Applied Catalysis A: General 287 (2005) 918

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Ethylbenzene dehydrogenation on Fe2O3-Cr2O3-K2CO3

catalysts promoted with transitional metal oxides
Nicu Dulamita a, Andrada Maicaneanu b,*, Dean C. Sayle c, Maria Stanca b,
Radu Craciun d, Maria Olea e, Cerasella Afloroaei b, Alexandrina Fodor a
a
Department of Chemistry, Faculty of Sciences, University of Oradea, 5 Armatei Romane St., 410087 Oradea, Romania
b
Department of Chemical Technology, Faculty of Chemistry and Chemical Engineering,
Babes-Bolyai University, 11 Arany Janos St., 400028 Cluj-Napoca, Romania
c
Department of Environmental and Ordnance Systems, Cranfield University, Royal Military College of Science, Shrivenham, Swindon SN6 8LA, UK
d
Arch Chemical R&D Center, 350 Knotter Drive, Cheshire, CT 06410-0586, USA
e
Ghent University, Laboratorium voor Petrochemische Techniek, Krijgslaan 281 S5, B-9000 Ghent, Belgium
Received 3 September 2004; received in revised form 22 February 2005; accepted 28 February 2005
Available online 6 May 2005

Abstract

The effect of titanium, vanadium and cerium oxides on the activity and selectivity of Fe2O3-based catalysts for ethylbenzene (EB)
dehydrogenation reaction has been examined in an integral fixed bed reactor. For all single- or double-promoted catalysts, the selectivity to
styrene was higher than that for the unpromoted catalyst. For the V2O5-promoted catalyst, an optimum content of 3 wt.% was found with
respect to the selectivity to styrene. Moreover, by promoting the standard catalyst with a combination of TiO2/CeO2 up to 6 wt.%, the
activation energy decreased by 10 kJ/mol. The physicochemical properties of the promoted Fe2O3-Cr2O3-K2CO3 catalysts were examined
using N2 adsorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. All catalysts were macroporous, 65
75% of pores having a radius larger than 150 A. No diffraction patterns specific to TiO2 or V2O5 were observed. A CeO2 crystalline phase was
present in the single promoted catalyst and in the double promoted with TiO2 as well. The average size of crystals was 48.6 nm for single and
21.4 nm for the double one. The XPS results confirmed the better dispersion of CeO2 in the presence of TiO2. Based on experimental data
several kinetic models were proposed and kinetic parameters were estimated using a non-linear least squares optimization procedure. The
LangmuirHinshelwoodHougenWatson (LHHW) kinetic model with surface reaction rate-determining step better described the experi-
mental data.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Dehydrogenation; Ethylbenzene; Styrene; Fe2O3-Cr2O3-K2CO3; Transitional metal oxides; LHHW kinetic model

1. Introduction dehydration of methylfenilcarbinol [9,17], oxidative

The common reaction pathway for styrene synthesis is
the catalytic dehydrogenation of ethylbenzene (EB) [116].
In a review paper, Cavani and Trifiro summarized and
presented the best industrial catalysts used in EB
dehydrogenation catalytic processes [8]. Other routes for
styrene synthesis were also reported, such as catalytic
* Corresponding author. Tel.: +40 264 593833x5738;
fax: +40 264 590818.
E-mail address: andrada@chem.ubbcluj.ro (A. Maicaneanu).
dehydrogenation of ethylbenzene [8,9,1828] or other
processes [8]. More than 90% of world production of
styrene is obtained by dehydrogenation of ethylbenzene in
the presence of superheated steam, at temperatures ranging
between 803 and 923 K, on a catalyst based on iron
oxide(III) and potassium oxide (as K2CO3) activated with
different promoters in a two fixed beds adiabatic reactor
[1,3,6,8].
The molecular formula for ethylbenzene molecule and
the corresponding binding energies (in kJ/mol) are given
below:

