Applied Catalysis A: General 212 (2001) 239245

Catalyst deactivation phenomena in styrene production

Garry R. Meima a, , P. Govind Menon b
aDow Benelux N.V., Hydrocarbons R&D, P.O. Box 48, 4530 AA Terneuzen, The Netherlands
b Laboratorium voor Petrochemische Techniek, Universiteit Gent, Krijgslaan 281, B-9000 Gent, Belgium

Abstract
Catalyst deactivation in the styrene process occurs by several mechanisms such as coke deposition, migration, loss and
redistribution of the potassium promoter, changes in the oxidation state of iron, and physical degradation. These changes are
interrelated and occur simultaneously. Recent investigations in these areas and novel adaptations of the catalyst and process
are discussed briefly in this review. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Styrene; Ethylbenzene dehydrogenation; Iron-oxide catalyst; Catalyst deactivation; Potassium ferrite; Potassium promoter

1. Introduction produces most of the styrene. The reaction is equilib-

Styrene is one of the most important monomers in
modern petrochemical industry. The world production
at present is approximately 20 million tonnes per year.
The styrene process was developed in the 1930s inde-
pendently and simultaneously by BASF in Germany
and by Dow Chemical in the USA. There is no direct
end use for styrene; it is mainly used for the produc-
tion of many different polymeric materials, the most
important being polystyrene, styreneacrylonitrile
and acrylonitrilebutadienestyrene (ABS). Another
important application is in styrenebutadiene latex.
The most important commercial production routes
for styrene are the catalytic dehydrogenation of ethyl-
benzene (EB) and the oxidation of EB to ethylben-
zenehydroperoxide, which is subsequently reacted
with propene to give styrene and propylene oxide.
The catalytic dehydrogenation route, in which
potassium promoted Fe-catalyst is typically used,
Corresponding author.
E-mail addresses: gmeima@dow.com (G.R. Meima),
gov@elptrs2.rug.ac.be (P.G. Menon).
rium limited and strongly endothermic. It can be run
either adiabatically or isothermally over a fixed bed
in which the reactants are passed over the catalyst bed
employing radial or axial flow. Steam is co-fed with
the EB and serves several purposes. Firstly, it delivers
the required heat and acts as a diluent resulting in a
shift to higher equilibrium conversions. Furthermore,
it limits the build up of carbonaceous deposits by
gasification. Finally as an oxidation agent, it renders
the iron oxide in an appropriate oxidation state.
The majority of the commercial units run adia-
batically and under vacuum at temperatures above
600 C. Typically overall conversions of EB above
50% are achieved with selectivity much higher than
90%. A good concise overview of these technologies
can be found in Ullmanns Encyclopedia of Industrial
Chemistry [1].
For economical reasons most styrene production
units have large capacities (in excess of 400,000 t
per annum). The catalyst slowly deactivates and typ-
ically needs to be replaced every 12 years. In view
of the scale this is a costly operation and, hence,
much research has been dedicated to understanding

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 8 4 9 - 8
240 G.R. Meima, P.G. Menon / Applied Catalysis A: General 212 (2001) 239245
and preventing the deactivation mechanisms involved.
From a survey of the literature four main reasons are
generally brought forward, i.e. build up of carbona-
ceous deposits, loss and/or redistribution of promoters
(mainly potassium), (change in) oxidation state of the
Fe-oxide and physical degradation. Many of these
features are interrelated and take place concurrently.
Still it is worthwhile to review these points separately
to arrive at a better understanding of the overall de-
activation process, especially as some contradicting
views exist. In this paper each of these features will
be reviewed. Also, recent trends in research to prevent
deactivation will be treated.
