Chemical Recycling of PET Research Articles

Chemical Recycling of Poly(ethylene terephthalate) (PET) by

Hydrolysis and Glycolysis*
Daniela Carta 1, Giacomo Cao 1"" and Claudio D'Angeli 2
1Dipartimento di Ingegneria Chimica e Materiali, Unitfi di ricerca del Consorzio Interuniversitario Nazionale La Chimica per
l'Ambiente e Centro Interdipartimentale di Ingegneria e Scienze Ambientali, Universitfi di Cagliari, Piazza D'Armi,
1-09123 Cagliari, Italy
2INCA International S.p.A., A Subsidiary of The Dow Chemical Company, Via Patroclo 21, 1-20151 Milano, Italy

** Corresponding author (cao@visnu.dicm.unica.k)

low molecular-weight products which can be purified and

reused as raw materials for the production of high-quality
chemical products. Depending upon the depolymerizing
agent, the chemical process applied in PET recycling can be
divided into five groups: methanolysis, glycolysis, hydroly-
sis, aminolysis, ammonolysis.
In this work, our attention is confined to the hydrolysis (neu-
tral, acid and alkaline) and glycolysis processes of PET chemi-
cal recycling. A schematic diagram of each of these proc-
esses is shown in Fig. 1.

Schematicdiagramof PET acid hydrolysisprocess

PET ~ I > excessacid
concentratedsulfuric acid P= 0.1 MPa
NaOH T=298-363 K > EG
> Na2SO.
calcium oxide or hydroxide ~ CaSO,

Schematic diagram of PET alkaline hydrolysis process

PET ~ > TPA
NaOH ~J> P= 1.4 - 2 MPa
wetting agent or surfactants T= 483-523 K > EG
calcium oxide or hydroxide > CaSO,
H2SO4 > sulfate salts
Schematic diagram of PET neutral hydrolysis process

PET >1 P= 1 - 4 MPa > TPA

T= 473-573 K
water or steam Transesterification catalyst
Introduction (alkali metal acetates) > EG

Poly(ethylene terephthalate) (PET) is an important thermoplas-

tic polyester, used in the form of fibers, sheets and films, whose Schematic diagramof PET glycolysisprocess
consumption is dramatically increasing in the world as a whole.
PET > P= 0.1 - 0.6 MPa > BHET
Such a level of consumption generates considerable amounts of T= 463-513 K >- oligomers
waste and scrap that could be recycled and/or recovered. EG > zinc acetate > EG
The recycling of PET can be carried out in several ways. A
very attractive strategy is the 'material recycling' which is Fig. 1: Schematic diagrams of PET hydrolysis and glycolysis processes
characterized by the collection, disintegration, and granula-
tion of waste polymer which is recirculated into production 1 Chemical Recycling Methods
[1,2]. Unlikely, this recycled PET cannot be used to make 1.1 Hydrolysis
products that have to meet very high quality standards.
Neutral hydrolysis. Neutral hydrolysis is typically carried
An interesting method of PET recycling, called 'chemical out contacting scrap PET with water or steam at a pressure
recycling', is based on the concept of depolymerizing the of 1-4 MPa and temperatures of 473-573 K. The main prod-
condensation polymer through solvolytic chain cleavage into ucts formed are ethylene glycol (EG) and terephthalic acid
(TPA). TPA is separated from the post reaction mixture by
* Part of this work was presentedat the '4~Convegno Consorzio Interuniversitario
Nazionale La Chimica per I'Ambiente (INCA)', Santa Marghedta Ligure (Italy), filtration, while a substantial volume of diluted EG is recov-
25-28 February 2001 ered through extraction or by distillation [3-5].

