C H A P T E R
12
PET depolymerization: a novel process for
plastic waste chemical recycling
Maurizio Crippaa,*, Barbara Moricob
a
gr3n SAGL, Lugano, Switzerland; bNextChem srl, L’Aquila, Italy
* Corresponding author. e-mail address: Maurizio.crippa@gr3n-recycling.com
1. Introduction to PET
Polyethylene terephthalate (PET or PETE) is a
member of the polyester family of polymers. PET
consists of polymerized units of the monomer
ethylene terephthalate, with repeating units
C10H8O4: Fig. 12.1 illustrates the repeating unit
of the PET molecule.
PET is a thermoplastic resin, and because of
its transparency, resistance, and gas barrier
properties, it is particularly suitable for the pro-
duction of bottles for carbonated beverages.
The main PET applications are bottles, films,
tubes, trays and blisters, containers, labels, etc.
PET can exist in the amorphous, partially and
highly crystalline state. Under the influence of
direct modifying additives, it can develop its
crystallinity after thermal treatment.
Originally patented and exploited by DuPont
Chemical Company during the research of new
polymers for the formation of fibers, nowadays
PET represents more than 50% of the world
production of synthetic fibers. PET is used
alone or mixed with cotton or wool to give the fi-
bers better washing, wear, and crease-resistance
Catalysis, Green Chemistry and Sustainable Energy
https://doi.org/10.1016/B978-0-444-64337-7.00012-4
properties. At the end of the 1950s, PET was
developed as a film. It was initially used for
video, photographic, and radiographic films, as
well as for use in packaging with flexible fea-
tures. Later, PET was modified for use in injec-
tion molded and extruded articles, mainly
reinforced with fiberglass. In the early 1970s,
PET was stretched through blowing techniques
that produced the first three-dimensionally ori-
ented structures that initiated the rapid exploita-
tion of PET for light, durable, and indestructible
bottles.
PET may be produced from monoethylene
glycol (MEG) and either terephthalic acid (TA)
or dimethyl terephthalate (DMT). The first path
is an esterification of TA with MEG, both derived
from crude oil, with elimination of water. In
chemical terms, ethylene glycol is a diol, an
alcohol with a molecular structure that contains
two hydroxyl (OH) groups, and TA is a dicar-
boxylic aromatic acid, an acid with a molecular
structure that contains a large, six-sided carbon
(or aromatic) ring and two carboxyl (CO2H)
groups. Under the influence of heat and cata-
lysts, the hydroxyl and carboxyl groups react
215 Copyright © 2019 Elsevier B.V. All rights reserved.
216 12. PET depolymerization: a novel process for plastic waste chemical recycling
FIGURE 12.1
to form ester (COeO) groups, which serve as the
chemical links joining multiple PET units
together into long-chain polymers. The overall
reaction can be represented as follows (Fig. 12.2):
As an alternative, a transesterification reac-
tion allows starting from the apparently more
easily purifiable DMT, rather than from TA, to
produce PET. In this case, methanol is eliminated
instead of water.
The extent of polymerization reaction,
apparent from the molecular weight of the poly-
mer, is a function of the polymerization condi-
tions and significantly affects the properties of
the resin that is produced. The polymerization re-
action product is a molten, viscous mass that can
be spun directly to fibers or solidified for later
processing as a thermoplastic material.
FIGURE 12.2
IV. Selected examples and case history
Repeating unit of the PET molecule.
Some changes in the chemical composition
can be introduced to develop specific properties
for various packaging applications and to adapt
the polymer to particular production equipment.
Usually the modifications are of a chemical na-
ture to facilitate the manipulation of the PET
among different crystalline forms. For example,
small concentrations of an appropriate como-
nomer such as isophthalic acid (IPA) or
1,4-cyclohexane-dimethanol reduce the rate of
crystallization and allow the production of
sheets and films of thicker bottles.
Once the polymer is formed, it is very difficult
to be purified, and for this reason the purity of
the starting materials is a key factor. The vacuum
distillation processes easily purify the ethylene
glycol, while the TA is purified by repeated
Overall reaction for PET production.
 2. The PET value chain
crystallization. High purity and high molecular
weight materials are needed for food packaging
applications.
The catalysts that are used in the polymeriza-
tion process are used in extremely low concen-
trations to promote reactions and ensure a
practical economic return. The most common
catalyst is antimony trioxide, but titanium,
germanium, cobalt, manganese, magnesium,
and zinc salts are also used, and small amounts
remain encapsulated in the polymeric matrix or
in the polymer chain itself.
The presence of the aromatic ring in the PET
repeating units gives the polymer notable stiff-
ness and strength, especially when the polymer
chains are aligned with each other in an orderly
arrangement. The crystallization typically occurs
when the material is stretched during the object
production. In this semicrystalline form, PET is
made into a high-strength textile fiber marketed
