Applied Catalysis A: General 358 (2009) 5458

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Co-oxidation of p-xylene and p-toluic acid to terephthalic acid in water solvent:

Kinetics and additive effects
Jin Won Kwak, Jae Sung Lee *, Kyung Hee Lee **
Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH), San 31, Hyoja-dong, Pohang 790-784, South Korea

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 20 December 2008
Received in revised form 29 January 2009
Accepted 29 January 2009
Available online 6 February 2009

Co-oxidation of p-xylene (PX) and p-toluic acid (p-TA) to terephthalic acid (TA) in water with Mn acetate
catalyst has been studied. Mn acetate showed better catalytic activity than Co acetate and no synergism
was observed between two catalysts. During the reaction, PX was transformed to p-TA while p-TA was
converted to TA by a radical reaction. In the co-oxidation, radicals generated from facile PX-to-p-TA
conversion would assist more difcult p-TA to TA conversion. Addition of CO2 in the oxygen promoted
the TA formation and suppressed the CO2 formation from the combustion of reactants. Additional
transition metals such as Ni and Ti also promoted the catalytic activity of Mn catalyst. Furthermore, a
synergism was observed between added CO2 and the added transition metal. Finally, the yield of
terephthalic acid reached about 95% with Mn + (Ti, Ni or Cr) catalyst system and CO2 addition.
2009 Elsevier B.V. All rights reserved.

Keywords:
Terephthalic acid
Co-oxidation
Water solvent
Manganese acetate
CO2 effect

1. Introduction
Puried terephthalic acid (TA) is an important petrochemical
product and the main source of polyethylene terephthalate, a
major material for textiles and bottles. About 42 million tons of TA
was produced in the world [1] and 5.6 million tons in Korea in 2006
[2]. Today most of TA in the world is produced by the Amoco-MC
process. In this process, p-xylene (PX) is oxidized by air at about
200 8C, 20 atm with soluble Co/Mn catalysts, acetic acid solvent
and a Br promoter. After oxidation, the nal cake called crude
terephthalic acid contains about 3000 ppm of 4-formylbenzoaldehyde (4-CBA) and 500 ppm of p-toluic acid (p-TA) as impurities.
Since the content of impurities is too high for polymerization, the
cake is hydrogenated to convert 4-CBA to p-TA in a subsequent
purication process [3]. Upon hydrogenation, p-TA is separated
from TA by crystallization. The nal puried TA contains less than
25 ppm of 4-CBA and 150 ppm of p-TA.
The Amoco-MC process is highly efcient and optimized with
extended experience of commercial operation. But it causes serious
environment, economy and safety problems by using the bromine
promoter and the acetic acid solvent. For example, anti-corrosive
materials like Ti are needed for the equipment because of the highly
corrosive bromine and acetic acid, which raises the initial investment
and maintenance cost. Further, this process needs various acetic acid

* Corresponding author. Tel.: +82 54 279 2266; fax: +82 54 279 5528.
** Corresponding author.
E-mail address: jlee@postech.ac.kr (J.S. Lee).
0926-860X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.01.037

recovery and recycling units from its aqueous solution, which add
investment and operating cost further. In addition, a large amount of
acetic acid is lost in real plants by combustion and handling and fresh
acetic acid is replenished to compensate for the loss. Moreover, in the
overall TA manufacturing process, PX oxidation is carried out in
acetic acid solvent but TA purication in water. Thus PX oxidation
and TA purication units should be strictly separated. It makes the
whole process more complicated and increases the operation cost
and risk. In particular, liquid bromine compounds cause serious
equipment corrosion and gaseous compounds bring environmental
problems in vent streams [4]. So installation of bromine scrubber is
essential to mitigate these problems in the downstream, which
pushes up the production cost further.
Many attempts have been made to remove the bromine and
acetic acid from the TA production process since 1970s [5,6].
Hronec and Ilavsky [7] proposed the co-oxidation of PX and p-TA in
water to produce TA at a high yield (more than 90%). Ishii and
Sakaguchi [8] carried out PX oxidation with N-hydroxyphthalimide (NHPI) as a promoter instead of Br, and the yield of TA was
near 95%. Dunn et al. [9] studied PX oxidation in a supercritical
water solution, which produced TA with about 80% yield. There
have also been a few reports on the improvement of Amoco-MC
type oxidation of PX, i.e. Co/Mn/Br catalysts in acetic acid. Thus,
Yoo et al. [10] found a promotional effect of carbon dioxide added
to the reaction mixture of the Amoco-MC oxidation.
Among the proposed methods of PX oxidation without Br
promoter and/or acetic acid solvent, we considered that cooxidation of PX and p-TA in water was a most promising one. It
needs neither obnoxious Br promoter nor corrosive acetic acid

