Propylene glycol Tempt Temperature
DEG Diethylene glycol Press Pressure
NH3 Ammonia wt weight
UPR Unsaturated polyester resins NA Not available
ZnMn2O4 Manganese(III)-zinc oxide EA Ethanolamine
NPS Non-ionic polymeric surfactants h hour
H2SO4 Sulfuric acid kW (or W) Kilowatt (or Watt)
H3PO4 Phosphoric acid min Minutes
ZnO Zinc oxide kJ (or J) Kilojoules (or Joules)
POMs Poly-oxo-metalates Kmol. (or mol.) Kilomoles (or moles)
o
ZnCl4 Tetrachlorozincate (or Zinc tetrachloride) C Degree Celcius
DESs Deep eutectic solvent N/m2 Newton per square meter
NaHCO3 Sodium bicarbonate % Percentage
b e and g e Beta- and gama w/w Weight per weight
Fe2O3 Iron(III) oxide (or Ferric oxide) Zn Zinc
HNO3 Nitric acid K Potassium
NaOH Sodium hydroxide Si Silicon
BHPT Bis (2- hydroxypropyl) terephthalate Fe Iron
k Reaction rate constant Mn Manganese
Ea Activation constant Ni Nickel
A Arrhenius constant O Oxygen
Zn(OAc)2 Zinc acetate Co Cobalt
MO Methacrylate oligoesters Mg Magnesium
UV Ultraviolet PbO Lead oxide
BHETA Bis (2- hydroxyethyl) terephthalamide m3 Cubic metre (volume measurement)
PUF Poly-urethane foams OAc Acetate
PIF Poly-isocyanurate foams Na2CO3 Sodium carbonate
OP Oligomeric plasticizers EDA Ethylenediamine
1. Introduction monomer, oligomers, intermediates and finished products in

consideration of economic impact, consumer demand, recycling
Polyethylene terephthalate (PET) is a polymer that has great legislation, and lower cost. Method adopted is the review of pre-
importance among the plastics in the world (Srithep et al., 2011). Its vious works to show the potency of the recycling method (mainly
thermoplastic recyclability makes it a first choice for various ap- chemical recycling) over other PET wastes management methods.
plications (Demirel et al., 2016; Helms and Russell, 2016). Its To highlights the superiority of glycolysis (sub-method) over others
properties, uses and industrial innovations that increases its con- along the current trends and potential future innovation and
sumers demand result in tons of its scrap creation in the environ- technology in order to improve the system and probably discover
ment (Cosnita et al., 2017). Its toughness, resilience non-degradable new products. This work shows the PET properties, uses and reason
nature that makes its waste increases over years constitutes hazard for recycling as presented in Table 1.
to environment when dumped after use, cause serious problems to The work review recycling methods to diminish PET in the
the environs (Leng et al., 2018) and called for its recycling. PET environment as a priority to other methods such as landfill,
waste accounts for 8% by weight and 12% by volume of the world's incineration and re-use and made the comparison as presented in
solid waste (Atta et al., 2007), with volumetric increment at Table 2.
alarming rate (Irwan et al., 2013). The problem in focus of this work The practical available methods for PET recycling are primary
is the elimination or reduction of PET plastic wastes and its pollu- recycling, mechanical or secondary recycling, chemical or tertiary
tion from the environments. The scope is to recycle it into its recycling, and energy recovery through incineration recycling.
1054 A.B. Raheem et al. / Journal of Cleaner Production 225 (2019) 1052e1064
Table 1
Properties, uses and reasons for PET recycling with references in the paper.
Properties Uses Recycling Necessitation
Light weight. Packaging. Ecological reasons.

Fair moisture proficient gas and alcohol barrier (no centerline Automotive, constructions, and industrial applications. Consumer demand.
porosity). Medical and health care applications. Recycling legislation and Lower
Highly durable. Preservation and distribution of foods. cost.
Excellent resistance to wear. Communication materials and others (Olaniyi, 2015; Kramar and
Low coefficient of friction. Bodrova, 2016).
High flexural modulus.
Superior dimensional stability and low market price.
Table 2
Comparison of landfill, incineration, re-use, and recycling of PET reduction methods with references in the paper.
Criteria Landfill Incineration Re-use Recycling
Space management Not better better better better

