Journal of Chemical Engineering of Japan, Vol. 39, No. 3, pp.

327–333, 2006 Research Paper

Hydrolysis of Dimethyl Terephthalate for the Production of

Terephthalic Acid
Myungsang SIM and Myungwan HAN
Department of Chemical Engineering,
Chungnam National University,
220 Gung-dong, Yuseong-gu, Daejeon 305-764, Korea

Keywords: Terephthalic Acid, Dimethyl Terephthalate, Hydrolysis, Mono Methyl Terephthalate, Kinetics

Hydrolysis of dimethyl terephthalate (DMT) to produce terephthalic acid (TPA) was studied using a
batch reactor. Zink acetate was used as a catalyst to promote the reaction rate. We found that the reac-
tion consists of two reactions: from DMT to mono methyl terephthalate (MMT) and then MMT to TPA.
The first reaction is relatively fast and irreversible while the second reaction is relatively slow and re-
versible. A kinetic equilibrium constant for the second reaction decreases with reaction temperature. A
kinetic model consisting of the two reactions for the hydrolysis fitted well with the experimental data.

Introduction be used directly in PET synthesis, it must be crystal-

Poly(ethylene terephthalate) (PET) is a
semicrystalline thermoplastic polymer. The polyester
resin is widely used in films, in bottles, and in fiber
due to its excellent characteristics such as thermal sta-
bility, clarity, strength and moldabilty. The amount of
PET production has been rising recently, leading to a
continuous increase in the generation of the plastic
waste. Disposal of the waste plastic has posed serious
environmental as well as economic problems. Chemi-
cal recycling can be a promising technology to deal
with these problems by converting the wastes to use-
ful feedstock materials for polyester production.
Chemical recycling through depolymerization of
PET can be carried out in various ways, for the pro-
duction of terephthalic acid (TPA), dimethyl
terephthalate (DMT) or hydroxyethyl terephthalate
(BHET), all of them being possible monomers for the
production of fresh polyester. Depending upon the
depolymerization agent, the depolymerization method
can be classified: methanolysis (Everette, 1992;
Naujokas and Ryan, 1991; Gamble et al., 1994), gly-
colysis (Vaidya and Nadkarni, 1987, 1988) and hy-
drolysis (Lamparter, 1985; Mandoki, 1986), etc.
Methanolysis produces DMT and ethylene glycol
(EG). The main advantage of this method is that it is
easier to purify DMT than the other monomers, BHET
and TPA, allowing a treatment of a lower quality feed
of PET. It is difficult to purify TPA from the reaction
mixture since it has low solubility and low vapor pres-
sure. To achieve TPA of an acceptable purity for it to
Received July 13, 2005. Correspondence concerning this arti-
cle should be addressed to M. Han (E-mail address:
mwhan@cnu.ac.kr).
lized a number of times. In polyester plants built re-
cently, TPA is mostly used as a feedstock for polyester
production. In this context, the combination of
methanolysis and hydrolysis can be proposed as a
promising alternative to obtain high-purity TPA from
low quality PET wastes (Schoengen et al., 1981).
In the combined Process, degradation in
methanolysis reduces the reaction effort necessary in
the hydrolysis plant. Moreover, a large quantity of con-
taminants, present in the original PET waste, is sepa-
rated during and after the first treatment, which favors
the product purification. In the hydrolysis step, DMT
produced in methanolyis instead of polyester waste is
hydrolyzed to TPA.
A kinetic model to describe the hydrolytic
depolymerization of melt PET has been studied
(Campanelli et al., 1993; Kao et al., 1998). However,
little effort has been made to investigate the kinetics
of DMT hydrolysis. In the present work, we are con-
cerned about the hydrolysis reaction of DMT to obtain
TPA. Zinc acetate was used as a catalyst to promote
the reaction rate. Zinc acetate was found to increase
the rate of PET hydrolysis by approximately 20%
(Campanelli et al., 1994). We investigated the influ-
ence of temperature, the water/DMT feed ratio, cata-
lyst concentration on TPA yield, the kinetics and rate
determining step during the hydrolysis.
1. Experimental
A batch type reactor was used for all the hydroly-
sis experiments. The reactor was made of stainless steel
316 and had an inner volume of 5 ml. The reaction
temperature was considered to be equal to that of an