J.W. Kwak et al. / Applied Catalysis A: General 358 (2009) 5458

solvent, yet can give high TA yields under similar reaction

conditions practiced in the current Amoco-MC process. However,
for practical application, further studies are necessary to improve
the TA yield from 90% to the level of the Amoco-MC process, i.e.
above 95%. Since the original reports in 1980s [7,1113], there has
been no work to extend or improve this interesting catalytic
reaction system. In attempt to improve the performance of PX
oxidation in water in the absence of Br promoter, we rst studied
the kinetics of the co-oxidation of PX and p-TA with soluble Mn
catalyst in water. Second, we investigate the effects of additives, i.e.
CO2 and additional transition metals on the performance of the
reaction system. Thus in the proposed new reaction system,
though Br and acetic acid were not utilized as a promoter and
solvent, respectively, high yield for terephthalic acid was obtained
by using a Ti promoter and CO2 addition.
2. Experimental
2.1. Oxidation of PX and p-TA
The reaction mixture made of PX (Junsei, reagant), p-TA (Aldrich,
98%), and distilled water were introduced to a 100 ml autoclave
(Autoclave Engineers, 316SS). A single or combination of manganese
(II) acetate tetrahydrate (Junsei, extra pure), cobalt (II) acetate
tetrahydrate (Aldrich, 99%), and other transition metal salts was
added to the autoclave as a soluble catalyst. While stirring at 500 rpm,
the temperature of the reactor was maintained by an electric furnace
controlled by a PID controller. At desired temperature and pressure,
oxygen (Linde, 99.8%) was continuously supplied to make up the
consumed oxygen through a mass ow controller (Brooks). The
amount of consumed oxygen was monitored by integrating mass
ow controller readings. If necessary, carbon dioxide (Linde, 99.6%)
was added to the oxidation system in a similar manner.
2.2. Analysis
After reaction, the off-gas was analyzed by a gas chromatograph
(GC, HP 5890) with a TCD detector and an Alltech CTR1 column (at
120 8C). Residual PX was extracted by n-hexane, and analyzed in a
GC (HP 6890) with a FID detector and a capillary column (DB-WAX,
60 m  0.32 mm  0.25 mm, J&W Scientic). The oven temperature for the GC was programmed from 110 to 250 8C for the
analysis of PX and n-hexane.
Solid products were dried for 12 h in an oven, and weighed and
dissolved in dimethyl sulfoxide (Junsei). The solution was analyzed
by high performance liquid chromatography (HPLC, Waters 2697)
using an Inertsil column (C18, D = 4.6 mm, L = 150 mm) and UV
detector (Waters 2487) at 254 nm. The mobile phase was
composed of 16.8 ml acetic acid, 160 ml acetonitrile and redistilled water to make up 1 l. The HPLC was operated in isocratic
mode at ambient temperature.

55

The para-toluic acid in products is separated from TA and

recycled for co-oxidation. In contrast, the conventional Amoco-MC
oxidation chemistry proceeds as follows:

(2)

Mechanistically, the Amoco-MC oxidation could be considered

as a two-step reaction, i.e. PX oxidation to p-TA, and then further
oxidation to the nal product TA [14]. The oxidation of the rst
methyl group of PX to p-TA is relatively easy with redox catalysis
by metal ions including Co(III) and Mn(III). However, the second
step oxidation of p-TA is severely hindered by deactivation effect of
carboxyl group against oxidation of the remaining methyl group.
Thus, PX oxidation with metal ion catalysts usually stops at p-TA
stage under mild conditions. But when a bromine compound is
introduced into the reaction, the reaction proceeds to completion
under mild conditions. The Br radical is responsible for activation
of p-TA by generating HOOC CH2 radical. The role of metal
catalysts here is to generate active Br radicals from inactive Br
ion.
In Amoco-MC chemistry, synergy between Co and Mn has been
well established with Co being the main catalyst component while
Mn is a promoter to facilitate Co(III)/Co(II) redox cycle [14]. Thus,
the effect of Co/Mn composition was rst investigated in cooxidation of PX and p-TA. As shown in Fig. 1, Mn alone showed
higher catalytic activity of TA production than Co alone almost by a
factor of 2 and the activity decreased monotonously as an
increasing amount of Mn(II) acetate was replaced by Co(II) acetate.
No synergism was observed between them. This result represents a
sharp contrast to the case of Amoco-MC oxidation [15]. Here, Co
shows higher activity than Mn, and signicant synergy between
them is observed. This different catalytic behavior suggests
different roles of the metal catalysts in the two systems. As
mentioned, the main role of metal catalysts in Amoco-MC
chemistry is to activate Br. In the co-oxidation of PX and p-TA
in water, the metals should activate reactants directly. In any case,

