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A: GENERAL
ELSEVIER Applied Catalysis A: General 133 (1995) 219-239
Review
Alternative processes for the production of styrene
F. Cavani *, F. Trifir6
Dipartimento di Chimica Industriale e dei Materiali, Universit~ di Bologna, Viale Risorgimento 4,
40136 Bologna, Italy
Abstract
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
2. Dehydrogenation of etylbenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
2.1. The chemistry of the reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
2.2. Catalyst compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
2.3. The role of steam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
2.4. The role of promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
3. Dehydrogenation of ethylbenzene and oxidation of hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
3.1. Catalyst and reactor configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
3.1.1. Injection of oxygen with the feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
3.1.2. Injection of oxygen in the effluent of the first dehydrogenation reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
3. 1.3. Injection of oxygen in the effluent of the dehydrogenation reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
3.2. The SMART process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
4. Oxidative dehydrogenation of ethylbenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
4.1. Catalytic oxidation with acid oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
4.1.1. The nature of 'active coke' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
4.2. Catalytic oxidation with redox oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.2.1. Catalytic oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.2.2. Non-catalytic oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
* Corresponding author. Tel. ( + 39-51 ) 6443680, fax. ( + 39-51 ) 6443682, e-mail cicatal@boifcc.cineca.it
5. M e m b r a n e t e c h n o l o g y ...................................................................................... 234
6. C o n c l u d i n g r e m a r k s ........................................................................................ 237
Acknowledgements ........................................................................................... 238
References ..................................................................................................... 238
1. Introduction
a slight irreversible deactivation of the catalyst (the lifetime is usually about two
years).
The following alternative techniques have been proposed to give a solution to
the above described problems:
oxidative dehydrogenation, in order to realize an exothermic reaction and shift
completely the equilibrium towards the product formation and to carry out the
reaction at lower temperature.
dehydrogenation, followed by oxidation of the hydrogen, in order to furnish the
heat of reaction from the inside, and in some cases (according to the chosen
solution) shift the reaction equilibrium.
membrane catalysis, in order to shift the equilibrium and to carry out the reaction
at lower temperature.
In the first part of this review the main aspects of dehydrogenation technologies
will be described, and in the latter, the alternative technologies will be examined.
F. Cavani, F. Trifirb /Applied Catalysis A: General 133 (1995) 219-239 221
'0
-100
-200
0
I
100
I
200
I
300
I
400
I
500
temperature, C
I
600
I
700
t -10
-20
80O
Fig. 1. Standard free energy, referred to as one mole of reactant, for the several reactions involved in the
ethylbenzene dehydrogenation.
2. Dehydrogenation of ethylbenzene
2.1. The chemistry of the reaction
The following reactions are involved in the dehydrogenation of ethylbenzene;
some of these reactions are thermodynamically favored at low temperature, while
others are at higher temperatures.
Direct reactions:
ethylbenzene ~ styrene+H2 (dehydrogenation)
ethylbenzene ~ benzene + C2H 4 (cracking)
ethylbenzene + Hz ~ toluene + CH4 (hydrogenolysis)
ethylbenzene + H20 ~ CO + H2 (steam reforming)
Consecutiue reactions
styrene ~ precursors of coke (oligomerization)
precursors of coke + H20 ~ CO2 + H2 (water gas shift)
precursors of coke ~ coke (dehydrogenation)
Fig. 1 shows the values of the standard free energy of reaction (referred to one
mole of reactant) for the various reactions as a function of temperature.
A reaction network which can explain all the main products is shown in
Scheme 1. Approaching equilibrium the selectivity to styrene decreases, not due to
the occurrence of consecutive reactions but rather due to the fact that the formation
of styrene is inhibited, and the rate of formation of the by-products via parallel
routes becomes more relevant. In fact, at low conversion the selectivity to styrene
approaches 100% with many different catalyst compositions.
H20 02
FeO i ~ FesO, ~ ~ Fe203
H2 H2
Scheme 2. Reactions of the variation of the valence state of iron oxide in the reaction medium.
increase of the rate of formation of the active phase, KFeO2, and minimization
of the deactivation rate under reaction conditions [4] ;
interaction of steam with K2CO 3 forming free KOH.