2. Coke deposition
The amount of coke deposited on a typical (pro-
moted) Fe-oxide catalyst during EB dehydrogenation
depends on several factors. Besides the specific cata-
lyst and promoters, important features are the steam to
oil ratio (steam/aromatics ratio, usually designated as
S/O) and the temperature used. Lower S/O ratios and
higher temperatures lead to higher coke levels. Contin-
uous gasification by steam (see Eqs. (1) and (2)) results
in a steady-state carbon deposit of about 36 wt.%
under typical EB dehydrogenation conditions [2].
C + H2 O CO + H2 (1)
CO + H2 O
CO2 + H2 (2)
Often K2 CO3 is considered to be the catalyst for the
gasification.
More extreme conditions can give rise to heavy cok-
ing and a deactivation of the catalyst. Little work has
been performed studying the effect of feeding EB in
the absence of steam. However, related systems have
been investigated in more detail. Buyanov et al. [3]
studied the coking mechanism of a Fe-oxide/Cr-oxide/
K-oxide systems for butene dehydrogenation at
600650 C both in the presence and absence of steam.
With no steam present reduction of the Fe-oxide takes
place and excessive carbon formation is observed.
The authors define a Fe-carbide cycle mechanism to
explain their results. An intermediate metastable car-
bide phase is formed which rapidly decomposes. The
model scheme is represented in Eq. (3).
(3)
Dilution with steam prevents the reduction of the
Fe-oxide to a certain extent and thus suppresses
the Fe-carbide formation. However, the authors
postulate that intermediate surface carbides are
formed.
Herzog and Rase [2] studied the influence of in
situ coke removal and the performance of a promoted
Fe-oxide catalyst for the production of styrene. In their
work they carefully separated the effect of coking from
other effects possibly occurring simultaneously such
as potassium redistribution. Steaming of the catalyst to
remove the carbonaceous deposits, without affecting
the potassium distribution, led to a strong increase in
activity.
Hirano [4] studied the effect of adding several alka-
line earth oxides to a K-promoted Fe-oxide catalyst.
There was no relationship between the amount of
coke deposited and the deactivation rate, leading the
author to the conclusion that coke was not a cause for
deactivation in his experiments.
Careful review of the literature data indicates that
a steady-state layer of coke is always present during
typical styrene synthesis conditions [2,5]. Coke gasifi-
cation is in equilibrium with coke build up. However,
operation at more severe conditions, i.e. lower S/O
ratios, higher temperatures or the loss of gasification
promoter can result in an imbalance of this delicate
equilibrium, leading to build up of coke and con-
current deactivation. This effect is enhanced by the
partial reduction of the Fe-oxide due to the formation
of metastable Fe-carbides.
In general, the exact role of coke on catalyst in it-
self is still controversial. Coke is certainly not (only) a
deactivating black layer or curse on catalysis. Menon
[6] has classified coke on catalysts into four general
types: harmful, harmless, invisible and beneficial. The
oxidative dehydrogenation of ethylbenzene to styrene
is considered as a typical case where coke on catalyst
is considered beneficial. In the 19701990 period,
results were reported from different laboratories de-
scribing a group of catalysts, such as aluminas and
various metal oxides and phosphates, all of which
showed comparable activity and selectivity for the
oxydehydrogenation of ethylbenzene to styrene. The
 G.R. Meima, P.G. Menon / Applied Catalysis A: General 212 (2001) 239245 241

work of Vrieland and coworkers [711] is a typical considered to be a factor of importance for the gasifi-
example of such non-selective catalysis by a variety cation activity.
of very different catalysts. Evidence gradually accu- Besides gasification of coke, probably one of the
mulated that the active site on these catalysts was not most important roles of potassium is that it forms a
the initial catalyst surface one started with, but a car- KFeO2 surface compound that is considered to be the
bonaceous overlayer which was initially deposited on active phase. Hirano [4,14] was the first to demon-
the surface (during which the catalyst exhibited a pe- strate this. Other groups have since then obtained
riod of induction in the activity). Later active carbon independent evidences to indicate that potassium fer-
itself, in particular carbon molecular sieve, was shown rite is indeed the active phase or one of the active
to be an active catalyst for the oxydehydrogenation phases in this catalyst.