3. Results and discussion

3.1. Catalysts and the reaction prole
The reaction studied here is the co-oxidation of PX and p-TA in
water as follows:

(1)
Fig. 1. Produced TA vs. mole fraction of Co in catalyst solution: reaction conditions
PX
6.4 g
(0.06 mol),
p-TA
12.24 g
(0.09 mol),
water
8 g,
Co(OAc)24H2O + Mn(OAc)24H2O = 0.36 mmol (xed), 195 8C, 22 atm (O2 8 atm,
water vapor 11 atm and PX vapor 3 atm), reaction time 3 h.

J.W. Kwak et al. / Applied Catalysis A: General 358 (2009) 5458

56

Table 2
Composition of deutrated compound in each intermediate.a.
Reaction time (min)

30
60c

Fraction of the isotope in the substance (%)

p-Tolualdehyde

p-TA

4-CBA

TA

10.2
9.4

8.8
5.4

0
3.0

0
2.8

a
PX 7 g (66.0 mmol), deutrated PX 1 g (9.1 mmol), p-TA 15.3 g (112.5 mmol),
water 6.5 g, Mn(OAc)24H2O 0.225 g (0.9 mmol) 195 8C, 27 atm (O2 8 atm, N2 5 atm,
water vapor 11 atm, PX vapor 3 atm), reaction time 3 h.
b
PX conversion: 42.3%.
c
PX conversion: 80.1%.

Fig. 2. The amounts of PX and TA vs. the reaction time. The amount of p-TA shows
the change from the initial amount. Inset shows the time change of oxygen
consumption: reaction conditions PX 8 g (75.5 mmol), p-TA 15.3 g (112.5 mmol),
water 6.5 g, Mn(OAc)24H2O 0.225 g (0.9 mmol), 195 8C, 27 atm (O2 8 atm, N2 5 atm,
water vapor 11 atm and PX vapor 3 atm).

the results are consistent with the initial report of Hronec and
Ilavsky [7] and only Mn(II) acetate was used as a catalyst in the
subsequent study unless stated otherwise.
The time course of the reaction is presented in Fig. 2 together with
the oxygen consumption prole (inset). The rapid conversion of PX
was observed at the beginning, but the reaction rate of PX conversion
became slower with reaction time and reached almost zero after
80 min. The amount of p-TA increased slightly initially with reaction
time and hit a broad maximum at 30 min, and then decreased
gradually. The formation of TA was observed from the beginning
with a steady rate up to 80 min, and then the rate became slower but
the formation continued until the end of the reaction. Oxygen
consumption continued at a steady rate up to about 80 min and then
almost stopped after then. Thus 80 min seems to be a proper reaction
time to convert PX to TA without much change in the amount of pTA. Further reaction beyond 80 min converted only p-TA to TA,
probably using oxygen dissolved in water.
Several control experiments were carried out to elucidate the
nature of this co-oxidation reaction. First, when 2,6-di-tert-butyl4-methoxyphenol (Aldrich, 97%) was added to the reaction system
as a radical scavenger, the reaction did not occur at all. This is
evidence that the co-oxidation of PX and p-TA in water is a freeradical reaction. From the relative study with substituted toluenes,
Hronec and Ilavsky [7] also proposed that the reaction proceeded
through a free-radical mechanism. This differs from the known
catalytic oxidation chemistry of alkyl aromatics in acetic acid
solvent, where an electron transfer mechanism prevails and Co(II)
acetate is more effective than Mn(II) acetate [16].
Table 1 lists results of other control experiments to show the
unique role of p-TA. Under the standard condition with Mn(II)
acetate in water without p-TA addition, PX conversion was 48.4%,
Table 1
Result of the co-oxidation of PX with various materials.a.
Reactant