0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.02.037
10 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918
l catalyst), composition closed to that obtained by Shell [2,4].
Considering the binding energy values, the dehydrogena-
tion of ethylbenzene to styrene could be accompanied by
several parallel-consecutive reactions, as follows:
C6 H5 CH2 CH3 C6 H5 CH CH2 H2
DH 117:6 kJ=mol (1)
C6 H5 CH2 CH3 ! C6 H6 C2 H4 DH 101:7 kJ=mol
(2)
C6 H5 CH2 CH3 H2 ! C6 H5 CH3 CH4
DH 64:5 kJ=mol (3)
C6 H5 CH2 CH3 ! 8C 5H2 DH 1:67 kJ=mol (4)
8C 16H2 O ! 8CO2 16H2 DH 795:9 kJ=mol (5)
Reactions (1), (2) and (5) are strongly endothermic and
favoured by high temperatures and low pressures, whereas
reactions (3) and (4) are exothermic and take place at low
temperatures. The coke formed in reaction (4) is reformed
with steam in reaction (5) [8,13,14]. Therefore, the overall
synthesis of styrene from ethylbenzene is a strong
endothermic process. In conventional conditions, the
superheated steam on a Fe2O3-K2CO3 catalyst supplies
the heat necessary for the process [2,4].
Many studies in the past years [10,1214,29] have
evidenced that at the reaction conditions, the active phase on
the Fe2O3-K2CO3 catalyst is potassium ferrite, KFeO2. The
role of other promoters in the FeKO system is to uphold
and support the KFeO2 phase formation and to stabilise it
under reaction conditions at a H2O(steam)/EB ratio as low as
possible. CeO2 [6,12,3036], V2O5 [15,30], Cr2O3
[4,6,8,30], ZrO2 [30], MoO3 [6,8,9,30] and WO3 [9,30]
were found to act as promoters in Fe2O3-K2CO3 catalyst for
dehydrogenation of ethylbenzene to styrene.
The acidbasic and redox properties of the catalyst, at an
optimum configuration in terms of composition, structure and
texture, will influence the conversion and selectivity to
styrene (reaction (1)). The catalyst configuration needs to be
tailored base on the binding energies in ethylbenzene
molecule. If the surface basic sites are strong enough to
abstract b-hydrogen from ethylbenzene, the break of the
lateral CC bond (263.7 kJ/mol) is promoted and, therefore,
the selectivity to toluene will increase (reaction (3)). If the
catalyst surface acidity is larger, a-hydrogen can be abstracted
from ethylbenzene, and the break of the phenylC bond
(364.2 kJ/mol) become more probably, therefore, a higher
selectivity to benzene will be obtained (reaction (2)).
Experimental tests, at laboratory and pilot scale as well,
performed by Dulamita et al. [15] indicated that the
optimum composition for the catalyst is: Fe2O3 (87 wt.%)
Cr2O3 (3 wt.%)K2CO3 (10 wt.%) (labelled as R1 standard
In this case, the specific rate of styrene formation has a
maximum value, and the activation energy is situated around
104.7  4.18 kJ/mol, in good agreement with that obtained
by Addiego et al. [16], 108.8  4.18 kJ/mol. All these
experiments were performed in a fixed-bed stainless
steel reactor, at atmospheric pressure, on a temperature
domain of 813913 K, with a H2O/EB = 3/1 mixture, at
LHSV = 0.5 h1. Other samples tested were those with the
following compositions: (a) Fe2O3 (77 wt.%)Cr2O3
(3 wt.%)K2CO3 (20 wt.%); (b) Fe2O3 (67 wt.%)Cr2O3
(3 wt.%)K2CO3 (30 wt.%); (c) Fe2O3 (57 wt.%)Cr2O3
(3 wt.%)K2CO3 (40 wt.%); and (d) Fe2O3 (97 wt.%)
Cr2O3 (3 wt.%).
In this work, the promoted R1 catalyst performances on
the ethylbenzene dehydrogenation probe reaction were
studied. The R1 catalyst was promoted with one metal oxide
(TiO2, V2O5 or CeO2, at a 3 wt.%) and/or with a
combination of two metal oxides (at a total of 6 wt.%) by
an adequate reduction of the Fe2O3 content. The catalyst
systems were characterized by BET-N2, X-ray diffraction
(XRD) and X-ray photoelectron spectroscopy (XPS).
Kinetic data were collected in a tubular reactor, operated
under integral conditions. These data were fitted to the
different kinetic models. The kinetic parameters for the
models were estimated by non-linear regression analysis,
using the ODRPack-package to process the experimental
data. From model discrimination procedures, based on
thermodynamic and statistical criteria (F-value, Bartletts
x2-test), the most suitable model was found to be a
LangmuirHinshelwoodHougenWatson (LHHW) model,
involving associative adsorption of ethylbenzene, styrene,
and hydrogen on the same kind of active centres and
considering surface reaction of adsorbed species the rate-
determining step of the process.
The scope of this study is to investigate the effect of some
promoters on catalytic activity and performance of a
standard R1 type catalyst based on the Fe2O3-Cr2O3-
K2CO3 system, using the ethylbenzene dehydrogenation
process as a probe reaction. These results can be of great use
to model and design catalysts for other dehydrogenation
processes used in fine organic synthesis.
2. Experimental
2.1. Catalysts preparation
The composition of the catalysts used in this study is
presented in Table 1. The catalysts were prepared as follows:
(type a) catalyst as a mixture between solid components
(Fe2O3, Cr2O3, CeO2) and a K2CO3 solution; (type b)
catalyst as a mixture between solid components (Fe2O3,
Cr2O3, K2CO3, TiO2, CeO2) and water; (type c) catalyst by
 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918
Table 1
Chemical composition and surface area of the oxide systems considered
Catalyst no. Composition (wt.%)
Fe2O3 Cr2O3 K2CO3
1a 87 3 10
2 84 3 10
3 84 3 10
4 84 3 10
5 81 3 10
6 81 3 10
7 81 3 10
a
Catalyst 1, with optimum composition R1-standard; a: mixture between solid components and K2CO3 solution; b: mixture between solid components and
water; c: mixture between solid components and a V2O5 + K2CO3 solution.
mixing solid components (Fe2O3, Cr2O3, TiO2, CeO2) with a