reaction [12]. The history of this development and the Muhler et al. [19], in close collaboration with BASF,
various types of evidences which support the role of conducted very comprehensive studies on the styrene
an active carbon overlayer have been reviewed in this catalyst system. They used a variety of sophisticated
journal by Vrieland and Menon [11]. and complementary experimental techniques and also
performed kinetic studies. From this elaborate study
they postulated a life cycle of a typical styrene cata-
3. Loss or redistribution of promoters lyst including the various solid-state transformations
occurring concurrently. This cycle is shown in Fig. 1.
As already indicated, alkali metals are important The active state of the catalyst is believed to be an
promoters for the gasification of carbonaceous de-
posits. The by far most applied alkali metal in com-
mercial styrene catalysts is potassium. Large amounts
in the order of 1030 wt.% are typically added [13,14].
K2 CO3 and KOH are often thought to be coke gasi-
fication catalysts [15,16]. The gasification function
of these compounds has been studied extensively and
an excellent overview of the mechanisms has been
given by Moulijn et al. [17] for the gasification by
CO2 . Similar mechanisms are considered to prevail
for steam gasification.
An interesting question is why potassium is clearly
the most used alkali promoter in commercial styrene
catalysts. Mross [18] indicates that this is most prob-
ably a result of secondary effects. Under operating
conditions the (part of) the Fe-oxide exists as Fe3 O4
(magnetite). Smaller alkali ions like, e.g. Li+ can more
easily migrate into the magnetite lattice and are no
longer available for the gasification reaction. Larger
ions, such as Cs+ , catalyze the gasification reaction so
strongly that also more styrene is gasified, resulting in
a lower selectivity. Another important effect, that has
to be taken into account, is the melting point of the
alkali-compounds present on the catalyst. Mross [18]
points out that the activity for graphite gasification is
approximately inversely proportional to the melting
points of the carbonates, i.e. Li2 CO3 > Cs2 CO3 > Fig. 1. Schematic life cycle of a prototype styrene catalyst with-
Rb2 CO3 > K2 CO3 > Na2 CO3 . Even the anion with out any promoter additives (with the exception of potassium) as
which the alkali metal was (formerly) associated was proposed by Muhler et al. [19].
242 G.R. Meima, P.G. Menon / Applied Catalysis A: General 212 (2001) 239245
equilibrium between potassium ferrite, KFeO2 , and
K2 Fe22 O34 . Hydrogen, formed as product of the reac-
tion, can play a havoc here: it reduces the active cata-
lyst to KOH and magnetite, Fe3 O4 . Once these phases
are formed, segregation of the phases occurs, lead-
ing to a potassium-rich core and a potassium-depleted
shell in each catalyst pellet or extrudate (this will be
treated in more detail later).
Stobbe et al. [16], studying the kinetics of
butene-1 dehydrogenation (as a model reaction) over
potassium-promoted Fe-oxide catalysts, also sup-
ported the active state being KFeO2 .
Goodman and his group [20], in collaboration
with Dow Chemical, studied the kinetics of the EB
dehydrogenation reaction. They concluded that the
creation of the active site was dependent upon the
formation of a Fe3+ metastable species, consistent
with the formation of a KFeO2 phase.
Finally, Lundin et al. [21] also identified KFeO2 as
the active phase. Using scanning electron microscopy
(SEM) and scanning Auger microprobe (SAM), they
observed patches of this compound on a catalyst,
which had been used for 9 months in a commercial
unit. For further details of this work, see the next
paper in this issue by Holmlid and Menon [22].
In view of the above-mentioned roles of potassium,
it is not surprising that its loss, changes in compo-
sition or migration will alter the catalytic properties
of the Fe-oxide. These effects have since long been
considered an important cause of deactivation [2,23].
