Catalysis Communications 5 (2004) 347–351

www.elsevier.com/locate/catcom

One-step selective oxidation over a Pd-based catalytic membrane;

evaluation of the oxidation of benzene to phenol as a model reaction
George D. Vulpescu a, Matthijs Ruitenbeek a, Lambert L. van Lieshout a,
Luci A. Correia b,*, Dick Meyer b, Paul P.A.C. Pex b
a
DSM Research, P.O. Box 18, 6160 MD Geleen, The Netherlands
b
ECN, P.O. Box 1, 1755 ZG Petten, The Netherlands
Received 27 February 2004; accepted 2 April 2004
Published online:

Abstract

The concept of a Pd-based catalytic membrane reactor (CMR) for the one-pot formation of phenol from benzene oxygen and
hydrogen via ‘‘in situ’’ generated H2 O2 was studied as a model reaction. Both technical and economic feasibility studies were
performed to validate this concept. Results from the literature were confirmed but additionally we observed the total oxidation of
benzene. Under the process conditions used, side-reactions such as total oxidation of hydrogen and benzene to water and CO2 are
favoured. This accounts for the observed low yield of phenol. Consequently, this interesting CMR concept is still far from com-
mercial application.
Ó 2004 Elsevier B.V. All rights reserved.

Keywords: Process intensification; One-pot reaction; Oxidation; Benzene; In situ hydrogen peroxide; Phenol; Pd-based catalytic membrane; Catalytic
membrane reactor; Commercial application; By-products

1. Introduction Application of H2 O2 in bulk chemistry has been re-

Nowadays, large-scale industrial chemical processes,
which generally involve several steps afflicted with the
generation of by-products and waste, are subject to
continuously increasing environmental concerns and
suffer from severe regulations. In addition, economical
drivers provide us with additional challenges for better
performance in terms of productivity and selectivity.
Hydrogen peroxide (H2 O2 ) chemistry can be very in-
teresting for bulk chemical applications with respect to
sustainable operation [1]. Being a strong oxidant with
excellent bleaching properties, H2 O2 has been a popular
oxidizing agent for decades in the textile, electronics,
and pulp and paper industries [2].
*
Corresponding author. Fax: +31-224-568615.
E-mail address: correia@ecn.nl (L.A. Correia).
cently reviewed in a few papers [3–5]. It was shown that
the use of H2 O2 as oxidant in these large-scale processes
could meet the above-mentioned requirements of better
performance and environmental concerns. However,
H2 O2 is too expensive compared to the frequently ap-
plied air and/or oxygen, and so there are no drivers for
economically sustainable and economic application.
In recent years, many efforts have been published in
the field of cheaper H2 O2 production. Alternative routes
avoiding the use of (anthra)quinone have been reported.
Direct routes of contacting hydrogen and oxygen in the
presence of a catalyst are described in a number of
patents. Among others are those using catalysts from
the Pt-group metals [6–13], Group VIII metals [14–18]
and Ir-based structures [19]. However, these catalytic
processes are inherently unsafe because of the use of a
potentially explosive H2 –O2 mixture in pressurized re-
action vessels (10–200 bars). Furthermore, these cata-
lysts not only promote H2 O2 formation but also its