under such trademarked names as Dacron, by
the American DuPont Company, and Terylene,
by the British Imperial Chemical Industries
PLC. The stiffness of PET fibers makes them
highly resistant to deformation, so they impart
excellent resistance to wrinkling in fabrics.
They are often used in durable-press blends
with other fibers such as rayon, wool, and cot-
ton, reinforcing the inherent properties of those
fibers while contributing to the ability of the fab-
ric to recover from wrinkling.
PET is also made into fiber filler in insulated
clothing, for furniture and pillows. When PET
is yarned in very fine filaments, it is used as arti-
ficial silk; otherwise, if the yarning is in large-
diameter filaments, it is used for carpets. Among
the industrial applications of PET are automobile
tire yarns, conveyor belts, and drive belts, rein-
forcement for fire and garden hoses, seat belts
(an application in which it has largely replaced
nylon), nonwoven fabrics for stabilizing
drainage ditches, culverts, and railroad beds,
and nonwovens for use as diaper top sheets
IV. Selected examples and case history
217
and disposable medical garments. PET is the
most important of the man-made fibers in
weight produced and in value.
2. The PET value chain
The great growth in the use of PET bottles has
generated worldwide interest in the recycling
and reuse of flakes of recycled PET (R-PET).
Especially PET bottles are almost worldwide
collected, sorted from other polymers, ground
and repeatedly washed to obtain clean R-PET
flakes useful for other applications. R-PET flakes
maintain transparency, even if they are not
completely translucent like virgin PET. Further-
more, it has excellent possibilities of use in the
textile sector and, mixed with virgin polymer,
is used for the production of new transparent
containers for detergents and occasionally for
new food bottles.
The value chain of PET is quite complex. It
consists of several steps that are linked in
cross-sectorial interactions involving multiple
companies across the European and worldwide
market.
The following picture gives an example of a
quantified PET value chain (Fig. 12.3):
Global virgin PET production for 2015 was 72
million tons, of which 48 million tons was amor-
phous PET used for fiber applications, 20 million
tons was solid-state PET used for packaging ap-
plications, and 4 million tons was used for film
(for a total of 24 million of tons). Note that addi-
tional postconsumer recycled inputs contribute
to the total production of PET fibers and bottles
[1].
The average life of PET packaging is 0.5 years,
whereas the average life of PET fibers is 5 years.
Each year, about 33 million PET fibers are
disposed and only a small part (lower than 0.1
million tons) are recycled. On the other hand,
218 12. PET depolymerization: a novel process for plastic waste chemical recycling
FIGURE 12.3
23 million tons of PET from bottles are disposed:
9 million tons are recycled, and the leftover land-
filled or incinerated. The PET packaging and fi-
bers recycled are used to produce new bottles
(3 million tons) or new fibers (6 million tons).
On a microscopic point of view, the main part
of produced PET is still landfilled or incinerated
[2].
Unlike other materials (i.e., aluminum or
glass), PET is reused and not recycled. Each
time that PET is reused the quality of the poly-
mer degrades, inevitably leading to dispersion
in the environment, landfill, or combustion for
energy generation. The PET value chain is not
closed: in fact, mechanical recycling is limited
by the compatibility between the different types
of polymers when mixed, as well as by the fact
that the presence of small amounts of a given
polymer dispersed in a matrix of a second poly-
mer may dramatically change the properties of
the latter, hindering its possible use in conven-
tional applications. For example, the presence
of low amounts of PVC in recycled PET strongly
reduces the commercial value of the latter, due to
the possible release of HCl during the PET
reprocessing. This problem is enhanced by the
IV. Selected examples and case history
PET value chain.
fact that PVC and PET are difficult to separate
from other plastic wastes.
Another difficulty with mechanical recycling
is the presence in plastic wastes of products
made of the same resin but with different colors,
which usually impart an undesirable gray color
to the recycled plastic [3,4].
If colored PET is collected and sorted together,
these numerous colored containers will require
extra sorting in PET recycling plants. For recy-
clers to sell the colored fraction, the material
would have to be tinted in black or gray, but
no market currently exists for such a material
in high quantities [5].
In addition, most polymers suffer a certain
degradation during their use due to the effect
of a number of factors such as temperature, ul-
traviolet radiation, oxygen, and ozone. This
degradation leads to a progressive reduction in
length and to a partial oxidation of the polymer
chains. Therefore, recycled polymers usually
exhibit lower properties and performance than
the virgin material and are useful only for unde-
manding applications.
Recycling plastics without prior separation by
resin produces a material with mechanical