PX conversion (%)

Formed TA (g)

PX 188 mmol
PX 75.5 mmol + p-TA 112.5 mmol
p-TA 188 mmol
PX 75.5 mmol + 4-CBA 112.5 mmol
PX 75.5 mol + TA 112.5 mol

48.4
100.0

20.0
4.1

0.4
13.8
0.5
7.6

a
Reactant 188 mmol, water 6.5 g, Mn(OAc)24H2O 0.225 g (0.9 mmol), 180 8C,
27 atm (O2 8 atm, N2 5 atm, water vapor 11 atm, PX vapor 3 atm), reaction time 3 h.

but the amount of formed TA was very small (0.4 g). Thus the
majority of PX was converted only to p-TA and a small fraction of it
was converted all the way to TA. When both PX and p-TA were
present as reactants, PX conversion was 100%, and TA was formed
with an apparent yield (based on PX consumption) of 111%. The yield
higher than 100% indicates that a signicant fraction of TA came
from p-TA. When p-TA alone was oxidized at the same condition, the
reactivity was negligible. When 4-CBA, another important intermediate in PX-to-TA conversion was used, substantial degrees of PX
conversion and TA formation were observed. But the effect was not
as good as the combination of p-TA and PX. Finally, TA itself did not
show any help in the conversion of PX. The results have
demonstrated the unique effectiveness of p-TA/PX co-oxidation to
transform PX to TA in water with Mn(II) acetate as the sole catalyst.
In another experiment, about 10% of deuterated PX (C6D4(CH3)2)
was mixed with the normal PX and co-oxidized with normal p-TA
under the standard conditions. Table 2 shows the isotope distributions in each product at reaction times of 30 and 60 min. Note that PX
is transformed to TA through these intermediates, i.e. PX ! ptolualdehyde ! p-TA ! 4-CBA ! TA. Most of the isotopes were
found in p-tolualdehyde and p-toluic acid at 30 min and then, they
spread out to the next step molecules with time of the reaction. The
result indicates that most of TA is originated from initial p-TA, while
PX is transformed to p-TA as shown below:

(3)

As mentioned, p-TA conversion to TA is much more difcult than

PX conversion to p-TA due to the ring deactivating effect of electronwithdrawing carboxyl group of p-TA. This is where bromine radicals
step in to activate methyl group of p-TA. Then, how p-TA could be
activated in the co-oxidation system? There are several examples of
PX oxidation together with a co-oxidizable organic compound such
as acetaldehyde, paraldehyde, and 2-butanone with Co/Mn catalysts
[17]. The action of co-oxidized compound as a promoter is due to its
facile conversion to very reactive radical species that could promote
the more difcult conversion step. In the present case, PX seems to
be the promoter that helps more difcult conversion of p-TA. In the
past, there was even a process to co-oxidize PX and p-toluic acid
monomethyl ester with CoMn catalyst to produce eventually
dimethyl terephthalate [17].
3.2. Effects of CO2 and additional metals
The co-oxidation of PX and p-TA in water with Mn(II) acetate
catalyst offers an eco-friendly process to manufacture TA without

J.W. Kwak et al. / Applied Catalysis A: General 358 (2009) 5458

57

Table 3
Effects of CO2 addition replacing a part of oxygen.a.
Total pressure
(atm)

CO2 fraction in
gas phase

O2 fraction in
gas phase

Residual PX
after reaction (g)

p-Toluic
acid (g)

4-CBA (g)

TA (g)

Generated COx
from reaction (g)

27
30
33
37

0.000
0.109
0.184
0.259

0.296
0.267
0.242
0.216

2.24
2.05
1.85
2.94

12.54
10.66
10.15
13.97

0.86
0.76
0.77
0.61

10.93
11.69
12.43
8.02

1.12
0.78
0.70
0.35

a
PX 8 g (75.5 mmol), p-TA 15.3 g (112.5 mmol), water 6.5 g, Mn(OAc)24H2O 0.225 g (0.9 mmol), 195 8C, reaction time 3 h. The base case was O2 8 atm, N2 5 atm, water
vapor 11 atm and PX vapor 3 atm.