solution containing V2O5 and K2CO3. The mixture of the
desired solid components, with granulation between 2 and
10 mm, were mixed in a blender for 30 min. The next step
was to add water or solution (as was mentioned before) over
the solid mixture and mix for another 30 min. The wet paste
(1420% water) was then extruded in cylinders shape with
4 mm in diameter and 56 mm in length. The granules were
dried for 2025 h at room temperature, 816 h at 383393 K
and then calcinated in air for 1 h at 1023 K, at 373 K h1
heating rate. After cooling at room temperature, granules are
kept in a dried, oxidant environment.
2.2. Catalysts characterization
BET, XRD and XPS measurements were performed on
fresh catalysts calcinated in air for 1 h at 1023 K.
BET surface area (Sa) measurements were performed
with N2 at 77 K, using a Quanta-Chrome Quantasorb Jr.
Sorption System. Prior to adsorption measurements the
catalyst samples were outgassed in N2 at 438 K for 12 h. The
measurements were made using helium containing 5%, 10%
and 15% N2, at liquid nitrogen temperature (77 K). The
estimated error for Sa results is 5%.
XRD patterns were obtained with a Rigaku XRD
diffractometer employing Cu Ka radiation (l = 1.54184 A)
and operated at 45 kVand 100 mA. From the XRD diffraction
patterns, the mean crystallite size (d) of the MOx crystallites
(M = Fe, Ce, V, Ti) was determined by line broadening
calculations, using the Scherrer equation: d kl=b cos u,
where l is the X-ray wavelength; k, the particle shape factor
(0.9 for cubic particles); b, the full width at half maximum (in
radians); and u, the diffraction angle [37]. X-ray diffraction
patterns from the catalysts were compared to standard
crystalline species (Fe2O3, Fe3O4, Cr2O3, CeO2, TiO2,
K2CO3, V2O3) [38] and assigned to the corresponding
crystalline species.
XPS data were obtained using a Perkin-Elmer Surface
Science instrument equipped with a magnesium anode
(1253.6 eV) operated at 300 W (15 kV, 20 mA), and a 10
360 hemispherical analyser, operated at 50 eV. Samples
were analysed as powders dusted onto double-sided sticky
tape. The XPS binding energies (BE) were measured with a
11
Preparation method SBET (m2 g1)
TiO2 V2O5 CeO2
a 4.32
3 b 6.56
3 c 4.38
3 a 2.39
3 3 c 3.64
3 3 c 5.42
3 3 b 5.33
precision of 0.2 eV or better, and were correlated with BE
from standard materials [39].
2.3. Activity measurements
Dehydrogenation of ethylbenzene (EB) in the presence of
steam was used as a probe reaction for determining the
catalytic activity and kinetic measurements. The measure-
ments were performed isothermal (on a temperature domain
of 813913 K), in a vertical, fixed-bed stainless steel reactor
(20 mm in diameter and 300 mm in length), equipped with a
heating system capable of controlling the temperature with
3 K accuracy. The catalyst bed with a volume of 40 cm3
was placed between two inert material (non-porous CSi)
layers, of the same volume, filled with particles having the
same size (0.851.00 mm). Reaction parameters (EB flow
rate = 20 cm3 h1, H2O flow rate = 60 cm3 h1, H2O/
EB = 3/1, LHSV = 0.5 h1, atmospheric pressure) were
maintained constant during testing.
Prior to the kinetic measurements, the catalyst was
thermally activated and regenerated in order to adjust the
iron oxidation state (Eq. (6)) and increase the formation of
the active phase KFeO2 [8,10,1214,29]. Thermal activation
of the fresh catalyst was obtained by heating the reactor at
913 K using a 373 K h1 heating rate. This procedure will
allow maintaining the mechanical strength of the catalyst.
The next step was the introduction of water and
ethylbenzene over the catalyst at the same temperature.
The coke formed during thermal activation was removed in
the presence of steam and air at 873 K. Then, steam and air
were passed over the catalyst until CO2 was not detected
anymore in the gaseous products.
H2 O H2 OO2
FeO Fe3 O4 Fe2 O3 (6)
H2 H2
The reaction products exit at the bottom of the reactor and
are condensed in a cooling flask using an ice-bath. The
volume of the liquid product and the flow rate of the gas
product are measured 1 h in stream at steady-state
conditions. The material balance of the process is checked
for two consecutive measurements, at each temperature
considered in the test.
12 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918
The gaseous reaction products, H2, CO2, CO, CH4 and
C2H6, were monitored with an on-stream Perkin-Elmer gas
chromatograph with TCD detector. Two packed columns,
Porapak Q one (4060 mesh) for CO2 and a molecular sieve
(5 A) for the rest of the components [40], were employed in
the TCD analysis. Liquid products analysis were performed
using a Perkin-Elmer 8500 gas chromatograph equipped
with a FID detector and a Supelco packed column (GP 5%
SP-1200/1.75% bentone 34 on 100/120 supelco-port). A
good reproductibility for benzene, toluene, ethylbenzene
and styrene analysis was achieved by direct injection into the
column of 1 mL condensed product mixed with n-pentane as
internal standard (99.9% purity).
3. Results and discussion
3.1. Catalyst characterization
The BET surface area of each catalyst, is presented in
Table 1. All catalysts are macroporous, with 6575% of
pores having a radius larger than 150 A. The pores volume
ranges between 0.1 and 0.25 cm3 g1.
Fig. 1 shows the XRD spectra for the R1 catalyst in
comparison with the TiO2 promoted and V2O5-promoted R1
catalysts. Based on the diffraction patterns observed, the R1
catalyst contains as main component Fe2O3 with hematite
structure, with inter-planar distances d = 3.673 (h0 1 2i),
2.696 (h1 0 4i) with 100% intensity, 2.514 (h1 1 0i) and
2.204, (h1 1 3i) [38]. It is interesting to see that the Fe2O3
