View Online / Journal Homepage / Table of Contents for this issue

Selective partial oxidation in supercritical water: the

continuous generation of terephthalic acid from para-xylene in
high yield

Paul A. Hamley,a Thomas Ilkenhans,a Jeremy M. Webster,a Eduardo Garcia-Verdugo,a

Eleni Venardou,a Matthew J. Clarke,a Rita Auerbach,a W. Barry Thomas,b Keith
Whistonb and Martyn Poliakoff*a

a School of Chemistry, The University of Nottingham, Nottingham, UK NG7 2RD.

E-mail: Martyn.poliakoff@nottingham.ac.uk
b DuPont Polyester Technologies, PO Box 2002, Wilton, Middlesbrough, UK TS90 8JF

Received 27th February 2002

Published on 24 April 2002 on http://pubs.rsc.org | doi:10.1039/B202087B

First published as an Advance Article on the web 24th April 2002

Downloaded by North Carolina State University on 24 September 2012

The continuous selective oxidation of p-xylene (p-X) by O2 (generated by thermal decomposition of aqueous
H2O2) catalyzed by MnBr2 in supercritical H2O at ca. 400 °C is reported for the first time. The selectivity for
terephthalic acid (TA) is > 90%. Compared to existing industrial processes, the reaction has the potential for a
significant increase in energy efficiency and a substantial reduction in waste. This reaction is significant because
the presence of H2O lowers the catalytic activity of MnBr2 in the conventional route to TA via oxidation of p-X in
CH3COOH.

Introduction
Terephthalic acid, TA, is a major commodity chemical and an
important intermediate for the production of polyester poly-
mers. The various routes for the manufacture of TA have
recently been reviewed.1 Current state-of-the-art technology
involves the continuous liquid phase oxidation of p-xylene (p-
X) using molecular O2 in a lower (e.g. C2–C6) aliphatic
monocarboxylic acid, e.g. CH3CO2H, with a homogeneous
heavy metal catalyst system usually incorporating a promoter,
e.g. bromine. CH3CO2H is particularly useful as the solvent
since it is relatively resistant to oxidation and increases the
activity of the catalytic pathway. The reaction is typically
carried out on a very large scale in a stirred reactor at 150–250
°C and 0.6–3 MPa and the optimized process is highly selective
with a yield of TA of at least 95%. The oxidation is a free radical
process, the mechanism of which has been investigated in
detail;2 key intermediates include p-toluic acid (p-Tol) and
4-carboxybenzaldehyde (4-CBA). In addition, benzoic acid
(BA) can be formed via decarboxylation of TA and other
intermediates.
This step reduces the 4-CBA to p-Tol and converts the various
coloured impurities to colourless products. The purified TA is
then recovered from solution by a series of crystallisation,
solid–liquid separation and drying steps. p-Tol is considerably
more soluble than TA in H2O and remains in the aqueous
mother liquor following crystallisation of TA.3,4
High purity TA can be obtained by carrying out the oxidation
in a different, continuous process5 with a high solvent:p-X ratio.
Co-precipitation of 4-CBA with TA is largely avoided since the
TA is not allowed to precipitate in any quantity during the
reaction. Furthermore, the conditions necessary to achieve this
also promote oxidation of 4-CBA and other intermediates to a
greater extent than conventionally. However, a continuous
process of this type necessarily involves using substantial
amounts of organic solvent. Such solvents are relatively costly
and, due to environmental restrictions, may require recovery
and recycling. In addition, CH3CO2H is flammable when mixed
with air or O2 under typical reaction conditions; this means that
a proportion of the organic solvent may be ‘lost’ due to
oxidation during the process.
Supercritical H2O, scH2O (Tc = 374 °C, pc = 22.1 MPa) has
been widely investigated as a medium for the total oxidation of
organic waste because of the relatively high solubility of many
organic compounds in scH2O and its complete miscibility with