At reaction conditions the potassium compounds,
especially KOH, are slightly volatile, leading to a
gas-phase transport to the outlet of the reactor. Also,
potassium migrates from the exterior to the core of the
catalyst pellet due to a temperature gradient resulting
from the endothermicity of the reaction.
Lee [23] examined the potassium distribution in a
catalyst pellet after 2000 h on stream. Based on the
results, he divided the remaining activity into three
zones. The exterior and center regions were both
almost inactive due to too little and excess of potas-
sium, respectively. There was only a narrow band
of catalyst with optimum promoter concentration.
Herzog and Rase [2] observed a similar distribution,
however, also large agglomerates of potassium were
also observed at the very exterior of the pellets.
Another problem associated with the loss of potas-
sium from the catalyst surface is the increase in the
acidity of the Fe-oxide. This leads to an increase of
cracking reactions to especially benzene and toluene
and, as a consequence, a lower selectivity [23].
There seems to be a general consensus on the
deactivating effect of potassium loss and migration.
However, there are several opinions about the under-
lying mechanism. Lee [23] considered transport of
K2 O to take place under the influence of the tem-
perature gradient. Also, chloride impurities present
in the feed reacted to form KCl, thus mobilizing the
potassium. Herzog and Rase [2] assumed a partial
pressure gradient as the driving force, without spec-
ifying the chemical composition of the components.
Mross [18] stressed the importance of the CO2 partial
pressure. He indicated that in zones of higher CO2
partial pressure the KOH is reacted to K2 CO3 , which
is relatively less volatile, according to the scheme
presented by reaction (4):
2KOH + CO2
K2 CO3 + H2 O (4)
This results in a depletion of KOH and in an enrich-
ment of K2 CO3 in zones where the CO2 concentration
is higher. At the reactor inlet the potassium exists
mainly in the form of KOH as a consequence of the
higher partial pressure of steam. Indeed more KOH
relative to K2 CO3 was found in the catalyst pellets at
the reactor entrance relative to the exit. This is shown
in Fig. 2.
Finally, extensive work from the group at Gteborg
University/Chalmers University of Technology indi-
cated that potassium could be lost as neutral atoms
or as excited states. Holmlid and coworkers [24,25],
studied the emission of potassium species from fresh
and used commercial styrene catalysts at 600800 C,
using ultra-high vacuum (UHV) and molecular-beam
techniques. From these studies, and taking into ac-
count the detailed mechanism of the solid-state trans-
formations proposed earlier by Ertls group [19] (see
Fig. 1), an energy diagram for the potassium promoter
in the iron-oxide catalyst for the styrene process
could be constructed [25]. It was concluded that the
potassium loss from the industrial styrene catalyst at
process temperatures (about 600 C) and above, but
under UHV conditions, occurs in the form of not only
K atoms, but also as excited states K , doubly excited
states K2 , and as clusters Kn .
 G.R. Meima, P.G. Menon / Applied Catalysis A: General 212 (2001) 239245
Fig. 2. Average weight percentage KOH vs. K2 CO3 in a catalyst particle as measured from the entrance of the reactor to the exit (from
Mross [18]).
4. Oxidation state
As already discussed above, several solid-state
transformations occur when considering the life cycle
of a typical styrene catalyst. Many studies have been
devoted to a better understanding of this effect in re-
lation to deactivation. Hydrogen is formed (locally) at
the catalyst surface, whereas steam and hydrocarbons
are present in the feed. This results in a complex and
dynamic system, especially at the high temperatures
(>600 C) involved. Moreover, solid-state changes,
that are kinetically slow, can still take place consider-
ing the typical lifetime of a styrene catalyst. Also, the
potassium migration described above slowly alters
the chemical composition of the catalyst.
Overall the feed composition is considered reduc-
ing at temperatures above 600 C. Lee [23] observed
that the iron compound in fresh catalyst consisted of
mainly Fe2 O3 (hematite) which is reduced to Fe3 O4
(magnetite). He noted that Fe3 O4 is more selective.