properties similar to timber, so it is often used for
the replacement of timber in certain applications.
A higher quality of recycled plastics is achieved
when separation by resin is carried out prior to
the remolding step. However, even in this case,
unless a food-contact process for recycled plas-
tics is not adopted, R-PET cannot be used in
food containers, unless direct contact with the
food can be avoided [4].
An alternative developed in recent years for
promoting the use of recycled plastics has been
the preparation of containers with a three-layer
wall. The middle layer is the thickest and is
made of recycled polymer, whereas the thinner
external and internal layers are made of virgin
material. With this approach, direct contact be-
tween the recycled polymer and both the con-
sumer and the product in the container is
avoided [4].
The minimum requirements for PET flakes to
undergo mechanical recycling are listed in
Table 12.1 [6].
Another path for PET recycle/reuse is the so-
called feedstock recycling, which is also known
as a chemical or tertiary process. It is based on
the decomposition of polymers by means of
TABLE 12.1 Minimum requirements of PET flakes
to undergo mechanical recycling [6].
Property
Flake size
Melting temperature
Viscosity (h)
Water content
Dye content
PVC content
Polyolefin content
Metal content
Yellowing index a
a
Yellowing index is a measure of the tendency of polymers to turn yellow
through photodegradation.
IV. Selected examples and case history
2. The PET value chain 219
heat, chemical agents, and catalysts to yield a va-
riety of products ranging from the starting
monomers to mixtures of compounds, mainly
hydrocarbons, with possible applications as a
source of chemicals or fuels. The products
derived from the plastic decomposition exhibit
properties and quality similar to those of their
counterparts prepared by conventional methods.
Some applied methods are these:
• chemical depolymerization by reaction with
certain agents to yield the starting monomers;
• gasification with oxygen and/or steam to
produce synthesis gas;
• thermal decomposition of the polymers by
heating in an inert atmosphere;
• catalytic cracking and reforming, where the
polymer chains are broken down by the effect
of a catalyst, which promotes cleavage
reactions;
• hydrogenation, where the polymer is
degraded by the combined actions of heat,
hydrogen, and in many cases, catalysts.
At present, feedstock recycling is limited by
the process economy rather than by technical
reasons. Three main factors determine the profit-
ability of these alternatives: the degree of separa-
tion required in the raw wastes, the value of the
products obtained, and the capital investment in
the processing facilities. In most of these
Requirement methods, some pretreatments and separation
0.4e8 mm operations must be carried out on the plastic
wastes prior to feedstock recycling, which results
>240
C
in an increase in recycling costs. According to the
>0.7 dL/g separation steps required, the different methods
<0.02% of feedstock recycling can be ordered as follows:
gasification < thermal treatments < hydrogena-
<10 ppm
tion < catalytic cracking < chemical depolymer-
<50 ppm ization [4].
<10 ppm Many of the projects on chemical recycling of
waste plastics have failed in the past due to the
<3 ppm
relatively low price of the derived products. In
<20 recent years, there has been a trend toward the
production of added value compounds such as
olefinic gases, paraffins, activated carbons, etc.
220 12. PET depolymerization: a novel process for plastic waste chemical recycling
2.1 Chemical recycling
In addition to disposal through a mechanical
process, a chemical attack can be used. Chemical
recycling consists of the depolymerization of
polymeric scraps transforming the PET back to
the initial raw material. The depolymerization
can be carried out through different processes,
which will be deepened in the following para-
graphs. All these processes are advantageous
from the economic point of view only in the
case in which the disposal concerns large quanti-
ties of polyester. However, the result is satisfac-
tory since it returns a product of excellent
quality and not depreciated. If recycling is not
possible, the PET is deposited in the landfill.
Given its chemical inertia, it remains sterile and
inert and therefore safe from the point of view
of pollution; furthermore, it does not release
any steam into the air or harmful substances to
the groundwater. However, precisely for these
reasons, there is an irreversible accumulation.
A further solution is represented by thermal re-
covery: PET is completely eliminated with the
sole emission of carbon dioxide and water. It
also has a good calorific value and is suitable
for energy production.
Chemical depolymerization of polyesters has
been mainly applied to PET, the most common
polyester on the market. Chemolysis of PET by
a variety of methods has been known for many
years. In fact, the chemical depolymerization of
PET can be considered the starting point of plas-
tic chemical recycling.
Different PET chemolysis methods have been
developed aimed at the production of TA, MEG,
dimethyl terephthalate or bis(hydroxyethyl)
terephthalate (BHET), all of them being possible
monomers for the reconstruction of fresh polyes-
ters. The exact monomer formed by PET depoly-
merization depends on the type of chemical
agent used to break down the polymeric chains.
In certain processes, the final product of PET che-
molysis is a mixture of polyols, useful in the
formulation of other polymers such as
IV. Selected examples and case history
unsaturated polyesters, polyurethanes, and pol-
yisocyanurates. This is an interesting case of
chemical recycling because the breakdown of
one polymer leads to the raw materials for the
preparation of a quite different class of plastics.
Depending on the depolymerization agent, poly-
ester chemolysis methods have been classified as
follows: glycolysis, methanolysis, hydrolysis,
ammonolysis, aminolysis, and combined pro-
cesses. All these PET degradation alternatives
are reviewed in the following sections.
2.2 Glycolysis
Glycolysis is the simplest and oldest method
of PET depolymerization. The first patents on
PET glycolysis were filed more than 30 years
ago. The method involves the reaction of PET,
under pressure and at temperatures in the range
180e240
C, with an excess of glycol, usually
ethylene glycol, which promotes the formation
of BHET. This monomer has to be purified, nor-
mally by melt filtration under pressure, prior to
its use in the production of new PET polymer.
Colors present in the starting PET wastes are
not usually or at least hardly removed by glycol-
ysis method. The depolymerization is carried out
in the presence of a transesterification catalyst,
usually zinc or lithium acetate.
Because the reaction rate is proportional to the