Generally, the TA obtained in the commercial oxidation is
insufficiently pure for direct use in polyester production since it
contains 4-CBA as a major impurity along with various colour-
forming precursors and coloured impurities. 4-CBA is usually
present because a substantial proportion of the TA precipitates
during the course of the reaction and, although 4-CBA may be
below its solubility limit, it tends to co-precipitate with TA.
Thus, the crude TA has to be purified before it can be used in
production of polyester. Purification typically involves dissolv-
ing the impure TA in water at high temperature, followed by
hydrogenation in the presence a supported noble metal catalyst.
Green Context
The use of supercritical or high temperature water as a
medium for the total oxidation of organics is well known as
a method of waste destruction. However, the selective
oxidation of hydrocarbons in this medium has received little
attention, despite the potential benefits of water as a
reaction medium. This article describes a very efficient and
high yielding continuous oxidation of p-xylene to tere-
phthalic acid using oxygen in supercritical water. The
selectivity to product is very high, and over-oxidation is not
a problem. In contrast to the current commercial process,
solvent oxidation does not occur, providing a clean and
effective route to this important product. DJM

DOI: 10.1039/b202087b Green Chemistry, 2002, 4, 235–238 235

This journal is © The Royal Society of Chemistry 2002

O2.6–8 In 1998, Holliday et al. described a batch process for the
synthesis of, inter alia, aromatic carboxylic acids from alkyl
aromatics in a reaction medium of sub-critical H2O using
molecular O2 as the oxidant.9 In particular, they reported that
TA could be generated at 564% yield by the selective oxidation
of p-X at 300–330 °C with O2 gas as the oxidant and MnBr2 as
the most effective catalyst. A recent paper by Dunn and
Savage10 confirms these findings and explored the reaction
conditions in greater depth. It also suggested that Holliday’s
analytical method might not have distinguished between TA
and other acids formed as part of the oxidation process. Both of
these studies9,10 were carried out in sealed autoclaves as batch
reactions and represent the first examples of selective oxidation
in near-critical or scH2O. If the reaction could be made
continuous and more selective, it would be potentially attractive
for the manufacture of TA, as the need for the CH3CO2H
solvent would be eliminated and the higher temperatures could
give enhanced energy recovery. Recently, one of the first
examples of continuous partial oxidation in scH2O was
Published on 24 April 2002 on http://pubs.rsc.org | doi:10.1039/B202087B
Downloaded by North Carolina State University on 24 September 2012
reported;11 the oxidation of cyclohexane, which was relatively
unselective both uncatalysed and in reactors lined with noble
metals. Here we report the first results from a long-running and
successful project aimed at developing the continuous labo-
ratory scale selective oxidation of p-X by O2 in scH2O.
Initially, reactions were tested in a 3 mL batch reactor, made
from 316L grade stainless steel, similar to that described
elsewhere.12 These tests showed that, even without any added
catalyst, oxidation of p-X could yield up to 44% TA (10 min,
308 °C) and, with an MnBr2 catalyst, up to 70% TA could be
generated in H2O from p-X in the presence of a large excess of
O2 (p-X+O2 1+36; 10 min, 315 °C, 15.6 MPa). The high excess
of O2 may have been needed because the narrow bore of our
batch reactor impedes efficient mixing of the gas and liquid
phases. The major difference between our experiments and
Holliday’s9 was that we used lower concentrations of MnBr2
(1000 ppm of bromide as opposed to 7000 ppm) but our overall
concentration of p-X was also considerably lower.
The continuous oxidation of p-X by O2 was carried out in
H2O from 200–400 °C and 24–28 MPa with MnBr2 as the
catalyst. The exotherm was minimised by using relatively dilute
solutions ( < 5% organic w/w). Initial experiments were carried
out with compressed O2 but it was found to be difficult to
control the gas on the small scale required for this work.
Therefore, we have used aqueous H2O2, which decomposes in
the preheater to generate O2. Tester and co-workers have shown
that there are no significant differences in the oxidation of
MeOH in scH2O using either O2 or decomposed H2O2 as the
oxidant.13 The configuration of the system is shown in Fig. 1,
where the key feature is the cross-piece, X, where a mixture of
scH2O and O2 is contacted with separate streams of p-X and a
cold solution of MnBr2.14 In the conventional process, Mn2+
acts as a homogeneous catalyst.2 However, in scH2O, the Mn
catalyst can rapidly hydrolyse and dehydrate to form solid
oxides like many other transition metal salts.15–19 The arrange-
ment shown in Fig. 1 allows catalysis to occur before the Mn
