J.

of Supercritical Fluids 39 (2006) 220–227

The catalytic oxidation of benzoic acid to phenol

in high temperature water
Joan Fraga-Dubreuil a , Juan Garcia-Serna b , Eduardo Garcia-Verdugo c , Lucinda M. Dudd a,d ,
Graham R. Aird d , W. Barry Thomas d , Martyn Poliakoff a,∗
a University of Nottingham, Nottingham NG7 2RD, UK
b University of Valladolid, Department of Chemical Engineering and Environmental Technologies, 47011 Valladolid, Spain
c University Jaume I, Department of Organic and Inorganic Chemistry, Campus Ctra. Riu Sec., 12071 Castellon, Spain
d INVISTA Textiles (UK) Ltd., Redcar, Cleveland TS10 4XX, UK

Received 22 December 2005; accepted 23 December 2005

Dedicated in memory of Professor E.U. Franck.

Abstract
The oxidation of benzoic acid (BA) to phenol (the Dow Phenol Process) has been studied in high temperature water (HTW) using a continuous
flow system over various metal oxide heterogeneous catalysts: NiO, CuO, Carulite® , MnO2 and Al2 O3 . Excellent selectivities (>99%) and good
yields for phenol (up to 70%) were obtained. The reaction conditions were optimised by varying the temperature, the pressure and the effect
of O2 . Experiments were carried out for sustained periods in order to study the catalyst deactivation. The results are presented in most of the
cases in dynamic conditions; results observed versus time-on-stream for each catalyst tested. Carulite® 300 catalyst was the most effective with a
good activity/robustness over time-on-stream. Activity and regeneration of the catalyst with oxygen is reported. Overall HTW shows considerable
potential as a medium for this process. Possibilities for extending this chemistry are discussed.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Benzoic acid; Phenol; High temperature water; Oxidative decarboxylation; Heterogeneous catalysis; Carulite®

1. Introduction Despite many attempts, no commercial process has been

Phenol is an important chemical for resins, fibres, and
medicine [1,2]. Although phenol is present in coal tar, nearly
all of the present world supply, 5 × 106 tonnes p.a., is manufac-
tured. There are six main industrial routes to phenol; of these,
only two do not use benzene as a raw material but cumene and
toluene instead. The choice between these processes is often
dictated by raw-material costs, process efficiency, capital cost,
by-product formation and the product purity required.
Currently, more than 90% of phenol is produced by the
cumene route [3] in which acetone is generated as a recyclable
by-product. High carbon yields and selectivities to both phe-
nol and acetone are achieved; however the economics of this
route depend critically on the demand for acetone and its selling
price.
∗ Corresponding author. Tel.: +44 115 9513520.
E-mail address: Martyn.Poliakoff@nottingham.ac.uk (M. Poliakoff).
developed for the direct oxidation of benzene to phenol, a poten-
tially very attractive route in terms of atom efficiency (100%
versus 62% for cumene and 75% for toluene) [4]. It has been
difficult to overcome problems such as catalyst deactivation, for-
mation of bi-phenyl derivatives and material burning.
In the Dow Process, phenol is produced from toluene in
two steps via BA: (i) toluene is oxidised in the liquid phase
(100–150 ◦ C, 0.2 MPa), in the presence of air and a cobalt salt
catalyst to BA with a residence time of 1 h and (ii) BA is then oxi-
dised in the liquid phase at ca. 200–250 ◦ C with air and a catalyst
mixture of copper and magnesium salts (as benzoates) to yield
phenol after hydrolysis of a phenyl benzoate intermediate [5].
Many attempts have been made to improve the oxidation
of BA to phenol. Poor yields and issues such as tar forma-
tion or the need for catalyst regeneration have been reported
in liquid phase processes. Therefore, considerable research has
been undertaken to find an effective vapor-phase method, which
is potentially simpler industrially for product purification and
catalyst regeneration. One of the more efficient catalysts for