Pollution (eco-friendliness) Land pollution Harmful smoke and gases No pollution It has control over it eco-friendliness
Land use policy High effect Low effect Very low effect Very low effect
PET waste reduction No reduction Total reduction Fair reduction Total reduction
Energy Nil Produces energy Nil It can consume or produce
PET product quality Not applicable Not applicable It is lower over time Original quality is achievable
Opportunity for proper handling, machining, and research. Nil Limited opportunity exists Very little Many opportunities exist
Primary recycling is the re-use of off or low grade and pure scrap (2-hydroxy ethyl) terephthalate (BHET), Terephthalic acid (TPA),
stuffs produced by the company that falls short of the specification. glycols, dimethyl terephthalate (DMT), chemicals or fuels, petro-
It is used directly by the recycling plant, and has low degree of leum liquids and gases, etc. The produced monomers are re-
contamination. It is the most favored, with ease of processing and polymerized into new PET packaging. Regenerated monomer can
low production cost, mainly with “in-plant” process furnishing be mixed with virgin materials to improve the quality. The mono-
with scrap of modulated history. mer/polymer purification can be achieved through distillation,
Mechanical recycling is the separation of the PET materials from crystallization, drying, and some additional chemical reactions.
its integrated contaminants and reprocessed by typical melt PET waste incineration is done to reclaim its energy. Its energy is
extrusion into granules (Shamsaei et al., 2017) or aggregate in enormous since its original source is petroleum, although with high
concrete mixes (Shariati et al., 2010). To increase the shear strength environmental impacts. High efficiency of new incinerators with
and ductility of composites materials (Shariati et al., 2011). The capacity to remove particulates and unhealthy gases is a boost to it
standard material strength ratio in relation to ductile ratio should (Subramanian, 2000). In the lack of other PET recycling possibilities,
be based on the American Concrete Institute (ACI) code as reported incineration energy recuperation is prefers to land filling. Also, EU
by Mohammadhassani et al., 2013. The process requires sorting, legislation such as the landfill directive put a check on landfills
decontamination, and treating by washing, drying and grinding operation and established a range of waste management targets
before re-use on its own or as a blend/melt filtration and reforming and goals for the years up to 2020 (Fischer et al., 2013). Incineration
of the PET waste materials. Blending of the recycling material with becomes an option when gathering, classifying and segregation of
the virgin ones, if desires, occurs during grinding or melting phases. waste are strenuous or not cost-effective, or the waste is harmful
Properties deterioration occurs because of reduction in the mo- and dangerous to handle. Then, the best option to manage such a
lecular weight of the mechanical recycled PET resin due to chain- waste is incineration to recover the stored chemical (thermal) en-
scission reactions provoked by the existence of water and trace ergy in the plastics waste. Although polymer waste is a high energy
acidic contaminants. yielding source, but incineration method is not a good disposal
Tertiary or chemical recycling is a well adopted recycling option ecologically owing to health threat from air borne toxic
method that follows the sustainability development principles. It is substances like antimony and phthalate esters (Mihucz and Za ray,
suitable for many industrial and commercial applications including 2016) and dioxin which comes from chlorine contained polymers.
food-contact ones that gives it more attraction for researchers’ in- Incineration of polymer wastes can never give zero emission, hence
terests. It is the transformation of PET chain in which its backbone is the necessity to consider other options.
degenerated into monomers (depolymerization). It can also arbi- Re-use of the PET bottles that ingest contaminants that could be
trarily break into larger chain fragments (random chain scission) absolved back into the drink or food is detriment to the health. PET
with associated gaseous products evolution. It is accomplished bottle refilling with alcoholic contents leads to digestion of the
either by solvolysis (solvents degradation) or by pyrolysis (heat macromolecular chains with unpredicted results. The option left is
degradation in the absence of oxygen or air, or in vacuum). This the reprocessing (recycling) of plastic materials. Fig. 1 shows the
depolymerized PET waste is with subsequent regeneration and rate of waste disposal method (%) by legislative bodies as in Flander
refining of emerged monomers (or oligomers), or transformation (Belgium), Joan Marc Simon (executive director) of Zero Waste
into new products. That is, the regeneration of monomer or oligo- Europe and European regional coordinator for “the global anti
mers is follows by the product purification to acceptable quality incineration alliance or global alliance for incineration alternatives
level suitable to reproduce PET materials or converting them into (GAIA)” (since 1990); Germany; Scandinavian countries (Denmark,
new products. In this method of recycling, the material is prepared Norway, Sweden, Finland and Iceland); European countries; U.S.
like the case of secondary recycling up to cutting into flakes or Environmental Protection Agency (EPA); European Union (EU)
pellet form. It is then process with chemicals to produce mono- (Seltenrich, 2013).
mers, oligomers and its mixtures (dimers, trimers etc.) such as bis This work emphasized mainly on the PET chemical recycling
Fig. 1. Rate of waste disposal method by respective legislation body modified from (Seltenrich, 2013).
methods in-depth, focused deeply on the kinetics of each methods methods, and glycolysis (sub-method). It highlighted the prospect
for proper handling of the PET materials depolymerization to for the conversion of glycolyzate into other PET recycling methods
improve or find more useful intermediate (like PET monomer) or products; simulation and microwave processing of PET wastes
finished products. Furthermore, the other methods used to convert recycling, as new trends for potential and efficient quantification of
PET wastes do not obey the concepts of sustainability development mass and energy balances synergy for further studies on economic
as does the chemical recycling. The environs is not surcharge dur- and environmental impacts on the habitat. 1t critically reviewed
ing chemical recycling and the issue of supplementary monomers and focused deeply on the kinetics of chemical recycling and
for the PET production does not arise. Hence more focus should be glycolysis methods for proper handling of the PET materials