Fig. 1. X-ray diffraction patterns for standard R1 catalyst based on Fe2O3-
Cr2O3-K2CO3 vs. the TiO2 (2) and V2O5 (3) promoted catalyst.
Fig. 2. X-ray diffraction patterns for standard R1 catalyst based on Fe2O3-
Cr2O3-K2CO3 vs. the CeO2 (4) and TiO2/CeO2 (7) promoted catalyst.
peaks remain clear in presence of TiO2 and V2O5. No
diffraction patterns specific to TiO2 or V2O5 were observed,
consequently it can be assumed that these crystallites are
small and below the XRD detection limit (less than 2 nm).
Fig. 2 shows the diffraction patterns specific to the single
and double CeO2-promoted R1 catalyst. The diffraction
patterns specific to CeO2 crystalline phase are clearly
observed in both promoted catalysts. However, the peak
broadening (e.g. Ce h1 1 1i peak) is different, indicating a
variation in crystalline particle size. The CeO2 crystals, from
catalyst 4 have an average size of dCeO2 48:6 nm
(calculated from CeO2 h1 1 1i peak breadth with Scherrer
equation), and those from catalyst 7 have significantly
smaller sizes, dCeO2 21:4 nm, therefore, are better
dispersed. Apparently, the presence of TiO2 promoter
helped to disperse CeO2 used as a second promoter. No
patterns specific to TiO2 was observed, so TiO2 is present in
the catalysts either as small crystallites or as amorphous
phase.
XPS data were collected for all the components (Fe, Cr,
K, Ce Ti, and V) from the catalysts considered in this study.
Fig. 3 shows the Fe2p XPS spectra for the unpromoted R1
catalyst in comparison to the TiO2-promoted and V2O5-
promoted catalysts. As it can be observed, the XPS spectrum
3=2
for R1 catalysts, shows the main Fe2p peak at BE = 710.7
3=2 1=2
and a DE of 13.6 eV between the Fe2p and Fe2p peaks.
These parameters correspond to a Fe3+ surface species in
Fe2O3 [39]. This is in good agreement with the XRD data
(see Fig. 1), which also showed the presence of crystalline
 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918
Fig. 3. Fe2p XPS spectra for standard R1 catalyst based on Fe2O3-Cr2O3-
K2CO3 vs. the TiO2 (2) and V2O5 (3) promoted catalyst.
Fe2O3 phase mostly, in R1 catalyst. The Fe2p signal from the
promoted catalysts show a shoulder at BE = 713.1 eV, which
indicates the presence on the surface of the catalysts of Fe2+
species, probable as FeO from a Fe3O4 structure.
A similar effect was observed for the CeO2 or CeO2-TiO2
promoted R1 catalysts, as observed in the XPS spectra from
Fig. 4. This fact indicates that in the promoted catalysts, the
Fe3+ species can be easily involved into a redox process
(Fe3+ is partially reduced to Fe2+), which will affect the
surface structure configuration and ultimately the catalytic
activity. Despite the fact that on the XPS spectra (Figs. 3 and
4) a shoulder can be identified at 713.1 eV only for the
promoted catalysts, the formation of Fe2+ species on the
catalyst surface could not be clearly identified by XRD
analysis (no XRD patterns specific to bulk Fe3O4 or FeO
crystalline species recorded in Figs. 1 and 2). The origin of
this shoulder can be attributed either to surface Fe2+ specie
formed during the X-ray exposure during the XPS analysis
or due to a mixed Fe-promoted species (currently under
further investigations). Thus, based on the current data, the
main surface iron species observed on all catalysts were Fe3+
species from Fe2O3. The weak XPS signals specific to the Cr,
Ti and Ce promoters indicate that these species are less
exposed on the catalyst surface, so most probably
incorporated into the main R1-catalyst crystalline structure.
Under these conditions, an electron transfer in situ,
between Fe2+ and Ti4+, or Fe2+ and V5+ or Fe2+ and Ce4+ is
possible and might help the catalytic behaviour of the
promoted catalysts. Using the XPS data specific to Ce3d and
compare the two CeO2-promoted catalysts, with and without
13
Fig. 4. Fe2p XPS spectra for standard R1 catalyst based on Fe2O3-Cr2O3-
K2CO3 vs. the CeO2 (4) and TiO2/CeO2 (7) promoted catalyst.
TiO2, it can be observed that the XPS intensity ratio of
ICe3d =IFe2p = 0.647 on catalyst 7, is higher then that recorded
of for ICe3d =IFe2p = 0.278 on catalyst 4, indicating that more
cerium is exposed on the surface of the catalyst 7 (the TiO2
promoted CeO2-R1 catalyst) than on catalyst 4 (only CeO2
promoted R1 catalyst). These XPS data correlates well with
the data recorded and determined from XRD line broadening
calculations for CeO2 which indicated larger CeO2 crystal-
line particles on catalyst 4 than on catalyst 7 (see Fig. 2).
These values (average crystalline sizes) can be used as a
measure of surface dispersion for a given crystalline phase or
component from a complex mixture (usually small crystal-
lites corresponds to good dispersion).
Taking in account the composition of the catalysts matrix,
formation of KFeO2 species is also a possible route
modification of Fe3O4 or Fe2O3 species. Analysing the
weak K2p XPS signal, it can be concluded that K2CO3 is
finely dispersed on the catalysts surface by calcination or
thermal activation. The peak from the XPS data associate to
carbonates species, appeared at a BE = 289.5 eV. This peak
can be attributed to K2CO3 species [39]. The strongest signal
was observed on catalyst 3. Therefore, the presence of the K-
O-Fe3+ entity as an active centre in the catalytic process can
be anticipated.
Using the information obtained from XRD an XPS
analysis of the R1-based catalysts combined with the
information reported in the literature [10,1214,29] on these
catalytic systems, the following solid state reactions
(reactions (7)(9)) possible occur, either during the catalyst
preparation (temperature up to 1023 K, and O-rich atmo-
14 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918

