Journal of Analytical and Applied Pyrolysis 106 (2014) 99103

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Journal of Analytical and Applied Pyrolysis

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Kinetics of alcoholysis of poly(ethylene terephthalate) in sub- and

super-critical isooctyl alcohol to produce dioctyl terephthalate
Junying Ding a , Jinyang Chen a,b, , Yimei Ji b , Pei Ni a , Zhilian Li b , Luyao Xing b
a
State Key Laboratory for Mineral Deposit Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, China
b
School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, China

a r t i c l e i n f o a b s t r a c t

Article history: The alcoholysis kinetics of poly(ethylene terephthalate) (PET) in sub- and super-critical isooctyl alcohol
Received 30 May 2013 (2-EH) to produce dioctyl terephthalate (DOTP) was studied with a batch reactor under the temperature
Accepted 1 January 2014 range from 533 to 653 K. Owing to the fast decomposition of DOTP to terephthalic acid (TPA) in the
Available online 24 January 2014
super-critical 2-EH, the kinetics was studied according to two conditions based on temperature less and
more than critical temperature of 2-EH as pseudo-rst-order reaction. In the sub-critical 2-EH about
Keywords:
the temperature range of 533593 K, the decomposition of DOTP was very slow, and thus the apparent
PET
activation energy of production rate of DOTP is determined to be 82.14 kJ/mol without taking into account
Sub- and super-critical isooctyl alcohol
Alcoholysis
decomposition of DOTP. Whereas, as for the super-critical 2-EH, the decompositions of DOTP should be
Dioctyl terephthalate taken into account, and a consecutive pseudo-rst-order reaction model from PET to DOTP, TPA and
Kinetics subsequent decomposition products is adopted. The apparent activation energies of production rates of
DOTP are 30.29 kJ/mol and the decomposition values of DOTP and TPA are 128.14 and 176.43 kJ/mol of
the super-critical temperature range of 613653 K.
2014 Elsevier B.V. All rights reserved.

1. Introduction that rstly glycolysis of 2-EH can be described as a molecular

Poly(ethylene terephthalate) (PET) is an important thermoplas-
tic polyester and has been widely used, thus waste PET treatment is
very necessary. It is known that PET is a condensation polymer and
it can easy cleaved at the ester linkage by appropriate solvent into
low molecular weight products which can be puried and reused
as raw materials for the production of high quality chemical prod-
ucts. Therefore, as for all treatment methods of waste PET, chemical
recycling of depolymerization into high value chemical products
have both environment and economy benet and have been gaining
more and more interest.
Recently the depolymerization of PET by hydrolysis [16],
methanolysis [7] and glycolysis [812] into the monomer of
terephthalic acid, dimethyl terephthalate and bis(2-hydroxyethyl
terephthalate) (BHET) were fully studied. Comparing with the
above low molecules, now there is a more valuable product
of very excellent plasticizer dioctyl terephthalate (DOTP) which
can be quickly produced by alcoholysis using sub- and super-
critical isooctyl alcohol (2-EH) in our previous work [13]. The
depolymerization mechanism was detailed studied and it shows
depolymerization process by transesterication between PET ester
groups and 2-EH in excess, to obtain the monomer DOTP, and
secondly the DOTP will decompose to produce terephthalic acid
(TPA), according to the following reaction scheme, PET + 2n(2-
EH) n(DOTP) mTPA.
In the process the main product of DOTP decomposes to produce
TPA quickly at the temperatures higher than the critical tempera-
ture of 2-EH (Tc = 613 K). Owing to the higher price of DOTP, the
product should be preferential considered, thus the kinetics of
production of DOTP under sub- and super-critical 2-EH should be
studied. Here, we describe the kinetic features of DOTP under sub-
and super-critical 2-EH and the object of this work is a better under-
standing of the reactivity difference in the two systems to obtain
DOTP based on our previous work [13] to give the result to process
design for industrial application.
2. Experimental
2.1. Materials

Corresponding author at: School of Environmental and Chemical Engineering,

The sample of PET slice was obtained from Tianjin Letai chemical
Shanghai University, Shanghai 200444, China. Tel.: +86 21 66137729;
industry Co. LTD (Tianjin, China) and it was cleaned with distilled
fax: +86 21 66137725. water and dried at 318 K for 12 h before use. Anhydrous 2-EH and
E-mail address: chenjy@shu.edu.cn (J. Chen). DOTP were purchased from Sinopharm Chemical Reagent Co. LTD

0165-2370/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2014.01.005
100 J. Ding et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 99103

(Shanghai, China). All reagents were used as purchased without

further purication.

