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Abstract
Supported iron catalyst was prepared from Mg–Fe–Al hydrotalcite-like compounds as precursors and successfully applied for the
ethylbenzene dehydrogenation to styrene. After the calcination, the iron-substituted hydrotalcite-like samples were converted to mixed oxides
with a high surface area as well as a mesoporous character; the XRD analysis indicates the formation of periclase Mg(Fe, Al)O as a main
phase. Catalytic tests of the Mg2FexAl1x catalysts showed that the styrene conversion increased with increasing the iron content up to
x = 0.75 and then decreased, while the selectivity was the highest at x = 0.25. The optimum temperature for the reaction was 550 8C, which
was lower than that used in the commercial process. No favorable effect of the addition of either CO2 or O2 in the reaction medium was
observed in this reaction. Actually, the pre-treatment with H2 resulted in an increase in the activity at the beginning of the reaction as well as a
stable activity during the reaction. The ethylbenzene conversion of 60% and the styrene selectivity of 95% were kept for 3 h over
Mg3Fe0.5Al0.5 catalyst at 550 8C. After the reaction for 3 h, the iron species on the catalyst was partially reduced to the valence state between
Fe2+ and Fe3+. The high catalytic performance can probably be attributed to the formation of partially reduced iron oxides on the surface of
catalyst and to the high surface area along with the porous structure, which originated from the Mg–Fe–Al hydrotalcite structure in the
precursors.
# 2005 Elsevier B.V. All rights reserved.
Keywords: Mg–Fe–Al hydrotalcite-like materials; Ethylbenzene dehydrogenation; The reduced iron oxide; Porous catalyst
0926-860X/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.04.033
Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231 221
structure and composition under reaction conditions by compounds as precursors for mixed oxide catalysts in
Muhler et al. [5,6] gave evidence for the existence of KFeO2 various reactions as reviewed by Cavani et al. [22]. Indeed,
which, in line with a proposal of Hirano [4], was interpreted Clause et al. [23] reported that the catalysts obtained by
as essential for high activity. KFeO2 was identified as the thermal decomposition of Ni–Al hydrotalcite precursors
active phase also by Lundin et al. [7] and Coulter et al. [8]. have very interesting properties, such as high thermal
Kinetic studies on model catalysts showed similar apparent stability and good metal dispersion. The latter behavior has
activation energies for K-promoted and unpromoted iron been attributed by Kruissink et al. [24] to the particular
oxide catalysts, suggesting that potassium only increases the structure of the hydrotalcite through a homogeneous
number of active sites, but does not change their nature [8]. distribution of the metallic cations in the brucite-type
Potassium stabilizes the catalyst against reduction [9] and sheets. The authors have reported that Mg–Ni–Al hydro-
supports the removal of coke. K2CO3 is believed to represent talcite-like compounds were effective as precursors of the
the active center for carbon gasification [4,10,11], whereas catalyst for steam and autothermal reforming of CH4
benzene and toluene as the main side products may be [25,26]. A new catalyst for the process of ethylbenzene
formed at different sites [4,8,12]. Experiments on unpro- dehydrogenation to styrene under a CO2 or O2 atmosphere
moted Fe2O3 gave clear evidence that defective surfaces are was obtained using vanadium-substituted Mg–Al hydro-
more active than well-ordered ones [13]. Ranke and co- talcite-like compounds as precursors [27,28]. Fe–Mg mixed
workers [14] reported that both unpromoted Fe2O3 and K- oxides with high surface areas around 200 m2 g1 and with
promoted model catalysts show a similar high starting mesopores around 15 nm in diameter were prepared from
activity, while that of Fe3O4 is clearly lower. Catalyst hydrotalcite-like compounds and tested as the catalysts in
deactivation by coking or oxide reduction was prevented by the Fisher–Tropsch reaction [29]. Moreover, surface acid/
the addition of potassium to the catalyst, and by the addition base properties and the reducibility of the iron of the
of water or a small amount of oxygen to the feed. catalysts were studied by microcalorimetric method and
Although the commercial catalysts are very active and Mössbauer spectroscopy [30]. Fe–Mg or Fe–Mg–Al mixed
selective, they have some disadvantages: (i) The active oxides were prepared from hydrotalcite-like precursors and
oxidation state is unstable; hematite (a-Fe2O3) is preferred were successfully tested as the catalysts for the reduction of
for styrene production, but tends to lower oxides and even to aromatic nitro compounds [31–33]. As for the dehydrogena-
elemental iron, both of which catalyze coke formation and tion of ethylbenzene, Fe–Mg–Al [34], Fe–Mg–Zn–Al [35],
dealkylation [15,16]. (ii) The catalysts have low surface and Fe–Zn–Al [36] mixed oxides were tested under a CO2
area. (iii) They are deactivated with time, being susceptible atmosphere. The activity losses over the Fe-Mg-Al catalysts
to poisoning by halides and residual organic chloride with time-on-stream were completely restored by oxygen
impurities [1]. The most serious deactivation is caused by pulses [34]. The Fe-Mg-Zn-Al catalysts afforded the highest
the loss of potassium promoter, which migrates in two ehylbenzene conversion of 53.8% and a styrene selectivity
directions as the catalyst ages. Potassium chlorides are found of 96.7% at 500 8C [35]. The Fe-Zn-Al catalysts were
down-stream in the water layer of the condensed product as effective and gave an areal rate of 4.15 mmol min1 m2
well as in catalyst pellets. In fact, a major migration of none the less the surface area was as low as 22.1 m2 g1
cat [36].
