World Applied Sciences Journal 8 (7): 839-846, 2010

ISSN 1818-4952
IDOSI Publications, 2010

Chemical Recycling of Poly Ethylene Terephthalate Wastes

1

M.H. Vakili and 2M. Haghshenas Fard

Department of Engineering, Islamic Azad University, Shahreza Branch, Isfahan, Iran

Department of Chemical Engineering, Isfahan University of Technology, Isfahan, Iran

1
2

Abstract: Chemical recycling of Polyethylene terephthalate, PET, wastage has been investigated in this study.
The aim of this work is recovery of terephthalic acid and ethylene glycols from PET waste. This process has
been done in two stages. At the first stage, reaction between PET waste and sodium hydroxide for production
of ethylene glycol and sodium terephthalate solution carried out in a stainless steel mix reactor. At the second
stage, reaction between produced sodium terephthalate and hydrochloric acid led to terephthalic acid
production. Some important parameters such as operating temperature and pressures and quantity of
consuming sodium hydroxide and hydrochloric acid have been studied. The optimum amount of sodium
hydroxide and hydrochloric acid were achieved 50gr and 166gr per 1kg of PET waste, respectively.
Operating temperature and pressure was achieved 180C and 1.5bar in the first stage.
Key words: Polyethylene terephthalate

Terephthalic acid

INTRODUCTION

Ethylene glycol

Chemical recycling

usage cycle by chipping them into very fine scraps,

heating, melting and remolding to new products.
Frequently in the mechanical methods the reground
scrap PET is blended with virgin PET, the other polymers
and also mineral to achieve useful materials for
different purposes.
Frounchi, et al. (1997) studied mechanical recycling
of PET beverage bottle. They blended recycled PET with
virgin PET to increase mechanical property of it. They
found that mechanical blending can be used for recycling
purposes without sacrificing of the virgin PET and to
reduce material cost in bottle fabrication [1]. Verney, et al.
(2005) blended PET waste with polycarbonate (PC) to
improve physical properties of mechanically recycled PET.
They found that the blends have better properties than
neat PET [2].
Navarro, et al. (2007) studied the influence of
polyethylene cap of the bottle in the mechanical recycling
of PET. They found that it is not necessary to totally
separate polyethylene contents, because small
percentages of PE may facilitate subsequent processing
of the material using injection [3].
Chemical recycling of PET waste consist of
depolymerization by hydrolysis, methanolysis, glycolysis
and aminolysis to obtain various monomers. The
hydrolysis of PET in presence of acid and base using
suitable solvents has been reported by several
researchers [4].

Due to upward usage of polymers and plastic

materials especially in throwaway applications, wastage
generation of these products is daily and relatively in
large volume. The plastic materials often are not
resolvable with microorganisms and lead to environmental
pollutions, so it is necessary to recycle and return of
these materials to the usage cycle.
Generally, plastics such as: polyethylene,
polystyrene, polyethylene terephthalate, polypropylene
and polyvinyl chloride, which used in packaging
industries are interested to be recycled.
One of the most important thermoplastic polyesters,
which widely used in applications such as textile fibers,
films and packing industries, is Polyethylene terephthalate
(PET). Due to properties such as: high transparency in
blown containers, high mechanical strength for minimum
thickness walls, negligible permeability to CO2 and
relatively low cost, soft drink bottles is the most important
application of PET, which produce a significant
household and municipal waste. Therefore it is necessary
to gain greater attention for recycling, PET waste bottle
due to ecological factor and for obtaining valuable
products.
There are two global methods for recycling of PET
waste, mechanical and chemical methods. In mechanical
methods, generally beverage bottle can be recycled to the

Corresponding Author: M.H. Vakili, Department of Engineering, Islamic Azad University, Shahreza Branch, Isfahan, Iran

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World Appl. Sci. J., 8 (7): 839-846, 2010