on polymers chemical recycling, especially PET to obtain fibers and depolymerization to improve on monomer or products yields, or
variant products in a sustainable manner. futuristic gate designs to find more useful intermediates and
The two notable recycling methods identified so far are me- finished products in a sustainable (green technology) manner.
chanical and chemical recycling. Mechanical recycling is not an
eternal resolution because of poor quality product arising (Sinha
et al., 2010). Hence more focus should be on chemical recycling, 2. Chemical recycling of PET
especially glycolysis that has exhibited to be more viable. The ver-
satilities of the chemical and mechanical PET recycling methods are PET is processed by the condensation reaction of terephthalic
compared in Tables 3 and 4. acid (TPA) with ethylene glycol (EG) or polycondensation of bis (2-
This work prioritize on the criteria and necessitation factors that hydroxyl ethyl) terephthalate (monomer), or by a trans-
adjudged recycling as the best method to manage PET wastes; esterification reaction between dimethyl terephthalate (DMT) and
benefits and drawbacks of mechanical and chemical recycling EG. Chemical recycling totally degrades PET into monomers such as
TPA, DMT, BHET, and EG or partially into oligomers or other
Table 3
Benefits and drawbacks of PET chemical recycling.
PET Chemical Recycling
Benefits Drawbacks
It broken down PET scrap into its monomers and/or its oligomers and other It attract higher manufacturing cost than mechanical recycling with no economic
chemicals (Lo pez-Fonseca et al., 2010). incentive due to higher production cost of chemically reprocessed PET in comparison
It solely obey ‘sustainability’ principles in comparison with other recycling with virgin PET (Kamber et al., 2010).
methods in the manufacture of indigenous raw material It requires large scale implementation for it to be cost-effectively viable (Hopewell
(Bartolome et al., 2012). et al., 2009).
It requires no additional resources for the manufacturing of PET
(Sinha et al., 2010).
It conserve the molecular weight (intrinsic viscosity) of the recycled PET
wastes (Lopez-Fonseca et al., 2010).
It can recycle contaminated and very complex waste stream to product
of required specification (Hopewell et al., 2009).
Assortment of the PET scrap problem can be classified and the commodity
properties maintain during the PET chemical recycling (Sadat-Shojai and
Bakhshandeh, 2011).
The work-ability suchlike print-ability and dye-ability of the final product can be
done to a desired grade during PET chemical recycling (Dawson, 2012).
Tarnish yellowing of PET product does not arise during PET chemical recycling
(Badia et al., 2012).
Table 4
Benefits and drawbacks of PET mechanical recycling.
PET Mechanical Recycling
Benefits Drawbacks
PET can be recycled mechanically through processes such as wastes separation, It cannot recycle thermoset PET, as it cannot be regenerated by heat (Park and Kim,
removal of contaminants and dirt, PET particles size reduction by grinding and 2014).
crushing, re-extrusion and re-processing for new PET manufacturing (Siddique
et al., 2008).
The process is very simple (Karayannidis and Achilias, 2007). The complexity nature of the waste stream hinders the recycling of contaminated
PET waste mechanically (Al-Salem et al., 2009).
It has low investment cost (Badia et al., 2009; Panda et al., 2010). Variegation of the PET waste and the product properties deterioration at each time
of recycling is a major problem for PET mechanical recycling (Bartolome et al., 2012).
It utilizes readily available and simple equipment (Sinha et al., 2010). The print-ability and dye-ability of the final product can be degraded due to cyclic
and linear oligomers generated during PET mechanical recycling (Dawson, 2012).
It has flexible feedstock supply (Al-Salem et al., 2009). The yellowing of mechanically recycled PET due to intra-molecular crosslinks and
oxidation reactions is a problem (Badia et al., 2012).
It exert little negative environmental impacts A thermal and hydrolytic digestion reduction in molecular weight (or intrinsic
(Thompson et al., 2009; Milani et al., 2011) viscosity) is a crucial problem in PET mechanical recycling (Lo pez-Fonseca et al.,
2010).
materials. The depolymerization is the transpose reaction of the Also in existence are some methods that are hybrid such as
polymer formation. PET chemical recycling techniques were chemical e mechanical (alkaline hydrolysiseextrusion), glycolysis-
employed interchangeably to processing of PET on a commercial hydrolysis, methanolysis-hydrolysis, and glycolysis-methanolysis
scale. It was initially seen as a way to utilize wastes emerging in the (Acar and Orbay, 2011). This work also shows processes require to
PET manufacturing cycle. Over a period, a drastic increment in the convert BHET (glycolysis product) into various products of other
utilization pattern of PET together with general consciousness, PET depolymerization methods as shown in Fig. 2. The primary and
brings about importance to be laid on used PET reprocessing. secondary products of depolymerized PET are presented in Table 5
Chemical reclaiming of PET and their various processes in the light and Fig. 2.
today were brought about by the historical and practical reasoning
of the researchers. 2.1. Alcoholysis method of PET recycling
Also, since current issue is focusing on industrial application
that requires sound technologies, good design plans, and sourcing It is the trans-esterification reaction of alcohol with PET at high
for prospective industrial waste streams (Ragaert et al., 2017). temperature (180e280 C) and pressure (2e4 MN/m2) accelerating
Breaking through into progressive application requires engineers by catalyst such as organometallic to produce dimethyl tere-
and researchers versatilities in PET chemical recycling kinetics, phthalate (DMT) and EG as monomers. Commonly used alcohol is
reactions, operating conditions and transport phenomena of the methanol (methanolysis), but ethanol and others can also be
system. employed as digestive medium. It has been practiced and tested on
The major PET depolymerization methods includes the che- a large scale for many years in the past, with attention shifting away
molysis of the polymeric materials with excess digestive reagents from it due to high corrosiveness and production cost. Industries
such as glycols (glycolysis); water, acid, and alkaline (hydrolysis); such as Hoechst, DuPont, Dow Chemicals, and Eastman have used
amines (aminolysis); alcohols like methanol, ethanol etc. (alco- methanolysis process.
holysis), and ammonia (ammonolysis) (Raheem and Uyigue, 2010; The reaction temperature can be achieved through heating or
Hoang and Dang, 2013). supplied by the superheated methanol vapors, while PET melting
2.2. Hydrolysis method of PET recycling
Functional ester group of the PET bottles or waste is hydrolyzed