1566-7367/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2004.04.002
348 G.D. Vulpescu et al. / Catalysis Communications 5 (2004) 347–351
decomposition to H2 O and O2 . Even when the H2 O2
aqueous solution formed is stabilized [14,17], the per-
formance of the catalyst is too poor for commercial
application.
Other routes, using CO, hydrogen and oxygen are
potentially safer, but require the use of a Pd-catalyst
with bidentate N-ligands and a quinone co-catalyst to
reach only moderate yields [20,21].
Very recently, Liu et al. [22] came up with a method
to extract H2 O2 from the peroxide working solution,
followed by direct application of the methanol extract in
an ammoximation reaction. By using this method, sep-
aration, purification and transportation are avoided,
and the use of organic solvents instead of aqueous H2 O2
solutions is achieved.
To our opinion, however, a real break-through in
H2 O2 chemistry could only lie in the direct synthesis of
H2 O2 from its elements [5] and its direct application in
an oxidation reaction in one pot [23]. Such a concept of
process intensification [24] could lead to the desired
economically feasible and sustainable use of H2 O2 in
bulk chemicals production. Recently, Niwa et al. [25]
reported a very interesting option for cheap and clean
H2 O2 technology in which H2 O2 is produced in situ and
reacts in one pot with an organic substrate.
The basics of this ‘in situ H2 O2 ’ concept are illus-
trated in Fig. 1 and are denoted as the ‘Niwa concept’.
This concept consists of a hydrogen-permeable Pd-based
membrane through which hydrogen is transported as an
active hydrogen atom towards the reaction side of the
membrane reactor containing oxygen and benzene.
Consequently, the formation of explosive mixtures and
the explosion risks are diminished. At the surface of the
catalytic membrane atomic hydrogen then reacts with
the molecular oxygen to produce an active oxygen spe-
cies (or what could be called ‘in situ H2 O2 ’), which
further reacts with the substrate [26,27].
In the Niwa concept the oxidation of benzene to
phenol has been chosen as a model reaction [25,26]. The
Fig. 1. Concept of in situ generation of H2 O2 and one-pot reaction
over a membrane catalyst [25,26]: S ¼ organic substrate, i.e., benzene;
P ¼ reaction product, i.e., phenol in this case.
experimental set-up consisted of a shell-and-tube reactor
loaded with a membrane consisting of a porous alumina
tube coated with a thin palladium layer. The reactor was
operated under relatively mild conditions, i.e. between
150 and 250 °C. Benzene was converted to phenol with a
selectivity of 80–90% and a conversion of 2–16% [25]
whereas the hydrogen consumed turned almost com-
pletely into water.
The information concerning the by-products is rather
poor. Dihydroxy compounds (cresols) and quinones
were detected in trace amounts whereas hydrogenated
compounds, i.e., cyclohexane, cyclohexanol, cyclohexa-
none, were hardly produced at all [25]. In a later paper,
Itoh et al. [26] suggested that oxidation and hydroge-
nation of benzene and/or phenol are competitive but
that under standard operating conditions oxidation
would be predominant. Furthermore, it was reported
that the hydrogen efficiency was quite low since the
production rate of water was 500–1000 times that of
phenol.
Curious about the potential of this new technology,
which is interesting from both technical (new technol-
ogy) and economic (cheap selective oxidant) points of
view, we have studied the ‘in situ H2 O2 ’ concept in more
detail. In this paper, we present the results of our tech-
nical and economical feasibility studies of the Niwa
concept.
2. Experimental
The equipment used for this study is an explosion-
proof Membrane Test Apparatus (MTA) containing a
shell-and-tube membrane module, a heating system, gas-
and temperature-control units and an analytical system.
For safety reasons the whole set-up was installed under
an exhaust hood and equipped with a hydrocarbons
detector. A schematic overview is given in Fig. 2.
Testing was performed with a mixture of benzene and
oxygen in nitrogen as carrier gas within the annulus of
the membrane reactor, whereas pure hydrogen was sent
as a dead-end flow in the inner side of the membrane
tube.
The analytical system consists of an on-line CO–CO2
detector (BINOS 100 NDIR-detector). The on-line GC-
TCD is equipped with a Chrompack Sil 5CB column for
measuring water, benzene, phenol and other by-prod-
ucts and a Chrompack Molsieve 5A column for the
measurement of O2 , H2 , and N2 . In addition, a con-
denser was placed at the outlet of the MTA and before
the on-line GC allowing collection of liquefied samples
of the product stream. This allowed the detection of
organic (by)products in the very low concentration
range (ppm) by a more sensitive off-line GC-FID device.
The Pd-membrane was prepared by electroless plat-
ing using an asymmetrical porous alumina tube devel-
 G.D. Vulpescu et al. / Catalysis Communications 5 (2004) 347–351 349

Fig. 2. Schematic overview of the test equipment.