2.2. Alcoholysis of PET

Based on our previous work [13] it is known that the optimal

weight ratio of 2-EH/PET is 4, thus here about 6 g PET and 24 g 2-EH
were put into a stainless batch type autoclave reactor which has
an inner volume of 40 ml. Owing to that the critical temperature
of 2-EH is 613 K, the temperature ranged from 533 to 653 K were
studied to know sub- and super-critical alcoholysis kinetics. After
the desired reaction time, the reactor was taken out from the fur-
nace and quenched in ice water bath in order to stop the reaction
immediately. The solid and liquid were separated by ltering.

2.3. Analysis of DOTP

Firstly the liquid products were added deionized water to wash
out water-soluble components such as ethylene glycol. Then the oil
phase was distilled to remove the reaction residual solvent 2-EH
and the residual liquid was analyzed by HPLC to determine DOTP.
The HPLC adopted an Agilent HP 1100 with a reverse-phase Zorbax-
C18 column and a UV detector set at 254 nm. Methanol was used
as a mobile phase at the ow rate of 1.0 mL/min and the injection
volume was 20 L for every measurement.
2.4. Analysis of residual PET and TPA
According to the observation result, the TPA is not dissolved
in the 2-EH and presents in solid phase. After reaction, the solid
products mainly including residual PET and TPA were dissolved
with 3 mol/l NaOH solution and the TPA became terephthalic acid
sodium to dissolve in water, thus residual solid PET and TPA were
separated by ltration. After ltration, the terephthalic acid sodium
solution was acidication with 3 mol/l HCl solution to separate
crystal solid TPA.
3. Results and discussion
Based on the previous work [13], the process of PET alcoholy-
sis by 2-EH to produce DOTP can be simplied into the following
reaction scheme of PET DOTP TPA. When the temperature is
below the critical temperature of 613 K of 2-EH, the decomposi-
tion of DOTP is very slow and there is nearly no TPA production.
Therefore, according to the temperature of critical point of 2-EH,
the kinetics will be studied based on sub-critical and super-critical
condition.
The weight ratios of WPET , WDOTP and WTPA are expressed as
Mt /m0 , where m0 is the initial weight of PET; Mt is the weight of
PET, DOTP or TPA at the reaction time t. According to the previous
observation result [13], the TPA is solid phase, thus, it is more suit-
able that the kinetic are discussed with the weight ratios of WPET ,
WDOTP and WTPA .
Fig. 1. The WDOTP of different temperatures with time and their tting curves with
Eq. (3) in sub-critical 2-EH.
condition in water or methanol medium [1417]. Thus, the produc-
tion rate of DOTP is given by Eqs. (1) and (2) as pseudo-rst-order
reaction.
dWPET
= k1 WPET (1)
dt
dWDOTP
= k1 WPET (2)
dt
The parameter k1 is the rate constant and t is the reaction time
(min). At the initial time (t = 0), WPET ,0 = 1 and WDOTP ,0 = 0, Eqs. (1)
and (2) are integrated with the initial conditions, and then the
WDOTP is expressed by Eq. (3).
WDOTP = 1 ek1 t (3)
The WDOTP in the temperature range from 533 K to 593 K with
time was given in Fig. 1. In order to obtain the reaction rate constant
k, Eq. (3) was changed to the following ln(1 WDOTP ) = k1 t. The
linear ts of data ln(1 WDOTP ) versus t were shown in Fig. 2 and
the k were calculated from the slope shown in Table 1. According
to the k1 values of different temperature, the tting curves in Fig. 1
were accorded with the experimental data, indicating the kinetic
model was reliable. But if comparing of the low temperatures of
533, 553 and 573 K with the high temperature 593 K, the linear t
of high temperature is relatively poor, indicating the decomposition
of DOTP should be taken into account at high temperature.

3.1. Sub-critical kinetics

On the basis of the results, a simple kinetic model was devel-

oped and used to analyze the data. As for the sub-critical kinetics,
the decomposition of DOTP should not be taken into account, thus
k1
the PET alcoholysis can be simplied into PET DOPT. It can
assume that the polymer depolymerization reaction rate is propor-
tional to the polymer concentration, i.e., it is a pseudo-rst-order
reaction relative to the polymer concentration.
In addition, owing to excess 2-EH, it can also assume that its
concentration has little effect on the reaction rate as the similar Fig. 2. The linear tting curves of ln(1 WDOTP ) versus reaction time t.
 J. Ding et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 99103 101

Table 1
The tting reaction rate constants (k1 ) according to Fig. 2.