by water in an acid, alkaline or neutral (water) medium at high
pressure and temperature to break the polymer chain to produce
monomers (TPA and EG). In the course of hydrolysis reaction, a
carboxylic acid and an alcohol are produced as presented in Fig. 3.
Neutral hydrolysis is the digestion of PET waste with water or
steam at temperature range 200e300 C and pressure range
1e4 MN/m2 in the presence of esterification catalysts such as alkali
metal acetates to produce highly purity TPA and EG (Sinha et al.,
2010). Temperature range of 245e265 C is highly recommended
to promote molten that fastening PET hydrolysis with excess water
of about 5:1 or more ratio of water:PET. Hydrolysis is slow in
comparison with methanolysis and glycolysis, because water is a
weaker nucleophile than methanol and EG.
Acid hydrolysis is the digestion of PET wastes with water in acid
environment to produce TPA and EG. It uses strong acid (˃ 87%
weight H2SO4, H3PO4 and 7e13 M HNO3) to depolymerize PET
waste into TPA and EG. It does not require high temperature and
Pressure, but too low temperature and low acid concentration gives
slow rate of hydrolysis. Acidic hydrolysis generally has corrosion
problem. Although H2SO4 is the commonly used acid, but it has
additional problem of producing large volume of liquid wastes that
contains inorganic salts and H2SO4. HNO3 has the precedence of
oxidizing EG to oxalic acid that is more value than TPA or EG. This
improve the economics of the process compare to the one that
produce TPA and EG only. Also, nitrogen oxide that forms in the
system is recycled by oxidation and the addition of water to form
Fig. 2. Chemical depolymerization processes reference in the paper.
HNO3.
Alkali hydrolysis is the digestion of PET wastes with alkali so-
lution such as 4e20% weight solution of NaOH (Karayannidis and
follows by its exposure to the methanol. The products composition Achilias, 2007) at temperature range of 200e250 C under pres-
are mixture of DMT (main product), glycols, phthalate derivatives, sure for many hours to produce alkali metal salt of TPA solution
and alcohols. This complexes products mixture makes it separation (sodium salt of TPA) from which TPA is precipitated by acidification.
and refinement to be very tedious and costly. It gives set back to the It is a saponification process and the commonly used alkali is NaOH.
use of this method and makes the choice of glycolysis and hydro- Hydrolysis is the sole depolymerization method that produce
lysis methods to be preferable. Also, the catalyst should be deac- pure TPA and EG that are directly use for PET production. The main
tivated after the termination of the reaction to avoid trans- disadvantage of hydrolysis practice is the use of high operation
esterification of DMT with EG into diethylene glycol terephthalate conditions of pressure (1.4e2 MN/m2), temperature (200e250 C)
and PET. and long reaction time of range 3e5 or more hours for total
The crude DMT produced is purified after it separation from the digestion of PET (Sinha et al., 2010). Also cost of TPA purification is
products mixture by (1) vacuum distillation or (2) cooling and high, which is a significant reason why it is not mostly use by some
precipitation, centrifugation and then crystallization. This process industries to manufacture food-grade recycled PET.
tolerate vast range of contaminants, except water that disturbs it
and poisons the catalysts to form diverse azeotropes. It was re- 2.3. Aminolysis method of PET recycling
ported that the expense of producing DMT through methanolysis
almost double that of virgin DMT production (Siddiqui et al., 2012). It is the digestion of PET waste with primary amines at tem-
Also methanolysis process corrosiveness makes it unsuitable to perature ranges of 20e100 C to produce corresponding mono- and
practice unlike glycolysis and neutral hydrolysis. di-amines of TPA and EG. Its common amines and catalysts implore
Industries new trends are the manufacturing of PET bottles are presented in Table 5. PET aminolysis reaction is shown in Fig. 4.
from TPA and other products (resins) from BHET and not DMT as The conversion of PET into products by methylamine, ethylamine,
base material (Bartolome et al., 2012). The DMT produced, through dimethylamine, trimethylamine, NH3 and NaOH shows close rate of
additional process, can be hydrolyzed into ethylene glycol (EG) reaction except for NH3 with low value. These solvents reaction
and pure terephthalic acid (PTA) that are monomers to be re- were expressed in terms of surface reaction model with 2/3 reac-
polymerized into PET bottles or as precursors for other products. tion order kinetics with respect to unreacted PET. Of all the amines
The additional processes require more chemical applications, as solvents, triethylamine has the highest products yield of
utilities, and operational units that increases the environmental monomers, TPA and EG with values near to theoretical ones. Other
and economic impacts of methanolysis process to the amines as solvent have lower products yields with intermediate
environment. products presence observed in them (Wakabayashi et al., 2012).
Methanolysis process has an advantage that its installation is The products of aminolysis such as bis (2-hydroxylethyl) ter-
feasible in the polymer production line as the same quality of virgin ephthalamide (BHETA) have the potential to undergo further re-
DMT and DMT obtained from methanolysis depolymerized PET actions to yield secondary value-added products as shown in
(Sinha et al., 2010). Also, methanol and EG produced can easily be Table 5. Aminolysis is rarely use in the industry for PET chemical
recovered and recycled (Al-Salem et al., 2009). recycling. According to Karayannidis and Achilias (2007), there are
Table 5
Chemical recycling of PET process, reagents, operating conditions, and products with references in the paper.
Process Reagents Operating Conditions Primary Products Secondary Products
Alcoholysis Alcohols (methanol, ethanol etc.) High temperature of (180 DMT and EG Mixture of mainly DMT TPA and corresponding alcohol;
(transesterification e280 C); pressure (2e4 MN/ and glycols (EG), then alcohols, and BHET; PET; UPR; ERD; VER; AR.
process) m2); catalyst: Organometallic phthalate derivatives.
(metal acetate of Zn, Mg, Co and
PbO); Ionic liquids etc.
Acid Hydrolysis Strong acids (Sulfuric, Phosphoric, and H2SO4: 25e100 C; 101325 N/ TPA and EG.(HNO3 /oxalic acid; and BHET; PET; UPR; ERD; VER; AR.
Nitric) m2.; 87 wt % Conc. (Sinha et al., nitric oxide /nitric acid)
2010) HNO3: 70e100 C.
Alkaline Hydrolysis Alkali (NaOH) and acid (H2SO4) for Tempt. (200e250 C); Press. (1.4 Corresponding alkaline metal salt of BHET; PET; UPR; ERD; VER; AR.
(saponification and acidification. e2 MN/m2); Time (3e5 h or TPA and EG. Then, acidification to TPA
acidification more) and salt of used acid.
processes)
Neutral Hydrolysis Water or Steam Tempt. (200e265 C); Press. (1 TPA and EG (High purity with excess BHET; PET; UPR; ERD; VER; AR.
(Esterification e4 MN/m2); time (2 h); Alkaline water). Problem: PET waste
process) metal acetate (Zinc acetate) contaminants is carried over with the
product, hence extensive purification of
TPA is required.
Aminolysis Amines of methyl-, ethyl-, propyl-, Tempt. (20e100 C), Catalysts EG and corresponding mono- and di- UPR (Elsaeed and Farag, 2009);
butyl-, ethanol-, triethylene tetra-, (Zinc acetate, Lead acetate, amines of TPA like N,N1-Dialkyl UPP (Shamsi et al., 2009); ERD;
hexamethylene di-, benzyl-; aniline;; glacial acetic acid, and terephthalamide (Alkyl amine); N,N1- synthesis of bisoxazoline (Shah
piperidine; hydrazine monohydrate potassium sulfate. Diallyl terephthalamide (Allyl amine); and Shukla, 2012), and NPS
and some polyamines (Sadeghi and BHETA (Ethanol amine); (Elsaeed, 2008).
Sayaf, 2012). Terephthalohydroxamic acid (Hydroxyl
amine hydrochloride); terephthalic
dihydrazide (Hydrazine hydrate); and
Bis (2- aminoethyl)
terephthalamide(n ¼ 1) or a,ѡ-
(aminoligo ethylene) terephthalamide
(n 2) (Ethylene diamine)..
Ammonolysis Ammonia (NH3) Temperature (70e180 C), low Terephthaldiamide (TPA di-amide) and Terephthalonitrile; p-
pressure. PET bottle tempt. (120 ethylene glycol (EG). xylylenediamine; 1, 4-bis
e180 C), Pressure (2 MN/m2), (amino-methyl) cyclohexane;
time (1e7 h), Zinc acetate (0.5 and 1, 4-bis (amino-ethyl)
w/w of PET) cyclohexane.
Glycolysis Glycol (EG or PG or DEG or TEG etc.) Temperature (180e240 C); EG (BHET, BHET dimer, oligomers).PG BHET; PET; UPR; ERD; VER; AR;
(transesterification high or low (102 kN/m2) (BHPT, BHET, hydroxypropyl e Poly-isocyanurate foams (PIF);
process) pressure; catalysts: Organic- hydroxyethyl terephthalate).DEG Poly- urethane foams (PUF);
metallic (e.g. Zn(OAc)2); ionic (oligoesters diols). Oligomeric plasticizers (OP);
liquids etc.) Azo-dyestuffs (AD)
parameters has been outlined by Sinha et al. (2010). Primary