using bromine compound and acetic acid. However, for practical

application, further studies are necessary to improve the TA yield
from 90% to the level of the Amoco-MC process, i.e. above 95%.
Carbon dioxide was added for the purpose by replacing a part of O2.
As shown in Table 3, the extent of PX conversion and the amount of
produced TA hit the maximum when CO2 was about 18% in the gas
phase. Above the concentration, the activity decreased probably due
to excessively reduced oxygen partial pressure. In addition,
generation of COx (CO and CO2) from reactant burning also decreased
as the partial pressure of CO2 increased. This provides signicant
advantage in practical applications by reducing the loss of reactants.
Regarding the promotional effect of CO2, two theories have
been proposed. First, CO2 was considered as an expanded solvent,
which helped the dissolution of O2 to the reaction media [18].
Second, CO2 was proposed to form metal peroxocarbonates (CO4)
with the catalyst and oxygen under Amoco-MC process conditions
of Co/Mn/Br in acetic acid solvent [10]. These peroxocarbonates
would promote the formation of PX radicals by oxygen transfer and
increase overall catalytic activity [1921]. In the co-oxidation of PX
and p-TA in water, these peroxocarbonates may play the similar
role of a promoter.
Some transition metal salts were added to Mn(II) acetate to
improve the catalytic activity (Table 4). All metals (except Fe)
showed promotional effects by improving TA yield. In particular, Ti
showed the best performance. In the optimization experiment of Ti
concentration, 5 mol% of Mn was found to be the optimum as
shown in Table 5. The performance remained almost constant
Table 4
Effect of various co-catalysts in manganese acetate-catalyzed co-oxidation of PX
and p-TA in water.a.
Co-catalyst

PX (g)

p-Toluic
acid (g)

4-CBA (g)

TA (g)

Generated
COx (g)

Base case
Ni
Zr
Ti
Fe
Cr

2.24
2.39
2.00
1.87
3.00
1.95

12.54
10.11
10.96
11.27
10.52
11.28

0.86
0.79
0.88
0.69
1.09
0.74

10.93
11.22
11.01
12.09
10.59
11.59

1.12
1.17
1.14
1.30
1.24
1.25

a
PX 8 g (75.5 mmol), p-TA 15.3 g (112.5 mmol), water 6.5 g, Mn(OAc)24H2O
0.225 g (0.9 mmol), 195 8C, 27 atm (O2 8 atm, N2 5 atm, water vapor 11 atm and PX
vapor 3 atm), co-catalyst 0.045 mmol, reaction time 3 h.

Table 5
Effects of various Ti concentrations in manganese acetate-catalyzed co-oxidation of
PX and p-TA in water.a.
Amount of Ti
(mmol)

PX (g)

p-Toluic
acid (g)

4-CBA (g)

TA (g)

Generated
COx (g)

0.0000
0.0225
0.0450
0.0675

2.24
2.05
1.87
2.25

12.54
10.11
11.27
10.30

0.86
0.74
0.69
0.68

10.93
11.41
12.09
12.02

1.22
1.47
1.30
1.20

a
PX 8 g (75.5 mmol), p-TA 15.3 g (112.5 mmol), water 6.5 g, Mn(OAc)24H2O
0.225 g (0.9 mmol), 195 8C, 27 atm (O2 8 atm, N2 5 atm, water vapor 11 atm and PX
vapor 3 atm), TiCl4, reaction time 3 h.

above that concentration. In all cases, addition of second metals

increased the COx generation slightly by reactant combustion.
In MC oxidation process with Co(II)/Mn(II)/Br catalyst,
addition of an additional third metal improve the performance
[14]. It was proposed that the third metal was inserted to the redox
cycle and raises the rate of redox reaction of the other ions.
Furthermore, the strength of the promotion was proposed to be
determined by the Lewis acidity of the added transition metal
[22,23]. In the present case, the action of the added metal, e.g. Ti,
could be to help redox cycle of Mn, and thus increase the amount of
more active Mn3+ ion by the following reaction;
Mn2 MN 1 ! Mn3 MN

(4)