Table 1 and CO2 , whereas the formation of phenol was detected

Characteristics of the Pd-membranes applied in this study and by Niwa in only very low amounts corresponding to a yield of
et al. [25]
only 7 mg of phenol per hour. No organic compounds
Membrane characteristics This study Niwa case Ratio other than phenol and unreacted benzene have been
Outer diameter (mm) 14.2 2.0 7.10 detected with the on-line GC-TCD or with the more
Length (mm) 72 100 0.72 sensitive GC-FID device after condensation of the
Surface area (m2 ) 3.2
103 0.6
103 5.11 products at the MTA outlet.
Thickness of the Pd layer 2.0
106 1.0
106 2.00
This means, although the ‘in situ H2 O2 ’ concept was
(m)
‘‘Volume’’ of Pd (m3 ) 6.4
109 6.3
1010 10.22 proven, a system of three main parallel reactions should be
Mass of Pd (g) 0.077 0.008 10.22 considered, in which the side-reactions are predominant:
C6 H6 þ H2 þ O2 ! C6 H5 OH þ H2 O ð1Þ
oped at the ECN laboratory. Its main characteristics are
presented in Table 1 and compared to the Niwa mem- 2H2 þ O2 ! 2H2 O ð2Þ
brane. The alumina support consisted of a strong course
porous structure with a mean pore diameter of 4.5 lm 2C6 H6 þ 15O2 ! 12CO2 þ 6H2 O ð3Þ
and a 90 lm thin alumina layer with a mean pore di- It is very important to note that Niwa et al. did not
ameter of 0.18 lm. The Pd-membrane was applied using report the oxidation of benzene to CO2 and H2 O (Eq. 3)
a PdCl2 plate bath [28] after first activating the outer [25,26]. It is unclear whether CO2 was undetected or not
surface of the support with Pd seeds. After plating, the looked for in the Niwa case. In addition, they reported
Pd membrane was subjected to a heat treatment to ob- the hydrogenation of the organic substrate [26] but we
tain a fully dense film. did not observe such a reaction in our system.
The results reported in this paper have been obtained The performance of the membrane tested in our study
by operating the membrane at 150 °C for a typical feed has been compared with the results of Niwa et al. [25] and
of 40 mmol/h benzene and 120 mmol/h oxygen in 690 Itoh et al. [26] and is summarized in Table 2 in terms of
mmol/h nitrogen. The hydrogen flow through the yield of phenol and water/phenol ratio and raw materials
membrane was 545 mmol/h. efficiency.
At a first sight, the results of Niwa are significantly
better than ours, i.e., a factor 15 for phenol productivity,
3. Results and discussion and a much higher benzene conversion and selectivity.
However, depending on how the phenol productivity is
In the technical evaluation of the ‘in situ H2 O2 ’ expressed, different ratios can be calculated. For example,
concept, proof of formation of phenol was the main by expressing the productivity in grams of phenol per m2
target. Furthermore, we have tried to identify and Pd surface per hour (g/m2 Pd/h), the Niwa case is more
quantify by-products. productive by a factor of 8, whereas a factor of only 2 is
Our study clearly denoted the formation of large calculated in favour of the Niwa case by using the amount
amounts of by-products from side reactions, i.e., H2 O of grams per hour.
350 G.D. Vulpescu et al. / Catalysis Communications 5 (2004) 347–351
Table 2
Comparison of the performance of the Pd-based membranes
Membrane productivity
Phenol H2 O/phenol ratio
(kg/kg Pd/h)
This work 0.1 120
Niwa and 1.5 500
co-workers [25,26]
Calculation of the water production based on the amount of water detected and based on the amount of water calculated from reaction
stoichiometry did not show any difference.
Nevertheless, it is worthwhile to recall that the
characteristics of the membranes used in our study and
in the Niwa case are different. In addition, the produc-
tivity of the membrane in the Niwa case corresponds to
the best-optimised system, which is not (yet) the case in
our work. One can assume that the yield reported by
Niwa et al. would be feasible in our system.
However, in comparison with more conventional di-
rect catalytic oxidation of benzene to phenol the space-
time yield of the Niwa concept is significantly less. For
example in the commercially developed oxidation of
benzene to phenol with N2 O (Solutia process) a selec-
tivity of >95% to phenol is achieved at >40% conver-
sion. This process, however, is only cost-effective if N2 O
can be obtained cheaply as a by-product of adipic acid
production [29]. In the ‘classical’ H2 O2 oxidation of
benzene to phenol a selectivity of 90+% has been re-
ported with catalysts based on TS-1 [30] and/or Ti-
MCM-41 [31] at reasonable conversion levels. It must be
stressed that the Niwa concept does not require N2 O or
expensive H2 O2 .
Concerning the raw materials efficiency in Table 2,
the difference can be attributed to the oxidation of
benzene that is not reported by Niwa et al. For the
hydrogen efficiency no data could be deduced for the
Niwa case. The values of H2 O/phenol ratio presented in
Table 2 show lower production of water in our system
compared to the Niwa case. In this respect, one can
assume that the performance of our membrane is better.
Another positive aspect revealed by our technical
evaluation was the stability of the Pd-membrane which