0896-8446/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2005.12.012
 J. Fraga-Dubreuil et al. / J. of Supercritical Fluids 39 (2006) 220–227 221

this reaction is copper with various metal promoters, supported
on carriers, e.g. alumina or kieselguhr [6–8]. Selectivities are
70–90% with yields of phenol of up to 50% per pass. Some
researchers have obtained even better results using NiO-based
catalysts with high selectivities and conversion of BA [9,10].
There have also been reports that the use of promoters such as
Na2 O [11] or V2 O5 [12] can improve the activity and the sta-
bility of the catalyst. However, acceptable selectivities can be
only obtained if the catalysts have been properly prepared by
calcination.
The properties of sub- and supercritical water (Tc = 374 ◦ C,
pc = 22.1 MPa) are unique [13] and have attracted the attention of
many scientists for developing more sustainable and alternative
processes in organic synthesis as well as in the field of nanoma-
terials [14,15]. For instance, in the area of selective oxidation of
methyl aromatics to their corresponding carboxylic acids, our
research team [16–18] and other groups [19] have demonstrated
many advantages in using high temperature water, HTW, as a
reaction medium. The oxidation of toluene to BA in supercriti-
cal water has been described using MnBr2 as catalyst via a batch
experiment to give a BA yield of 63% [19a].
The study of the oxidation of toluene to phenol in HTW would
be attractive because, traditionally, toluene is oxidised to BA in
the liquid phase at a temperature between 90 and 200 ◦ C using
homogeneous Co/Br catalyst, sometimes in combination with
Mn/Br [20,21]. An organic solvent such as acetic acid is often
needed and the reaction requires relatively long residence times
(0.5–3 h). Oxidation in the vapor-phase has also been reported
using heterogeneous catalysts [22]. However, for both liquid and
vapor-phase, the selectivity to BA is sometimes unsatisfactory.
The gas phase oxidation of BA to phenol has been performed
with O2 over heterogeneous catalysts in the presence of H2 O as
steam [6–12]. However, the main challenge for any HTW pro-
cess is to find heterogeneous catalysts which are stable under
the harsh conditions of HTW [23,24]. The most promising sys-
tems are transition metal oxides, especially for oxidations [25]
because metal oxides can be very stable and, indeed, can be
synthesized in HTW [14,15].
There are relatively few papers reporting heterogeneously
catalysed selective oxidations in HTW compared the huge num-
ber on total oxidations (gasification) [26]. The thermal decar-
boxylation of the isomeric dicarboxylic acids has been studied in
HTW [27] and, very much in the tradition of Professor Franck’s
pioneering work, the decarboxylation has been monitored by
Raman spectroscopy [16,28]. In this paper, we investigate the
oxidation (oxidative decarboxylation) of BA to phenol over a
selection of different metal oxide heterogeneous catalysts in
HTW.
2. Experimental
2.1. Apparatus and procedure
Reactions were carried out using a tubular continuous flow
reactor at Nottingham. Because the maximum solubility of BA
in H2 O at ambient conditions is ca. 3400 ppm, a concentration
of 2500 ppm was chosen to avoid precipitation during pumping
the organic feed. The reactor configuration in Fig. 1 was set up
to accommodate a fixed-bed catalyst in 15 cm of 1/2 in. tubing
with a maximum allowable pressure and temperature of 30 MPa