Neutral hydrolysis of waste PET with different

amounts of water and different catalysts, in presence of
xylene has been studied by Guclu, et al. (2003) [5].
Thermal and hydrolysis depolymerization of
PET has also been studied by Sao and Cloyed [6].
Methanolysis of PET waste is used to form monomers,
dimethyl terephthalate (DMT) and ethylene glycol (EG).
Kurokawa, et al. (2003) studied methanolysis of PET in
the presence of aluminium tiisoproxide catalyst to form
monomers. They found that using a toluene/methanol
mixed solvent (20 vol. % toluene) instead of pure
methanol, lead to obtain maximum yield of monomers,
88% for DMT and 87% for EG [7].
Genta, et al. (2006) used supercritical methanol
for PET depolymerization instead of vapor methanol.
They found that the rate of PET depolymerization in
super critical methanol is faster than that of PET
depolymerization in vapor methanol [8]. Yang, et al. (2002)
study effect of some parameter on methanolysis of PET
waste in supercritical methanol. They found that both
yield of DMT and degree of PET depolymerization were
seriously influenced by the temperature, weight ratio of
methanol to PET and reaction time, whilst the pressure
has no considerable effect, when it is above critical point
of methanol [9]. Ghaemy M. and Mossaddegh K. (2005)
studied glycolysis of PET waste using ethylene glycol.
They investigated some parameter such as: reaction time,
volume of EG, catalysts and their concentrations on the
yield of glycolysis [10]. Karayannidis, et al. (2004) used
glycolysis of waste PET to produce alkyd resins. They
found that mechanical properties of produced resin are
comparable with conventional general purpose resin [11].
Dullius, et al, (2006) also applied chemical recycling of
waste PET to alkyd resins synthesis [12]. Shukla, et al.
(2006) used glycolysis method for recycling waste PET
into useful auxiliaries. The advantages of this method
were that chemicals used during depolymerization of
PET are inexpensive and comparatively less harmful to
the environment [13]. Aminolysis is another method of
chemical recycling of PET waste, which has been little
explored as compared to other technique. Shukla, et al.
(2006) method to produced bis (2-hydroxy ethylene)
terephthalate (BHETA) by aminolysis of PET waste.
They used excess of ethanolamine in the presence of
different simple chemicals, namely glacial acetic acid,
sodium acetate and potassium sulphate, as catalyst.
They obtained good yield of BHETA as 91% [14].
Parra, et al. (2004) obtained High value carbon materials
from PET recycling use of pyrolysis and subsequent
activation of PET [15]. Barriocanal, et al. (2004)
also studied producing of carbon materials from PET
recycling [16].

In the present work hydrolysis by sodium hydroxide

has been used for recycling of PET waste. Some important
variables such as operational temperatures, pressures
and the quantity of consuming sodium hydroxide and
hydrochloric acid have been studied.
Experimental: The experimental works carried out in two
stages. At the first stage, a reaction between PET and
sodium hydroxides according to the following reaction
has been done:
PET + 2nNaOH nNa 2C8H4O4 + nC2H6O2

Ethylene glycol and sodium terephthalate are the

products of this step. Sodium terephthalate reacted with
hydrochloride acid at the second stage of the process
according to the following reaction:
Na 2C8H4O4 +HCl C8 H6O4 +2NaCl

MATERIALS AND MATHODS

The PET used in all experiments was procured from
Polyethylene terephthalate beverage bottles. Before
charging the PET in the reactor, the bottles were cut down
into 1mm 1mm to 6mm 6mm flakes. Sodium hydroxide
85%w and hydrochloric acid 1molar as the main reactants
and water as a solvent have been used in the reactions.
10 liters, high-pressure pilot-plant steel reactor was
used for all experiments. The pilot plant is shown in
Figure 1. The reactor was well equipped with an anchor
impeller to ensure proper mixing. It was also equipped
with a shell around it to circulate hot oil used for heating
the reactor contents. Heat transfer oil can be hot by a
thermal element in a vessel and can be recycling through
the whole heating system by a pump. Also the reactor
was equipped with a total condenser at top of the vessel.
The vapor products can be collected in a small steel
vessel and discharged through a valve as a final liquid
product. The reflux ratio can be changed to achieve the
optimum conditions.
First Stage: 1kg PET and 4lit water were charged in the
reactor. Then 20gr sodium hydroxide was added to
reactor. Water has been used as a solvent for reactants.
The temperature of reactor was set at 110C. This
temperature was provided with circulating hot oil in the
shell around the reactor. When the temperature reached
to the set value, in 5min intervals, pH of the reactor
solution was measured.
The reaction will be completed, when the pH became
constant at basic range.
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World Appl. Sci. J., 8 (7): 839-846, 2010

Fig. 1: Pilot plant for chemical recycling of PET

RESULTS AND DISCUSSION

For determination of optimum reaction temperature,

we can measure the conversion percent under different
temperatures.
Produced Ethylene glycol went to the condenser
during the process and collected in a steel vessel. At the
end of the reaction, Sodium terephthalate was discharged
from the reactor and was washed and dried.