was shown through 3–4 days of continuous operation
with a leak-proof membrane. Incidentally hot spots
occurred in case of operating under very oxygen-rich
conditions leading to failure of the membrane. This is
now avoided by operating under less severe conditions.
In case of prolonged reaction Niwa et al. reported
membrane deterioration expressed by release of the Pd-
layer from the alumina support tube [25].
Based on the current productivity of our membrane
system, we have made an estimation of the technical
feasibility of building a virtual 200 kta plant using the ‘in
situ H2 O2 ’ process. It appeared that a reasonable
number of membrane tubes would be necessary, about
Raw materials efficiency (%)
Benzene Hydrogen
Conversion Selectivity Conversion Selectivity
3.8 4.1 6.8 0.2
15.0 80.0 n.a. n.a.
250 tubes of 1 m length, whereas the amount of Palla-
dium would not exceed 300 g for the virtual plant. This
means that, building a plant based on this concept is
technically feasible, even with the current poor perfor-
mance of our membrane system.
In parallel with the technical feasibility study, we
have performed an economical evaluation of the ‘in situ
H2 O2 ’ concept using the process data of Niwa et al. [25].
The results have been compared with the available data
of the Hock industrial process (currently the cheapest
phenol technology) and the ‘classical H2 O2 ’ route using
benzene and H2 O2 aqueous solution to produce phenol
[32,33].
It appeared very clearly that the ‘in situ H2 O2 ’ route
is more attractive compared to the ‘classical H2 O2 ’ route
as concerns variable costs and investment costs. This is
in line with the expectations since the ‘in situ’ route
avoids separation, purification and transport of H2 O2
solution, whereas the use of aqueous-acetonitrile reac-
tion media is no longer a prerequisite for reaction with
an organic substrate.
With respect to the industrial Hock process, the ‘in
situ H2 O2 ’ route presents the advantage of significantly
lower investment costs but due to the poor yield it is
much more expensive in terms of variable costs (by
about three times). This means that, especially the very
low efficiency of the raw materials is the major barrier
for potential commercial application of the catalytic
membrane reactor (CMR) ‘in situ H2 O2 ’ concept.
The positive aspect is that the concept is operated in a
CMR and this generally presents advantages over
common reactors [34,35], i.e. the possibility to control
the feed rate of the reagent through the membrane and
contact time in the reactor. All these control possibilities
lead to higher conversion, selectivity and safer operation
(H2 and O2 are not in direct contact) of the CMR.
Consequently, improving the performance of the ‘in situ
H2 O2 ’ concept would require, in a first step, the opti-
misation of the process conditions since the formation of
phenol should be favoured over the side-reactions. Most
probably, a new design of the catalytic Pd membrane
would be necessary to suppress the catalytic total oxi-
dation process, while the development of a new CMR is
necessary for avoiding hot spots. In addition, the use of
 G.D. Vulpescu et al. / Catalysis Communications 5 (2004) 347–351
air instead of pure oxygen could make the process more
competitive.
Despite such major technical challenges, there are
clear drivers for further developments of this innovative
system. First, the ‘in situ H2 O2 ’ concept is a good op-
portunity for a break-through in selective oxidation
technology. Secondly, the investment for the ‘in situ
H2 O2 ’ route appeared already attractive (cheaper)
compared to the current Hock technology, whereas the
energy aspects are similar or slightly in favour of the
new concept.
4. Conclusions
The formation of phenol by the catalytic oxidation of
benzene in a Pd-based catalytic membrane reactor, as
described by Niwa et al., was confirmed. However, de-
spite the achieved proof of principle of ‘in situ H2 O2 ’,
our study provided clear evidence of significant forma-
tion of by-products via two main side-reactions, which
are predominant under the applied experimental con-
ditions. These are the total oxidation of hydrogen to
water and the total oxidation of benzene to carbon di-
oxide and water. The latter was unreported in the lit-
erature for such a membrane system so far. In addition,
we do not confirm the hydrogenation of the organic
substrate reported in the literature.
Based on the technical and economic evaluations, the
Pd-based catalytic membrane reactor system is currently
far from commercial application. The main challenge
would be to significantly increase the phenol produc-
tivity and the efficiency of the raw materials, and so to
decrease the variable costs that are too high compared
to the current industrial processes.
Acknowledgements
The authors acknowledge financial support via the
EET-Kiem programme (02129/4800002003). G.V. is
grateful to the European Commission for the grant as
Postdoctoral Researcher at DSM in the Marie Curie
Industry Host Fellowship Programme (HPMI-CT-1999-
00007).
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