390 ESPR - Environ Sci & Pollut Res 10 (6) 390 - 3 9 4 (2003)
9 ecomed publishers, D-86899 Landsberg, Germany and Ft. Worth/TX 9 Tokyo ~ Mumbai 9Seoul * Melbourne ~ Paris
Research Articles
Despite the apparent simplicity of its basic mechanism, the
neutral hydrolysis of PET is a complex process which is not
fully understood. There is a common agreement that the
neutral hydrolysis has an autoaccelerating character. The
hydrolysis is typically considered as a non-diffusion con-
trolled process where the water concentration is constant.
Nevertheless, two different kinetic models have been pro-
posed, and are summarized as follows along with the rel-
evant main assumptions:
1) Half-order kinetic model
9 Autocatalytic reaction mechanism
9 Catalytic effect of the carboxyl end-groups are taken
into account
9 Specific chain-end process
2) Classic second-order kinetic model
9 No autocatalysis
9 Crystallinity and hydrophilicity changes induced by
chain scission are taken into account
9 Simple second-order random scission process
Three main sources of difficulty for the investigation of neu-
tral hydrolysis have to be considered:
1) The role of chain ends
2) Morphological changes induced by the degradation
3) Type of scission of chain (random or specific chain-end
process)
The effect of chain ends was either neglected [6-7] or taken
into account through different approaches [8-12].
A systematic study by Ravens et al. [8] in the early 60s of
the hydrolytic degradation of PET revealed that the hydro-
lytic scission of polyester chains above their glass transition
temperature was an autocatalytic reaction and the process
was a rate-controlled chemical reaction. Each chain scission
uses up one water molecule and creates one carboxylic end
group. Hence, the extent of reaction can be followed by
measuring the number of carboxyl ends present when vary-
ing the hydrolytic degradation time. The built-up of termi-
nal acid groups is responsible of autocatalytic phenomena
that can explain the autoaccelerating character of the reac-
tion. According to this interpretation, the reaction is catalyzed
by hydrogen ions produced by the carboxyl end groups.
Some authors [13] suggested that autocatalysis is not needed to
explain the behavior of PET during its hydrolysis. It was sug-
gested that the physical effects linked to the increase in cristallinity
and hydrophilicity could explain this autoaccelerating charac-
ter. It has been observed by several authors that the crystallinity
increase during the hydrolysis can be attributed to a chemi-
crystallization process. It was estimated that about 5-6 monomer
units enter the crystalline phase per chain scission.
PET is a semicrystalline thermoplastic polyester, thus built of
amorphous and crystalline regions. Water absorption and thus
chain scission are only possible in the amorphous phase, ow-
ing to the impermeability of crystals. The chain segments pre-
viously entrapped in the amorphous phase are then liberated
and become sufficiently mobile to enter into the crystalline
phase. The drastic increase in the crystallinity cannot be ig-
nored in a kinetic study of hydrolysis. Allen et al. [14], ex-
plored the degradation of PET materials under environmental
conditions, exposing bottles to 45-100% relative humidity.
ESPR - Environ Sci & Pollut Res 10 (6) 2003
Chemical Recycling of PET
They observed a difference in the degradation rates associated
with differences in the initial crystallinity of the materials. The
strong influence of crystallinity on the rate of hydrolytic deg-
radation of PET is believed to be due to the fact that crystallites
act as barriers to moisture and oxygen diffusion. The initial
crystallinities of PET determine the degradation rates as well
as the nature of the degradation conditions.
The other problem related to the hydrolysis is the type of
chain scission. Launay et al. [13] stated that the hydrolysis
is a second-order, random-chain scission process, while
Ballara and Verdu [15] proposed that the rate of a specific
chain end process is higher than the random one. They ob-
served the existence of a weight loss of PET during the reac-
tion that suggested that the rate of hydrolysis is higher at
terminal than at internal ester groups. The weight loss is
linked to the extraction of the smaller molecular fragments
resulting from a hydrolysis reaction near the chain ends. The
major extractable products are monomeric TPA and/or EG.
Larger fragments would have a lower solubility in water