catalyst has had time to decompose. To demonstrate the need for
this configuration, a control experiment was run mixing the
catalyst solution (1000 ppm bromide) with H2O and high
pressure gaseous O2 prior to preheating to 385 °C and 24 MPa.
With 1% p-X added downstream of the preheater, the maximum
carbon recovery in the solid product was 22–69% w/w with a
yield of TA only between 11–18%. Subsequent inspection of
the preheater showed significant corrosion to the internal
surface of the pipework with a black precipitate (MnO2 by
XRD) coating the pipework. By contrast, up to 90% of the
MnBr2 was recovered in the product solution (Mn: AAS, Br:
AgNO3 titration) by using the mixing arrangement shown in
Fig. 1.
The results from a selection of runs are summarised in Table
1. Taken together, the results demonstrate the selective
236 Green Chemistry, 2002, 4, 235–238
View Online
oxidation of p-X to TA can be achieved in scH2O. The yield of
TA is highly sensitive to a range of variables, including the
ratios p-X+O2 and p-X+catalyst, the reactor residence time, and
the reactor temperature. In general, the selectivities in optimized
runs were steady over a period of hours, see Fig. 2, but the
overall yields often fluctuated because of minor inconsistencies
in the performance of the various components, which are
inevitable in so small a reactor of this complexity. Nonetheless,
the best yields of TA (examples 10–13) have exceeded 90%,
close to those of the current optimized industrial process. The
purity of the best recovered samples of TA contained lower
levels of oxidation intermediates than commercial crude TA.
Run 1 is a typical unoptimized run with modest overall yield
and poor selectivity for TA. Doubling the residence time and
increasing the O2 feed, run 2, reduces the yield of solids but
increases the selectivity for TA over the key impurity 4-CBA.
By contrast, halving the residence time produces a striking
improvement in both the yield and the selectivity for TA, run 3.
Increasing the residence time and simultaneously reducing the
reactor temperature from 400 to 350 °C, run 4, still gave ca.
50% yield of solid with reasonable selectivity for TA. Reducing
the temperature further with low concentrations of catalyst, runs
5–7, almost completely stopped the reaction with no isolable
solid products. However, the yield at 300 °C could be restored
by increasing the catalyst concentration to 1632 ppm Br; even
45% of the stoichiometric amount of O2 gave modest amounts
of TA, run 8, and 178% O2 with the mixing zone heated to 378
Fig. 1 Diagram of the continuous reactor for oxidation of p-X. A solution
of H2O2 is pumped into a tee-piece where it is mixed with cold water. The
H2O2/H2O mixture is then heated to ca. 400 °C in the preheater, PH,
consisting of a 6 m coil of 1/4 inch o.d. stainless pipe cast into an aluminium
block where the H2O2 decomposes to O2.20 The O2 + H2O fluid now passes
through the cross-piece, X, where it is contacted with the p-X and solution
of MnBr2 catalyst, fed in from their own pumps (the precise mixing
geometry is important for the success of the process). The reaction mixture
is passed through the reactor, R, which is identical to PH (for short residence
times R can be replaced by a short length of Hastelloy tubing). After R, a 4%
solution of cold NaOH is injected to prevent precipitation of TA, before the
solution passes through the cooling coil, C, and back-pressure regulator,
BPR. Other components are labelled as follows:, valves (“P” indicates a
pressure release valve); F, 0.5 mm filter; NRV, non-return valves; P,
pressure transducer; Prod, products; T, thermocouple (the aluminium heater
blocks of PH and R also contain thermocouples, not shown); lagged
pipework is shown as a thicker line. Br2 rapidly induces stress–corrosion
cracking in stainless steel at high temperatures with corrosion rates being
highest in regions of steep thermal gradients.21 This effect is exacerbated in
small-scale apparatus because the temperature gradients are usually steeper
than in large equipment. Therefore, Hastelloy is used for the final section of
the catalyst feed-pipe and other areas of high corrosion. All pipe work liable
to corrosive failure is protected inside wider bore stainless steel pressure
tubing to contain any inadvertent leaks. (NB: the Figure is not drawn to scale
and safety trips connected to the more critical pressure transducers have
been omitted. NaOH would almost certainly not be needed in larger scale
apparatus, where the larger bore of the pipe work would reduce the
problems of blocking. The NaOH also causes precipitation of the Mn2+
which can be recovered from the filter, F, as metal oxide/hydroxides. The
absence of Mn2+ in the product solution was confirmed by atomic
absorption. The flow rate of NaOH is adjusted to match the expected flow
of TA with a 3 2 excess of NaOH. PH and R supplied by NWA GmbH;
Pumps, Gilson 305 or equivalent; BPR, Tescom, model 26-1722-24-090).
 View Online

