Chemical Engineering Communications

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SYNTHESIS OF TEREPHTHALIC ACID BY

CATALYTIC PARTIAL OXIDATION OF p-XYLENE IN
SUPERCRITICAL CARBON DIOXIDE

Dae Sung kim , Young Ho Shin & Youn-Woo Lee

To cite this article: Dae Sung kim , Young Ho Shin & Youn-Woo Lee (2015) SYNTHESIS
OF TEREPHTHALIC ACID BY CATALYTIC PARTIAL OXIDATION OF p-XYLENE IN
SUPERCRITICAL CARBON DIOXIDE, Chemical Engineering Communications, 202:1, 78-84, DOI:
10.1080/00986445.2013.825611

To link to this article: https://doi.org/10.1080/00986445.2013.825611

Published online: 04 Sep 2014.

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Chemical Engineering Communications, 202:78–84, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0098-6445 print/1563-5201 online
DOI: 10.1080/00986445.2013.825611

Synthesis of Terephthalic Acid by Catalytic Partial

Oxidation of p-Xylene in Supercritical Carbon Dioxide
DAE SUNG KIM1, YOUNG HO SHIN2, and YOUN-WOO LEE1
1
School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University,
Seoul, South Korea
2
Argonne National Laboratory, Energy Systems Division, Argonne, Illinois, USA

Supercritical (sc) fluids are considered to be a promising alternative to toxic organic solvents in a variety of processes. In this work,
a study of the synthesis of terephthalic acid (TPA) from p-xylene (PX) using supercritical carbon dioxide (scCO2) as a reaction
medium was performed. The effects of various process parameters were investigated, including temperature, residence time, and
catalyst loading. The maximum molar yield of TPA that was achieved was less than 35%. The oxidation reaction for producing
TPA was unfavorable under most conditions, which is likely due to the poor solubility of the CoBr2 catalyst in scCO2. This
was able to be improved by the addition of a small amount of acetic acid or water to the reaction mixture, resulting in improved
PX conversion and TPA yield. Furthermore, it was found that the use of an organic cobalt alternative could improve the yield.
Keywords: Alternative process; Catalyst solubility; p-Xylene; Partial oxidation; Supercritical carbon dioxide; Terephthalic acid