Potassium is the main promoter of Fe203; it increases the activity by more than
one order of magnitude, and also slightly increases the selectivity to styrene and
the stability of the catalyst. It has been well established in the last years that the
promotional role of potassium consists of the formation of a surface ternary com-
pound, KFeOz, which constitutes the active phase [2-4]. Another further role
played by potassium is the formation of well dispersed K 2 C O 3, which acts as catalyst
for the gasification with steam of carbonaceous deposits [ 1,2].
KFeO2 is metastable at low temperature and in the presence of oxygen and water
vapor; this is the reason why only recently in-situ characterization techniques
allowed its formation under reaction conditions to be demonstrated unequivocally
[3,4].
The role of the other promoters for the F e / K / O system is to favor the formation
of KFeO2 and stabilize it under reaction conditions at lower steam-to-hydrocarbon
ratios. Cr and A1 are considered to be structural promoters as they can enter in the
F e 3 + compounds; MgO may act as a support not only for KFeO2 but also for K2CO 3
increasing the selectivity and also the stability of the catalyst [2].
Ce oxide increases the activity and Mo the selectivity; therefore the presence of
both promoters is suggested in an improved catalyst composition [ 5 ].
the internal supply of the heat for the endothermic reaction, thus avoiding costly
reheating supplied by superheated steam or with heat exchangers, and also min-
imizing cracking reactions by shortening inter-reactor lines;
the shift of the dehydrogenation equilibrium by consuming hydrogen, so achiev-
ing higher product yields. Higher yields are obtained both by increasing the
conversion and by increasing the selectivity when moving far from the equilib-
rium.
The oxidation of hydrogen is realized by a suitable oxidation catalyst whose
properties must include:
to be selective only in the oxidation of hydrogen, thus avoiding the oxidation of
the reagent and of the product;
to be stable in the severe reaction conditions, i.e., at high temperature (550-
650C) and in the presence of steam;
to be very active, in order to consume all oxygen at the end of the oxidation zone,
for safety reasons and for the stability of the catalyst in a downstream dehydro-
genation reactor.
This type of process can be applied with dehydrogenating catalysts which are
stable or not poisoned in the presence of steam; in fact this type of process is also
referred to as 'steam oxidation dehydrogenation'. This is the reason why the appli-
cation of this technology is claimed in the dehydrogenation of ethylbenzene using
iron oxide-based catalysts in the presence of steam and in the dehydrogenation of
paraffins only with either spinel-type supports or supports based on alumina doped
with rare earth, which are particularly stable in the presence of steam.
Alternatively, for catalysts which are sensitive to water, the concentration of
steam can be kept low by controlling the amount of added oxygen.
catalyst bed, with an oxidation catalyst based on Pt or Pd. The oxidation catalyst is
inserted in the dehydrogenation reactor by mixing or layering the two catalysts, or
by supporting the active metal on the conventional iron oxide-based dehydroge-
nation catalyst.
Similar solutions have also been claimed for the dehydrogenation of alkanes;
Drehman and Walker [ 8 ] proposed a single polyfunctional catalyst with dehydro-
genation and oxidation properties for the dehydrogenation of n-butane in the pres-
ence of steam. The proposed catalyst seems to be a traditional dehydrogenation
one, based on tin and alkali-promoted Pt, supported on a spinel compound. In order
to obtain higher selectivity to olefins and to minimize the oxidation of hydrocarbons,
hydrogen is introduced in the feed.
In patents, assigned to UOP, Imai and Jan [ 9 ] described a polyfunctional catalyst
for paraffin dehydrogenation, constituted of tin/alkali-doped, alumina-supported
platinum. The authors found in pilot plant tests a selectivity of 95% for the H2
oxidation (the balance was made up of oxygen consumed in hydrocarbon oxida-
tion). Besides alkali metals, other promoters were selected including scandium,
yttrium, lanthanum and actinium [ 10]. This type of catalyst is resistant to severe
hydrothermal conditions.