Table 1 Continuous oxidation of p-xylene in scH2O at 25.0 MPa

Results for product

Reactor conditions Feed
Analysis of productse
Res. MnBr2
timea/ Catalyst, Yield of all By-prods.
Run min T/°C p-Xb (%) O2c (%) [Br2]/ppm solidsd (%) TA (%) 4-CBA (%) p-Tol (%) BA (%) (%)

1 1.09 400 0.58 87–93 1632 26–37 12.9–25.5 8.0–22.4 14.4–40.8 1.4–5.2 1.1–2.9
2 2.17 400 0.58 111 1632 13–30 9.3–21.3 0–1.6 5.9–12.0 4.9–7.9 0–0.9
3 0.54 400 0.58 115 1632 71 51.9–63.8 0 0–5.95 5.9–11.8 0–1.6
4 2.08 350 0.7 120 975 45–61 45.3–61.2 3.2 6.58–17.6 6.2–9.8 0
5 12.8 300 0.58 149 537 0 0.1–0.4 0 0 0 0.1
6 12.8 250 0.58 149 537 0 0–0.3 0 0–0.14 0 0.2–1.2
7 11.7 200 0.58 149 537 0 0 0 0–13.9 0 0–1.2
8 2.42 300 0.58 45 1632 13–98 13.0–26.4 8.5–11.5 35.4–64.1 2.4–3.7 4.3–5.6
9 2.43 300f 0.58 178 1632 42–81 71.6–81.8 0 0 4.9–7.1 0
10 0.3 400g 0.58 120 1640 72–100 91.8–94.1 0 0 5.8–8.2 0
11 0.3 400g 1.5 180 1640 69–95 92.1–93.8 0 0 6.3–8.0 0
12 0.15 400g 1.5 180 1640 74–90 93.5–95.3 0 0 4.7–6.5 0
13 0.15 400g 2.0 120 1640 79–85 92.1–95.1 0 0 4.9–7.9 0
Published on 24 April 2002 on http://pubs.rsc.org | doi:10.1039/B202087B
Downloaded by North Carolina State University on 24 September 2012

a The residence time was defined as the total reactor volume divided by the volumetric flow-rate. The total volume was taken as the sum of the volume of
the tubular reactor, pipework and fittings between the mixing pieces; the first to mix the reactants to initiate the reaction and the second to quench the reaction
with the addition of NaOH. The volumetric flow-rate was based on the physical properties of H2O at the mixing conditions, as published in International
Steam Tables and by the US National Institute of Standards and Technology. b p-X concentration in reactor (w/w). c 3 mol of O2, the stoichiometric amount
needed to convert p-X to TA is taken to be 100%. d Yield calculated for aliquots collected over 30 min periods (every 15 min for runs 11–13). e Analysis
by HPLC of recovered solution (see Experimental section); maximum range of values found by analysing all of the samples collected during the course of
a particular run. f Mixing zone held at 378 °C. g Temperature at mixing piece, followed by a smaller volume reactor, constructed from a 50 cm length of 1⁄4
inch o.d. Hastelloy C276 pipework.