Introduction the great need for the development of alternative processes

Terephthalic acid (TPA) is an important intermediate in
polymer synthesis. Most commercially manufactured TPA
is used to produce polyethylene terephthalate (PET) resin
and polyester fibers. Worldwide production of TPA has
increased at an annual rate of over 10% for the five years
from 2001 to 2006 (Wang, 2006), and the annual production
capacity of TPA in Korea was reported to be 6.39 million
tons in 2011 (Choi, 2011).
TPA is synthesized by liquid phase oxidation of p-xylene
(PX) in acetic acid with Co, Mn, and Br catalysts (Cincotti
et al., 1997; Hyatt, 1984; Partenheimer, 1995). According
to the known reaction pathway illustrated in Figure 1
(Kim et al., 2003), methyl groups on both sides of the phenyl
ring are partially oxidized by means of catalytic assistance
and are converted to carboxylic acid groups.
Although existing conventional processes are well
established and generally exhibit good performance, some
drawbacks in terms of green engineering need to be over-
come. The large volume of acetic acid used as a solvent is
one of these issues, as its strong acidity and reactivity cause
corrosion of the reactor materials. In addition, during the
process, acetic acid can react with O2, decomposing to
H2O and CO2, causing solvent loss. Environmental regula-
tions that control the use of toxic chemicals are becoming
more stringent (Kim et al., 2003), further demonstrating
Address correspondence to Youn-Woo Lee, School of Chemical
and Biological Engineering, Seoul National University, 1
Gwanak-ro, Gwanak-gu, Seoul 151-744, South Korea. E-mail:
ywlee@snu.ac.kr
for producing TPA. The main focus of the research in this
area is the substitution of the toxic reaction medium with
a more environmentally friendly alternative (Dunn and
Savage, 2002; Dunn et al., 2002; Hamley et al., 2002; Kim
et al., 2002a, 2002b).
Supercritical fluids are considered to be a promising
alternative technology that can be used as a substitute for
a number of existing chemical processes. The great attention
being paid to supercritical fluids is mainly due to the
dramatic change in fluid properties, including density,
viscosity, diffusion coefficient, and dielectric constant near
the critical point. The liquid-like density means that
supercritical fluids can behave as solvents to numerous
compounds, whereas the low viscosity and high diffusivity
give them gaseous properties. Many groups have reported
using supercritical fluids in the synthesis of TPA, with most
of this work focusing on the replacement of acetic acid with
subcritical and supercritical water (Dunn et al., 2002;
Hamley et al., 2002; Kim et al., 2002a; Kwak et al., 2009;
Partenheimer, 2005). However, only a small number of
studies have involved the use of supercritical CO2 (scCO2).
As reported in a Japanese patent, Tetsuo (2000) synthesized
a scCO2 soluble Co compound and applied it to the partial
oxidation of aromatic carboxylic acids using scCO2 as a sol-
vent. Zhao’s group (Xu and Zhao, 2006) presented a basic
study using scCO2 at the International Symposium on Super-
critical Fluids held in Kyoto, Japan in 2006. However, no pub-
lished journal articles have reported on this technology so far.
CO2 is considered to be an environmentally benign and
safe solvent because of its nontoxicity and nonflammability
Synthesis of TPA From p-Xylene in scCO2
Fig. 1. The main reaction pathway of TPA synthesis by partial oxidation of PX.
(Jessop, 2011). In addition, as CO2 is one of the final oxi-
dized products of organic compounds, solvent loss due to
oxidation does not occur. Under supercritical conditions,
the density of CO2 can be easily controlled by adjusting
the temperature and pressure, meaning that scCO2 can dis-
solve numerous chemical compounds, which is not possible
with gaseous CO2. Furthermore, the process of separating
the solvent from the system should be easier. Owing to these
interesting properties, CO2 has received great attention for
various industrial applications such as extraction (Herrero
et al., 2006), recrystallization (Jung and Perrut, 2001), and
polymerization (Cooper, 2000).
Thus, in this work, the feasibility of synthesizing TPA by
catalytic partial oxidation of PX in scCO2 was investigated
experimentally under various conditions. In addition, the
necessity for the development of a novel catalyst that is
stable and can be homogenized in scCO2 is discussed. The
effects of additives for improving the molar yield of TPA,
without substituting the catalyst, were also examined.
Experimental Section
Materials
PX (98.5%) was obtained from Junsei Chemical Co., Ltd.
(Japan). p-Tolualdehyde (TALD; 97%), p-toluic acid (PT;
98%), 4-carboxybenzoaldehyde (4CBA; 97%), TPA (98%),
and all other common reagents were obtained from Sigma-
Aldrich Inc. (USA). Co stearate (CoST; > 95.0%), Co(II)
hexafluoroacetylacetonate (CoHF; > 95.0%), and NaBr
(99.5%) were obtained from Tokyo Chemical Industry Co.,
Ltd. (Japan). Methanol (99.8%) and dimethyl sulfoxide
(DMSO; 99.0%) were obtained from Samchun Chemical
Co., Ltd. (South Korea). CO2 and O2 were obtained from
Hyupsin Gas Co., Ltd. (South Korea).
Apparatus
Figure 2 shows a schematic diagram of the experimental appar-
atus used in this study. All reactions were performed in 32 mL
cylindrical vessel–type batch reactors that were connected to a
gas feeder with stainless steel tubing (1=16 inch outer diameter).
The reactors were made of Ti in order to minimize any effect of
reactor materials on the catalytic reaction (Dunn and Savage,
2002; Xu and Zhao, 2006). The maximum allowable working
temperature and pressure of the titanium reactor were 553 K
and 30 MPa, respectively. A molten salt bath filled with a mix-
ture of NaNO3, KNO3, and Ca(NO3)2 was used to heat up the
79
Fig. 2. Experimental apparatus for partial oxidation of PX in
scCO2: 1, O2 cylinder; 2, CO2 cylinder; 3, mass flow controller;
4, heat exchanger (cooler); 5, pump; 6, heat exchanger (heater);
7, shaker; 8, PID controller; 9, molten salt bath; 10, reactor.
reactor. The internal temperature of the salt bath was measured
using a K-type thermocouple probe dipped into the salt and
adjusted by a proportional-integral-derivative (PID) controller.
A horizontally reciprocating shaker was used to stir the reac-
tor. A high-pressure pump was used to inject the CO2, and a
mass flow controller was used to measure the amount of O2
flowing into the reactor.
The solubility of CoHF and CoST in scCO2 was investi-
gated by observing their cloud points in a solubility measur-
ing apparatus designed to measure the values at temperatures
up to 373 K. A schematic diagram of this equipment is
represented elsewhere (Kim et al., 2005).
Procedure
Predetermined amounts of PX and catalyst were first loaded
into the reactor; it was then sealed and connected to the
gas feeder. CO2 was pressurized up to 2.0 MPa at 298 K,
followed by pressurizing with O2 up to 3.2 MPa. The reactor
was then filled with CO2 until the pressure gauge indicated
6.0 MPa. It was subsequently separated from the gas feeder
and immersed in the preheated molten salt bath for the
desired residence time. During the reaction, the shaker
shook the reactor horizontally to agitate it at a frequency
of 37 shakes per min. After the operation was complete,
the reactor was rapidly removed from the salt bath and
quenched in a cold water bath. All nongaseous products
were collected from the cooled reactor by dissolving in a
mixture of dimethyl sulfoxide (DMSO) and methanol (1:1,
v=v). The gaseous products were not collected or analyzed
in this work.
80 D. S. Kim et al.