The direct participation in the activation of reactants may not

be signicant because these metals are much less active than Mn
when they are used alone. The formation of Mn3+ may also be
responsible for the increased COx formation, because high valent
metal ions are known for their high activity for decarboxylation
reactions.
When the co-catalyst and CO2 were added simultaneously, PX
conversion and TA production were improved further as shown in
Table 6, relative to the cases that only one kind of additives was
used. The amount of 4-CBA also became less than the result of cocatalyst experiment or CO2 addition experiment. The change of COx
generation was almost the same as the increase by the additive
metal and suppression by added CO2 might cancel each other.
Apparently a synergetic effect is operating between two additives
of CO2 and a transition metal on co-oxidation with Mn(II) acetate.
Thus, the overall catalytic activity rises more than the sum of the
individual performances of additive CO2 and transition metal. The
synergism was particularly strong for CO2 and Ni.
Fig. 3 summarizes schematically ideas on the roles of catalyst/
promoter components in the co-oxidation of PX and p-TA in water,
especially for activation of less reactive p-TA. The Mn3+ ion is
considered to be the main catalytic component responsible for
generation of radicals from p-TA. The generation of p-TA radical is
assisted by facile PX radical generation, i.e. hydrogen abstraction
from PX followed by the reaction between the PX radical and O2.
The Mn redox cycle could be accelerated by several species, i.e.
added second transition metal, peroxide species derived from
Table 6
Manganese acetate-catalyzed co-oxidation of PX and p-TA in water with CO2 and
co-catalyst.a.
Co-catalyst (g)

PX (g)

p-Toluic
acid (g)

4-CBA (g)

TA (g)

Generated
COx (g)

Base case
Ni
Zr
Ti
Fe
Cr

2.24
1.90
2.10
1.85
2.02
2.10

12.54
10.04
10.21
10.24
9.98
10.16

0.86
0.66
0.82
0.59
0.92
0.64

10.93
12.91
11.48
14.02
12.88
13.66

1.12
0.86
0.84
0.91
0.84
0.89

a
PX 8 g (75.5 mmol), p-TA 15.3 g (112.5 mol), water 6.5 g, Mn(OAc)24H2O
0.225 g (0.9 mmol), 195 8C, 33 atm (O2 8 atm, N2 5 atm, water vapor 11 atm, PX
vapor 3 atm and CO2 6 atm), co-catalyst 0.045 mmol, reaction time 3 h.

58

J.W. Kwak et al. / Applied Catalysis A: General 358 (2009) 5458

p-TA conversion would assist more difcult p-TA to TA conversion.

Addition of CO2 in the oxygen promoted the TA formation and
suppressed the CO2 formation from the reactants. Additional
transition metals such as Ni, Ti also promoted the catalytic activity
of Mn catalyst. Furthermore, a synergism was observed between
added CO2 and the second transition metal. The yield of
terephthalic acid reached about 95% with Mn/Ti, Ni or Cr catalyst
system and CO2 addition.
Fig. 3. Roles of catalyst components and added CO2 on activation of p-TA. Note the
possible origin of the synergism between transition metal M and CO2.

various radicals, and peroxocarbonate species derived from added

CO2 and O2. Among the peroxide species, the one derived from PX
would be dominant and this could be the route, by which facile PX
oxidation assists the more difcult p-TA oxidation. The peroxocarbonate species could also assist the redox cycle of the second
metal (M), which could be responsible for the observed synergy
between the second metal and CO2 addition.
In any case, with these additives described above for cooxidation of PX and p-TA in water, TA was produced with yield
about 95% under the following conditions: 195 8C, 33 atm (O2
8 atm, N2 5 atm, water vapor 11 atm, PX vapor 3 atm and CO2
6 atm), Mn catalyst 0.16 mol% and Ti, Ni or Cr 0.008 mol%. Since the
rate of reaction in Fig. 2 is similar to that observed in the
conventional Amoco-MC process, the similar yield could be
translated to the similar productivity. Hence, the performance
similar to that of the conventional Amoco-MC process has been
realized in a highly environment friendly process.
4. Conclusion
In co-oxidation of PX and p-TA to TA in water, Mn acetate
showed better catalytic activity than Co acetate and no synergism
was observed between two catalysts. During the reaction, PX was
transformed to p-TA while p-TA was converted to TA by a radical
reaction. In the co-oxidation, radicals generated from facile PX-to-

Acknowledgements
This work has been supported by National Research Laboratory
program, Korean Institute of Industrial Technology Evaluation &
Planning and Korean National Cleaner Production Center, and
sponsored by Samsung Petrochemical Corporation.
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