amines of divergent types and in different forms have been used for
aminolytic modification operations of PET fiber surfaces.
2.4. Ammonolysis method of PET recycling
Fig. 3. PET hydrolysis reaction reference in the paper.

It is the digestion of PET materials with ammonia (NH3) at
temperature range 70e180 C under pressure. PET bottles waste is
no familiar report for the utilizing of this method on a commercial feasibly digested at temperature range 120e180 C and a pressure
scale. Partial aminolysis has established its utilization in the of 2 MN/m2 (low pressure can also be used) for 1e7 h with a suit-
enhancement of PET properties in the production of fibers with able catalyst such as Zinc acetate (0.5%) to yield terephthaldiamide
defined properties. Its industrial application on superficial partial (TPA di-amide) and EG. TPA di-amide serves as intermediary
aminolytic PET fibers degradation in order to modify and amelio- product to manufacture terephthalonitrile that can further be
rate the quality of fiber coloration and its technical and application converted through hydrogenation (þH) to produce p-xylylenedi-
amine or 1, 4-bis (amino-methyl) cyclohexane. Anhydride
Fig. 4. PET aminolysis reaction modified from Elsaeed and Farag (2009).
ammonia is used to treat PET waste in EG medium to produce TPA trihydrate. Processing of PET depolymerization with EG without
amide. TPA amide can be a precursor material to produce tereph- little BHET addition, using normal method cannot be agitated
thalonitrile and further to p-xylylenediamine or 1, 4-bis (amino- owing to the resultant effect of solidification and increment in
ethyl) cyclohexane. PET:NH3 ratio of 1:6 at 70 C and low pressure depolymerization time in the homogeneous reaction process. Gly-
in EG can produce as high as 87% yield of TPA di-amide. The ob- colyzate products (oligomers) from digested PET is use to produce
tained amide can be filtered, washed with water, and desiccated at secondary products as presented in Table 5.
a temperature of 80 C, to achieve product purity of 99% or more. The process development of PET glycolysis requires detail data
on product characterization and kinetics. The data is gotten through
2.5. Glycolysis method of PET recycling experimental procedures and resulting kinetic parameters that
vary with assumed kinetic model and applied data fitting proced-
Glycolysis is a trans-esterification reaction of PET wastes with ure. A kinetic model can be proposed and simulated via the
excess glycol at temperature range 180e240 C and high pressure experimental data. Reaction rate constant (k), activation energy
in the presence of catalyst to produce BHET. This method involves (Ea), Arrhenius constant (A), reactants conversion rate and prod-
the breaking down of PET ester linkages by a glycol (EG, DEG, and ucts yields are the parameters to be evaluated during process at a
PG) to produce BHET, dimer, and oligomers (Sinha et al., 2010). The given set of operating conditions of temperature, pressure, catalyst,
products get if PG is used are bis (2- hydroxyl propyl) terephthalate and reagent:PET:catalyst ratios. Process characteristics of current
(BHPT), BHET, and hydroxyl propyl e hydroxyl ethyl terephthalate. method can be simulated and developed to show complete
The common catalysts employ are organometallic such as metal chemical recycling of PET using a process flow chart as presented in
(Zn, Co, Mg and so on) acetate, oxides, ionic liquids and others. It is Fig. 5.
the most widely used commercially of all the PET chemical recy- The products are PET monomer (BHET) and oligomers (mostly
cling methods, and has been practiced by famous companies like dimer and little trimer) (Pti cek Sirocic et al., 2013). Higher ratio of
DuPont, Dow Chemicals, Goodyear, Shell Polyester, Zimmer, East- EG:PET (5:1) favors lower molecular weight Product (monomer)
man, Kodak and others. (Achilias, 2014) while lower EG:PET ratio (<4:1) favors higher
molecular weight product (oligomers) (Sinha et al., 2010). At high
2.5.1. Kinetics of waste PET glycolytic degradation EG/PET ratio, optimum temperature and pressure, higher reaction
Glycolytic depolymerization of PET reaction kinetics depends on time favors monomer production with very little dimer in the
reaction parameters such as temperature, reaction time, reagent or product composition (Chaudhary et al., 2013). EG and PET reaction
glycol concentration (glycol:PET ratio), catalyst concentration beyond 1 h contain product mixture of BHET and little BHET dimer.
(catalyst:PET ratio), pressure (gaseous phase), and solid reactant PG was first preferred to EG in UPR production, because of PG
surface area (solid phase e 127.5 mm PET particle size). Most of the compatibility with styrene. Although, UPR form from EG degrada-
glycolysis reaction noted to occur at atmospheric pressure except tion of PET is stronger than that of PG, but it set in time and very
gaseous phase rate of reaction that is promoted by high pressure. stiff. The problem is solved by the addition of hydroquinone that
Also fine grinding size of PET that exposes large surface area of it delay setting time during processing. Also, BHET-MA formed at
that promote high rate of reaction favors its glycolysis depoly- 180 C and 4 h has number average molecular weight (Mn) of
merization. The order of their strength over the glycolysis digestion 1460 g/mole and weight average molecular weight (Mw) of 2462 g/
reaction of PET are: catalyst concentration > temperature > reac- mole, with BHET conversion of 98.4e100%. The values are within
tion time. The glycol concentration can be kept changing in con- commercial UPR ranges of 1200e3000 g/mole Mn and
formity with glycolysis products different significant functionalities 2500e5500 g/mole Mw (Duque-Ingunza et al., 2013). Lower mo-
with the other parameters constants. Its kinetic is first order with lecular weight gives poor mechanical properties of cured resin
PET((Al-Sabagh et al., 2014a; Lo pez-Fonseca et al., 2011; Shukla while too high molecular weight increases the viscosity and cause
et al., 2008) and second order with regards to EG concentration resin processing problem. EG is used where very strong adhesive