and a lower diffusivity in PET matrix.
Several research studies were conducted on the reaction ki-
netics for the neutral hydrolytic depolymerization of PET at
low temperatures (i.e. less than 473 K) [7-9,13-15].
However, the effort of those authors was mainly focused on
measuring the degradable properties of the material so that
the conversion of PET hydrolysis were rather low. Thus,
their results were not applicable to the practical depolymeri-
zation process in which the PET is depolymerized into the
original feedstock (TPA and EG). PET hydrolysis below its
melting range (518-538 K) is an extremely slow reaction,
hardly perceivable by ordinary analytical methods limited
by physical factors such as diffusion and crystallinity. Physi-
cal factors are less important for the case of hydrolysis above
the melting range which is therefore more effective. In fact,
whereas the cleavage of esters groups of polyesters in the
melt state is an extremely rapid reaction, hydrolysis in the
solid state turns out to be a complex process which highly
depends on chain mobility and permeability. Because hy-
drolysis proceeds significantly faster in the molten state than
in the solid state, it has been found advantageous to carry
out hydrolytic recycling at a temperature above the melting
point of PET. In practice, the process is usually run at a
pressure of 1-4 MPa and temperature of 473-573 K with a
ratio by weight of PET to water ranging from 1:2 to 1:12.
Although the process for the hydrolytic depolymerization
of PET at high temperatures has been revealed in a number
of patents, the investigations on the corresponding reaction
kinetics for this kind of process are scarce in the literature
[10,12,16,17].
Kao et al. [12] studied the kinetic of the depolymerization
of molten PET in water in a stirred batch reactor at tem-
peratures of 508,523 and 538 K.
The reaction extent for kinetic study is defined as moles of
carboxylic acid per gram of PET used.
The conversion of PET hydrolysis was fast at temperatures
higher than 523 K and was high even in a short time interval.
Kinetics plots show that a second-order model cannot describe
the reaction rate of PET and it is proposed that the hydrolysis
391
Chemical Recycling of PET
possesses an autocatalytic mechanism induced by the carboxyl
group, as has already been observed for PET hydrolysis with
low conversions at temperatures below the melting point.
An autocatalytic model of half-order fits the experimental
data better than the second-order model. The activation
energy for PET hydrolysis calculated from the slope of the
Arrhenius plot was 123 KJ/mol.
The autocatalytic model with half-order in carboxylic acid
concentration suggests that the hydrogen ion formed by the
dissociation of the carboxylic group of TPA (pKi=3.51 and
pK2=4.82) may catalyze the depolymerization of PET. In agree-
ment with the autocatalytic model of the carboxyl group, the
concentration of hydrogen ion is assumed to be proportional
to the square root of the carboxylic acid concentration.
It is then suggested that a typical mechanism of nucleophilic
addition-elimination induced by the hydrogen ion is respon-
sible of PET hydrolysis, as indicated below:
-C6H4-CO-O-C2H4-O- + H + ~-~
C 6H4-C(OH +)-o-C2H 4-0- (1)
-C6H4-C(OH§ ~ + H20
(2)
~C6H4-C(OH)2-(OH+)-C2H4-O-
~C6H4-C(OH)2-(OH+)-C2H4-O- <-0
~C6H4-C-(OH+)-OH + HO-C2H4-O- (3)
-C6H4-C-(OH+)-OH ~ -C6H4-COOH + H+ (4)
Campanelli et al. [16], suggested that essentially complete
depolymerization could be obtained within two hours at 538 K
for an initial reactor loading of 5.1 water/g PET. However,
it would be desirable to reduce the reaction time through
the use of appropriate catalysts, in order to facilitate the
development of an economic depolymerization process.
It is known that metal salts are able to catalyze the hydroly-
sis of some simple esters in aqueous solutions. Zinc acetate
has been found to be a good catalyst for thermal and glyco-
lytic degradation of PET.
Campanelli et al. [17] studied the effect of zinc catalysts in
the hydrolytic depolymerization of PET melts in excess wa-
ter at temperatures of 523-538-553 K. The addition of the
zinc salts resulted in a little increase in the rate of the hy-
drolysis reaction. The hydrolysis reaction apparently occurs
at the interface of a PET in water emulsion; the catalytic
effect of zinc salts is attributed to the electrolytic destabili-
zation of the polymer-water interface during hydrolysis. The