sphere) or during the thermal activation and dehydrogena-

tion process (temperatures up to 913 K and H-rich atmo-
sphere, in presence of steam).
3Fe2 O3 Ofrom crystalline CeO2 ;V2 O5 or Cr2 O3 ! 2Fe3 O4 (7)

Fe3 O4 K2 CO3 ! 2KFeO2 FeO CO2 (8)

Fe2 O3 K2 CO3 ! 2KFeO2 CO2 (9)

The formation of Fe3O4 in Fe2O3 (the Fe3+/Fe2+

equilibrium) suggests possible electron transfer from Fe2+
to Ti4+, V5+ and Ce4+ with formation of Lewis acid centres,
such as Fe3+, or basic centres, such as Ti3+, V4+ and Ce3+.
These redox centres will probably influence the catalysts
activity by increasing selectivity in styrene and decreasing
the CO2 content from the product which was monitored Fig. 5. Light hydrocarbon (benzene, toluene) vs. styrene content in the
during the kinetic measurements. reaction product, obtained at 793853 K temperature range.

3.2. Catalytic activity data
The activity of the unpromoted and promoted Fe2O3-
based catalysts was evaluated in the reaction of ethylbenzene
dehydrogenation to styrene. Efficiency, conversion and
selectivity in reaction products were determined. Table 2
shows performances of R1 catalyst in comparison with the
V2O5-promoted R1 catalysts, at various concentrations of
V2O5 (up to 4 wt.%). Conversion of over 50% and a
selectivity of 96% in styrene were obtained for an optimum
content of 3 wt.% V2O5 (catalyst 11). It can be also observed
that selectivity in benzene and toluene, side products in the
dehydrogenation process, was significantly minimized (see
Table 2). At lower V2O5 concentration (under 3 wt.%), the
catalyst surface is mainly basic, therefore, more toluene will
be formed by EB hydrocracking (reaction (3)) than benzene
(reaction (2)). A level of promoter higher than 3 wt.% V2O5
has a negative effect on the selectivity in styrene (5% lower).
At this V2O5 concentration, the catalyst surface becomes
sufficient acid to form more benzene by cracking (reaction
(2)) than toluene (reaction (3)). R1 catalyst performances
were also tested as a function of TiO2 and CeO2 content (2
4%). In both cases, the promoter content of 3% proved to
increase the selectivity in styrene to over 91% in case of
TiO2-promoted catalyst (853 K) and over 92% in case of
CeO2 promoted catalyst (843 K). In Fig. 5 is presented the
variations in light hydrocarbons content for unpromoted and
promoted R1 catalysts, as a function of styrene in output
flow, at various reaction temperatures. As observed, the
catalyst 3, which is the V2O5-promoted R1 catalyst, showed
the lowest light hydrocarbon content, indicating that V2O5 is
the most efficient promoter followed by catalyst 4 (the
CeO2-promoted R1 catalyst). For a styrene content of 65% in
the output flow, light hydrocarbon amount decreases from
15% for catalyst R1 to 7.5% for catalyst 2, to 6.3% for
catalysts 4, and to 4.3% for catalyst 3.
Toluene to benzene selectivity ratio for the reaction
products stream can be considered as a criterion for catalyst
effectiveness, since basic sites from the catalysts surface
promote styrene and water gas formation from the coke and
coke precursors [8] on the catalyst surface (see Table 2).
Tables 3 and 4 show the performances for all catalysts
(R1, single promoted and double promoted catalysts), at
various temperatures. Again, the best catalysts were proved
to be the V2O5 and CeO2 promoted catalysts, showing the
highest selectivity in styrene at higher EB conversion and
lower reaction temperatures. Single promoted R1 catalysts
can work with high performances in the temperatures range
of 823893 K. From data presented in Table 4, the double
promoted catalysts with TiO2, V2O5 and CeO2 (catalysts 5