Figure 2 shows the conversion variation of first

reaction with temperature. It can be seen that the
maximum conversion is a bout 92% that occurred
at 180C and increasing temperature has no considerable
effect on conversion. At this temperature the
pressure of reaction is 1.5bar. Figure 3 shows the
variation of needful sodium hydroxide quantity with
conversion in the first reaction. From this figure,
500gr of sodium hydroxide is needful per 1kg of PET for
92% conversion.
Figure 4 shows the conversion variation of second
reaction with temperature. It can be seen that the maximum
conversion is about 88% that occurred at 90C. Figure 5
shows variation of reaction time of two reactions with
conversion. From this figure, it can be clearly seen that
the reaction time for 92% conversion is about 180min for
first reaction and it is 90min for second reaction in
88% conversion.

Second Stage: In this stage terephthalate salt obtained

from former stage react with hydrochloric acid and
produce terephthalic acid. In this step, Sodium
terephthalate was washed with water to remove residual
sodium hydroxide and then was dried. 453gr sodium
terephthalate obtained from first stage and 166gr
hydrochloric acid and 2 lit water were charged in the
reactor. Temperature was set on 40C. In 5min intervals,
solution pH was measured.
Obtained terephthalic acid was insoluble in water and
was settled at the bottom of the reactor. It was discharged
from the reactor, washed with water and dried.
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Conversion(%)

World Appl. Sci. J., 8 (7): 839-846, 2010

100
90
80
70
60
50
40
30
20
10
0
100

120

140

160

180

200

80

100

Temperature (c)

Fig. 2: conversion variation of first reaction with temperature

600

NaOH(gr)

500
400
300
200
100
0
0

20

40

60

Conversion(%)

Conversion(%)

Fig. 3: NaOH quantity variation with conversion in the first reaction

100
90
80
70
60
50
40
30
20
10
0
20

40

60
Temperature(c)

Fig. 4: conversion variation of second reaction with temperature

842

80

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World Appl. Sci. J., 8 (7): 839-846, 2010

180

Time(min)

150
120
Second Reaction

90

First Reaction

60
30
0
0

50

100

Cinversion(%)

Fig. 5: variation of reaction time of two reactions with conversion

Fig. 6: IR spectrum of ethylene glycol obtained from reaction between PET and sodium hydroxide

Fig. 7: IR spectrum of pure ethylene glycol as a reference sample

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World Appl. Sci. J., 8 (7): 839-846, 2010

Fig. 8: IR spectrum of obtained terephthalic acid from reaction between terephthalate sodium and hydrochloric acid

Fig. 9: IR spectrum of pure terephthalic acid as a reference sample

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World Appl. Sci. J., 8 (7): 839-846, 2010

The IR spectrum of the products compared with IR

spectrum of reference samples. Figure 6 and Figure 7
show the IR spectrums of obtained ethylene glycol from
the reaction between PET and sodium hydroxide and pure
ethylene glycol as a reference sample. It can be seen that
IR spectrum of ethylene glycol obtained from the reaction
nearly coincide on IR spectrum of the reference sample
and alcoholic group specified with 3425 number, can be
observed on the spectrum. Figures 8 and 9 show the IR
spectrums of obtained terephthalic acid from reaction
between terephthalate sodium and hydrochloric acid and
pure terephthalic acid as a reference sample. From this
figure, it can be seen that IR spectrum of terephthalic acid
obtained from reaction nearly coincide on IR spectrum of
the reference sample. At the IR spectrum of proof sample
numbers of 3434 is relate to carboxylic group, 1383 is
relate to aromatic cycle and 1687 relate to carbonyl group
while these number at IR spectrum of terephthalic acid
obtained from reaction are 3432, 1393 and 1583
respectively. These results show a good agreement with
the references data, indicating that the purity of the
products in the mentioned method is acceptable.

2.

3.

4.
5.

6.

7.

CONCLUSION

8.

Concerning to various methods of chemical recycling

of PET, it was seemed that hydrolysis of PET with sodium
hydroxide is a suitable and easy process and the purity of
the products in this method is acceptable. In this method
polyethylene terephthalate waste bottles were converted
to the ethylene glycol and sodium terephthalate salt.
The needful sodium hydroxide for reaction with 1kg
of PET was obtained 500gr. Optimum value of temperature
for reaction between the PET and sodium hydroxide was
obtained 180C. At this temperature reaction conversion
was 92%. The reaction time in this stage was about
180min. The amount of produced ethylene glycol was
200ml and terephthalate salt was 453 per 1kg of
consuming PET.
Optimum value of temperature for reaction between
sodium terephthalate and hydrochloric acid obtained 90C
at 88% conversion. The reaction time in this STEP was
about about 90min. in this stage 166gr hydrochloric acid
per 453gr sodium terephthalate was used and 433gr
terephthalic acid was obtained.