Fig. 1. Flow scheme for HTW oxidation of BA to phenol using a heterogeneous catalyst. Temperatures in the reactor were measured by in situ Inconel® thermocouples,
one measuring HTW at the exit of the pre-heater (T2), one in the cross-piece (T3) and another one at the outlet of the reactor (T5). They were monitored and recorded
along with pressures using PicoLogTM software. Apart from the main reactor, the rest of the equipment was similar to the one that has been previously described [16]
(pressure relief valve, PRV, heaters, cooler, filters and Tescom® back pressure regulator, BPR). A cold stream of BA in water was mixed with HTW (water which has
been pre-heated as in the oxidation of xylenes) via a cross-piece M before passing through the heterogeneous fixed-bed catalyst. The H2 O2 solution was pumped
into the system and decomposed in a pre-heater under the required experimental conditions to generate a homogeneous mixture of O2 and HTW [29].
222 J. Fraga-Dubreuil et al. / J. of Supercritical Fluids 39 (2006) 220–227
at 420 ◦ C. Commercially available heterogeneous catalysts NiO
(Fischer Scientific), CuO (Aldrich), Carulite 300® , Carulite 110
TR® (Carus Chemicals, Inc.), MnO2 (Aldrich) and activated
neutral Al2 O3 (Acros) were tested.
We have investigated the effect of varying (i) pressure (from
14 to 25 MPa), (ii) the temperature (from 200 to 400 ◦ C), (iii)
the type and the amount of catalyst, (iv) the concentration of O2
via H2 O2 decomposition and (v) the flow rates. In a typical run,
the flow rates were H2 O, 5 mL/min and BA aqueous solution
(2500 ppm), 1 mL/min. First, the reactor was pressurised and
heated with water to the required conditions, then, the aqueous
solution of BA was pumped. Experiments were carried out for
between 2 and 8 h and continued on subsequent days as required.
In most cases, our results are presented as product analysis ver-
sus time on stream for each catalyst tested. In this way, it is
possible to follow the deactivation of a catalyst and to obtain a
greater understanding of the process. Reactivation of the catalyst
was studied using O2 generated from decomposition of H2 O2 .
Samples were collected sequentially for periods of 4 min every
10–15 min and then analysed by off-line HPLC.
2.2. Analysis
Analysis was carried out with Hewlett Packard 1050 Series
HPLC apparatus equipped with an XTerra® RP18 3.5 ␮m,
30 mm × 150 mm column (Waters) and an oven temperature of
40 ◦ C; detection was at 254 and 230 nm with a 10 ␮L injec-
tion volume. A gradient elution from 35% acetonitrile and 65%
buffer solution (NaOAc/AcOH) to 80 and 20%, respectively,
was used at a flow rate of 0.7 mL/min over 12 min. After an
isocratic period of 2 min, the solvent ratio was reduced to the
original level, over 4 min. Every compound (acid and interme-
diates) was calibrated by HPLC prior to analysis of the samples.
The actual yield was calculated by HPLC as a percentage of
the expected yield based on the measured amount of organic
and water pumped into the apparatus. The selectivity was cal-
culated by HPLC as a percentage based on the molar amount of
a particular aromatic component in the solution recovered from