with EG served as both reactant and catalyst in PET glycolysis force is required (automotive composites). DEG that degraded PET
(Viana et al., 2011). The optimum conditions are 180e250 C (but into oligoesters diols with long chains well improve the flexural
metallic acetate catalysts are ineffective at temperature beyond properties of the UPR. A new UPR formulation called ethylene-
245 C), 0.5e8 h, 0.5e1% catalyst (w/w of PET) (Chaudhary et al., diethylene diester has evolved by the digestion of PET with DEG
2013). Zinc acetate catalyst is the best among the metal acetate, as its terephthalate part which is used in the manufacturing of
but newly developed ecofriendly ionic liquids catalysts are better molding compound. The use of TPA direct for the manufacturing of
(Wang et al., 2009). UPR has sublimation problem. Hence, use of glycolytic products like
The process is slow in the absence of catalyst, unless at very high BHET, BHPT and so on are recommended. This make glycolyzate to
temperature and pressure (glycolytic PET depolymerization sus- be more versatile than hydrolysate in the UPR, and other resins
tainability process). Hence employment of trans-esterification productions. Hence hydrolysate should be modified to glycolyzate
catalyst is necessary. Its digestion requires three stages: breaking before further reaction into the required resins. Another advantage
into oligomers (trimer inclusive), then dimers, and finally mono- of glycolysis practice is that BHET produced can simply be coherent
mer. In the course of reaction, the glycol diffuses into the polymer into a standard PET production plant (Imran et al., 2010). Sangalang
and cause it to swell up which invariably increasing its diffusion and Bartolome (2015) researched on kinetic investigation of het-
rate. It then attack and break the ester bond in the chain and erogeneous PET glycolysis nucleation-controlled depolymerization.
degenerate the PET into lower fractions. BHET and oligomers Activation energy of 29 kJ/mol was obtained as the near value to
formed are in equilibrium with one another and can be switched to report experimental and simulation activation energy of thermal
the left (BHET production) by addition of BHET into the glycolysis
process reactor. Addition of little BHET into the reactor before PET
digestion commence, encourage the solubility of PET which accel-
erate depolymerization. Oligomers form during glycolysis solution
produced cooling that advance the crystallization of BHET. Excess
EG results in rapid reaction, but too excess EG may cause DEG Fig. 5. Typical glycolysis depolymerization of PET process flowchart (Aguado et al.,
formation that can be inhibited by the addition of sodium acetate 2014).
and glycolytic breakage of a PET ester bond at range of 12e19 kJ/ 2.5.4. PET glycolysis depolymerization catalysts
mol. Aguado et al.(2014) carried out glycolysis digestion of PET Divergent catalysts had been developed and some work are still
waste using the process flowchart in Figure (5) with operating in progress as considered in the subsequent subsections.
conditions of EG/PET ratio of 6:1, 208 C, and 2.5 h reaction time,
0.2% (w/w of PET) catalyst, to obtain 85% yield of BHET with 2.5.4.1. Organometallic catalysts (heavy metal salts). They are first
approximately 97% purity. BHET yield of 85.6% was obtained at EG/ set of catalysts developed such as acetate of Zn, Mg, Co and PbO that
PET ratio of 5:1, 196 C, 3 h and 1% (w/w of PET) zinc acetate catalyst are famous as the conventional trans-esterification catalysts for the
(XI et al., 2005). Glycolysis was investigated to be a potent way for glycolysis and other PET depolymerization methods with zinc ac-
the manufacturing of derivative value added materials (glyco- etate as the most prominent one (Lo pez-Fonseca et al., 2010; Chen
lyzate). BHET, Dimers, Trimers, and Oligomers can serve as raw et al., 2013b). They are commonly used due to high PET conversion
materials for the manufacturing of unsaturated polyester resin and selectivity of BHET. Viana et al. (2011) used it to obtain 100%
(UPR) or methacrylate oligoesters (MO). Alkyl resins can be pro- PET conversion while Yasir et al. (2017) depolymerized PET scrap
duced as enamel paints or coatings by curing UPR with styrene at using Zn(OAc)2 catalyst and thiodiglycol to obtain bis (2- (2-
ambient temperature. Wood surfaces coatings, paints and other hydroxyethyl thio ethyl terephthalate)) that is a corrosion inhibi-
applications formulations can be produced by curing MO with UV tor for steel. They have some disadvantages like intense reaction
irradiation. So, PET recycling is not just a partial resolution to solid- conditions, slow reaction rates (few of them), strenuous recycling of
waste problem, but as well bestow to the protection of raw the catalyst. Also their metal components toxicity is high and
petrochemical products and energy. A typical glycolysis depoly- makes them to be unfriendly to the environment. Al-Sabagh et al.
merization of PET process flowchart is shown in Fig. 5. (2016) reported both Zinc and lead to be heavy metals with nega-
tive potency on the environment. This effect the recommendation
and utilization of mild catalyst like ionic liquid that increase the
2.5.2. Theoretical and simulation research on PET glycolysis reaction rate, recyclable and eco-friendly. Some metallic oxides
depolymerization catalysts have been efficiently used too. Imran et al. (2013)
Some theoretical and simulation works were effectuated for PET researched on the manganese, cobalt, and zinc based mixed oxide
glycolysis depolymerization with various reagents, catalysts, and in the form of ZnO (hexagonal), metal oxide spinel (Co3O4 and
operating conditions (Raheem et al., 2018). Asakuma et al. (2010) Mn3O4), and mixed metal oxide spinel (ZnMn2O4, CoMn2O4, and
worked on the mechanism of PET polymerization using both ZnCo2O4) as novel catalysts for the PET chemical recycling. See
experimental and theoretical (numerical) data acquired from further examples in Table 6.
quantum chemistry calculations, and different alcohols were used