Font Freide et al. [ 11 ] described an oxidation catalyst based on cordierite-
supported platinum, for the dehydrogenation of n-paraffins in the presence of
oxygen. The reaction is carried out at temperatures close to 800C, where dehydro-
genation occurs thermally in the gas phase; the oxidation catalyst supplies the heat
of reaction by oxidizing hydrogen.
Bricker et al. [ 12] claimed a process for the dehydrogenation of ethylbenzene
with a dual catalyst. The oxidation catalyst is still a tin, alkali-doped platinum one,
but special emphasis was given to the property of the support to resist the severe
hydrothermal conditions. The alumina, after the impregnation with tin, is calcined
at a higher temperature than that of dehydrogenation; the resulting support has an
apparent bulk density of 0.2 ml/g, with more than 40% of its pore volume consti-
tuted of pores with a size larger than 150 nm.
dehydrogenation reactors
J. . . . I
. . . . . . . . . . . . . . . . . .
_ separation
I I I zone
A !,i Ii A. . . . . ,
I i,i
,- - ; steam r~'~- -,
, super~atorl I' I I I' I ~ , , I Io~oas
steam I i i i i i ~ I |
, t---..4, I I = ?wasteheat I 1--,
steam , ~..J , I I : exche--ers I I styrer~
I I I l
(xYg_e.n)_,L~. _
alr _ . . . . . . _ .
~._,J condensete
compressor ethylbenzene
+ water vapor
Fig. 2. Simplified flow sheet for the UOP process for the dehydrogenation of eythylbenzene and oxidation of
hydrogen (adapted from Ref. [ 151 ).
In other patents from UOP a process with a dual catalyst for the dehydrogenation
of both ethylbenzene and paraffins is claimed, where the oxidation catalyst is not
only inserted between two dehydrogenation reactors, but is also placed before the
first reactor, where hydrogen added to the feed (or coming from the recycle) is
oxidized in order to supply the heat to the first dehydrogenation stage [ 15 ]. Fig. 2
displays a scheme of the reactor configuration. The amount of the oxidation catalyst
is about 30% of the dehydrogenation one and clearly operates with a higher space
velocity. In the case the process is used for paraffin dehydrogenation, the percentage
of water in the stream must not exceed 2% (achieved by controlling the amount of
injected oxygen), in order to avoid the deactivation of the dehydrogenation catalyst.
The claimed oxidation catalyst was Pt, doped with alkali or alkaline earth elements.
The SMART process for the synthesis of styrene combines the Lummus tech-
nology with the UOP concept for oxidative reheating by selective catalytic oxidation
of hydrogen [6]. The flow sheet of the process is shown in Fig. 4; the oxidation
catalyst is inserted in the second and third reactor. Fig. 5 reports the design of
F. Cavani, F. Trifirb / Applied Catalysis A: General 133 (1995) 219-239 227
dehydrogenetion
reactor
fractionating
r- . . . . . . . . . . . .
ate_m__ _ _ -v zone
'-f,~G asas
'i h y d r o c a r b o n s to
, styrene r e c o v e r y
i
i
i
i
i
= oxidation , = water
o x y g e n .~ react or Ic , ' .... "
..... i
-- t i
ethylbenzene
Fig. 3. Simplified flow sheet of the UOP process for the dehydrogenation of ethylbenzene and oxidation of
hydrogen: injection of oxygen in the effluent of the dehydrogenation reactor (adapted from Ref. [ 16 ] ).
h y d r o g e n oxidation
ethylbenzene
dehydrogenation
"~_ . . . . . . . . . . . . . . . . . . . . . . . . . . .
styrene ~ h y d r o g e n oxidation
. . . . . . . . . . . . . . . . . . . . . . . . .
i
hydrogen 4.. . . . . . . . ~ .......... , it P. . . .
ethylbenzene
Fig. 4. Simplified flow sheet of the SMART process (adapted from Ref. [6] ).
utlet
steam and air
i
feed i
.,~uent
~oxidation cat.