T (K) k1 (min1 )

533 0.00411
553 0.01221
573 0.02159
593 0.02681

With increasing temperature, the reaction rate constant k

increases, especially the value 0.02681 at the temperature of 593 K
(close to the critical temperature of 613 K) is much higher than
the value 0.00411 at the temperature 533 K (far away from the
critical temperature), indicating that high temperature accelerates
the alcoholysis of PET to produce DOTP. The result can explain the
reason why in the previous work under sub-critical condition [13]
without any catalysis the alcoholysis reaction rate of PET is much Fig. 4. The linear tting curves of ln WPET versus reaction time t.
faster than traditional reaction at reux temperature under ambi-
ent pressure even if with catalysts.
consecutive reaction and is described by the following reaction Eq.
The rate constant k can be expressed in Arrhenius form of ln
(5).
k = (Ea /RT) + ln A, where A is the pre-exponential factor, Ea is
the activation energy (J mol1 ), R is the universal gas constant k1 k2 k3
PET DOTP TPA Unidentied products (5)
(8.314 J mol1 K1 ), and T is the temperature (K). Then accord-
ing to Arrhenius equation, the line tting relation of ln k and 1/T It was the same as sub-critical kinetic treatment that the excess
gives apparent reaction activation energy Ea and Arrhenius pre- 2-EH was not taken into account and thus Eqs. (6)(8) were
exponential factor A. obtained.
The relation of reaction rate constant k1 and temperature was dWPET
= k1 WPET (6)
linearly tting shown in Fig. 3. According to Arrhenius equation, dt
the line tting relation of ln k1 and 1000/T gives that the apparent
dWDOTP
reaction activation energy (Ea ) is 82.14 kJ/mol and corresponding = k1 WPET k2 WDOTP (7)
dt
pre-exponential factor A is 5.61 105 . Thus, the alcoholysis kinetic
equation of PET in sub-critical 2-EH to produce DOTP is shown as dWTPA
= k2 WDOTP k3 WTPA (8)
Eq. (4). dt
Eqs. (6)(8) are integrated with the initial conditions:
82.14 WPET = WPET ,0 = 1, WDOTP = WTPA = 0 at t = 0. Then the WPET , WDOTP
ln k1 = + ln(5.61 105 ) (4)
RT and WTPA are expressed by Eqs. (9)(11).

WPET = ek1 t (9)

3.2. Super-critical kinetics k1
WDOTP = (ek2 t ek1 t ) (10)
k1 k2
As for super-critical kinetics, the decomposition of DOTP should
be taken into account. Because the sum of WPET , WDOTP and WTPA k1 k2
is less than 1 especially at the highest temperature 653 K, indicat- WTPA = [(k3 k2 )ek1 t (k3 k1 )ek2 t
(k2 k1 )(k3 k1 )(k3 k2 )
ing that the TPA should decompose to some unidentied products.
Therefore, we assumed that the reaction is a pseudo-rst-order + (k2 k1 )ek3 t ] (11)

Fig. 4 is the linear ts of data ln WPET versus t and the k1 were

calculated from the slope shown in Table 2. On the basis of the reac-
tion rate k1 , the value k2 was determined for the curve tting using
the data of WDOTP with the least squares method according to Eq.
(10). With the same method, the value k3 was determined by Eq.
(11) based on k1 and k2 . The values of k2 and k3 were also given
in Table 2. The tting curves were depicted with the experimen-
tal data given in Figs. 5 and 6. The curves were accorded with the
experimental data, indicating that the kinetics model is suitable.
The result shows that the production rate of k1 has much higher
increase from 0.02681 to 0.06200 min1 at the same tempera-
ture interval of 20 K from sub-critical temperature of 593 K to

Table 2
The tting reaction rate constants (k1 , k2 and k3 ) on the basis of Eqs. (9)(11).

T (K) k1 (min1 ) k2 (min1 ) k3 (min1 )