polymer surface area, it is advisable to first
reduce the size of the raw PET waste to small
particles by grinding, cutting, etc.
2.3 Methanolysis
PET methanolysis is based on the treatment of
PET with methanol at relatively high tempera-
tures (180e280
C) and pressures (20e40 atm),
which leads to the formation of dimethyl tere-
phthalate and ethylene glycol as the main
products.
The reaction proceeds usually in the presence
of typical transesterification catalysts, the most
 2. The PET value chain
widely used being zinc acetate. Other catalysts
employed in PET methanolysis are magnesium
acetate, cobalt acetate, and lead dioxide. Origi-
nally, PET methanolysis was developed by PET
manufacturers as a process aimed at the recov-
ery and treatment of polyester wastes generated
during the production cycle to increase the poly-
ester yield. However, with the increase in envi-
ronmental public concern, methanolysis began
to be considered a feasible alternative for the
recycling of PET residues present in the solid
waste stream.
The products of the methanolysis are usually
separated and purified by distillation or crystal-
lization. Purified DMT can be reintroduced into
the PET polymerization process with properties
similar to those of virgin DMT.
Compared to BHET, the monomer obtained
by PET glycolysis, DMT is produced by metha-
nolysis with a higher purity in regard to physical
contaminants. Nevertheless, some organic impu-
rities cannot be completely removed, which may
cause some poor color.
A number of methods for PET methanolysis
have been described in the patent literature,
operating under both batch and continuous con-
ditions. One of the major problems with the
continuous process is the difficulty of intro-
ducing the solid polyester wastes into the meth-
anolysis reactor working under high pressure.
For this reason, methanolysis often takes place
in batch systems, with all the problems and lim-
itations associated with batch operation.
Recently, PET methanolysis has been carried
out with supercritical methanol at a temperature
of 300
C and pressure above 80 atm. Under
these conditions, PET decomposition was much
faster than when using liquid methanol, leading
to the production of DMT and some oligomers.
2.4 Hydrolysis
Reaction of PET with water allows the poly-
ester chains to be broken down into TA and
IV. Selected examples and case history
221
MEG. The process can be carried out under
neutral, acidic, or basic conditions. A crucial
aspect of this chemical recycling method is the pu-
rity and properties of the obtained TA to achieve
the specifications normally required for direct
esterification to produce fresh PET polymer. TA
is usually purified by crystallization from solvents
such as acetic acid, whereas a variety of proce-
dures have been reported to remove the different
impurities present in the hydrolysis product.
Several patents have been filed dealing with
the acid hydrolysis of PET by reaction with
concentrated sulfuric acid (>14.5 M). The pro-
cess takes place at temperatures between 25
and 100
C with a duration of just a few minutes
at atmospheric pressure. The hydrolysis product
is treated with sodium hydroxide to neutralize
the TA produced, which causes the formation
of the corresponding TA sodium salt, which is
soluble in water. The solution obtained is usually
of a dark color, but this can be removed by ion-
exchange columns. In the final stage of the pro-
cess, the resulting solution is again acidified to
reprecipitate TA, which is obtained with a purity
>99%. One of the major drawbacks of this pro-
cess is the corrosion induced by the reaction
mixture and the formation of large amounts of
liquid wastes, containing inorganic salts and sul-
furic acid, which must be disposed of.
The alkaline hydrolysis of PET involves treat-
ing the polyester with an aqueous solution of so-
dium hydroxide (4e20 wt%) under pressure at
temperatures between 200 and 250
C for periods
of several hours. Under these conditions the so-
dium salt of TA is formed, and by acidification,
TA is recovered from the solution as a precipitate.
A promising PET chemolysis method is
neutral hydrolysis based on treatment with
liquid water or steam. In contrast with the acid
and alkaline hydrolysis, PET is degraded
without the formation of unwanted liquid efflu-
ents containing inorganic salts. Moreover,
although some decrease in the pH occurs due
to TA formation, the reaction system is not corro-
sive, so standard materials can be used in the
222 12. PET depolymerization: a novel process for plastic waste chemical recycling
apparatus. Neutral hydrolysis is usually per-
formed under pressure (10e40 atm) at tempera-
tures in the range 200e280
C. Alkali metal
acetates are typically used as catalysts to pro-
mote PET hydrolysis. The reaction proceeds
more slowly than the acid hydrolysis, several
hours being required to achieve high PET con-
versions. When the hydrolysis is carried out
with steam, the steam acts as a major source of
heat for the hydrolysis zone; it stirs up the waste
material, accelerating the hydrolysis reaction,
and its partial condensation provides the liquid
water necessary for the reaction.
3. DEMETO: a new route for PET
chemical depolymerization
DEMETO technology is based on an interna-
tionally patented technology owned by a
start-up company, Gr3n: it foresees to bring at
the industrial level (through a completely func-
tional pilot plant) the usage of microwaves as pro-
cess intensification approach (through an
electromagnetic promoting effect) of the well-
known alkaline hydrolysis depolymerization
FIGURE 12.4
IV. Selected examples and case history
reaction. Such a reaction was, up to now, econom-
ically unfeasible due to a certain number of tech-
nologic constraints that DEMETO finally solves.
DEMETO started in 2010e11 in a lab scale
experimentation aimed at proof of concept of
the technology to be applied for PET depolymer-
ization. The depolymerization reaction, improved
by microwaves, was tested in batch. During the
years 2012e14 the process was tested in a contin-
uous manner, and a first arrangement on the mi-
crowave reactor was developed. During the
following 3 years, the project was partially
funded by the European Commission (EU),
through the project SYMBIOPTIMA: a contin-
uous microwave reactor, having a capacity of
10 kg/h was realized and successfully operated.
In the same period, the DEMETO project was
lunched and, in 2017, was granted by the EU
more than 9 million euros. The route from lab to
DEMETO is shown in Fig. 12.4.
The DEMETO project is mainly focused on the
construction and management of a pilot plant
having a capacity of 60 kg/h of inlet PET. The
plant is under construction and is installed in
an industrial site in the center of Italy, inside
the facilities of NextChem.
From lab to DEMETO.
 3. DEMETO: a new route for PET chemical depolymerization 223