To observe the cloud point, a high-pressure viewing cell was
evacuated, and 20 mg of solute was loaded into it. Approxi-
mately 20 g of liquid CO2 was then added to the cell, and its
weight was calculated as the difference between the initial and
final weights of the cylinder vessel. The temperature was con-
trolled by circulating water through the jacket outside of the cell.
The solution in the cell was compressed by moving the piston,
finally reaching a transparent single phase. The pressure was
then slowly reduced until the solution turned cloudy.
Analysis and Characterization
The resulting samples were filtered and analyzed using an
Agilent 1100 high-performance liquid chromatography
(HPLC) system. The wavelength of the ultraviolet detector
was 254 nm. The temperature, injection volume, and flow
rate were maintained at 303 K, 20 mL, and 1 mL=min,
respectively. A Waters SunFire C-18 column with a length
of 150 mm, an inner diameter of 4.6 mm, and a particle size
of 3.5 mm was fitted to the HPLC system. A gradient elution
method was used to detect reaction products over a wide
range of polarities. The eluent initially consisted of 18% acet-
onitrile and 82% aqueous solution of 0.1 wt.% phosphoric
acid. The acetonitrile concentration was then gradually
increased to 30% from 15 to 20 min, and maintained at that
concentration until 35 min. It was then increased to 60%
from 35 min to 40 min, and then maintained until 50 min.
After one run was complete, the system was allowed to
re-equilibrate at the initial eluent concentration for 10 min.
For quantitative analysis of the reaction products, cali-
bration of standards with four different concentrations was
carried out, and calibration curves for each species were made
by plotting concentration versus peak area. Molar yields of
each species were calculated using the following equation:
Molar yield of component; % ¼number of moles of each
product after the reaction

initial number of moles
of PX loaded into the reactor
Results and Discussion
All experimental conditions and the following results are
summarized in Table I. Even though the compounds indi-
cated in the known reaction pathway of Figure 1 were
considered and analyzed in this work, there was a substantial
loss of aromatics. The PX remaining after the reaction tends
to decrease with reaction temperature and retention time. In
most cases, almost half of the initial PX was converted to
unknown compounds. The loss of PX during oxidation
was also reported by previous studies (Pérez et al., 2011a,
2011b), and the PX mostly burned to CO2. In this work,
the amount of CO2 generated was not possible to be ana-
lyzed since excessive CO2 already existed in the reactor as
a solvent.
The highest TPA yield of this work was compared with
the previous results using supercritical fluids as solvents

Table I. Experimental conditions and molar yields of reaction products

Molar yield of reaction

Catalyst products, %
Temperature, Time, PX loading, loading, Additive,
Entry K h mL Catalyst g=mL PX mL=mL PX PX TALD PT 4CBA TPA