9.

10.

11.

12.

13.

REFERENCES
1.

14.

Frounchi M., M. Mehrabzadeh and R. Ghiaee, 1997.

Studies on Recycling of Poly(ethylene terephthalate)
Beverage Bottles, Iranian Polymer J., 6: 269-272.
845

Fraisse F., V. Verney, S. Commereuc and M. Obadal,

2005. Recycling of polyethylene terephthalate)/
polycarbonate blends, Polymer Degradation and
Stability, 90: 250-255.
Navarro, R., S. Ferrandiz, J. Lopez and V.J. Segui,
2007. The influence of polyethylene in the mechanical
recycling of polyethylene terephthalate, J. Materials
Processing Technol., pp: 1-7.
Mankodi, J.W., 1986. US Pat., 4: 605-762.
Guclu, G., T. Yalcinyuva, S. Ozgimus and M. Orbay,
2003.
Hydrolysis of waste polyethylene
terephthalate and characterization of products by
differential s canning calorimetry, Thermochemica
Acta, 404: 193-205.
Sao, K.S. and D. Cloyd, 1991. Kinetics of Hydrolysis
and Thermal Degradation of Polyester Melts, J.
Polymer Sci., 42: 845-853.
Kurokawa, H., M. Ohshima, K. Sugiyama and
H. Miura, 2003. Methanolysis of polyethylene
terephthalate (PET) in the presence of aluminum
tiisopropoxide catalyst to form dimethyl terephthalate
and ethylene glycol, Polymer Degradation and
Stability, 79: 529-533.
Genta, M., T. Iwaya, M. Sasaki and M. Goto, 2007.
Supercritical methanol for polyethylene terephthalate
depolymerization: Observation using simulator,
Waste Management, 27: 1167-1177.
Yang, Y., Y. Lu, H. Xiang, Y. Xu and Y. Li, 2002.
Study on methanolytic depolymerization of PET with
supercritical methanol for chemical recycling, Polymer
Degradation and Stability, 75: 185-191.
Ghaemy, M. and K. Mossaddegh, 2005.
Depolymerization of poly(ethylene terephthalate)
fibre waste using ethylene glycol, Polymer
Degradation and Stability, 90: 570-576.
Karayannidis, G.P., D.S. Achilias, I.D. Sideridou and
D.N. Bikiaris, 2005. Alkyd resins derived from
glycolized waste poly(ethylene terephthalate),
European Polymer J., 41: 201-210.
Dulius, J., C. Ruecker, V. Oliveira, R. Ligabue and
S. Einloft, 2006. Chemical recycling of post-consumer
PET: alkyd resin synthesis, Progress in Organic
Coating, 57: 123-157.
Shukla, S.R., A.M. Harad and L.S. Jawale, 2006.
Recycling of waste PET into useful textile auxiliaries,
Waste Management.
Shukla, S.R. and A.M. Harad, 2006. Aminolysis of
polyethylene
terephthalate
waste
Polymer
Degradation and Stability, 91: 1850-1854.

World Appl. Sci. J., 8 (7): 839-846, 2010

15. Parra, J.B., C.O. Ania, A. Arenillas, F. Rubiera and

J.J. Pis, 2004. High value carbon materials from PET
recycling, Applied Surface Sci., 238: 304-308.
16. Barriocanal, C., M.A. Diez and R. Alvarez, 2005.
PET recycling for the modification of precursors in
carbon materials manufacture, J. Analytical and
Applied Pyrolysis, 73: 45-51.
17. Lecomte, H.A. and J.J. Liggat, 2006. Degradation
mechanism of diethylene glycol units in a
terephthalate polymer, Polymer Degradation and
Stability, 91: 681-689.

18. Carvalho, M.T., E. Agante and F. Durao, 2006.

Recovery of PET from packing plastics mixtures by
wet shaking table, Waste Management.
19. Awaja, F. and D. Pavel, 2005. Review of Recycling of
PET, European Polymer J., 41: 1453-1477.
20. Paci, M. and F.P. La mantia, 1999. Influence of small
amounts of polyvinylchloride on the recycling of
polyethylene terephthalate, Polymer Degradation and
Stability, 63: 11-14.

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