3.1 The DEMETO technology
DEMETO is based on a chemical route for
PET recycling and, particularly, on the alkaline
hydrolysis of PET. The depolymerization reac-
tion at the base of the technology is as follows
(Fig. 12.5):
According to the stoichiometry of the reac-
tion, 1 mol of PET repeating unit produces
1 mol of the intermediate sodium terephthalate
and 1 mol of ethylene glycol. Sodium tere-
phthalate is converted in 1 mol of TA. Sodium
hydroxide is added in excess with respect to
the stoichiometric value, and hydrochloric acid
is added to keep the pH of the solution low
enough to have the precipitation of the insoluble
TA. Sodium chloride is obtained as by-product
of the overall process.
The alkaline depolymerization reaction is
assisted by microwave radiation: heating by mi-
crowave irradiation, compared with conventional
thermal heating, provides some advantages such
as rapid heating with high specificity without
contact with material and shorter reaction times.
The reaction is carried out at high pressure
and high temperature, and it has been demon-
strated that the conversion of PET is complete.
Results from lab scale and prepilot scale tests
have been compared with data coming from
literature [7]: some authors refer to processes car-
ried out at high temperature (200e250
C) and
pressure (1.4e2 MPa). The use of microwave
irradiation for PET depolymerization by alkaline
hydrolysis provides a significant reduction in re-
action time (less than 30 min) compared with the
conventional heating methods. Depolymeriza-
tion of PET waste was complete and TA yield
reached more than 98%.
DEMETO technology claims a reaction time of
10 min to complete the depolymerization of PET
flakes even if the process is carried out at lower
pressure and temperature with respect to similar