613 0.06200 0.002670 0.001730

633 0.07684 0.004220 0.006130
Fig. 3. Relationship between reaction rate constants and temperature in sub-critical 653 0.08917 0.01061 0.01436
2-EH.
102 J. Ding et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 99103
Fig. 5. The WDOTP of different temperatures with time and their tting curves with
Eq. (10) in super-critical 2-EH.
super-critical 613 K, indicating super-critical uids can very quickly
depolymerize the PET. For every reaction condition, the k1 is greater
than the k2 and the result indicates that alcoholysis of PET to DOTP is
faster than the decomposition of DOTP to TPA. But with increasing
reaction temperature, the decomposition rate of DOTP increases.
Therefore, as for the production of DOTP from alcoholysis of PET,
owing to decomposition rate of DOTP increases very quick with
increasing temperature, the temperature and time should be con-
trolled carefully to avoid the its decomposition in super-critical
2-EH.
As the same method of the sub-critical condition, the linearly t-
ting curves (Fig. 7) of reaction rate constant k1 , k2 and k3 in Table 2
with temperature give the corresponding Ea and pre-exponential
factor A. In super-critical 2-EH of the temperature range from 613
to 653 K, the alcoholysis Ea of PET to DOTP is determined to be
30.29 kJ/mol. Compared with the Ea value 82.14 kJ/mol of sub-
critical condition, the super-critical Ea decreases greatly and the
result is the reason why using super-critical uids can very quickly
depolymerize plastics for chemical recycling [18,19].
Furthermore, comparing with the alcoholysis Ea 49.9 kJ/mol of
PET with super-critical methanol of the temperature range from
553 to 583 K [20], it shows that although the range of tempera-
ture of sub-critical 2-EH is similar with the super-critical methanol,
the Ea of sub-critical 2-EH alcoholysis is greater than the value
of the super-critical methanol. Whereas the range of temperature
Fig. 6. The WTPA of different temperatures with time and their tting curves with
Eq. (11) in super-critical 2-EH.
Fig. 7. Relationship between reaction rate constants and temperature in super-
critical 2-EH.
of super-critical 2-EH has great difference with the super-critical
methanol, but the Ea has less difference. Therefore, the Ea indicates
that the super-critical condition has more important effect on the
depolymerization rates comparing with temperature and molecule.
The result is consistent with that the diffusion of molecule has less
effect on reaction rate in super-critical uids [21,22].
The decomposition Ea of DOTP and TPA are similarly calculated
to be 128.14 and 176.43 kJ/mol, respectively. The result shows that
the Ea of production DOTP is much lower than its decomposition,
indicating that the high yield of DOTP can obtain with feasible reac-
tion time.
The corresponding pre-exponential factors of k1 , k2 and k3 are
determined to be 23.84, 1.78 108 and 1.98 1012 . Thus, the con-
secutive reaction kinetic equations of Eq. (5) are shown in following
Eqs. (12)(14).
30.29
ln k1 = + ln(23.84) (12)
RT
128.14
ln k2 = + ln(1.78 108 ) (13)
RT
176.43
ln k3 = + ln(1.98 1012 ) (14)
RT
4. Conclusion
On the basis of the different mechanism of sub- and super-
critical condition, the alcoholysis kinetics of PET with 2-EH to
produce DOTP was obtained as pseudo-rst-order reaction. Under
the super-critical condition of 2-EH, the DOTP produced from PET
alcoholysis decomposes quickly, thus the kinetics for the produc-
tion of DOTP should consider its decomposition, whereas, in the
sub-critical 2-EH, the decomposition of DOTP is very slow and its
decomposition can be neglected.
The apparent reaction activation energy of production of DOTP
is 82.14 kJ/mol in the sub-critical temperature range of 533593 K,
but the corresponding value in the super-critical temperature range
of 613653 K decreases greatly to 30.29 kJ/mol, indicating that plas-
tics can be quickly depolymerized to low molecule materials for
chemical recycling with super-critical uids. But as for the case of
the product DOTP, its decomposition is disadvantageous in super-
critical condition, therefore, the temperature and time should be
controlled carefully to increase the yield of DOTP in super-critical
2-EH.
According to the result of kinetics of production DOTP from PET
alcoholysis with sub-critical and super-critical 2-EH, the different
type reactor should be adopted. As for the sub-critical process,
 J. Ding et al. / Journal of Analytical and Applied Pyrolysis 106 (2014) 99103
owing to the long time for PET alcoholysis to DOTP and negligi-
ble decomposition of DOTP, the batch-type reactor is a preferable
choice. Whereas, although the reaction rate of PET alcoholysis to
DOTP is very fast, the decomposition of DOTP cannot be neglected,
and thus in order to keep the high efciency and high yield of DOTP,
the continuous ow reactor is more t for the super-critical pro-
cess. The type reactor can easily and effectively control the reaction
time of samples to avoid decomposition of DOTP. The kinetic data
of the work gives important theoretical foundation to industrial
application of the environmentally friendly process of alcoholysis
of waste PET with sub- and super-critical 2-EH to produce DOTP.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (No. 20777048), the Shanghai Leading Aca-
demic Discipline Project (No. S30109), the Innovation Program
of Shanghai Municipal Education Commission (No. 09YZ30), and
the Opening Project of State Key Laboratory for Mineral Deposit
Research (No. 17-1112-9).
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