Table 2
Comparative performances for catalyst 8a as a function of V2O5 concentration (at 873 K, H2O/EB = 3/1, LHSV = 0.5 h1)
Catalyst no. Catalyst composition (wt.%) Performances (%)
XEB hSt SB ST SSt
a
8 R1etalon 49.05 39.36 7.72 12.03 80.25
9 R12.0% V2O5 49.12 44.97 3.09 5.35 91.56
10 R12.5% V2O5 47.26 44.69 2.15 3.28 94.57
11 R13.0% V2O5 52.99 50.82 1.54 2.55 95.91
12 R14.0% V2O5 52.30 46.99 7.00 3.15 89.85
a
Catalyst 8 has R1etalon composition, but it was prepared in the same conditions as catalysts 912; St: styrene; XEB: ethylbenzene conversion; hSt: efficiency
FEBinitial FEBunreacted F
component in the product
in styrene; SB, ST, SSt: selectivity in benzene, toluene and styrene; F: mass flow rate; XEB % FEBinitial  100; S % FEB FEB  100.
initial unreacted
 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918 15

Table 3
Catalytic activity of unpromoted and single promoted Fe2O3-K2CO3-Cr2O3 (R1) in ethylbenzene dehydrogenation, at various temperatures (H2O/EB = 3/1,
LHSV = 0.5 h1)
Catalyst no. Temperature (K) Performances (%)
XEB hSt SB ST SSt
R1 (1) 813 48.86 42.78 4.79 7.65 87.56
823 45.84 39.70 5.47 7.90 86.61
833 51.06 45.90 4.98 7.07 89.91
853 54.66 46.93 3.80 5.17 85.85
883 68.88 51.62 13.22 11.76 75.03
R13%TiO2 (2) 833 46.47 42.52 3.13 5.36 91.50
853 58.90 53.72 3.97 4.80 91.22
873 58.61 52.79 3.83 6.09 90.07
883 67.13 59.31 4.71 6.92 88.35
R13%V2O5 (3) 803 30.78 28.09 2.61 6.11 91.96
823 47.94 43.73 2.47 6.31 91.22
853 46.81 44.61 1.47 3.22 95.31
873 56.97 52.52 3.09 4.73 92.18
883 50.91 48.16 1.60 3.81 94.59
R13%CeO2 (4) 833 47.14 43.79 2.58 4.51 92.89
838 50.88 47.20 2.81 5.46 92.77
843 51.11 47.41 2.80 4.44 92.76
848 54.62 50.13 2.82 5.39 91.78
853 59.07 52.89 3.31 7.17 89.54

7) show that light hydrocarbon amount decreased to 1.5
4.2%. Catalyst 5 promoted with TiO2-V2O5 is showing
conversion between 39% and 52% and selectivity of 96
95% at temperatures of 853883 K. Catalyst 6 promoted
with V2O5-CeO2 is showing conversion of 4253% and
selectivity of 9493%, at 813833 K. The best performances
were obtained on catalyst 7, which is promoted with TiO2-
CeO2, this catalyst showing high values for conversion, 56
80%, and selectivity, 9694%, at 833883 K.
3.3. Ethylbenzene dehydrogenation kinetic data
Experimental kinetic data were obtained on catalysts 17,
using the EB dehydrogenation as probe reaction. These
measurements were performed in the same experimental
setup as that used for activity measurements, with the reactor
operated in an integral way, at six different temperatures and
within a wide range of EB partial pressures, with the
volumetric velocity varying between 0.45 and 0.55 h1, in
the absence of diffusional limitations. Several kinetic
models were tested. All these models considered the
reaction of the adsorbed ethylbenzene with a free active
site of the same type or of different type as the one involved
in its adsorption, to give adsorbed styrene and adsorbed or
not adsorbed hydrogen. As concerned the hydrogen
adsorption, both possibilities, with and without dissociation,
were tested.
It was found that the LHHW kinetic model (Eq. (12), non
dissociative adsorption of hydrogen on the same type of
active sites), which also fulfilled statistical and thermo-

Table 4
Catalytic activity of unpromoted and double promoted Fe2O3-K2CO3-Cr2O3 (R1) in ethylbenzene dehydrogenation, at various temperatures (H2O/EB = 3/1;
LHSV = 0.5 h1)
Catalyst no. Temperature (K) Performances (%)
XEB hSt SB ST SSt
R13%TiO23%V2O5 (5) 853 34.87 37.43 1.76 1.95 96.29
863 41.26 39.41 2.18 2.30 95.51
873 46.01 43.98 1.25 2.60 95.58
883 51.60 48.86 1.38 2.95 94.68
R13%V2O53%CeO2 (6) 813 41.48 38.90 2.29 3.92 93.78
823 48.01 45.21 2.14 3.69 94.17
833 52.45 48.64 2.66 4.60 92.74
R13%TiO23%CeO2 (7) 833 55.62 53.58 1.44 2.22 96.33
853 57.82 55.29 2.07 2.30 95.62
873 67.43 64.18 1.83 2.99 95.18
883 79.90 68.86 1.91 3.62 94.46
16 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918