Courty and Le Page [26] mention that the catalyst is
more stable after a reduction of the Fe2 O3 to Fe3 O4
after the first 200 h of operation. Also, Yang et al.
[27] using Mssbauer Spectroscopy concluded that
reduction of Fe2 O3 to Fe3 O4 takes place. They did
not observe KFeO2 and suggested that the active site
was promoted by a rapid electron exchange between
Fe2+ and Fe3+ catalyzed by potassium. On the other
hand, based on X-ray diffraction results of used and
steam treated catalysts, Herzog and Rase [2] con-
243
cluded that changes in performance cannot be related
to the Fe-oxide crystallite structure.
Probably the most elaborate study using advanced
surface techniques has been performed by Muhler
et al. [19,28]. These authors reached the conclusion
that the catalyst precursor contains an excess of Fe3+
ions. These ions are not incorporated into the Fe2 O3
lattice but form a ternary compound K2 Fe22 O34 . This
compound is unstable at typical styrene synthesis con-
ditions resulting in the formation of KFeO2 , which is
considered to be the active phase (see Fig. 1). Con-
currently Fe2 O3 is slowly reduced to Fe3 O4 , which
is regarded to be an inactive phase. During the run
KFeO2 is also slowly reduced to Fe3 O4 . However,
the K2 Fe22 O34 serves as a potassium storage medium
supplying the surface with a near-monolayer coverage
of potassium ions and preventing the reduction of the
Fe3+ -ions. Irreversible deactivation occurs when the
K2 Fe22 O34 becomes exhausted.
Stobbe et al. [16] support the above deactivation
mechanism, however, they have shown that the KFeO2
phase is not sufficiently active in catalyzing carbon
gasification to suppress coking entirely. They con-
clude that complete suppression of coking requires
the additional presence of highly dispersed potassium
carbonate.
Irrespective of the exact deactivation mechanism,
all literature points to the fact that solid-phase trans-
formations occur in the catalyst during styrene synthe-
sis conditions. Most recent literature indicates that the
244 G.R. Meima, P.G. Menon / Applied Catalysis A: General 212 (2001) 239245
reduction of Fe3+ -containing phases should be pre-
vented. Probably the formation of KFeO2 serves this
function. Commercial styrene catalysts often contain
a myriad of other promoters such as Cr2 O3 , CeO3 ,
MoO3 , MgO, V2 O5 , CuO, and WO3 [13,29,30].
Especially the addition of Cr is considered to stabilize
the Fe3+ oxidation state as structural promoter.
5. Physical degradation
The physical degradation of a Fe-oxide catalyst
during styrene synthesis has since long been recog-
nized as an important problem [23,31]. The cause is
closely related to the change in oxidation state of the
Fe-oxide as described in the previous section. Un-
der reaction conditions Fe2 O3 (hematite) undergoes
a reduction to Fe3 O4 (magnetite). Hematite has a
hexagonal lattice structure whereas magnetite has a
cubic lattice structure. This lattice structure change,
along with the high mechanical forces in the catalyst
bed, results in degradation or a pulverization of the
catalyst particles. Also, the slow local density changes
due to the migration of the potassium promoter con-
tribute in a weakening of the catalyst crush strength.
Moreover, due to the local depletion of the promoter
higher coking levels are attained and the pores of the
catalyst can become plugged. The overall result of the
above processes is that the pressure drop over the cat-
alyst bed becomes larger, which adversely affects the
selectivity and yield. This deactivation process may
be partially counteracted by gradually increasing the
reaction temperature and thus maintaining the con-
version during the lifetime of the catalyst. However,
this leads to an increase of non-selective cracking
reactions and eventually this becomes uneconomical
and the catalyst needs to be changed.
Hirano [4] studied the effect of adding a series of
alkaline earth oxides such as MgO, CaO, SrO, and
BaO to a potassium promoted Fe-oxide catalyst.