Copyright © 2006 The Society of Chemical Engineers, Japan 327


Fig. 1 Schematic diagram of the experimental apparatus
for TPA synthesis
oil bath in which the reactor was immersed. The ex-
perimental apparatus is shown in Figure 1.
Experimental procedures are as follows. We im-
mersed several reactors with a feed of the same com-
position and the same amount of catalyst in an oil bath
simultaneously. The oil bath was maintained at a de-
sired temperature. We agitated the reaction contents
by shaking the reactors at 90 rpm to reduce the influ-
ence of mass transfer. The hydrolysis reactions were
carried out at temperatures between 473 and 503 K.
The reaction time was varied from 5 min to 8 h. When
the specified reaction time for each reactor was met,
the corresponding reactor to the specific reaction time
was removed from the bath and quenched quickly in
an ice bath to stop the reaction proceeds. This proce-
dure continued until final reaction time was over. Then,
the reaction contents were dried over 12 h to remove
water from the contents completely. This is because
TPA is slightly soluble in water so that water in the
reaction product may cause some experimental errors.
The water/DMT ratio and catalyst concentration were
also varied to examine the effect of the variable on the
hydrolysis reaction.
The reaction products, DMT, MMT, and TPA,
were analyzed by G.C.-FID. The G.C. column used for
this analysis was a BP21 capillary column and had a
dimensions of 25 m length and 0.53 mm internal di-
ameter. DMF (dimethyl formamide) was used as a sol-
vent for DMT, MMT, TPA. The gas chromatography
was calibrated by injecting various amounts of pure
components with benzoic acid as an internal standard.
Oven temperature of the gas chromatography was tem-
perature programmed to rise gradually from 160°C to
260°C. DMT (99+%), MMT (97%) and TPA (98%) for
this analysis were supplied by Sigma-Aldrich Co. Zink
acetate (98%) was a product of Hayasi Pure Chemical
Industries, Ltd. DMF (99%) and benzoic acid (99.5%)
328
Fig. 2 Effect of reaction temperature on TPA yield: reac-
tion time, 8 h; water/DMT weight ratio, 2; catalyst
concentration, 2 g/l
were supplied by Samchun Pure Chemical Co., Ltd and
Duksan Pharmaceutical Co., Ltd. High-purity helium
(99.999+%), hydrogen and air were used as carrier gas.
The water used was of high-purity HPLC grade.
2. Results and Discussion
The main products of DMT hydrolysis were MMT
and TPA (Schoengen et al., 1981). The reaction yield
depends on reaction temperature, reaction time, cata-
lyst concentration, water to DMT ratio. In the present
work, we investigated the kinetics of DMT hydrolysis
from 1 to 6 of water to DMT weight ratio at tempera-
tures of 200–230°C. We obtained from 0.6 to 0.9 of
TPA yield at the experiments using a batch reactor.
2.1 Temperature dependence of TPA yield
The temperature dependence of the yields of TPA
is shown in Figure 2. The TPA yields were obtained
from a series of runs for the hydrolysis reaction for 8 h
at reaction temperatures of 200–230°C. The reaction
time was chosen to be enough for reaching reaction
equilibrium from our experimental data. TPA yield
decreases with reaction temperature. This result sug-
gests that the hydrolysis reaction is equilibrium-lim-
ited and the reaction equilibrium of the hydrolysis de-
creases with temperature. Rising temperature increases
the reaction rate but decreases the reaction yield, which
is characteristic of reversible exothermal reactions.
2.2 Reaction pathway
The time dependencies of DMT, MMT, and TPA
are presented in Figure 3. DMT concentration de-
creases exponentially as the reaction proceeds. MMT
concentration rises and then falls to some equilibrium
concentration. TPA rises continuously to some equi-
librium concentration. The characteristic of the con-
centration–time curves for three components is found
in the reaction consisting of two elementary reactions:
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
 Fig. 4 Two-step reactions for TPA synthesis from DMT

Fig. 5 Effect of water/DMT ratio on TPA yield

yield increases with the water/DMT ratio but it tends

to saturate above 4 or 5. However, excess water leads
to not only an increase of energy consumption but also
remarkable increase in capital cost. It appears that the
water/DMT ratio of 4–5 is optimal in a batch reactor.
2.4 Kinetics
A kinetic model of DMT hydrolysis was con-
structed considering the following two reactions based
on our experimental results.