~dehydrogenet. cat.
dehydrogenation
catalyst
dehydrogenation catalyst
and oxidation catalyst
Fig. 5. Reactor configuration in the SMART process (adapted from Ref. [6] ).
reactor configuration. The gas flows radially from the center, where the oxidation
catalyst is inserted, while in the external part the conventional dehydrogenation
228 F. Cavani, F. Trifirb / Applied Catalysis A: General 133 (1995) 219-239
catalyst is placed. The two beds of catalysts are separated by screens. The removal
of hydrogen formed in the first reactor shifts the equilibrium to the formation of
higher yields of styrene in the second one. With three reactors, a conversion per
pass higher than 80% can be obtained, at the same styrene selectivity as for the
conventional process. It is interesting to observe that these values are similar to the
best ones obtained in the oxidative dehydrogenation of the ethylbenzene with a
carbon molecular sieve [17].
The SMART process can be used to revamp conventional dehydrogenation
plants, in order to increase the capacity with low investment costs. An example has
been given by Romatier et al. [6] ; the revamping of an existing plant producing
272 000 t/year of styrene has been increased in capacity to 400 000 tpa by adding
two new reactors in a three-stage dehydrogenation process; the existing reactors
are not modified, and the new reactors are added in series. The feed rate can be
increased by 10%, in view of the increased ethylbenzene conversion, and corre-
spondingly the reduced recycle stream.
~ benzene~
carbOnoxides
Scheme 4. Reaction pattern in oxidative dehydrogenation of ethylhenzene (from Ref. [ 18] ).
Table 1
Catalytic performance of various catalysts in the oxidative dehydrogenation of ethylbenzene to styrene
SnO2-P205 450 38 82 [ 25 ]
Zr phosphate 450 55 86 [ 22 ]
SIO2-A1203 450 62 71 [ 26]
Clinoptilolite 475 59 85 [ 27 ]
Na sodalite 475 44 85 127 ]
Pr/Mo/AI/O 500 67 86 11281
Ce4 (P207) 3 550 71 89 [ 24 ]
Al(PO3)3 530 72 91 1241
Ce phosphate 605 76 90 [ 24 ]
Ge phosphate 540 54 64 [ 29 ]
Zr/Sn phosphate 500 64 83 [ 30]
Carbon molsieve CMS AX21 350 80 90 [ 17]
Carbon molsieve Ambesorb 575 300 82 73 [31 ]
230 F. Cavani, F. Trifirb/Applied Catalysis A: General 133 (1995) 219-239
Therefore, the investigated oxides are not catalysts, but rather 'carriers of the
active component'. The formation of the 'active coke' in both internal volume and
on external surface of the different oxides explains the low differences in catalytic
performance observed for the different classes of metal oxides and phosphates, as
shown in Table 1, as well as the higher yield in styrene obtained at much lower
temperature with molecular sieve carbon. With metal oxide carriers higher tem-
peratures are most likely necessary to form and to maintain a certain stationary
amount of 'active coke'.
In the case of 'oxides as carriers' usually conversions not higher than 70% have
been reported. This limitation on conversion is essentially due to the fact that the
conversion of oxygen reaches 100%. In fact, the oxygen-to-styrene ratio in most
publications and patents is not higher than 1, with a preferred concentration of
ethylbenzene of 10%. The choice of this composition, the best for achieving a good
selectivity, requires a costly dilution of air with nitrogen or steam and also causes
oxygen starvation at high conversion. However, it is the preferred composition due
to safety reasons, in order to operate outside the flammability region. The lower
and higher limits of ethylbenzene in air at 30C (those for styrene are similar) are
1.0 and 6.7%, respectively; therefore, operation with 10% ethylbenzene in air would
be unsafe, not at the inlet of the reactor but rather inside it, when the composition
of the reacting mixture enters the flammability zone. The choice of 10% oxygen
with about 10% ethylbenzene gives safe conditions in all sections of the plant
layout.
In order to increase the conversion to values which are economically competitive
with dehydrogenation an oxide carrier presenting higher selectivity must be devel-
oped.