He observed that especially MgO had good charac-
teristics. A high stability was observed which was
attributed to the fact that MgO prevented the pore de-
struction of the catalyst. Lee [23] reported that mate-
rials such as hydraulic cement and calcium aluminate
can be used to give improved strength. Dellinger et al.
[32] have patented that CaO improves the moisture
stability and resistance to swelling and cracking. This
promoter clearly increased the crush strength of the
catalyst.
6. Recent trends in deactivation prevention
Clearly deactivation of styrene catalysts is complex.
Several deactivating mechanisms are interrelated and
take place concurrently. Probably a good distinction
can be made on the basis of reversibility of deacti-
vation. Many of the described solid-state transforma-
tions leading to physical degradation of the catalyst
are irreversible. Also, the slow transport of the potas-
sium promoter can be considered to be of a permanent
nature. On the other hand, (excessive) carbon deposits
can be removed by steaming of the catalyst. However,
it should be realized that the amount and composition
of the coke layer depends on the promoter level and
the steam to oil ratio employed.
Definitely, most attention has been devoted to the
irreversible deactivation mechanisms. A trend has
been to add several modifiers to the catalyst both as
structural promoters and as (improved) gasification
agents. Stabilizing the Fe3+ oxidation state of the iron
oxide decreases the deactivation rate of the catalyst.
These added components may also raise the tempera-
ture threshold for the thermal desorption of K species
from the catalyst, as proposed by Holmlid et al. [33].
Further optimization is still expected to occur. Shell
[34] has patented improvements in catalytic perfor-
mance by pre-doping Fe-oxide with promoters prior
to formulation of the catalyst. However, a disadvan-
tage of addition of increasing promoter levels is that
generally the costs and the complexity of catalyst
preparation increase.
Stobbe et al. [31] have developed methods to sup-
port promoted Fe-oxide onto a MgO support material.
Coke formation could be limited by subjecting the cat-
alyst to a suitable pretreatment. A supported system
can prevent the physical degradation of the catalyst
particles. Boot et al. [35] have used ZrO2 as carrier
material with good results.
Other recent patents by Shell and Idemitsu [36,37]
stress the importance of the pore structure of the final
Fe-oxide catalyst. Shiraki and Matsui [37] pretreated
a commercial styrene catalyst with hydrogen at a
temperature ranging from 350 to 600 C. This resulted
in a pore structure change such that only macropores
 G.R. Meima, P.G. Menon / Applied Catalysis A: General 212 (2001) 239245
remained. Importantly the catalyst deactivation rate
was reported to be reduced from 1/3 to 1/2 of that of
a non-hydrogen pretreated sample. The authors also
mention that the formation of KFeO2 is promoted by
this treatment.
Finally, recent publications [3840] indicate that the
use of CO2 instead of steam can suppress the deactiva-
tion of the catalyst. In these cases supported Fe-oxide
systems were used, i.e. Al2 O3 and ZSM-5, respec-
tively. Increased energy savings were also claimed.
An earlier publication [41] also mentions a beneficial
effect of CO2 with respect to catalyst deactivation.
Addition of small amounts of CO2 (0.10.5 mol%)
to the feed over a commercial catalyst resulted in a
suppression of the catalyst activity decay, albeit at
the cost of a slight decrease in the rate of styrene
formation.
In conclusion it can be said that much work has
been, and still is, devoted to understanding and pre-
venting styrene catalyst deactivation. Over the years
this has led to the development of improved styrene
catalysts with a longer time on stream. It is expected
that further improvements will continue, especially
considering the scale of production and the costs
involved with deactivation.
Acknowledgements
The authors express thanks to Prof. Guy B. Marin
and Dow colleagues Joe Pelati and Michael Smith for
their critical comments on the manuscript. Ms. Isabelle
Sack is thanked for her help in the literature survey.
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