as solvents in the PET digestion to explore for the reaction mech- 2.5.4.2. Non-toxic metal salts (ionic liquid) catalysts.
anism. The activation energy was calculated from the optimized Metal-containing ionic liquids are effective and green catalysts
structure of the ground state and was compared with the one ob- developed to replace toxic heavy metal acetate catalysts. They are
tained through experimental data. The findings was that the evo- applicable under low temperature and pressure with no emission of
lution of rings from alkoxyl groups and carbonyl atoms at the toxic materials to the environment. Their separation from products is
transition state is highly necessary when the ester bonds of PET are by hydration (water) and filtration for re-use of the catalyst. Their
broken. Hence, smaller alcohol molecule was suggested for PET catalyzed system products separation and purification are easier than
digestion reactions than larger alcohol molecules, since they are that of organometallic systems (George and Kurian, 2014). The three
more efficiency in rings formation. available types are basic, acidic, and neutral ionic liquid catalysts.
Acidic ionic liquids are unstable at temperature above 180 C (Wang
et al., 2009). Basic ionic liquids catalysts synthesis is complex and
2.5.3. Microwave glycolysis depolymerization of PET expensive, but has good PETglycolysis depolymerization acceleration.
PET glycolysis depolymerization under microwave heating has The synthesis of neutral ionic liquids catalysts is simple and inex-
some edge over the conventional heating medium. It was observed pensive, stable even at higher temperature, not cost to procure, good
that microwave heating lower the activation energy (Ea) of the acceleration of PET glycolysis depolymerization, and most eco-
reaction, increase the rate of reaction with higher rate of reaction friendly among all of them. They are developed by incorporating
constant (k) value, and invariable lower the reaction time. Lower Ea metals on ionic liquids. Examples are promoted Cu- and Zn- acetate
of 29 kJ/mol and Arrhenius constant of 5.6 min1 reported incorporated ionic liquids such as 1-butyl-3-methylimidazolium
(Sangalang and Bartolome, 2015). The reaction time were reported acetate-promoted copper acetate (Cu(OAc)2-[Bmim][OAc]) and 1-
as 2 min, 5 min and some within the range of 20e45 min. Achilias Butyl-3-methylimidazolium acetate-promoted zinc acetate
et al. (2010) glycolysed PET with DEG under microwave irradia- (Zn(OAc)2-[Bmim][OAc]) that were used for the digestion of 100% PET
tion with total depolymerization (100%) of PET achieved at steady (Al-Sabagh et al., 2014b). Impregnation of [Bmim-Fe] [(OAc)3] on
microwave power higher than 150 W for 2 min, or 100 W for 5 min, bentonite for waste PET glycolysis was done by (Al-Sabagh et al.,
and conventional heating of 480 min with reaction rate of 0.81873 2015). A fast and effective glycolysis of PET catalyzed by poly-oxo-
min1 and 305 kJ/mol. Chen et al. (2013b) studied the PET glycolysis metalates (POMs) K6SiW11MO39 (H2O) (M ¼ Zn2þ, Mn2þ, Co2þ, Ni2þ)
under microwave irradiation kinetics using excess EG:PET (5:1), was done by Geng et al. (2015) to achieve 100% conversion of PET.
zinc acetate catalyst (1% w/w of PET), microwave power of 500 W, Some other eco-friendly catalysts already investigated for PET
196 C temperature, and 35 min reaction time to obtain 78% BHET glycolysis depolymerization are sodium carbonate (Na2CO3), sodium
yield at Ea of 36.5 kJ/mol. Diware et al. (2012) depolymerized PET bicarbonate (NaHCO3) and potassium sulfate and can better substi-
scrap in a batch reactor using glycolysis method and performed cost tute zinc acetate under the same operating conditions (Pingale and
evaluation, profitability and break-even analysis. It is used for Shukla, 2008; Lo pez-Fonseca et al., 2011). Yue et al. (2014) used 1-
feasibility study of the production technology for its commerciali- methyl-3-butyl imidazolium tri-chloride [(Bmim)]Cl3 to depoly-
zation, and break-even point estimation for the process to show merized PET as shown in Fig. 6.
adequate return on the investment for industrial significance. PET
glycolysis depolymerization was reported to be endothermic re- 2.5.4.3. Deep eutectic solvent catalyst. Wang et al. (2015b) used
action (Khoonkari et al., 2015). deep eutectic solvent [DESs] [n(urea)/n(ZnCl2)] to glycolysed PET
Table 6
Various study on glycolysis depolymerization of PET.
Reactants Reactants Ratio Catalyst/special condition Catalyst/PET (w/ Temp Press. (x Time PET Conv BHET Yield References
(w/w) w) Ratio (oC) 101325 N/m2) (min.) (%) (%)
EG/PET 4:1 TNT (Titanate Nanotubes) 0.0033 196 NA 120 100 76.7 (Lima et al., 2017)
EG/PET 4:1 Zinc acetate 0.0033 196 NA 120 100 82.6 (Lima et al., 2017)
EG/PET 4:1 Nano ZnO (55 nm) 0.0005 190 NA 80 100 90 (Alzuhairi et al., 2017)
EG/PET 10:1 (Mg-Zn)-Al layered double hydroxide 0.01 190 1 180 100 75 Eshaq and Elmetwally
(LDH) (2016)
EG/PET 4:1 n(urea)/n(ZnCl2) (eco-friendly) 0.05 170 1 30 100 83 Wang et al. (2015b)
EG/PET 4:1 Bmim2[CoCl4] 0.2 175 1 90 100 95.7 Wang et al. (2015a)
EG/PET 4:1 SiW11Zn (8 times recycling) 0.0013 185 1 30 100 84 Geng et al. (2015)
EG/PET 7:1 Zn/Al mixed oxides (1st order rxn) 0.01 196 NA 20 92.6 82 Chen et al. (2015)
EG/PET 6:1 Zn(OAc)2 0.002 208 1 150 NA 85 Aguado et al. (2014)
EG/PET 3.7:1 g e Fe2O3 (10 times re-used) 0.0005 300 10.8 60 NA >90 Bartolome et al.
(2014)
Glycol/ 6:1 Zn(OAc)2 (microwave) 0.005 190 NA 30 100 98 Chaudhary et al.
PET (2013)
EG/PET 5:1 Zn(OAc)2 (microwave 500 W) 0.01 196 NA 35 97.12 78 Chen et al. (2013b)
EG/PET 17.2:1 ZnMn2O4 (tetragonal spinel) 0.01 260 5 60 100 92.2 Imran et al. (2013)
EG/PET 5.63:1 SO42-/ZnO-TiO2 (sulfated binary oxide) 0.003 180 1 180 100 91.9 Zhu et al. (2012)
(4 x re-used)
EG/PET 2.45:1 Na2CO3 0.01 196 NA 60 75 78.8 pez-Fonseca et al.
Lo
(2011)
DEG/PET 9:1 Potassium acetate (K(OAc)2) 0.01 210 1 180 100 93.94 Raheem and Uyigue
(2010)
into BHET due to its low cost, easy preparation, low toxicity, good
biological compatibility and similar characteristics to the ionic
liquids (ILs). 100% PET conversion and 83% BHET selectivity were
achieved.
2.5.4.4. Re-generate or recoverable catalysts. These are the catalysts