Another factor which can contribute to the non-complete conversion obtained
with the oxide carriers is the strong adsorption of styrene which negatively influ-
ences the rate of transformation of ethylbenzene, as can be deduced from the rate
equations developed by Schraut et al. [ 33 ]. A modification of the catalyst aimed
at facilitating the styrene desorption can contribute to increase the yield to styrene.
O.
Scheme 5. Aroxyl groups in 'active coke' deposited on acid oxides (from Ref. [33] ).
SIMS analysis it was found that the deposited coke is similar to anthraquinone
[34,36].
The activity of coke in the oxydehydrogenation of ethylbenzene has been attrib-
uted to the redox couples which form on the edge of its graphitic structure, after
interaction with oxygen. In the absence of molecular oxygen, 'active coke' [ 22,28 ]
and carbon molecular sieves [17,31] are practically inactive and do not form
hydrogen. A decrease of the oxygen-to-ethylbenzene ratio in feedstock leads to a
decrease of ethylbenzene conversion and to an improvement of styrene selectivity
[ 23 ]. It has been hypothesized that these redox couples consist of quinone/hydro-
quinone and aroxyl/phenol groups. A representation of the mechanism proposed
by Emig and Hofmann [22] is given in Scheme 6; styrene forms after a concerted
mechanism of hydrogen abstraction while carbon oxides partially form from the
combustion of coke.
The different selectivities found on different catalysts, notwithstanding the pos-
session of comparable amounts of coke, has been attributed to the different surface
properties of coke. The most selective coke is that one that is less oxidizable by
oxygen, while the least selective coke is that one that is easily burnt to carbon
oxides even in the presence of high amounts of ethylbenzene [ 38].
The carbon molecular sieve AX21 investigated by Grunewald and Drago [ 17]
presents a surface area of approximately 3000 ~ g , with an oxygen content of
Table 2
Performance of carbonaceous catalysts in the oxidative dehydrogenation of ethylbenzene [ 17,31 ]
6%. It likely that the chemical nature of this oxygen is similar to the quinone-type
proposed to form in active coke when this is supported on oxide carriers. The higher
activity of molecular sieve can be attributed to its high surface area, but the surface
area cannot be the only parameter. In fact the activity data reported in Table 2, for
different types of carbonaceous materials [ 17,31 ], cannot be interpreted only on
the basis of differences in surface area. This is also confirmed by the fact that the
micropores blocking during the reaction, due to polymerization of styrene and
thermal decomposition to coke, did not remarkably affect the catalyst activity [ 23 ].
Apparently, most of the reaction occurs in mesopores and in macropores, as well
as in the external surface area.
The data on PPAN, AC and AX21 were collected after 20 h time-on-stream
[17]. In particular, AX21 was stable after one week on stream. The data on
Ambesorb [ 31 ] were collected after only 1 h of reaction; longer periods of reaction
deactivated the catalyst very quickly.
I
40~ "
20-
0 I I | 1
0 20 40 60 80 100
vanadia content, wt.%
Fig. 6. Ethylbenzene conversion as a function of vanadia content in the catalyst (from Ref. [ 18] ).
V205 and some unspecified dopant, at the following conditions: temperature 480C,
feed composition E B / O J H 2 0 / N 2 1/ 1/8/20 molar ratio.
Other authors [ 39] also found the highest value of activity and selectivity at the
9% V205, but these values remained unchanged up to 14% of vanadia content. The
best performance was obtained at 520C with a conversion of 65 % and a selectivity
of 93.5%; residence time was 0.4 s and feed composition was EB/O2/H20/N2 1/
1/8/20 (molar ratio).
The performances obtained with redox catalyst are very similar to those obtained
with acid oxides. The only difference is the presence of an higher amount of steam
when redox oxides are used, in order to suppress bulk combustion.
According to some authors [ 18,39] the active sites for the selective oxydehy-
drogenation are surface clusters of V 5+ and V 4 in octahedral coordination. At
low vanadium concentration isolated vanadium species form, in tetrahedral and
octahedral coordination, while when the vanadium content is increased the amount
of vanadium in octahedral coordination increases, with formation of associated
vanadium species, and the catalytic activity is correspondingly increased. For even
higher concentrations of vanadium a Mg-vanadate phase forms and the activity
drops. Hanuza et al. [39] suggested that the sites which abstract hydrogen from
ethylbenzene are surface V 5 = O bonds, while V 4 species dissociate molecular
oxygen.