1 423 2 0.2 CoBr2 0.1 — 52.2 nd nd nd nd

2 453 2 0.2 CoBr2 0.1 — 44.3 0.1 nd nd nd
3 523 2 0.2 CoBr2 0.1 — 31.5 3.1 15.2 0.4 1.1
4 538 2 0.2 CoBr2 0.1 — 8.5 0.3 30.2 1.0 10.5
5 423 4 0.2 CoBr2 0.1 — 47.1 nd nd nd nd
6 473 4 0.2 CoBr2 0.1 — 48.4 0.2 nd nd nd
7 523 4 0.2 CoBr2 0.1 — 21.2 1.8 23.6 2.4 8.4
8 538 4 0.2 CoBr2 0.1 — nd nd 0.3 0.2 30.8
9 523 8 0.2 CoBr2 0.1 — 13.5 0.1 36.8 1.1 30.5
10 523 16 0.2 CoBr2 0.1 — nd nd 2.4 0.4 32.3
11 523 24 0.2 CoBr2 0.1 — nd nd 0.6 0.3 33.7
12 523 4 0.2 CoBr2 0.2 — 8.4 0.2 18.9 0.8 12.7
13 523 4 0.2 CoBr2 1.0 — 10.3 0.1 1.2 0.7 25.6
14 523 4 0.2 CoBr2 2.0 — 6.6 0.2 0.8 0.7 27.6
15 523 4 0.2 CoBr2 0.1 Acetic acid, 1 8.2 nd 9.4 0.9 29.7
16 523 4 0.2 CoBr2 0.1 Water, 1 13.5 nd 9.7 0.8 24.5
17 423 4 0.4 CoBr2 0.1 — 48.5 nd nd nd nd
18 423 4 0.4 CoHF, 0.29, 0.1 — 10.5 1.1 21.2 10.3 22.4
NaBr
19 423 4 0.4 CoST, 0.22, 0.1 — 19.2 1.5 11.5 5.2 24.2
NaBr
nd ¼ not detected.
Synthesis of TPA From p-Xylene in scCO2 81
Table II. Comparison of the experimental conditions with highest TPA yields of PX oxidation with previous studies using super-
critical fluid solvents
Temperature, Pressure, Reactor type Reactor Highest TPA
Reference Solvent K MPa Time Catalyst (material) volume, mL yield, %

This work scCO2 523 17 24 h CoBr2 Batch (Ti) 32 33.7

Xu and Zhao, scCO2 423 10 2h CoBr2 Batch (Ti) 150 23
2006
Tetsuo, 2000 scCO2 393 13 2h Co(TDFAH) Batch (Teflonb) 20 60
þNaBra
Kim et al., scH2O 647 30 30 min none Batch 1379 0.549
2002a (Hastelloy-C)
Dunn et al., scH2O 653 24c 7.5 min MnBr2 Batch (stainless 1.54 57
2002 steel)
Hamley et al., scH2O 673 25 0.3 min MnBr2 Continuous — 94.1
2002 (Hastelloy-C)
a
Co(TDFAH) ¼ cobalt tridecafluorohexanate.
b
Inside of the reactor was coated with Teflon.
c
Pressure was calculated using density of scH2O (0.4 g=mL) at 380 K. The density data was adopted from http://webbook.nist.gov/chemistry.

(Table II). Compared with catalytic oxidations in scH2O,

reaction conditions were milder and relatively lower TPA
yields were obtained from the catalytic oxidations in scCO2.
However, using a scCO2-soluble catalyst the TPA yield
was significantly enhanced even at the lowest temperature.
In scH2O conditions, most PX decomposed to undesired
products without catalyst, supposedly due to the strong reac-
tivity of scH2O. Higher TPA yield was obtained with a cata-
lyst and shorter retention time in a batch system (Dunn et al.,
2002). It is clear that the continuous scH2O system has an
advantage of obtaining high TPA yield, because the continu-
ous system can prevent further decomposition of products
by allowing extremely short retention time.