the reactor as a fraction of the molar amount of all aromatic
products. No analysis of carbon oxides was conducted.
Powder XRD data were obtained on a θ–2θ diffractometer
(Phillips XPERT) using Cu K␣ radiation. Samples of catalysts
were dried in an oven at 80 ◦ C and ground in a pestle and mortar.
The samples were scanned across the 2θ range of 5–80◦ . The
computer software, PC IDENTIFY, was used to compare the
data obtained to the library of patterns in the JCPDS database.
All the peaks seen in the catalyst could be matched to substances
in the library.
3. Results and discussion
3.1. NiO
NiO was found to be a rather unselective catalyst for the oxi-
dation of BA to phenol. Fig. 2 shows that, although most of the
BA was destroyed, poor phenol selectivity was observed (ca.
20%). The main product of the reaction was benzene resulting
Fig. 2. Continuous oxidation of BA to phenol over NiO (6 g) at 360 ◦ C and
25 MPa.  Phenol yield,  phenol selectivity,  benzene yield and ♦ BA recov-
ery.
from the thermal decarboxylation of BA and a 13% maximum
yield of phenol was achieved. The aromatic recovery was also
poor as only 50–60% of material was accounted for. Therefore,
it seems that a substantial proportion of material was totally oxi-
dised in the process. The highest phenol yield was obtained after
only 30–45 min, but then, after 2 h the catalyst lost its activity
and unreacted BA started to pass through the reactor. After 2.5 h,
the reactor tube blocked completely due to compaction of the
catalyst in the reactor tubing.
3.2. CuO
The reactor was charged with 4.4 g copper(II) oxide powder
and the effect of temperature was examined at 25 MPa. Further
experiments were carried out at 340 ◦ C and 20 MPa using 6 g of
catalyst. The results were compared with two control runs with
no catalyst (i.e. an empty reactor) in the presence and absence
of O2 . The results in Table 1 suggest that CuO is a much better
catalyst than NiO for producing phenol selectively (>99%) from
BA in HTW.
Only 1–3% of phenol was obtained in absence of catalyst
(entries 9 and 10) whereas an optimum yield of 28% was
achieved in presence of 6 g of CuO (entry 8). Temperatures of
greater than 340 ◦ C were required to produce phenol (10–13%
yield). A further increase in temperature from 350 to 390 ◦ C pro-
duced no improvement in the yield of phenol, which remained
around 12%. However, the phenol selectivity decreased when
the temperature was increased, because benzene is formed. The
benzene may originate from the thermal or catalytic decarboxy-
lation of BA, which occurs more readily at higher temperatures.
Decreasing the pressure to 14 MPa and feeding O2 increased the
phenol yield slightly to ca. 25%, but the carbon loss increased
under these conditions due to the presence of O2 . In every run,
there was an induction period or lag time of about 1–1.5 h as
shown in Fig. 3, characterised by an increase in phenol yield
and BA recovery. This induction occurred prior to obtaining opti-
mum phenol yields, which suggests that BA may be adsorbed
 J. Fraga-Dubreuil et al. / J. of Supercritical Fluids 39 (2006) 220–227 223