Table 5
Values of estimated parameters for LHHW model and their standard errors for a 95% confidence interval on the R1 catalyst
Temperature (K) k (kmol (h atm kg)1) K (atm1) KA KB KC
823 0.014  1.24e3 0.276  6.22e3 3.481  7.27e3 1.846  1.17e3 1.488  1.4e3
833 0.017  1.43e3 0.183  4.91e3 2.225  1.05e3 0.826  1.55e3 0.744  1.67e3
843 0.020  1.62e3 0.451  1.19e3 2.665  8.88e3 0.930  1.17e3 1.002  1.12e3
853 0.024  2.97e3 0.619  8.53e3 2.279  2.20e3 0.637  2.26e3 0.811  2.09e3
863 0.028  2.35e3 0.407  8.03e3 2.022  2.16e3 0.376  2.27e3 0.571  1.97e3
873 0.033  2.93e3 0.689  3.41e3 1.862  3.42e3 0.337  2.81e3 0.497  2.59e3

dynamic criteria, gave the best fit of the experimental data of [43,44], the adsorption factor K0i can be calculated as a
the catalytic dehydrogenation of EB to styrene. Kinetic data function of adsorption standard entropy, DS0ai ,
analysis was made based on a generalised Langmuir  0
Hinshelwood mechanism [4143] applied to the reaction: DSai
K0i exp (16)
R
Ag ! Bg Cg (10)
and
where A: ethylbenzene; B: styrene; C: hydrogen.
In the presence of a catalyst, reaction of A takes place in DS0ai S0ai  S0gi (17)
adsorbed phase:
where S0ai is the standard entropy for compound i in the adsorp-
A   B  C (11) tion state on the half of the catalyst surface and S0gi , corresponds
to standard entropy in gaseous phase at 1 atm [4547].
If the rate-determining step is reaction of A in adsorbed If the kinetic model (12) is correct, the thermodynamic
phase, then the reaction rate will be: criteria have to be also satisfied:
kKA pA  1=KKB KC pB pC 0 <  DS0ai < S0ai (18)
rp 2
(12)
1 KA pA KB pB KC pC
41:8 < DS0ai < 51:04  0:00586DHa0i (19)
where K, KA, KB, KC, are the equilibrium and adsorption
equilibrium constants and k is the rate coefficient. From Eq. (16) DS0ai values can be calculated as follows:
Using the ODRPack, the kinetic parameters were
estimated for catalysts 17. The results for R1 catalyst are  70.319 J/mol K for ethylbenzene;
shown in Table 5.  249.894 J/mol K for styrene; and
Subsequent processing of the kinetic data allowed us to  123.298 J/mol K for hydrogen.
establish some temperature dependences for reaction
parameters from Eq. (12): Criteria represented by Eqs. (18) and (19) are fulfilled
  in totality for all three species considered in the system.
Ea Therefore, model (12) it was proved to be good from both
k k0 exp  (13)
RT kinetic and thermodynamic points of views.
In Table 7 are presented the calculated values for
K exp18:7 0:021T (14) activation energy and pre-exponential factor, for the
catalytic ethylbenzene dehydrogenation process on unpro-
and for adsorption constants, relations like: moted and promoted R1 catalysts, using the LHHW model.
  Due to the fact that activation energy varies with the metal
DHai
Ki K0i exp  (15)
RT
Table 7
where i: A, B, C. Calculated values for activation energy and pre-exponential factor and their
standard errors for a 95% confidence interval, for ethylbenzene dehydro-
In Table 6 are presented values for adsorption factors K0i
genation on unpromoted and promoted R1 catalysts
and for heat of adsorption DHai . After Boudart and Vannice
Catalyst no. Ea (kJ/mol) Pre-exponential factor,
k0  104
Table 6 R1 (1) 103.1  5.1 4.87  0.61
The values for adsorption factor, K0i and heat of adsorption, DHai , for the R1-TiO2 (2) 99.1  6.3 5.00  0.27
three species involved in the process R1-V2O5 (3) 115.6  10.5 4.10  0.70
R1-CeO2 (4) 103.7  8.2 4.74  0.31
I A B C
R1-TiO2-V2O5 (5) 113.8  6.9 4.19  0.49
4 14
K0i 2.123  10 8.839  10 3.625  107 R1-V2O5-CeO2 (6) 114.0  12.1 4.18  0.39
DHai (kJ/mol) 65830 209396 103151 R1-TiO2-CeO2 (7) 94.3  5.9 5.37  0.35
 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918
oxide or pair of metal oxides used to promote the R1 catalyst,
it can be assumed that TiO2, V2O5 and CeO2 are structural
promoters, which modifies the chemical nature and the type
of active sites from the R1 catalyst.
During the activation period, the number and nature of
the surface active centres are modified due to the presence of
the promoter. These promoters will modify the acidbasic
character of the catalyst surface, and/or the redox
configuration. Cerium from CeO2 or vanadium from
V2O5 may be involved in the Fe3+ + e ! Fe2+ redox
process, which will ultimately affect the redox character of
the catalysts (e.g. the formation of KFeO2 phase). These
structural changes in the catalyst surface affect the EB
conversion and styrene selectivity (see Tables 3 and 4).
Next step is to discuss the compensation effect for our