5. Membrane technology
second dehydrogenation
first dehydrogenation reactor: multitubular third dehydrogenation
reactor membrane reactor reactor
ceramic membrane
permeable to hydrogen retentate outlet,"
\ _ I ethylbenzene, styrene
I '-' IE ;i " I7 - - * H2,
dehydrog. ' .......... [e~'rens
i! ;r !i
ca~
! i ........................
ir?i !~i~ }:2i)i}
Fig. 8. CMR: reactors configuration in the process for hydrocarbons dehydrogenation developed by Shell (adapted
from Ref. [44] ).
permeate with hydrogen in the membrane reactor. Hydrogen, with small amounts
of hydrocarbons, permeates through the membrane walls. The post-dehydrogena-
tion reactor treats the hydrogen-rich permeate stream, in order to transform the
reagents which have permeated together with hydrogen through membrane walls.
The latter consist of a layer of aluminum oxide membrane (pore size 10 nm,
thickness 4-10/zm) on a porous y-alumina support (pore size 5-10 nm, thickness
4 mm).
In ethylbenzene dehydrogenation, with a F e / K / V / L i / C r / O catalyst, at a tem-
perature of 625C and with a LHSV of 0.65 h-~, a conversion of 65% and a
selectivity of 94% have been obtained, while without membrane the conversion is
only the 50.7%. A ceramic membrane has been investigated by Wu and Liu [46]
to dehydrogenate ethylbenzene and separate hydrogen in order to increase the yield
in styrene. They proposed an hybrid system where a packed-bed reactor, filled with
a Fe/K oxides-based catalyst, is followed by a membrane reactor also filled with a
dehydrogenation catalyst. The hybrid solution has been proposed in order to avoid
the permeation of ethylbenzene when the concentration of hydrogen is low.
Moser et al. [47] have investigated the dehydrogenation of ethylbenzene with
an alumina membrane reactor, in both CMR and IMCR systems. In the latter
configuration, a conventional dehydrogenation catalyst has been located inside the
tube of porous alumina on the feed site. In the CMR configuration, the pores of the
membrane were first filled with a solution containing the catalyst, in order to achieve
a dispersion of the active components. The conversion of ethylbenzene was
increased above the equilibrium value by 10%, with the IMCR, and by 20-23%,
with the CMR configuration.
Oxygen-permeable membranes have been used in catalytic and electrocatalytic
membrane reactors, for the dehydrogenation with oxygen, hydrogen oxidation and
for the oxidative dehydrogenation of ethylbenzene. Michaels and Vayenas [21 ]
F. Cavani, F. Trifirb /Applied Catalysis A: General 133 (1995) 219-239 237
Table 3
A comparison of the best results reported for the different methods of styrene synthesis from ethylbenzene
6. Concluding remarks
Table 3 summarizes the best catalytic performances obtained with the different
technologies; dehydrogenation is the only process widely used at a commercial
level. The SMART technology is commercially available, but to our knowledge it
has found .no industrial application till now. The other methods of synthesis are at
a research level. Oxidative dehydrogenation gives better performances in terms of
238 F. Cavani, F. Trifir6 /Applied Catalysis A: General 133 (1995) 219-239
conversion and selectivity than the industrial dehydrogenation process. The best
performance in terms of conversion/selectivity are claimed with the non-catalytic
oxidation on redox oxides, where 92% of selectivity were obtained at 98% conver-
sion. However, for these two alternative technologies the lifetime of catalysts has
not yet been evaluated and therefore pilot plant studies must be carried out in order
to obtain informations about the modifications of catalytic performances with time-
on-stream and about the productivity achievable. It is also necessary to gain a more
quantitative knowledge of all the by-products. In fact, even if present in traces, the
nature and amount of by-products can determine the final success of these new
technologies.
Acknowledgements
This work was sponsored by MURST (Ministero dell' Universit~ e della Ricerca
Scientifica).
References
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