FIGURE 12.5 DEMETO chemical recycling route.

IV. Selected examples and case history

224 12. PET depolymerization: a novel process for plastic waste chemical recycling
literature data. The inlet stream to the DEMETO
depolymerization process is PET flakes, powder,
or fibers. As an example, the characteristics of
the flakes are illustrated in the following table
(Table 12.2).
The bigger concern related to PET chemical
recycling is the presence of contaminants that
can be found in the waste mixed with the flakes.
Contaminants derive from the PET production
and manufacturing processes and can be divided
into various categories, as follows.
PVC/polyolefine: Polymers other than PET
can be present as contaminants in the flakes.
They mainly derive from bottle caps and rings
that are generally made of PP or PE. Regarding
PVC, there are PVC bottles that resemble PET
bottles. PVC is used to produce safety seals on
PET bottles (such as mouthwash bottles) that
need to be removed before PET reuse/recycle.
PVC is also used as liners inside bottle caps
and closures. While this is no longer being
used in the United States, occasional bottles
with PVC liners will occasionally appear. It is
also possible to find PVC derived from labels
wrapped around the PET bottles. Polyolefines
are easily removed by flotation from the inlet
streams, and if the removal process is not perfect
the chemical inertness at the alkaline conditions
TABLE 12.2 Characteristics of PET flakes [8].
Characteristics Value
Crystallized PET flakes Min 0.6 to max 8 mm
Residual water Max 0.6%
Intrinsic water Min 0.70 dL/g
Real PET flakes density 1.35e1.38 g/cm3
Apparent PET flakes density 0.65e0.70 g/cm3
PVC contaminant Max 30 ppm
Polyolefine contamination Max 10 ppm
Metal contamination Max 10 ppm
Other contamination Max 10 ppm
IV. Selected examples and case history
is easy removed after the depolymerization of
the PET. PVC, if exposed to severe conditions
in terms of pressure and temperature, can release
chlorine or hydrochloric acid. Another concern is
related to the different melting points of polyole-
fine/PVC and PET: the purification process can
be affected by the presence of other polymers
during the cooling of the process stream in
which they can solidify and cause fouling and
obstruction of equipment.
Metals: In general, recycled PET includes
various metal catalyst residues that can be used
for the PET manufacturing process, as summa-
rized in Table 12.3 [9]. These metal ions, which
promote transesterification and polycondensa-
tion reactions, lead to chemical heterogeneity of
the recycled PET that affects the melt rheological
behavior.
Colorants: these components are added to the
polymers to give a color to the PET final product.
They can be used in form of dyes or pigment. To
produce colored packaging, colorants in low
concentrations (usually less than 500 ppm) are
generally added at either the resin or the
container manufacturing stage. Colorants can
be organic as well as inorganic type. The
Table 12.4 gives a list of some colorants usually
used for PET.
TABLE 12.3 Various metal ions in recycled PET and
their origins.
Metal Concentration
ions (ppm) Origin
Sb 220e240 Polycondensation catalyst
Co 50e100 Polycondensation catalyst
Mn 20e60 Transesterification catalyst
Ti 0e80 Polycondensation catalyst
Fe 0e6 Incorporated during
washing
Na, Mg, Si e Food additives
Antimony oxide remains the most common in current use.
 3. DEMETO: a new route for PET chemical depolymerization 225
TABLE 12.4 Examples of colorants applied in PET 3.2 The DEMETO process description
industry.
The process for the depolymerization of PET
Name CAS Notes can be considered structured in two parts, the re-
Carbon Black 98615-67-9 pigment action and the purification of the monomers.
Here follows a description of each section.
Blue 104 116-75-6 soluble
Green 7 1328-53-6 pigment
Brown 24 68168-90-3 pigment
3.2.1 Reaction
The reaction is carried out in a new concept
tubular reactor. More tubes are arranged inside
a reactive unit to satisfy the capacity of the plant.
Many of the most durable pigments consist of Each tube is provided with an Archimedean
metallic oxides, such as titanium dioxide. These screw moving inside a microwave field. Micro-
offer properties such as heat stability, light stabil- waves are used to preheat the reaction mixture
ity, chemical inertness, lack of bleeding and and to promote the reaction. Each tube is fed
migration, desired electrical characteristics, and by a mixture of PET, sodium hydroxide, and
low absorption. Zinc oxide can be used too. ethylene glycol pressurized at the pressure level
Typical properties of titanium dioxide and zinc of the reaction. A microscopic material balance
oxide are as follows [10] (Table 12.5). around the reactor allows that for 1 kg/h of
Titanium oxide must be completely removed PET entering the tube, about 0.5 kg/h of sodium
during the depolymerization reaction as the hydroxide and 5 kg/h of ethylene glycol are
monomers to be recovered must be pure and added. The reactive environment has no effect
comparable with conventional ones. The on contaminants (colorants, titanium oxide,
removal of titanium dioxide is a critical step metals) that go across the reactor unmodified.
due to the low dimension of the crystals of the The mixture coming from the reactive unit is
oxide (in general, bigger than 0.2 m). Titanium therefore composed of sodium terephthalate,
oxide in r-PET gives the polymer a certain level water, ethylene glycol, and sodium hydroxide
of opacity, degrading the characteristics of the (the excess with respect to the stochiometric
recycled monomer products. requirement). It appears as a viscous slurry,
brown in color, to be cooled down before further
treatment.
TABLE 12.5 Properties of titanium dioxide and zinc
oxide.
3.2.2 Purification section
Titanium oxide Zinc oxide The stream coming from the reactor must be
Property Anatase Rutile processed to recover the monomers with a very
high purity. The purity to be reached is equal
Average particle size (m) 0.3 0.2e0.3 0.2 to that of the corresponding monomers pro-
Density (g/cm )3
3.9 4.1 5.6 duced by crude oil. So, the following table shows
Refractive index 2.55 2.76 2.01
the characteristics of ethylene glycol and TA to
be produced [11] (Tables 12.6 and 12.7).
Tinting strength 1200 1600 210 The first operation is the recovery of sodium
Oil absorption (lb/100 lb) 18e30 16e48 10e25 terephthalate from reaction slurry, and this is car-
Hardness (Mohs) 5e6 6e7 4þ
ried out by a solid separation system. The solid
has a residual moisture of about 45%e50% and