stability of emulsions is influenced by the zinc salts that af-
fect the surface charge of the disperse phase droplets. In
particular, electrostatic repulsion between disperse phase
droplets are weakened by the electrolyte, so that the rate of
coalescence increases. Less thermal and mixing energy is
required to form an interface than in absence of electrolytes,
since they decrease the stability of PET-water interface. The
result is an increase of the rate of hydrolysis. However, be-
cause the hydrolysis rate constant increase only about 20%
using salt catalysts, their effect on monomer production is prob-
ably not crucial. In fact, most of the processes regarding neu-
tral hydrolysis are carried out without a catalyst.
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Research Articles
Acid hydrolysis. Acid hydrolysis is performed by contacting
scrap PET with concentrated sulfuric acid (minimum 87% by
weight). This acid levels allowed the process to take place in a
pressureless apparatus, typically without requiring external
energy supply. The products obtained are TPA and EG [18,19].
The latest studies about acid hydrolysis are related to the kinet-
ics of hydrolysis PET powder in sulfuric and nitric acid [20,21].
In both studies, PET powder from waste bottles was degraded
at atmospheric pressure but in the former case the concentra-
tion of sulfuric acid was 3-9 M, the temperature 423-463 K
and the hydrolysis time 12 hours; in the latter one, the concen-
tration of nitric acid was 7-13 M, the temperature 343-373 K
and the hydrolysis time was 72 hours. In both cases, the kinet-
ics of the hydrolysis could be explained by a modified shrinking
core model under chemical reaction control [22] and the reac-
tion temperature is below the melting range of PET; thus, the
reaction proceeds at the solid-liquid interface and the effects of
the changing effective surface area of PET on the reaction has
to be taken into account. Using HNO3, as well as H2SO4, it was
observed that the rate of hydrolysis increases with:
1) The increase of acid concentration (this suggests that
hydrogen ions may catalyze the hydrolysis)
2) The decrease of particle size (with decreasing particle
size, the surface area available for the reaction increases)
3) The increase of temperature (as expected when a chemi-
cal reaction is rate determining).
It can be stated that hydrolysis catalyzed by the hydrogen
ion is rate-determining on the PET surface.
Although all these similarities, there are some differences
between the two acid media for hydrolysis, regarding the
analysis of the process.
The kinetics of the hydrolysis of PET in HNO 3 could be ex-
plained by a modified shrinking core model under chemical
reaction control, where the effective surface area is proportional
to the degree of unreacted PET, which is in turn affected by the
deposition of the product TPA on the surface of unreacted PET
particles. The particle size decreased with reaction time, but no
cracks were observed on the surface of the particles. It was
suggested that the rate of hydrolysis is suppressed by both the
deposition of TPA and the decrease in surface area. The modi-
fied shrinking-core model scheme for the degradation of PET
particles by HNO 3 is shown in Fig. 2 [21].
The kinetics of the hydrolysis of PET in H2SO4 could be
explained by a modified shrinking-core model under chemi-
cal reaction control, where the effective surface area is pro-
portional to the degree of hydrolyzed PET, which is in ad-
diction affected by the formation and growth of pore and
crack on PET powder [23].
Fig. 2: Acid Hydrolysis with nitric acid: Modified shrinking-core model.
Adapted from Yoshioka T, Okayama N, Okuwaki A (1998) Ind Eng Chem
Res 37, 336-340
ESPR - Environ Sci & Pollut Res 10 (6) 2003
Research Articles
Cracks
,/
O O
0 0
0
/ Chen et al. [31] studied the glycolysis by EG under pressure
PET particle
Terephthalic Acid
Fig. 3: Acid Hydrolysis with sulfuric acid: modified shrinking-core model.
Adapted from Yoshioka T, Motoki T, Okuwaki A (2001): Ind Eng Chem
Res 40, 75-79
The modified shrinking-core model scheme for the degrada-
tion of PET particles by H2SO 4 is shown in Fig. 3 [20]. The
formation of pores and cracks increase the effective surface
area. In fact, the degree of degradation of PET using H2SO 4
reached 100% at 3 M, 463 K, 1 hour, whereas it reached a
maximum of 91.3% at 13 M, 373 K, 24 hours using HNO 3.
Furthermore, the activation energy was 101.3 KJ/tool using