Effect of Temperature and Residence Time

Figure 3 shows the molar yields of TPA synthesized at vari-
ous temperatures and residence times. Below 473 K, no TPA
was detected in the HPLC measurements, even with an
extended residence time of 4 h. There was also a lack of
significant amounts of intermediate products. Note that
typical liquid phase oxidation occurs at 423–483 K under
Co-Mn-Br catalyst (Wang et al., 2007). Between 473 and
538 K, the molar yield of TPA increased with temperature
and residence time, with a 30.8% maximum molar yield
achieved at 538 K and a residence time of 4 h. However,
additional experiments carried out above 538 K could not
be performed because of the temperature limit of the Ti
reactor. The molar yield of TPA significantly increased with
extended residence time at the same reaction temperature,
and PT was the most abundant among the intermediates.
These results indicate that oxidation of PX occurred rela-
tively slowly in scCO2, in comparison with previous studies
using other solvents such as subcritical and supercritical
water (Dunn and Savage, 2005).
To evaluate the effect of residence time on PX oxidation
in more detail, reactions were conducted up to 24 h at 523 K.
Changes in molar yield of the reactant and products
Fig. 3. Molar yield of TPA according to reaction temperature
and residence time (0.2 mL PX, 0.1 g CoBr2=mL PX).
according to the residence time are shown in Figure 4. There
was very little HPLC detection of other reaction products
apart from those represented in Figure 1. From the obtained
results, we propose three possible reaction pathways. The
first of these is that some of the PX could have been oxidized
and decomposed by side reactions, without coming into con-
tact with the catalyst. Even though the conversion of PX
reached 100% at 8 h, the molar yields of PT and TPA were
36.8% and 30.5%, respectively. In addition, there was very
little detection of other intermediates, indicating that
approximately 30% of the PX might have been converted
to other components that were not detected by the analytical
methods used in this study. This could be due to the low
solubility of CoBr2 in scCO2. Although the Co-catalyzed
82
Fig. 4. Molar yield of major reaction products according to resi-
dence time at 523 K (0.2 mL PX, 0.1 g CoBr2=mL PX).
oxidation reaction is much faster than other non-catalyzed
oxidation reactions, the probability of PX coming into con-
tact with the catalyst would be significantly limited by the
difference in polarity between catalyst and solvent. The
second possible pathway is that the TPA was synthesized
by catalytic or noncatalytic partial oxidation of PX accord-
ing to the typical reaction pathway shown in Figure 1. The
third possible pathway is that the PT, an intermediate
product and the rate-determining compound in the TPA
synthesis, could not be further oxidized to the TPA and
was decomposed to other compounds. After 8 h, production
of PT did not increase any further. The rate of TPA pro-
duction also became slower after 8 h, but the molar yield
did not decrease, unlike that of PT. This means that some
of the PT produced during the reaction could be thermally
degraded due to the harsh conditions of high temperature
and long residence time. These complex and unclear
mechanisms may be responsible for the interesting curve
shape produced, which varies in comparison with a typical
reactant-intermediate-product yield versus time curve.
Effect of Cobr2 Loading
It is clear that CoBr2, which is an ionic compound, is almost
insoluble in scCO2. Under the experimental conditions
described here, CoBr2 cannot be mixed homogeneously with
scCO2, resulting in a limitation of contact with the reactant.
Thus, partial oxidation of PX in scCO2 would be hetero-
geneous and therefore unfavorable in comparison with the
conventional oxidation method using acetic acid as a sol-
vent. To evaluate the extent to which catalyst solubility
effected the reaction, the amount of CoBr2 loaded into the
reactor was increased in order to enhance the probability
of contact with the PX (Figure 5). When the CoBr2 loading
was more than 1 g=mL PX, the molar yield of PT fell
D. S. Kim et al.
Fig. 5. Molar yield of PT and TPA with various CoBr2 loadings
(523 K, 4 h, 0.2 mL PX).
sharply, and that of TPA, in contrast, greatly increased.
The sum of the yields of PT and TPA did not fluctuate
greatly with catalyst loading. Since the reaction system is
heterogeneous due to the insolubility of CoBr2 in scCO2,
the contact area between the catalyst and the reactant can
be determined only by catalyst loading. This indirectly sug-
gests that using a scCO2-soluble catalyst is essential for
enhancing catalytic accessibility, thus increasing TPA pro-
duction in this solvent system. The use of a scCO2-soluble
catalyst might also mean that the reaction conditions could
be milder. Furthermore, at a lower temperature with the
same pressure, more PX can dissolve in the scCO2 because
of the increase in the density of the sc fluid. Hence, an
enhancement of homogeneity in the reaction system could
reduce processing costs in addition to increasing product
yield.
Effect of Additives
Figure 6 shows the effects of additives on the partial oxi-
dation reaction of PX. In spite of the addition of only a
small amount (1 mL=mL PX) of acetic acid or water, the