IV. Selected examples and case history

226 12. PET depolymerization: a novel process for plastic waste chemical recycling

TABLE 12.6 Characteristics of ethylene glycol.

No. Parameter UAB “NEOGROUP” specification Testing method (standard)

1. Appearance Transparent, colorless liquid WN-B005-0465D
2. Acid number, mg KOH/g 0.03 WN-B010-1046D
3. Chlorides content, ppm 2 WN-B010-1011D
4. Sulfates content, ppm 20 WN-B010-1017D

5. Water content, wt.% 0.1 WN-B010-1065D

UV transition
6. 220 nm, % 70 WN-B010-1151D
250 nm, % 90
275 nm, % 95
7. DEG content, % 0.05 WN-B010-1020D

8. AA, ppm 10 WN-B010-7144D

9. Index “APHA” 5 WN-B010-1052D
10. Ash content, ppm 10 WN-B010-1014D
11. Fe content, ppm 0.2 WN-B010-1055D
12. Index “APHA” is a 4 h boiling (index) 20

must be dried to reduce the contaminants
entrainment. The solid is then treated with hy-
drochloric acid to produce TA, which is very
insoluble in water, and then can be easily sepa-
rated and recovered. The next crystallization sec-
tion allows one to obtain pure TA with the
correct size distribution (the same of the commer-
cial TA). Ethylene glycol, which comes from the
liquid recovered from the first solid separation,
is purified by distillation. The distillation is car-
ried out in two steps, under vacuum to avoid
the glycol deterioration. A part of contaminants
(mainly colorants) are recovered and wasted
from the bottom of the second column.
From 1 kg/h entering the reactive unit, it is
possible to produce about 0.8 kg/h of pure TA
and 0.3 kg/h of ethylene glycol.
After monomers recovery and purification, a
stream mainly composed by brine is recovered.
Brine can be used in a chloro-alkali system to
produce hydrochloric acid and sodium hydrox-
ide, which are required by the depolymerization
and purification process. In this way the process
can be considered self-consistent. From 1 kg/h
of PET entering the reactor, about 0.6 kg/h of so-
dium chloride is generated.
The brine is fed to the electrolyzer, where it re-
acts producing caustic soda, chlorine, and
hydrogen according to the reaction:
1 1
NaCl þ H2 O/ Cl2 þ H2 þ NaOH
2 2
Finally, hydrogen is burnt with chlorine in a
dedicated oven to produce hydrochloric acid
through the reaction:
1 1
Cl2 þ H2 /HCl
2 2

IV. Selected examples and case history

 3. DEMETO: a new route for PET chemical depolymerization 227
TABLE 12.7 Characteristics of terephthalic acid.

UAB “NEOGROUP”
No. Parameter specification Testing method (standard)

1. Acid number, mg KOH/g 674  3 WN-B010-1027D

2. 4-CBA, ppm 25 WN-B010-1048D
3. Moisture, wt.% 0.2 WN-B010-1028D
4. Index “APHA” 10 WN-B010-1030D
5. p-Toluic acid, ppm 150 WN-B010-1148D

6. Ash content, ppm 15 WN-B010-1033D

7. Fe content, ppm 2 WN-B010-1097D
8. Color “b”” 2.5 WN-B010-1144D
9. Benzoic acid, ppm 100
10. Total heavy metals (Mo, Cr, Ni, Fe, Ti, Mn, Co), ppm 10

11. Share of undissolved materials in ammonia, ppm 10

25
e
12. Particle size, % 20 WN-B010-1035D

5
0

Chlor-alkali unit is a well-known and well- 3.2.3 Contaminants removal

established plant, running for more than a cen-
tury, whose continuous evolution led to new
and more advanced solutions, especially for
what concerns the cells, starting from mercury
cells, going to diaphragm cells, and now with
membrane cells. Plant architecture is almost
fixed, because it has been optimized in years
of operation. The main contaminant levels in
the feed for a membrane cell are listed in
Table 12.8 [12].
To treat the brine coming from the depoly-
merization process, a brine purification step
is required to reduce the contaminants to the
levels indicated in the table. Contaminants
are removed along the purification process
and upstream of the chlor-alkali package.
Contaminants (colorants, titanium oxide,
metals) are removed across the purification
step. Colorants are recovered by filtration on
an activated carbon bed. Two activated carbon
filters are used along the process to eliminate col-
orants in the main streams of the process.
Titanium oxide is eliminated by filtration: the
cut-off of the used filter is 0.2 mm because this is
the threshold under which titanium losses its
opacity properties.
Metals, mainly antimonium, is not a big issue
for DEMETO technology, as its concentration
along the treatment is very low (under 10 ppm).
Brine coming from the depolymerization pro-
cess is further treated to reduce the contaminants