reaction on different catalysts. Compensation effect [48]
considers a linear dependence between pre-exponential
factor (Eq. (13)) and the activation energy:
ln k0 a bEa (20)
Using the least square fitting procedure to process data presen-
ted in Table 7, a linear dependence was obtained, as follows:
ln k0 12:051  0:0123Ea (21)
2 transition state.
(with R = 0.9983)
Several other studies [16,34,49,50] report values which
are in good agreement with our results. The kinetic model
proposed (Eq. (12)) was a good fit for pseudo-homogeneous
models, such as the one used for the modelling of the
ethylbenzene dehydrogenation to styrene reaction on
catalysts based on iron oxide [5154]. During the process,
under steady-state conditions, all catalysts were thermally
activated. The model indicate that is necessary the formation
of active centres, such as K-O-Fe3+, Fe3+-O-Ce3+, Fe3+-O-
Ce4+ or mixed oxides, such as K-Ti4+-Fe3+-O and K-V5+-
Fe3+-O in order the reaction to occur.
Considering the LHHW model (Eq. (12)) and the
suggestions of Weiss and Schlogl [55], we consider that by
adsorption of EB molecule on the R1 catalyst a p electronic
system is formed as a result of the interaction with Fe3+ acid
centres, which allows elimination of two hydrogen ions from
two CH ethylic groups on basic centres with formation of an
intermediary phase when electrons are transferred to Fe3+.
This mixed acidbasic and redox reaction leads to adsorption
of styrene and to an intermediary catalytic state with two
surface hydroxyl groups and two Fe2+ ions.
2Fe3 O2 EBad ! 2Fe2 OH Stad (22)
In the next stage of the catalytic cycle, desorption of
styrene (St) and H2 takes place in the same time with the re-
oxidation of Fe2+ to Fe3+.
2Fe2 OH Stad ! 2Fe3 O2 St H2 (23)
A reaction mechanism can be formulated and proposed
for EB dehydrogenation on the catalyst 27, considering the
17
entities or the mixed oxides identified by catalyst
characterization. The superficial acid-base reaction involves
O2 from the crystalline lattice of Fe2O3. The Fe2+ species
formed in the redox process, Eq. (22), can be re-oxidized by
CeO2 or TiO2. These components from the catalyst lattice
will act as oxygen transporters from water [36], according to
the Eqs. (24) and (25), given bellow:
2Fe2 O2 2CeO2 ! Fe2 O3 Ce2 O3 (24)
Ce2 O3 H2 O ! 2CeO2 H2 (25)
Cerium oxide (CeO2) is a well-known oxygen storage
capacitor [24]. From its crystalline structure, cerium can
donate or take oxygen to/from the system. The Ce4+ ion from
the Fe3+-O-Ce4+ entity oxidise EB, after a conventional
basic mechanism. The Ce3+ ion from Fe3+-O-Ce3+ entity
gives a bi-functional character to the active centre in which
Fe3+ is a Lewis acid centre and Ce3+ is a basic centre [36].
On such an active centre, two simultaneous phenomena can
take place: the a-hydrogen of the ethyl group interacts with
the acid centre of the catalyst and b-hydrogen interacts with
the basic centre (see Eq. (26)). Aromatic nucleus can
stabilise the positive charge from the a-carbon in the
26
4. Conclusions
The iron oxide based catalyst performance with the
optimum formula of Fe2O3 (87 wt.%)Cr2O3 (3 wt.%)
K2CO3 (10 wt.%) = R1 was improved by promoting it with
one or two transitional metal oxides by lowering the Fe2O3
contents. By promoting the R1 catalyst with TiO2 and
combination of TiO2/CeO2 (up to 6 wt.%) the activation
energy was decreased (R1-TiO2, Ea = 99.1  6.3 kJ/mol; R1-
CeO2, Ea = 103.7  8.2 kJ/mol; R1-TiO2-CeO2, Ea = 94.3
 5.9 kJ/mol), while the conversion and selectivity in the
ethylbenzene dehydrogenation to styrene is increased. Besides
the well-known effect of the promoters which might favour the
formation and stabilization of KFeO2 system [10,1214,29],
we also found out that particle size and crystalline phase of the
CeO2, TiO2 or V2O5 influenced the activity of the promoted
catalysts by increasing the acidbasic and redox active sites
from the catalyst surface. Using a non-linear regression
analysis, the kinetic data were analysed and found to fit well
with a LHHW model. The reaction on the surface of the
catalyst was found to be the rate-determining step.
18 N. Dulamita et al. / Applied Catalysis A: General 287 (2005) 918
Acknowledgements
The authors are grateful for the assistance of Dr. James
Jackson and Dr. Simon Garrett from Department of
Chemistry and Dr. Dennis Miller from Chemical Engineer-
ing Department at Michigan State University, East Lansing,
USA. Dr. Radu Craciun would also like to thanks the
Alexander von Humboldt Foundation, Bonn, Germany.
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