Table 1
Effect of temperature, pressure and amount of CuO catalyst on the selectivity and yield of phenol

Entrya T (◦ C) p (MPa) Yields (%)b Phenol selectivity (%)b

BA recovery Benzene Phenol

1 200 25 92 0 0 –
2 350 25 75 0 12 >99
3 360 25 69 0 13 >99
4 370 25 63 0 12 >99
5 380 25 66 6 10 64
6 390 25 70 4 11 72
7c 340 14 30 0 24 >99
8d 340 20 52 0 28 >99
9e 340 20 96 0 2 >99
10f 340 20 82 0 3 >99
a All reactions were carried out using the following flow rates: F
water = 4.5 mL/min, Forg = 1 mL/min except for entries 7–10, Fwater = 5 mL/min. Entries 1–7: 4.4 g
CuO, entry 8: 6 g CuO.
b Yields and selectivities of product(s) calculated via HPLC as mean of samples collected in sequential periods of 4 min every 10 min.
c Optimum yield obtained after 140 min, presence of 4 equiv. O .
2
d Optimum yield obtained after 160 min.
e No catalyst.
f 3.6 equiv. O , no catalyst.
2

on the catalyst surface before producing phenol. Following the
induction period, the catalyst did not show appreciable deacti-
vation over 2 h. The highest phenol yields were obtained when
more catalyst was employed (6 g rather than 4.4 g) (entry 8
and Fig. 3). The optimum balance of selectivity to phenol and
carbon loss is observed at ca. 340 ◦ C and 20 MPa. X-ray diffrac-
tion (XRD) analysis of the CuO collected after the experiments
showed that Cu(II) has been reduced to Cu(I) (as Cu2 O), support-
ing a mechanism in which oxygen from the catalyst participates
in the reaction.
Two mechanisms have previously been suggested for the
catalysed oxidation of BA by CuO and by NiO catalysed oxi-
dation of BA. In one mechanism [5c], the reaction involves the
formation of a copper dibenzoate intermediate, which is con-
verted to a phenylbenzoate or benzoylsalicylic acid, followed
by hydrolysis to phenol. A second paper [10] proposed a nucle-
ophilic aromatic substitution of hydrogen by an oxygen ion,
or more probably the formation of a peroxoacid, which would
result in the formation of phenol after oxygen transfer to the
ortho position and subsequent decarboxylation.
3.3. Carulite® —CuO and MnO2 supported on Al2 O3
Commercial Carulite® catalysts have been used for catalytic
partial [30] or total [25,31] oxidation of organic materials. These
catalysts are composed of 40–60% MnO2 and 1–3% CuO, sup-
ported on X-ray amorphous Al2 O3 . An initial experiment was
carried out over 6 g of ground pellets (1–2 mm diameter) of
Carulite 300® at 14 MPa and 340 ◦ C in presence of 18% molar
NaOH (Fig. 4) because Miki et al. [11] have reported that the
reaction can be promoted by addition of Na2 O via the formation
of sodium benzoate. As the reaction proceeded, phenol yields
increased, reaching a maximum of 65% at 134 min with selectiv-