IV. Selected examples and case history

228 12. PET depolymerization: a novel process for plastic waste chemical recycling

TABLE 12.8 Maximum contaminant levels in brine.

Contaminants Allowable level

Calcium and magnesium <20 ppb as calcium

Na2SO4 <7.0 g/L
Sr <0.4 ppm (if SiO2 ˂5.0 ppm)

<0.02 ppm (if SiO2 ¼ 15 ppm)

SiO2 <5.0 ppm
Ba <0.5 ppm (if I ¼ 0.20 ppm)
<1.0 ppm (if I ¼ 0.10 ppm)
<0.05 ppm (if I ¼ 0.50 ppm)
I <0.20 ppm

Chlorates <14.0 g/l as ClO

3

Fe <0.1 ppm
Ni <0.1 ppm
Al <0.10 ppm
Br <30 ppm
Cr <1.0 ppm

F <1.0 ppm
Hg <0.2 ppm
TOC (total organic carbon) <10 ppm
Total heavy metals <0.30 ppm as Pb
Total suspended solid 99% light transmittance as referred to distilled water

Membranes designed for the production of chlorine and caustic soda through electrolysis of NaCl pure brine are
composite thin polymer films reinforced with a fabric made of Teflon. Membranes have sulfonate and carboxylate
polymer layers with surface modifications to enhance gas release from the membrane. To give optimum
performance, membranes require a pure brine having impurities in full accordance with the table.

that can act as poison for the electrolytic mem-
brane cell. An activated carbon filter and a
chelating resin tower are used for this purpose.
4. Conclusions and future trends
The chemical recycle of PET is a very impor-
tant challenge for the future. Nowadays a big
effort is dedicated to the development of a
sustainable process that allows the complete re-
covery of PET from fibers or packaging.
DEMETO will contribute to the demonstration
of a new route for the recovery of monomers
and the production of new virgin “PET” having
the same characteristics of the original. The pilot
plant will demonstrate the concept at the base of
DEMETO and will constitute the base for the
scale-up of the process on industrial scale. Data
coming from pilot plant experimental phase

IV. Selected examples and case history

 Further reading 229
will be used to verify energy consumption and [2] M. Bertele, A Business Model for Successful Commer-
techno-economic feasibility of the process on an cial Deployment. Brussels, 2017.
[3] S. Hulse, Plastic Product Recycling. A Rapra Industry
industrial scale. The business plan, built on Analysis Report, 2000.
data coming from the pilot plant, will give the in- [4] J. Aguado, D. Serrano, Feedstock Recycling of Plastic
struments to develop a business model to be Watstes, 1999.
applied in the industrial development phase. [5] https://www.recyclingtoday.com/article/pre-
europe-plastics-hdpe-pet-recycled/.
[6] H.K. Webb, et al., Plastic degradation and its environ-
mental implications with special reference to poly(eth-
List of abbreviations and acronyms ylene terephthalate), Polymers 5 (1) (2012).

[7] A. CATA, et al., Alkaline hydrolysis of polyethylene
BHET Bis(hydroxyethyl) terephthalate terephthalate under microwave irradiation, Revue
DEMETO Modular, scalable, and high performance depo- Roumaine de Chimie 62 (6e7) (2017).
lymerization by microwave technology [8] https://www.dentispet.it/.
DMT Dimethyl terephthalate [9] S.H. Park, S.H. Kim, Poly(ethylene terephthalate) recy-
IPA Isophthalic acid cling for high value added textiles, Fashion and textiles
MEG Monoethylene glycol 1 (2014) 1.
PET Polyethylene terephthalate [10] P. Salminen, Using Recycled Polyethylene Tere-
PETE Polyethylene terephthalate phthalate (PET) in the Production of Bottle Trays, De-
PVC Polyvinyl chloride gree thesis, 2013.
R-PET Recycled PET [11] NEOGROUP, Project Internal Documents.
TA Terephthalic acid [12] 3V-Tech, Project Internal Documents.

References
[1] GreenBlu, Chemical Recycling. Making Fiber-To-Fiber
Further reading
Recycling a Reality for Polyester Textiles. [1] https://www.demeto.eu.

IV. Selected examples and case history