H-NO 3 and 88.7 KJ/mol using H2S04, respectively. Thus,
patents regarding chemical recycling of PET by acid hydroly-
sis make use of H2SO 4.
Alkaline hydrolysis. Alkaline hydrolysis is typically carried out
contacting PET scrap with caustic soda aqueous solutions which
are characterized by concentration levels of 4--20 wt%. The
saponification reaction takes place in autoclave reactors at 483-
523 K and at 1.4-2 MPa for about 3-5 hours. Once the reac-
tion is over, the solution is filtered to remove the insoluble im-
purities and it is then acidified with a strong acid (typically
sulfuric acid) to precipitate TPA. The latter is filtered off, washed
with fresh water and dried. On the other hand, EG formed
during the reaction remains in the aqueous phase, and can be
separated by extraction or distillation [24,25].
There are very few studies about the kinetics of alkaline
hydrolysis. In particular, Ramsden and Phillips [26] investi-
gate the effect of solvent on the kinetics of alkaline depoly-
merization of PET. They found that the process is first-order
with respect to hydroxide ion concentration and the activa-
tion energy for that reaction in water is 69+_13 KJ/mol. This
value is lower than the reported activation energy for the
neutral solid-state heterogeneous hydrolysis (94.5+2 KJ/mol
[7]; 101.6 KJ/mol [8]). The alkaline hydrolysis may there-
fore offer advantages over the neutral hydrolytic route.
1.2 Glycolysis
Glycolysis is conducted contacting PET scrap with EG in a wide
range of temperatures (453-523 K) during a time period of
0.5-8 hours. The main product of deep glycolysis by EG is the
monomer of PET, bis(hydroxyethyl)terephthalate (BHET) that
can be polymerized after purification to produce PET [27,28].
Most of the studies regarding the chemical recycling of PET
by glycolysis are related to applications of glycolized prod-
ucts to produce polyols for unsatured polyester or poly-
urethane [29,30]. Very few studies regarding the kinetics of
the glycolysis reaction are available.
Two different kinetic models have been proposed for glyco-
lysis by EG:
ESPR - Environ Sci & Pollut Res 10 (6) 2003
Chemical Recycling of PET
1) The rate of depolymerization is proportional to the square of
EG concentration. These results suggest that EG acts as both
a reactant as well as a catalyst in the glycolysis reaction [31].
2) Kinetic model of first-order in both EG and ethylene di-
ester concentrations, for small reaction times. These re-
sults suggest that EG does not play a significant role as
an internal catalyst in the glycolysis reaction [32].
(0.1-0.6 MPa; T= 463-513 K). The mechanism of pressu-
rized depolymerization of PET can be divided in two steps:
PET+EG ~ BHET + oligomers (5)
BHET ~ oligomers + EG (6)
The products resulting from glycolysis consisted of PET,
dimer and trimer. The first step (chain scission) is very fast;
an equilibrium reaction exists between BHET and oligomers
after the scission reaction of the polymer chains is completed.
In the case of a high EG/PET ratio, oligomers higher than
trimer were not detectable, because the scission reaction
occurs quickly and randomly. Oligomers having higher mo-
lecular weight (n=10) are detected for lower EG/PET ratios.
Thus, the EG/PET ratio can be used to regulate the degree of
polymerization of a product. In order to depolymerize PET to
a short-chain length, a sufficient amount of EG is required.
The depolymerization rate is dependent on pressure, tem-
perature and EG/PET ratio.
In particular, under a constant pressure, temperature and
PET concentration, the depolymerization rate is assumed to
be proportional to the square of the EG concentration.
As mentioned above, a different kinetic model is proposed
by Campanelli et al. [32] that studied the reaction of PET
melts with EG a T=518-548 K in a pressure reactor.
The rate of glycolysis can be written as:
-d[EG]/dt = kc[EG ] [EDE] (7)
where lEG] and [EDE] are the concentration of ethylene
glycol and ethylene diester groups, respectively.
It was found that the activation energy was 92 KJ/mol.
In this work, the effect of zinc salts has also been studied.
The electrolytic destabilization of the water-PET interface
was considered to be responsible of this catalytic activity. It
was observed that zinc salts increase the reaction extent be-
low 518 K, while it does not promote any further increase
in the glycolysis rate at 538 K.
Below 518 K, the glycolysis reaction occurs between solid