Fig. 4. Continuous oxidation of BA to phenol over Carulite 300® (6 g) at 340 ◦ C

Fig. 3. Continuous oxidation of BA to phenol over CuO (6 g) at 340 ◦ C and
20 MPa.  Phenol yield and ♦ BA recovery.
and 14 MPa in presence of 18% mol NaOH. Note that the BA feed was stopped
during the period marked O2 , while 100 equiv. of O2 with respect to the BA were
pumped through the system. It is clear that the phenol yield is restored by this
O2 . Lines are labelled as in Fig. 5, namely  phenol yield,  phenol selectivity,
 benzene yield and ♦ BA recovery.
224 J. Fraga-Dubreuil et al. / J. of Supercritical Fluids 39 (2006) 220–227
ities between 90 and 95%. However, after 160 min, the activity of
the catalyst began to decrease gradually; the reaction produced
about 5–7% benzene and BA recovery increased.
After 280 min, the BA feed was stopped and only oxy-
gen (H2 O2 solution) was pumped (100 equiv. O2 based on the
organic flow which had previously been fed) under the same
conditions of T and p. When the BA feed was restarted, the phe-
nol yield reached 70% and selectivities were again very high
(∼95%). This regeneration can be understood if we assume that
CuO is the active component of the catalyst. Then, our results are
consistent with Cu(II) being gradually reduced and BA adsorp-
tion on the catalyst becomes less as the oxygen of the catalyst is
consumed in the reaction (CuO to Cu(II)benzoate and then for-
mation of Cu(I)benzoate). It seems clear that Cu(II)O has been
regenerated in presence of O2 from Cu(I)benzoate or Cu2 (I)O
formed during the process, and furthermore, it seems that the
reactivation was complete.
The experiment was repeated in the absence of NaOH, but the
reaction appeared to be less efficient. The highest yield achieved
was 46% and the selectivity to phenol decreased from 90 to 60%
as the catalyst deactivated. This supports the results reported
previously concerning the benefit in forming sodium benzoate
in situ [11]. Unless justified by improved phenol yields, there are
some disadvantages in performing the reaction at low pressure
(14 MPa): the phenol selectivity decreases and some benzene is
formed when the catalyst is deactivating. Therefore, we focused
on reaction pressures >20 MPa and in absence of NaOH in order
to prevent thermal decomposition at these conditions.
The experiment was repeated at 25 MPa and the effect of
varying the temperature (300–400 ◦ C) was studied in pres-
ence of 1 equiv. of O2 in order to maintain the catalyst activ-
ity. The results presented in Fig. 5 show that, if the tem-
perature is >350 ◦ C, the phenol yields and BA conversion
increase (up to 30% at 400 ◦ C). However, the phenol selec-
tivity decreases with more benzene being formed. When the
temperature was lowered back to 300 ◦ C (337 min), our initial
results were reproduced with a phenol selectivity approaching
100%.
Fig. 5. Effect of temperature on the continuous oxidation of BA to phenol over
Carulite 300® (6 g) at 25 MPa in presence of 1 equiv. O2 . Note that the best
performance in terms of selectivity is observed at temperatures <350 ◦ C and
that the effects of temperature appear to be reversible.  Phenol yield,  phenol
selectivity,  benzene yield and ♦ BA recovery.
Fig. 6. Continuous oxidation of BA to phenol over Carulite 300® (6 g) at 350 ◦ C
and 20 MPa. Number of O2 equivalents injected in the system: (a) 11.2; (b) 112;
(c) 0.9; (d) 0.45; (e) no O2 .  Phenol yield and ♦ BA recovery.
Fig. 6 shows a longer run to study the catalyst lifetime and
the effect of O2 concentration on its regeneration at 350 ◦ C and
20 MPa. Phenol selectivity was higher than 99% throughout the
run since almost no benzene was produced. An induction period
was again observed during which the BA was probably adsorb-
ing onto the catalyst leading to the increase of phenol yields to
almost 30%. After this induction, which was generally between
1 and 2 h, the BA recovery increased up to about 80% while
the yield of phenol decreased very slowly to a steady value of
10–12% after a 10–11 h operation time. As soon as O2 was intro-
duced, even with the BA solution feed continuing, the recovery
of organic material dropped dramatically, suggesting that BA,
along with phenol is almost totally oxidised to gaseous carbon
oxides. However, the catalyst was almost completely regener-
ated with the excess of O2 used (11.2 equiv.); when the oxygen
feed was stopped and only water was pumped with the BA feed
on, phenol was produced very quickly again and yields reached
their previous levels. Similar results were obtained each time O2
was supplied. The only drawback was that organic material was
totally oxidised by the excess of O2 during catalyst regeneration.
In an attempt to limit this over-oxidation, the reaction was
conducted with lower oxygen concentrations (from 0.9 to no
equivalent), so that an ideal compromise between catalyst reac-
tivation and organic breakdown could be found. The results show
that although O2 was supplied at only a low concentration, the
phenol yield decreased while the BA recovery increased. No
by-products such as benzene were observed. It seems that BA
which accumulated on the surface of the catalyst (as copper I or II
benzoate)—possibly along with the intermediates of the reaction
(for instance phenyl benzoate) and phenol—was decomposed to
carbon oxides when O2 was fed.
These results suggest that in presence of O2 the catalyst is
more active for total oxidation rather than the selective oxida-
tion of BA to phenol. This confirms previous observation on
the activity of CuO based catalysts for gasification of phenol in
HTW [25,31]. Thus, feeding BA and O2 simultaneously does
not seem to be a fruitful strategy.
The experiment was repeated (350 ◦ C and 20 MPa) with a
large amount of catalyst (8.3 g) and a longer run (15 h) was
 J. Fraga-Dubreuil et al. / J. of Supercritical Fluids 39 (2006) 220–227 225