molar yield of TPA was significantly increased compared
with the reaction without additives (8.4%), with values
reaching 29.7% and 23.7%, for acetic acid and water,
respectively. The additives also significantly improved PX
conversion and TPA selectivity. It was shown that acetic
acid was a slightly more effective additive than water. It is
hypothesized that, under the given conditions, the reactant,
catalyst, and reaction medium were not mixed homoge-
neously in the absence of an additive. Thus, the addition
of acetic acid or water to the reaction system could play a
role in enhancing the solvating power and polarity of scCO2.
From the results, it is suggested that acetic acid and water
are likely to exist homogeneously in scCO2, despite the lack
of solubility data at high temperatures. These highly polar
additives could help the scCO2 dissolve polar compounds
Synthesis of TPA From p-Xylene in scCO2
Fig. 6. Effect of additives on partial oxidation of PX (523 K, 4 h,
0.2 mL PX, 0.1 g CoBr2=mL PX).
such as CoBr2, resulting in an enlargement of the contact
area between the reactant and catalyst. The exact mechanism
by which the additives helped the oxidation reaction is yet to
be fully understood; however, the introduction of such com-
ponents could be an effective way to enhance the molar yield
of the target compound without replacing the catalyst.
Effect of scCO2-Soluble Co Compounds
It has been shown that there is a requirement for a catalyst
that is soluble in scCO2, which has the additional benefit
of enabling milder reaction conditions (Jessop et al., 1994).
A Japanese patent (Tetsuo, 2000) claimed that a perfluoro-
aliphatic Co carboxylate, which is a newly synthesized
scCO2-soluble catalyst, could achieve high TPA yield and
PX conversion in the partial oxidation reaction. Rather than
synthesizing a new scCO2-soluble catalyst, in this work, two
possible candidates, CoST and CoHF, were purchased and
tested. A cloud point for CoBr2, CoST, and CoHF was pre-
liminarily assessed at 343 K, in order to check their solubility
in scCO2. CoBr2 did not exhibit a cloud point at any press-
ure, and the particles remained as they were found in the cell.
The cloud point of CoST was observed at 12.4 MPa; how-
ever, the CoHF behaved differently. The CoHF solution
became transparent as the pressure increased, maintaining
this transparency when the pressure was subsequently
reduced. This indicates that the cloud point pressure of
CoHF is much lower than the initial pressure in the cell.
Based on these preliminary tests, the divalent Co compounds
were strongly expected to be soluble in CO2 under the given
conditions, despite the lack of solubility data above 343 K.
NaBr was used as a source of bromine in accordance with
the details of the patent (Tetsuo, 2000). The loading amount
of Co and Br was adjusted to the equivalent number of
moles to the 0.1 g=mL PX of CoBr2 previously used. The
reaction temperature was set to 423 K to enable clear
83
Fig. 7. Comparison of catalytic activities of selected organic Co
compounds (423 K, 4 h, 0.4 mL PX).
observation of the catalytic effect while avoiding decompo-
sition of the organic Co compounds. As shown in Figure 7,
when CoBr2 was used, no TPA was detected; however, the
molar yield of TPA reached more than 22.4% and 24.2%
when CoST and CoHF were used as the catalyst, respect-
ively. Even though these organic Co compounds have not
been previously identified as suitable catalysts for this parti-
cular reaction, they were found to significantly promote the
catalytic oxidation. This is further evidence that there is a
necessity for the development of new catalysts suitable for
use in scCO2.
Conclusions
The use of scCO2 rather than the conventional toxic reaction
media was investigated for the PX oxidation process. The
highest molar yield of TPA achieved was 33.7%, at 523 K
with a residence time of 24 h, which was much lower than
the yields obtained from other conventional methods. In
order to increase both the reaction rate and yield, additives,
such as acetic acid or water, and selected catalysts expected
to be soluble in scCO2 were introduced. The small amount of
water or acetic acid was hypothesized to work by enhancing
the solubility of the CoBr2 in the scCO2, resulting in a TPA
yield approximately three times higher than in the absence of
an additive, at 523 K with a residence time of 4 h. It was
observed that the alternative organic forms of Co led to
the synthesis of TPA at 423 K for 4 h, while no TPA was
detected when using CoBr2. From the obtained results, it
is proposed that the addition of compounds that can act
as a co-solvent, or the development of a novel catalyst, is
greatly needed to achieve successful application of CO2 as
an alternative reaction solvent for TPA synthesis. Although
the scCO2 oxidation process is in its initial stages and many
questions still need to be answered, the results of this work
provide useful insights into the feasibility of scCO2 for a
novel TPA production process.
84
Acknowledgments
The authors appreciate project support from Honam Petro-
chemical Corporation. This research was also supported by
the second stage Brain Korea 21 program by a National
Research Foundation of Korea Grant funded by the Korean
Government (Ministry of Education, Science, and Technology,
MEST).
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