PET and liquid EG.
At temperatures greater than 518 K the glycolysisreaction occurs
in a singleliquid phase. The observation that zinc salts do not have
catalytic activity on the glycolysisof the melts can be explained by
the fact that the influence of the interfacial properties of zinc salts
are not important in a single-phase reaction. In an earlier work,
zinc compounds were found to catalyzethe hydrolytic depolymeri-
zation of PET melts. This difference in catalytic activity between
hydrolysis and glycolysiscan be due to the differences in solubility
of PET and its oligomers in water and EG; EG is known to be a
better solvent for PET oligomers than water. Also in the work of
393
Chemical Recycling of PET
Chen et al. [33] it was found that the activation energy for gly-
colysis with EG with addition of zinc acetate (85 KJ/mol) was
lower than the one without addition of a catalyst (108 KJ/mol).
2 Conclusions
In the present work, we confine our attention to the hy-
drolysis (neutral, acid and alkaline) and glycolysis processes
of PET chemical recycling. In particular, we review and
analyze the relevant kinetic mechanism assumed to provide
a qualitative as well as a quantitative description of the above
processes. Along these lines, the main results obtained so
far can be summarized as follows.
The neutral hydrolysis has an auto-accelerating character. Two
different kinetic models have been proposed: a half-order ki-
netic model and a classic, second-order kinetic model. The main
sources of difficulty for the investigation of neutral hydrolysis
are: the role of chain ends, morphological changes induced by
the degradation and the type of scission of a chain. The use of
salt catalysts increase hydrolysis rate constant only by about
20%, thus most of the processes regarding neutral hydrolysis
are carried out without catalyst.
The kinetics of PET powder hydrolysis in HNO 3 could be
explained by a modified shrinking core model under chemi-
cal reaction control, where the effective surface area is pro-
portional to the degree of unreacted PET, which is also af-
fected by the deposition of the product TPA on the surface
of unreacted PET particles. No cracks were observed on the
surface of the particles.
On the other hands, the kinetics of the hydrolysis of PET in
HzSO 4 could be explained by a modified shrinking-core model
under the chemical reaction control, where the effective surface
area is proportional to the degree of hydrolyzed PET, which is
also affected by the formation and growth of pore and crack on
PET powder. The degree of degradation of PET using H2SO4
reached 100% at 3 M, 463 K, 1 hour, whereas it reached a
maximum of 91.3% at 13 M, 373 K, 24 hours using HNO 3.
The process of alkaline hydrolysis is first-order with respect
to hydroxide ion concentration and the activation energy
for that reaction in water is lower than the reported activa-
tion energy for the neutral solid-state heterogeneous hydroly-
sis. The alkaline hydrolysis may therefore offer advantages
over the neutral hydrolytic route.
To describe glycolysis by EG, two different kinetic models have
been proposed: in the first one, the rate of depolymerization is
proportional to the square of EG concentration (EG acts as
both a reactant as well as a catalyst in the glycolysis reaction);
in the second one, the kinetic model is first-order in both EG
and ethylene diester concentrations (EG does not play a sig-
nificant role as an internal catalyst in the glycolysis reaction).
Zinc salts increase the glycolysis extent below 518 K, while
they do not promote any further increase in the glycolysis rate
at 538 K. The result that zinc salts have no catalytic activity on
the glycolysis of the melts can be explained by the fact that the
interfacial properties of zinc salts are not important in a single
phase reaction. However, zinc compounds catalyze the hydro-
lytic depolymerization of PET melts; this difference in catalytic
activity between the hydrolysis and glycolysis of PET melts can
be due to the fact that EG is a better solvent for PET than water.
394
Research Articles
It may be concluded that further experimental and theoretical
investigations are required to shed light on the promising proc-
esses of PET chemical recycling considered in this work.
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Received: May 8th, 2001
Accepted: November 28th, 2001
OnlineFirst: December 31st, 2001
ESPR - Environ Sci & Pollut Res 10 (6) 2003