Table 2
Oxidation of BA to phenol over different metal oxides

Entrya T (◦ C) p (MPa) Catalyst O2 equiv. BA recovery (%) Phenol yieldb (%) Phenol selectivityb (%)

1 340 14 Carulite 110 TR® – 56.6 26.8 >99

2 340 14 Carulite 110 TR® 4 42.6 26.5 >99
3 320 20 MnO2 – 92.2 0 –
4 350 20 Al2 O3 – 92.0 1.5 >99
a All reactions were carried out using the following flow rates: Fwater = 5 mL/min, Forg = 1 mL/min.
b Optimum yields and selectivities of product(s).

performed to establish the lifetime of a fresh Carulite® sample
in the absence of O2 (Fig. 7). We obtained a set of results similar
to before but, interestingly, phenol was produced in a higher
yield, 50%. This could be due to a larger amount of catalyst
being used with a corresponding increase in the total number
of the active sites on the surface of the catalyst. Although the
surface area of Carulite 300® in pellet form is quite high (ca.
260 m2 /g), an increase of the surface area may be responsible
for more phenol being produced. Whilst the relative activity
decreased, the catalyst continued to produce phenol for quite
some time. Even after this prolonged period (∼15 h), we again
obtained reactivation of the catalyst and phenol production at
almost the same yields as before, after O2 was injected in the
system for 1 h. This demonstrates the relative robustness of the
Carulite 300® under these experimental conditions [32].
Commercial Carulite 110 TR® (6 g of spherical pellets, Carus
Chemical) was also investigated as a catalyst. As in the case of
Carulite 300® , very good phenol selectivity was observed even
at lower pressures (14 MPa, Table 2). Although the composi-
tion of the catalyst is very similar to Carulite 300® , the BET
surface area is slightly lower, ca. 170 m2 /g (versus 260 m2 /g),
which might explain the lower phenol yields obtained under
same experimental conditions. The lower yields could also be
due to the fact that Carulite 110 TR® was used in pellet form
(not ground), so the number of available active sites may have
been less. Again, the presence of an excess of O2 (4 equiv.) did
not improve the yields because the organic material was totally
oxidised (entry 2).
Bulk MnO2 and Al2 O3 , which are the main components of
Carulite® catalysts, did not individually display any catalytic
activity in the reaction as no phenol was produced (entries 3 and
4) but they may increase the surface area of the active catalyst
compared to the use of bulk CuO.
4. Conclusion
The oxidative decarboxylation of BA to phenol has been stud-
ied in HTW using commercial heterogeneous catalysts such as
NiO, CuO, Carulite® , MnO2 and Al2 O3 . The best catalyst for
this reaction was Carulite 300® , which displayed a relatively
high robustness and good activity under the experimental con-
ditions used in this work. The HTW environment provides a
suitable medium for the selective catalytic oxidation of BA to
phenol. No reaction intermediates were detected and the main
by-product, benzene, was obtained in very small amounts. The
reaction is efficient because fast hydrolysis and decarboxylation
of reaction intermediates are achieved. Although the regenera-

Fig. 7. Continuous oxidation of BA to phenol over Carulite 300® (8.3 g) at

350 ◦ C and 20 MPa. During the time interval marked by arrows, the BA feed
was stopped and 4 equiv. O2 were injected in the system in absence of BA. O2 Fig. 8. Potential extension of the process of BA to phenol in HTW to the
feed was then stopped and BA feed restarted 30 min later.  Phenol yield and oxidative decarboxylation of other acids to produce a wide range of phenolic
♦ BA recovery. compounds of industrial interest.
226 J. Fraga-Dubreuil et al. / J. of Supercritical Fluids 39 (2006) 220–227
tion of the catalyst with O2 is successful to obtain good phenol
yields over several cycles and long periods of time, the organic
material adsorbed on the catalyst is totally oxidised to COx gases
over the period of regeneration of the catalyst. Simultaneous
feeding of O2 and BA decreases the selectivity to phenol as
the catalyst is more active for total oxidation. A slow induction
period (1–2 h) is always observed when the BA feed is started.
Our work on the oxidative decarboxylation of BA to phenol
now opens up the exciting possibility of performing this reaction
with other potential diacid feedstocks or related compounds to
produce a wide range of important phenolic intermediates (see
Fig. 8). These include hydroquinone 2, resorcinol 3, catechol 4,
hydroxybenzoic acids 5–7, and cresols 8–10 from the oxidative
decarboxylation of the diacids (terephthalic, iso-phthalic and
ortho-phthalic acid) and related compounds (e.g. para- , meta-
, ortho-toluic acid). We intend to explore these possibilities in
future investigations.
Acknowledgements
We thank our coworkers and collaborators from INVISTATM
Performance Technologies for their help and support. We are
grateful for funding from INVISTATM , the EPSRC, EU Marie
Curie Programme and the Royal Society. We also thank M.
Guyler, R. Wilson and P.A. Fields from the workshops at the
School of Chemistry, University of Nottingham for assistance
on technical and engineering issues.
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