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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-


cently reviewed in a few papers [3–5]. It was shown that
Nowadays, large-scale industrial chemical processes, the use of H2 O2 as oxidant in these large-scale processes
which generally involve several steps afflicted with the could meet the above-mentioned requirements of better
generation of by-products and waste, are subject to performance and environmental concerns. However,
continuously increasing environmental concerns and H2 O2 is too expensive compared to the frequently ap-
suffer from severe regulations. In addition, economical plied air and/or oxygen, and so there are no drivers for
drivers provide us with additional challenges for better economically sustainable and economic application.
performance in terms of productivity and selectivity. In recent years, many efforts have been published in
Hydrogen peroxide (H2 O2 ) chemistry can be very in- the field of cheaper H2 O2 production. Alternative routes
teresting for bulk chemical applications with respect to avoiding the use of (anthra)quinone have been reported.
sustainable operation [1]. Being a strong oxidant with Direct routes of contacting hydrogen and oxygen in the
excellent bleaching properties, H2 O2 has been a popular presence of a catalyst are described in a number of
oxidizing agent for decades in the textile, electronics, patents. Among others are those using catalysts from
and pulp and paper industries [2]. 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-
*
Corresponding author. Fax: +31-224-568615. action vessels (10–200 bars). Furthermore, these cata-
E-mail address: correia@ecn.nl (L.A. Correia). 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 experimental set-up consisted of a shell-and-tube reactor
aqueous solution formed is stabilized [14,17], the per- loaded with a membrane consisting of a porous alumina
formance of the catalyst is too poor for commercial tube coated with a thin palladium layer. The reactor was
application. operated under relatively mild conditions, i.e. between
Other routes, using CO, hydrogen and oxygen are 150 and 250 °C. Benzene was converted to phenol with a
potentially safer, but require the use of a Pd-catalyst selectivity of 80–90% and a conversion of 2–16% [25]
with bidentate N-ligands and a quinone co-catalyst to whereas the hydrogen consumed turned almost com-
reach only moderate yields [20,21]. pletely into water.
Very recently, Liu et al. [22] came up with a method The information concerning the by-products is rather
to extract H2 O2 from the peroxide working solution, poor. Dihydroxy compounds (cresols) and quinones
followed by direct application of the methanol extract in were detected in trace amounts whereas hydrogenated
an ammoximation reaction. By using this method, sep- compounds, i.e., cyclohexane, cyclohexanol, cyclohexa-
aration, purification and transportation are avoided, none, were hardly produced at all [25]. In a later paper,
and the use of organic solvents instead of aqueous H2 O2 Itoh et al. [26] suggested that oxidation and hydroge-
solutions is achieved. nation of benzene and/or phenol are competitive but
To our opinion, however, a real break-through in that under standard operating conditions oxidation
H2 O2 chemistry could only lie in the direct synthesis of would be predominant. Furthermore, it was reported
H2 O2 from its elements [5] and its direct application in that the hydrogen efficiency was quite low since the
an oxidation reaction in one pot [23]. Such a concept of production rate of water was 500–1000 times that of
process intensification [24] could lead to the desired phenol.
economically feasible and sustainable use of H2 O2 in Curious about the potential of this new technology,
bulk chemicals production. Recently, Niwa et al. [25] which is interesting from both technical (new technol-
reported a very interesting option for cheap and clean ogy) and economic (cheap selective oxidant) points of
H2 O2 technology in which H2 O2 is produced in situ and view, we have studied the ‘in situ H2 O2 ’ concept in more
reacts in one pot with an organic substrate. detail. In this paper, we present the results of our tech-
The basics of this ‘in situ H2 O2 ’ concept are illus- nical and economical feasibility studies of the Niwa
trated in Fig. 1 and are denoted as the ‘Niwa concept’. 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 2. Experimental
membrane reactor containing oxygen and benzene.
Consequently, the formation of explosive mixtures and The equipment used for this study is an explosion-
the explosion risks are diminished. At the surface of the proof Membrane Test Apparatus (MTA) containing a
catalytic membrane atomic hydrogen then reacts with shell-and-tube membrane module, a heating system, gas-
the molecular oxygen to produce an active oxygen spe- and temperature-control units and an analytical system.
cies (or what could be called ‘in situ H2 O2 ’), which For safety reasons the whole set-up was installed under
further reacts with the substrate [26,27]. an exhaust hood and equipped with a hydrocarbons
In the Niwa concept the oxidation of benzene to detector. A schematic overview is given in Fig. 2.
phenol has been chosen as a model reaction [25,26]. The 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
Fig. 1. Concept of in situ generation of H2 O2 and one-pot reaction range (ppm) by a more sensitive off-line GC-FID device.
over a membrane catalyst [25,26]: S ¼ organic substrate, i.e., benzene; The Pd-membrane was prepared by electroless plat-
P ¼ reaction product, i.e., phenol in this case. 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 Raw materials efficiency (%)
Phenol H2 O/phenol ratio Benzene Hydrogen
(kg/kg Pd/h)
Conversion Selectivity Conversion Selectivity
This work 0.1 120 3.8 4.1 6.8 0.2
Niwa and 1.5 500 15.0 80.0 n.a. n.a.