°C, run 9, gave yields comparable to those observed by Holliday
et al.9 and by us in batch reactions at similar temperatures.
By contrast, the best yields and selectivities were obtained by
using a shorter reactor to give very short residence times, < 20
s. Runs 10–13 all demonstrate more than 90% selectivity for
TA, with no detectable 4-CBA or p-Tol. The yields are
relatively insensitive to changes in residence time and concen-
tration of O2 at these conditions. The only major impurity
identified is BA, which off-line experiments in our batch reactor
have shown can be formed in modest amounts by heating TA in
scH2O. Additional measurements were carried out to confirm
the overall mass balance for the continuous oxidation. Thus, a
solid product with a composition of 92.1% w/w TA and 7.9% w/
w BA was collected over a timed interval of 15 min in run 13.
In this period, 0.681 g of p-X was fed to the experimental unit
and the solid recovered was 1.009 g giving a measured carbon
recovery of 97.4%.
Our results suggest that the mechanism of oxidation of TA in
scH2O is similar to that in CH3COOH although the presence of
Fig. 2 Plot showing the variation in selectivity observed during a
continuous run. Samples were collected at 15 min intervals after the reactor
had reached stable conditions, as listed in run 13 in Table 1. Others refers
to the by-products as listed in the Experimental section.
high amounts of water ( > 4–5%) is known2 to reduce the
activity of MnBr2 drastically at 200 °C. We suggest that the
catalyst is not deactivated so strongly in scH2O because the
polarity of the supercritical fluid is lower than that of liquid
H2O. The concentration of MnBr2 is substantially less than that
used by Holliday et al.9 but our concentration of p-X is also
substantially lower.
In this paper, we have shown for the first time that it is
possible to oxidize p-X continuously in scH2O with high
selectivity for TA. Most of the experimental difficulties
associated with the small-scale of our apparatus have been
overcome and a systematic investigation of reaction conditions
is now possible. Even without complete optimization, the
process generates almost no 4-CBA, one of the most problem-
atic impurities in current commercial processes for manufactur-
ing TA. Furthermore, the process totally eliminates the use of
organic solvents and has promise as a potentially cleaner route
to manufacture of TA.
Experimental
CAUTION: This type of oxidation is potentially extremely
hazardous, and must be approached with care and a thorough
safety assessment must be made.
Before each run, the apparatus was hydrostatically pressure
tested when cold, and was then heated with a flow of pure water
(5–10 ml min21). Once the operating temperature had been
reached, the pumps for p-X, H2O2, MnBr2 and NaOH were
started. Typically, an experiment was run for 4–8 h. The
products were collected for sequential periods of 15–60 min and
analysed. A weighed portion of the product solution was
acidified with 2 M HNO3 (alternatively H2SO4 or HCl could be
used) to precipitate TA and other components. The solid was
filtered off, washed with cold distilled H2O and air dried in a
dessicator over silica gel and weighed. Purity was verified
principally by HPLC. The TA was recovered and the yield
calculated as a percentage of the stoichiometric amount
expected from the measured amount of p-X pumped into the
apparatus.
As pointed out by Dunn and Savage,10 reproducible analysis
of TA is quite challenging. The selectivity was determined by