DMT + H2O → MMT + CH3OH (1)

Fig. 3 Dynamic molar concentrations of (a) DMT, (b) MMT,
MMT + H2O → TPA + CH3OH (2)
and (c) TPA at different reaction temperatures

We assumed that the reactions are first order with

respect to concentration of each component. The reac-
one is an irreversible reaction from DMT to MMT and tion rate of each component during the batch can be
the other is a reversible reaction from MMT to TPA. expressed as:
Therefore, we proposed the reaction pathway illustrated
in Figure 4.
d
2.3 Influence of water/DMT ratio on hydrolysis [DMT] = − k1[DMT][H 2 O] (3)
If the hydrolysis reaction is equilibrium-limited, dt
excess water can shift the reaction equilibrium, lead-
ing to the rise of TPA yield. Figure 5 shows that TPA

VOL. 39 NO. 3 2006 329

 Table 1 Frequency factors and activation energies
from the Arrhenius plot

K 0 [l mol–1 h–1] E [J mol–1]

k1 8.911 × 108 9.275 × 104
k2 1.475 × 105 6.283 × 104
K2 1.157 × 10–14 –1.269 × 105

Fig. 7 Arrhenius plot of the reaction equilibrium constant

for the reaction from MMT to TPA

d d
Fig. 6 Arrhenius plot of rate constants for TPA synthesis: [CH 3OH] = [ H 2 O] (7)
dt dt
(a) reaction from DMT to MMT; (b) reaction from
MMT to TPA
where k 1 and k 2 refer to reaction rate constants for
Eqs. (1) and (2), respectively. K2 refers to a reaction
equilibrium constant for Eq. (2) and is defined as:
d
[MMT] [TPA][CH 3OH]
dt K2 = (8)
= k1[DMT][H 2 O] [MMT][H 2 O]

 1 
− k2 [MMT][H 2 O] − [TPA][CH 3OH] ( 4) The values of k1, k2, and K2 were determined by
 K2  regressing the experimental data using the proposed
model. The first reaction (Eq. (1)) is relatively fast
compared to the second reaction (Eq. (2)). For the sec-
d  1  ond reaction, the reaction equilibrium shifts toward an
[TPA] = k2 [MMT][H 2 O] − [TPA][CH 3OH] unfavorable reverse reaction with increasing tempera-
dt  K2 
ture. It indicates that the second reaction is a rate-
(5) determining step among the two reactions.
Figures 6 and 7 show the temperature dependence
of the rate constants and equilibrium constant in the
d hydrolysis reaction of DMT. We obtained the values
[ H 2 O]
dt of activation energy and frequency factor for each re-
= − k1[DMT][H 2 O] action from the Arrhenius plots. The parameter values
are shown in Table 1. Using the linear regression
 1 
− k2 [MMT][H 2 O] − [TPA][CH 3OH] (6 ) (Sigma Plot, Rockware, Inc.), we calculated that the
 K2  R-square, indicating the linearity of fitting to the tested
model, was 0.993 for Eq. (1) and was 0.985 for the
rate constant of Eq. (2). The R-square was 0.995 for