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 250 tubes of 1 m length, whereas the amount of Palla-
characteristics of the membranes used in our study and dium would not exceed 300 g for the virtual plant. This
in the Niwa case are different. In addition, the produc- means that, building a plant based on this concept is
tivity of the membrane in the Niwa case corresponds to technically feasible, even with the current poor perfor-
the best-optimised system, which is not (yet) the case in mance of our membrane system.
our work. One can assume that the yield reported by In parallel with the technical feasibility study, we
Niwa et al. would be feasible in our system. have performed an economical evaluation of the ‘in situ
However, in comparison with more conventional di- H2 O2 ’ concept using the process data of Niwa et al. [25].
rect catalytic oxidation of benzene to phenol the space- The results have been compared with the available data
time yield of the Niwa concept is significantly less. For of the Hock industrial process (currently the cheapest
example in the commercially developed oxidation of phenol technology) and the ‘classical H2 O2 ’ route using
benzene to phenol with N2 O (Solutia process) a selec- benzene and H2 O2 aqueous solution to produce phenol
tivity of >95% to phenol is achieved at >40% conver- [32,33].
sion. This process, however, is only cost-effective if N2 O It appeared very clearly that the ‘in situ H2 O2 ’ route
can be obtained cheaply as a by-product of adipic acid is more attractive compared to the ‘classical H2 O2 ’ route
production [29]. In the ‘classical’ H2 O2 oxidation of as concerns variable costs and investment costs. This is
benzene to phenol a selectivity of 90+% has been re- in line with the expectations since the ‘in situ’ route
ported with catalysts based on TS-1 [30] and/or Ti- avoids separation, purification and transport of H2 O2
MCM-41 [31] at reasonable conversion levels. It must be solution, whereas the use of aqueous-acetonitrile reac-
stressed that the Niwa concept does not require N2 O or tion media is no longer a prerequisite for reaction with
expensive H2 O2 . an organic substrate.
Concerning the raw materials efficiency in Table 2, With respect to the industrial Hock process, the ‘in
the difference can be attributed to the oxidation of situ H2 O2 ’ route presents the advantage of significantly
benzene that is not reported by Niwa et al. For the lower investment costs but due to the poor yield it is
hydrogen efficiency no data could be deduced for the much more expensive in terms of variable costs (by
Niwa case. The values of H2 O/phenol ratio presented in about three times). This means that, especially the very
Table 2 show lower production of water in our system low efficiency of the raw materials is the major barrier
compared to the Niwa case. In this respect, one can for potential commercial application of the catalytic
assume that the performance of our membrane is better. membrane reactor (CMR) ‘in situ H2 O2 ’ concept.
Another positive aspect revealed by our technical The positive aspect is that the concept is operated in a
evaluation was the stability of the Pd-membrane which CMR and this generally presents advantages over
was shown through 3–4 days of continuous operation common reactors [34,35], i.e. the possibility to control
with a leak-proof membrane. Incidentally hot spots the feed rate of the reagent through the membrane and
occurred in case of operating under very oxygen-rich contact time in the reactor. All these control possibilities
conditions leading to failure of the membrane. This is lead to higher conversion, selectivity and safer operation
now avoided by operating under less severe conditions. (H2 and O2 are not in direct contact) of the CMR.
In case of prolonged reaction Niwa et al. reported Consequently, improving the performance of the ‘in situ
membrane deterioration expressed by release of the Pd- H2 O2 ’ concept would require, in a first step, the opti-
layer from the alumina support tube [25]. misation of the process conditions since the formation of
Based on the current productivity of our membrane phenol should be favoured over the side-reactions. Most
system, we have made an estimation of the technical probably, a new design of the catalytic Pd membrane
feasibility of building a virtual 200 kta plant using the ‘in would be necessary to suppress the catalytic total oxi-
situ H2 O2 ’ process. It appeared that a reasonable dation process, while the development of a new CMR is
number of membrane tubes would be necessary, about necessary for avoiding hot spots. In addition, the use of
G.D. Vulpescu et al. / Catalysis Communications 5 (2004) 347–351 351

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