Green Chemistry, 2002, 4, 235–238 237


direct injection of the solution recovered from the reactor onto
an HPLC column using a method specially developed for these
experiments. Gradient elution with solvents CH3CN (16.7%)
and buffer (83.3 to 60% and back to 83.3%) was used. The stock
buffer solution was prepared by dissolving 15 g anhydrous
CH3CO2Na in 250 ml de-ionised water, before adding
CH3CO2H (50%, 100 ml). The pH was adjusted to 3.9 ± 0.01
with 5% CH3CO2H, before diluting to 500 ml. The dilute buffer
was prepared by diluting 30 mL of the stock buffer solution to
500 ml with de-ionised water. The injection volume with needle
wash was 1 mL. A Waters Xterra reverse phase C18 column,
maintained at 40 °C, was used ( flow rate 0.7 ml min21, run time
14 min; UV detection at 230 nm). The oxidation intermediates
analysed were 4-carboxybenzaldehyde (4-CBA), p-toluic acid
(p-Tol) and benzoic acid (BA). In addition, some samples were
analysed for minor by-products, including 2,6-dicarboxy-
fluorenone, isophthalic acid, benzene-1,2,4-tricarboxylic acid,
2,4A,5-tricarboxybiphenyl, diphenic acid, 4,4A-dicarboxybenzo-
phenone, 2,6-dicarboxyanthraquinone, 2,6-dicarboxyfluorene
Published on 24 April 2002 on http://pubs.rsc.org | doi:10.1039/B202087B
Downloaded by North Carolina State University on 24 September 2012
and 2,6-dicarboxyanthracene. GC analysis was also used on
some samples to determine volatile components, e.g. unreacted
p-X.
Acknowledgements
We thank EPSRC (Grant Nos GR/K84929 & GR/N06892), ICI
Engineering Technology, DuPont Polyester Technologies,
NWA GmbH and the Gatsby Foundation for their support. We
are grateful to Dr C. Boix, Dr A. Cabañas, Dr J. A. Darr, Dr M.
W. George, Dr D. A. Graham, Dr D. H. Gregory, Mr M. Guyler,
Dr S. M. Howdle, Dr G. H. Jones, Dr P. Kritzer, Dr E. Lester,
Dr R. Oliver, Dr W. Partenheimer, Prof. G. Pattenden, Dr K.-H.
Pickel, Dr R. J. Pulham, Dr J. Runnacles, Dr P. Saxton and Mr.
K Stanley for their help and advice.
238 Green Chemistry, 2002, 4, 235–238
View Online
References
1 K. Weissermel and H.-J. Arpe, in Industrial Organic Chemistry,
Weinheim, 1997.
2 W. Partenheimer, Catal. Today, 1995, 23, 69.
3 E. Hindmarsh, J. A. Turner and A. M. Ure, Process for the production
of terephthalic acid, Eur. Pat., EP-A-0502628, 1991.
4 E. Hindmarsh, J. A. Turner and D. Parker, Process for the production
of terephthalic acid, Eur. Pat., EP-A-0498591, 1991.
5 J. A. Turner, D. J. Royall, D. S. Hugall, G. H. Jones and D.
Woodcock, Process for the production of terephthalic acid, World.
Pat., WO-A-98/38150, 1998.
6 R. W. Shaw, T. B. Brill, A. A. Clifford, C. A. Eckert and E. U. Franck,
Chem. Eng. News, 1991, 69, 26.
7 P. E. Savage, Chem, Rev., 1999, 99, 603.
8 P. E. Savage, S. Gopalan, T. I. Mizan, C. J. Martino and E. E. Brock,
AIChE J., 1995, 41, 1723.
9 R. L. Holliday, B. Y. M. Jong and J. W. Kolis, J. Supercrit. Fluids,
1998, 12, 255.
10 J. B. Dunn and P. E. Savage, Ind. Eng. Chem. Res, 2002, released on
the web.
11 R. Richter and H. Vogel, Chem. Ing. Tech., 2001, 73, 1165.
12 P. Aleman, C. Boix and M. Poliakoff, Green Chem., 1999, 1, 65.
13 B. D. Phenix, J. L. DiNaro, J. W. Tester, J. B. Howard and K. A.
Smith, Ind. Eng. Chem. Res, 2002, 41, 624.
14 D. A. Graham, P. A. Hamley, T. Ilkenhans, M. Poliakoff and D.
Woodcock, Production of Aromatic Carboxylic Acids, World Pat.,
WO 02/02201, 2002.
15 T. Adschiri, K. Kanazawa and K. Arai, J. Am. Ceram. Soc., 1992, 75,
1019.
16 R. L. J. Smith, P. Atmaji, Y. Hakuta and K. Arai, in Separation of
metals from sim waste streams, ed. P. Rudolph von Rohr and C.
Trepp, Elsevier, Netherlands, 1996.
17 A. Cabañas, J. A. Darr, E. Lester and M. Poliakoff, Chem. Commun.,
2000, 901.
18 A. Cabañas and M. Poliakoff, J. Mater. Chem., 2001, 11, 1408.
19 K. J. Ziegler, R. C. Doty, K. P. Johnston and B. A. Korgel, J. Am.
Chem. Soc., 2001, 123, 7797.
20 E. Croiset, S. F. Rice and R. G. Hanush, AIChE J., 1997, 43, 2343.
21 P. Kritzer, N. Boukis and E. Dinjus, J. Supercrit. Fluids, 1999, 15,
205.