330 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN


Fig. 8 Results of fitting: reaction temperature: (a) 210°C,
(b) 230°C; water/DMT weight ratio, 2; catalyst con-
centration, 2 g/l
the equilibrium constant in Eq. (2). Figure 8 shows
the experimental results and the simulated ones based
on the fitted parameters and the proposed model in
terms of the dynamic molar concentrations of DMT,
MMT, and TPA. The proposed model is shown to yield
good predictions for the dynamic molar concentrations.
2.6 Influence of catalyst concentration on hydroly-
sis
Figure 9 shows the effect of catalyst concentra-
tion on the TPA yield. The yield of TPA increases with
catalyst concentration. The reaction proceeded even
without a catalyst and the rate of the catalyzed reac-
tion was directly proportional to the catalyst concen-
tration. The TPA yields were obtained varying catalyst
concentration when the DMT to water ratio were 1:2
and the reaction proceeds 2 h at the temperature of
210°C.
The overall rate of disappearance of reactant DMT
can be expressed as follows:
VOL. 39 NO. 3 2006
Fig. 9 Effect of catalyst concentration on TPA yield: re-
action time, 2 h; water/DMT weight ratio, 2; reac-
tion temperature, 210°C
d
− [DMT] = k1′ [DMT][H 2 O] + k1′′ [DMT][H 2 O]CC
dt
( )
= k1′ + k1′′ CC [DMT][H 2 O] ( 9)
where CC represents the catalyst concentration for the
hydrolysis reaction which has the unit of g-catalyst/
reactor volume l. Here, k′ refers to the rate constant
for the reaction without catalyst and k′′ is the rate con-
stant for the reaction with catalyst. Equations (4)–(7)
can also be modified to involve the effect of catalyst
concentration on the hydrolysis kinetics in the same
manner.
We can find reaction rate constants k′ and k′′ by
making a series of runs with different catalyst concen-
trations. This was done by plotting the observed k value
against the catalyst as shown in Figure 10. The figure
shows that the reaction rate constants increase linearly
with the catalyst concentration. The slope of the plot
is k′′ and the intercept k′.
We can determine the observed k1 and k 2 by com-
paring the simulation results with the experimental
ones. The simulation data was calculated by integrat-
ing Eqs. (3)–(7).
The reaction rate for uncatalyzed hydrolysis,
which is represented by the rate constant k′, can be
accelerated also by terephthalic acid, which is a prod-
uct of this reaction and can act as an acidic catalyst.
Hydrolytic depolymerization of PET was found to pos-
sess a kinetic model of autocatalysis by the hydrogen
ion formed by the dissolution of the terephthalic acid,
which can be dissociated to a hydrogen ion in water
(Kao et al., 1998).
The hydrolysis reaction rate is catalyzed by zinc
catalyst as well as terephthalic acid. Temperature de-
pendence of the rate constants k1 and k2 is shown in
Figure 6. Linearity of the Arrehenius plot supports that
331
 The maximum of TPA yield that we could reach by
using the ordinary batch reactor was 90%. The limita-
tion in getting a good TPA yield was found to be caused
by the reaction equilibrium constraint.
We proposed a kinetic model to describe the hy-
drolysis reaction which transforms DMT to TPA. We
found that the reaction consists of the following two
reactions:

DMT + H 2O → MMT + CH3OH (13)

DMT + H2O → TPA + CH3OH (14)

The first reaction proceeds fast and irreversible.

The second reaction is slow and reversible and the re-
action equilibrium constant decreases with tempera-
ture. It indicates that the second reaction is a rate-de-
termining step. Dependencies of the rate constants and
equilibrium constant on reaction temperature were cor-
related by Arrhenius plots, which shows activation
energies of 9.275 × 10 4 , 6.238 × 10 4 , –1.269 × 10 5
J/mol for k 1, k2 and K2. Simulation results based on the
proposed model and the fitted parameters were shown
to well represent our experimental data. We also con-
sidered the effect of catalyst concentration on the re-
action rates in the proposed simulation model.

Acknowledgment
This work was supported by the Resource Recycling R&D
Center, Korea.
Fig. 10 Evaluation of rate constants from a series of runs
with different catalyst concentrations at the reac- Nomenclature
tion temperature of 220°C: (a) k 1, (b) k2 CC = catalyst concentration [g/l]
[DMT] = concentration of DMT [mol/l]
[H2O] = concentration of water [mol/l]
K = reaction equilibrium constant [—]
k′ and k′′ should have similar temperature dependence. k = reaction rate constant [l/mol/h]
We assumed that the rate constants, k′ and k′′, have the [MMT] = concentration of MMT [mol/l]
same activation energy. Campanelli et al. (1994) also [MeOH] = concentration of methanol [mol/l]
reported that zinc catalyzed hydrolysis of PET melts [TPA] = concentration of TPA [mol/l]
t = reaction time [h]
has not clearly different activation energy from that
calculated from the uncatalyzed data (i.e., <Subscript>
autocatalyzed by terephthalic acid). Therefore, the rate 1 = related to Eq. (1)
constants considering the effect of both the catalyst 2 = related to Eq. (2)
and reaction temperature can be written as follows.
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