that can be used, re-covered, treated, and re-used with the ability to
still perform excellently after recovery. Researchers developed some
green (eco-friendly), efficient, re-usable and economical catalysts
for PET glycolysis depolymerization. Lots of works has been done on Fig. 6. PET glycolysis mechanism in the presence of metal e containing ionic liquids
(Yue et al., 2014).
it and more are still in progress. Wang et al. (2015a) researched on
the first e row transition metal e containing ionic liquids (ILs) as
recyclable (8 times) highly active catalysts for the glycolysis of PET in
were developed to replace conventional heavy metal catalysts. g -
EG. IL catalysts such as [bmim]2 [CoCl4] and [bmim]2 [ZnCl4] (bmim -
Zeolite is found to be more active in PET depolymerization than b e
1 e butyl e 3 e methyl e imidazolium) have superior thermal sta-
Zeolite owing to its high Si/Al ratio and large mesopore surface. It
bility and display elevated catalytic activity in juxtaposition to
uses redox reactions for its PET glycolysis depolymerization cata-
traditional catalysts, conventional IL and functional ILs catalysts.
lytic action for its high surface area providing more active sites,
[bmim]2 [CoCl4] was reported to have 100% PET conversion, 81.8%
thermal stability and better crystallinity. This nanoparticle catalysts
BHET selectivity and 95.7% BHET yield. A work on the PET glycolysis
can efficiently be recovered by magnetic decantation and are re-
over Mg-Al mixed oxides catalysts derived from hydrotalcites was
usable. Shukla et al. (2008) depolymerized PET with both b e and
conducted by Chen et al. (2013a) and can be recycled three (3) times
g e zeolites (natural and environmentally safe large pore alumi-
after calcination. BHET yields were gotten to be BHET first (81.3%),
nosilicate with large void spaces) as trans-esterification catalysts,
second (64.2%), third (62.7%), and fourth (38.8%) respectively. This
and obtained pure crystalline BHET (65% yield) with little dimer
shown that three times recycling is the best for Mg-Al mixed oxides
products that is economic viable and eco-friendly process.
catalyst. These calcined Mg-Al hydrotalcites and their mixed oxides
(Bartolome et al., 2014) developed an effective super paramagnetic
catalysts are inexpensive, non-toxic, heterogeneous catalytic pro-
g-Fe2O3 nanoparticles catalyst with large surface area (average size
cess in the presence of the mixed oxides, and are potential
of 10.5 ± 1.4 nm and 147 m2/g) for PET glycolysis depolymerization.
replacement for homogeneous catalysts during glycolysis reactions.
Another calcination-able catalyst are solid catalysts of SO2 4 /ZnO,
SO2 2
4 /TiO2, and SO4 /ZnO-TiO2 that were investigated by (Zhu et al., 2.5.4.6. Other types of catalysts. Horn et al. (2012) studied mecha-
2012). Lewis base ionic liquid (1-butyl-3-methylimidazolium ace- nisms of organo-catalytic amidation and trans-esterification of ar-
tate) [Bmim][OAc] have been investigated to obtain 100% PET con- omatic esters as a model for the PET depolymerization. Organo-
version and 58.2% BHET yield with six times re-use achieved the catalyzed digestion of PET into ester and amide products were
same result. The pH before and after reaction (as important done using B3LYP functional theory. A model processes that include
parameter for Lewis base ionic liquid catalysts functionality) were the trans-esterification and amidation of methyl benzoate (MB)
8.0 and 6.5 respectively (Al-Sabagh et al., 2014a). with ethylene glycol (EG), ethylenediamine (EDA), and ethanol-
amine (EA) organo-catalyzed by 1,5,7-triazabicyclododecene (TBD)
2.5.4.5. Large surface area catalysts. Some effective large pore and and 1,8-diazabiocyclo [5.4.0] undec-7-ene (DBU). TBD as a lone
surface area, and eco-friendly catalysts such as b e and g e zeolites catalyst mechanisms was compared with TBD and DBU catalyzed
Table 7a
Merits of PET glycolysis depolymerization method.
Merits
It is the most studied depolymerization method with advantage in simplicity, flexibility, and moderate capital expenses (Sabnis et al., 2012; Park and Kim, 2014).
It requires lower quantities of polyol as depolymerization reagents that convert PET into monomers (Sabnis et al., 2012).
It has various means of recovery and purification such as:
1. Extraction with hot water (6.7 103 m3 H2O/kg of BHET ratio), followed by crystallization at 4 C.
2. Vacuum distillation of EG/H2O mixture (high percentage purity of EG > 99% can be recovered), and the obtained EG can be re-used in a new glycolysis process.
3. Two e stage evaporation systems can also be employed to separate and purify glycolysis products (BHET, Oligomers, and EG) (Raheem et al., 2018; Duque-Ingunza
et al., 2014; Goh et al., 2012).
Ability to optimize the PET depolymerization glycolysis method, increases its global efficiency, and makes it a viable economical recycling technology (Duque-Ingunza
et al., 2014).
Its product mixture of BHET and Oligomers can be used directly to produce new PET (except for food applications) (Park and Kim, 2014; Imran et al., 2013).
It requires mild reaction conditions such as temperature of value range 180e250 C and atmospheric pressure (Eshaq and Elmetwally, 2016).
The separation of glycol produced from the digestion solvent may not be necessary for resins production and some finished products. Unlike in hydrolysis and
methanolysis that co-produced glycol must be disengaged from the water and methanol respectively (Imran et al., 2010).
PET glycolysis depolymerization process can simply be integrated into a conventional PET manufacturing plant, and the reclaimed BHET can be solely or mixed with fresh
BHET and used for both DMT and TPA based PET manufacturing processes (Karayannidis and Achilias, 2007; Park and Kim, 2014).
pez-Fonseca et al., 2010; Wang
It is eco-friendly, because all the chemical used (with glycols and catalysts recycling etc.) and products are non-toxic and non-corrosive (Lo
et al., 2010).
Its products are BHET and Oligomers (dimer, trimer, tetramer etc.), that are used to manufacturing ER, UPR, vinyl ester resin (VER), polyisocyanurate foams, alkyd resins,
and polyurethanes foams with improved properties (Imran et al., 2010; Al-Sabagh et al., 2016). Hence, glycolyzate is more versatile than hydrolyzate (TPA- sublimes) in
the UPR, and other resins productions (Karayannidis and Achilias, 2007).
It has the benefit of using divergent class of cheap and effective catalysts as organo-metallic (Zn(OAc)2), eco-friendly ionic liquids (Al-Sabagh et al., 2016).
BHET as the only product can be achieved over an extensive period of time or with little dimer (Khoonkari et al., 2015)
Table 7b
Limitations of PET glycolysis depolymerization method.
Limitations
Its products, if not further purified, cannot eradicate contaminants such as catalyst residue, additives, dyes etc. associated with it (Al-Sabagh et al., 2016).
BHET obtained from PET waste glycolysis depolymerization cannot be purified by conventional method such as vacuum distillation, because polymerization may occur
(Inada and Sato, 2007).
Viability of PET glycolysis depends on the feed specifications, because the costliness of the glycolysis method is resolved by the processing of the PET flakes before
glycolysis and refining of the product to free it from contaminant. It is determined by the PET waste and its final products level of contaminants (Allen et al., 2016).
Glycolysis cannot handle low quality PET wastes to produce high quality PET suitable for food packaging without further purification (Sinha et al., 2010).
processes with supplemental molecule of amine or alcohol acting limitations of both mechanical and chemical recycling. It shows
as a co-catalyst. It was reported that blended of an organo-catalyst that extensive scope of applications can be achieved through me-
with a molecule of amine or alcohol as co-catalyst is somewhat chanical recycling. While, chemical recycling afford us the forma-
more activating than a lone catalyst. Nucleophilic attack is envis- tion of newer chemicals that serve as intermediate products for the
aged to be the rate determining step in reactions including EDA and manufacturing of value added products together with savings in
EG. TBD was instituted to be a superior catalyst than DBU in the the resources. It was shown that PET chemical recycling has expe-
amidation of MB with EDA. Organo-catalysts activates alcohols rienced different recycling methods (glycolysis, hydrolysis, meth-
readily than amines for nucleophilic attack. Activation energy was anolysis and so on), with glycolysis as the most successful one.
the same for both amidation and trans-esterification, but a ther- In this research, chemical glycolysis method of PET recycling was
modynamic amide product is favorably formed rather than ester. It critically reviewed in consideration of the degradation agents, reac-
was reported that DBU is less active than TBD in amidation re- tion process and conditions, kinetics of reactions, catalysts used,
actions, and that TBD and DBU have near catalytic activity in the products of degradations and their potential applications. It shows
esterification of methyl benzoate, and that DBU is more active in that the reaction criterion as reaction time, temperature, catalyst
the esterification of PET with EG. Also, esterification with EG shown concentration, and PET: reagent ratio have crucial effect on the
to be more favorable than amidation by EDA due to the fact that effective and efficient PET depolymerization. The impact of the reac-
catalysts activate alcohols (EG) more than amines in nucleophilic tion parameters were showing to follow the order: catalyst concen-
attack. Table 6 shown more work on it. tration > reaction temperature > reaction time. The PET conversion
increases with increment in the reaction time. The glycolysis response
2.6. Merits and limitations of glycolysis PET depolymerization was very fast in the first one hour, with only BHET and its dimer
method remain in the products after two hours. Total depolymerization was
achieved at three hours with the aids of some catalysts. Reaction time
Glycolysis method has some benefits as well as drawbacks over of many hours can be reduced to few minutes through microwave
the other methods during PET depolymerization process. These are heating. High temperature and Excess reagent (diol) favors glycolysis
presented in Table 7a,b. PET depolymerization. Kinetic has shown the order of PET glycolysis
depolymerization to be first to PET and second to EG.
The review of authors works provide us with wide choice of
3. Conclusion catalysts from organo-metallic ones, with zinc acetate as the most
proficient, to eco-friendly ones like sodium carbonate, up to the
Sequence to solve the environmental impacts arising from the present ionic liquid catalysts. It shows the basis of choosing a
PET plastic wastes and shows the current evolution trend of new catalyst on its ability to accelerate up the reaction rate,
products from recycled PET. This work shows the merits and
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Current Developments in Chemical Recycling of Post-Consumer Polyethylene

Article in Journal of Cleaner Production · April 2019

Ademola Bolanle Raheem Zainura Zainon Noor

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Contents lists available at ScienceDirect

Journal of Cleaner Production

Current developments in chemical recycling of post-consumer

List of acronyms AD Azo-dyestuffs

1. Introduction monomer, oligomers, intermediates and ﬁnished products in

Properties Uses Recycling Necessitation

Light weight. Packaging. Ecological reasons.

Criteria Landﬁll Incineration Re-use Recycling

Space management Not better better better better

PET Chemical Recycling

PET Mechanical Recycling

2.2. Hydrolysis method of PET recycling

Functional ester group of the PET bottles or waste is hydrolyzed

Process Reagents Operating Conditions Primary Products Secondary Products

parameters has been outlined by Sinha et al. (2010). Primary

2.4. Ammonolysis method of PET recycling

Fig. 3. PET hydrolysis reaction reference in the paper.

2.5.4.4. Re-generate or recoverable catalysts. These are the catalysts

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