potassium occurs within the catalysts pellets, because the In the present work, a series of Fe–Mg–Al mixed oxides
center of the pellets operates at a slightly lower temperature were prepared from the corresponding hydrotalcite-like
than the periphery due to the endothermicity of the reaction. precursors and were tested for the dehydrogenation of
In addition, potassium migrates also to the cooler part of the ethylbenzene. Catalytic behaviors of Fe–Mg–Al mixed
reactor (exit) [1,15,16]. Also, the toxicity of the chromium oxides are completely different from those reported in the
compounds causes damage to humans and to the environ- preceding papers [34–36]; no favorable effect of either the
ment [1,16]. Therefore, the search for new catalyst systems additions of CO2 and O2 or the oxidation pre-treatment of
which have high surface areas and can stabilize the active the catalyst on the activity was observed, whereas the
state of iron, in the absence of potassium, is much needed. reduction pre-treatment afforded the catalyst with somewhat
Aluminum was proved to be an excellent promoter, higher activity as well as higher stability. The results of
preventing sintering in iron-oxide catalysts [17,18]. Hirano detailed studies on the catalyst structure and the activities
[19] studied the effect of adding a series of alkaline earth will be reported in this paper.
oxides such as MgO, CaO, SrO, and BaO to a K-promoted
iron oxide catalyst, among which especially MgO had good
characteristics. Stobbe et al. [20] have developed methods to 2. Experimental
support promoted iron oxide onto an MgO support material.
A supported system can prevent the physical degradation of 2.1. Catalyst preparation
the catalyst particles.
The starting materials can also play a significant role in The Mg–Fe and Mg–Fe–Al hydrotalcite-like precursors
the catalytic performance [21]. There has been for the past were synthesized using a co-precipitation of nitrates of each
years an increased interest in using hydrotalcite-like metal component, following the method by Miyata and
222 Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231
Okada [37] after minor modifications. An aqueous solution rate of 10 8C min1 from ambient temperature to 1100 8C
containing the nitrates of Mg2+, Fe3+ and Al3+ (300 ml) was using a mixture of 5 vol.% H2/Ar at a rate of 100 ml min1 as
added slowly with vigorous stirring into an aqueous solution reducing gas, after passing through a 13 molecular sieve trap
of sodium carbonate (300 ml). By adjusting the pH of the to remove water. We used a U-shaped quartz tube reactor, the
solution at 10 with an aqueous solution of sodium hydroxide, inner diameter of which was 6 mm; it was equipped with a
we caused a heavy slurry to precipitate. After the solution TCD for monitoring the H2 consumption. Prior to the TPR
was aged at 60 8C for 24 h, the precipitates were washed measurement, 50 mg of sample was calcined at 550 8C for 1 h
with de-ionized water (1000 ml), dried in air at 110 8C for in Ar gas flow at a rate of 20 ml min1. N2 adsorption (77 K)
24 h, and calcined at 550 8C for 12 h in a muffle furnace in a study was used to examine both BET surface area and the
static air atmosphere. As a control, imp-Fe/MgO and imp-Fe/ porous property of the Mg–Fe–Al mixed oxide. The
g-Al2O3 catalysts were prepared by incipient wetness measurement was carried out on a Bell Japan Belsorp
method using magnesia (UBE) and alumina (JRC-ALO8) 18SP instrument (volumetric); all samples were pre-treated in
as the carrier. vacuum at 200 8C for 12 h before the measurements. The
pore-size distribution was evaluated from the adsorption
2.2. Characterizations of catalysts isotherm by the Dollimore and Heal (DH) method [39].
Table 2
Mössbauer parameters of supported iron oxide catalysts
Catalyst Component Site ISa QSb LWc Bhfd Rel. contr. (%)e Phases by XRD
3+
Mg3Fe0.5Al0.5 Doublet Fe (1) 0.42 0.68 0.52 65.0 Mg(Fe, Al)2O4
Doublet Fe3+(2) 0.20 0.73 0.52 35.0 Mg(Fe, Al)O
Mg3Fe0.5Al0.5 (after reaction) Doublet Fe3+(1) 0.44 0.74 0.59 48.2 Mg(Fe, Al)2O4
Doublet Fe3+(2) 0.27 0.79 0.59 51.8 Mg(Fe, Al)O
imp-Fe/MgO Doublet Fe3+(3) 0.37 0.67 0.51 64.0 MgFe2O4
Doublet Fe3+(4) 0.15 0.77 0.51 36.0 Mg(Fe)O
imp-Fe/g-Al2O3 Doublet Fe3+(5) 0.51 0.88 0.67 18.9 Superpara Fe2O3
Doublet Fe3+(6) 0.26 0.89 0.67 63.7 Tetrahedral Fe-oxide
Sextet Fe3+(7) 0.36 0.22 0.50 50.1 17.4 a-Fe2O3
a
Isomer shift (mm s1).
b
Quadrupole splitting (mm s1).
c
Line width (mm s1).
d
Inner magnetic field (T).
e
Relative contribution.
Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231 225
Table 3
Ethylbenzene dehydrogenation over supported Fe catalystsa
Catalyst Conversion (%) of ethylbenzene Selectivity (%)
Styrene Benzene Toluene Hydrogenb
Mg3Fe0.5Al0.5 58.5 91.2 5.0 3.7 86.4
imp-Fe/g-Al2O3 34.0 92.8 4.6 2.6 70.0
imp-Fe/MgO 36.9 92.8 4.8 2.4 69.2
a
Reaction conditions: catalyst weight, 150 mg; reaction temperature, 550 8C; reaction time, 1 h; N2/Ar, 10/30 ml min1; ethylbenzene, 1.5 mmol h1.
b
Calculated based on the stoichiometry of ethylbenzene dehydrogenation to styrene.
Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231 227
the highest ethylbenzene conversion of 53.8% and a styrene Further increase in the reaction temperature to 600 8C
selectivity of 96.7% at 500 8C. Moreover, Mg–V–Al resulted in a decrease in the ethylbenzene conversion
mixed oxide prepared from the HT precursors showed high together with a drastic decrease in the styrene selectivity.
activity in the dehydrogenation of ethylbenzene in the Also at 600 8C, benzene formation was significantly
presence of CO2; the XRD analysis indicates the formation enhanced, suggesting an occurrence of thermal cracking
of Mg3V2O7 and Mg2Al2O4 in bulk, while the XPS results reactions of ethylbenzene. This was supported by the fact
point to the presence of a mixture of V5+ and V4+ ions on that significant coke formation was observed on the catalyst
the surface [27]. This Mg–V–Al mixed oxide showed after the reaction.
high activity also in the presence of O2; the highest
ethylbenzene conversion of 38% was obtained with a 3.5. Effect of pre-treatment on catalytic behavior of
styrene selectivity of 98% at 450 8C [28]. In the present Mg3Fe0.5Al0.5
work, addition of neither CO2 nor O2 showed any
favorable effect in the dehydrogenation of ethylbenzene Temperature programmed reduction (TPR) of
on Mg3Fe0.5Al0.5 mixed oxide. The effect of the addition Mg3Fe0.5Al0.5 mixed oxide showed two reduction peaks
of oxygen in the dehydrogenation of ethylbenzene on at 433 and 907 8C (Fig. 9). Shen and co-workers [43]
Mg3Fe0.5Al0.5 mixed oxide is shown in Fig. 7. With reported that the TPR of Mg2Fe1Al1 mixed oxide showed
increasing partial pressure of O2, the ethylbenzene two peaks at 506 and 904 8C. At the first TPR peak (506 8C),
conversion first decreased and then inversely increased hematite (a-Fe2O3) was reduced to Fe2+ and Fe0 ((2) and
accompanied by an increase in CO2 selectivity. Styrene (3)) while Mg(Fe, Al)2O4
formation was significantly suppressed in the presence of
O2, indicating that Mg3Fe0.5Al0.5 mixed oxide catalyzed a-Fe2 O3 þ MgO þ H2 ! Mg1x FeII O þ H2 O (2)
the combustion reaction and was not effective for the
oxydehydrogenation of ethylbenzene. The addition of a-Fe2 O3 þ H2 ! a-Fe þ H2 O (3)
CO2 simply resulted in a decrease in the ethylbenzene
conversion; none the less, the selectivities to styrene,
toluene, and benzene were not affected. Moreover, during
the reaction for 3 h, the ethylbenzene conversion gradually
decreased in the presence of CO2 while no substantial
decline was observed in the absence of CO2. These results
suggest that CO2 does not work as the oxidant on
Mg3Fe0.5Al0.5 mixed oxide as observed on Mg–V–Al
mixed oxide [28] or on Cr-MCM-41 [49].
The effect of the reaction temperature on the dehydro-
genation of ethylbenzene on Mg3Fe0.5Al0.5 mixed oxide is
shown in Fig. 8. When the reaction temperature was
increased from 500 to 575 8C, the ethylbenzene conversion Fig. 9. Temperature programmed reduction of Mg3Fe0.5Al0.5. Heating rate,
increased, while the styrene selectivity slowly decreased. 10 8C min1; in a mixture of 5 vol.% H2/Ar at a rate of 100 ml min1.
228 Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231
was transformed into Mg1xFexO (4). The second TPR peak and also that Mg3Fe0.5Al0.5 sample exhibited a much broader
(904 8C) corresponded to peak width and significantly larger QS in the Mössbauer
spectra after the dehydrogenation reaction (Table 2).
MgðFeIII ; AlÞ2 O4 þ H2 ! Mg1x FeIIx O þ H2 O þ MgðAlÞO After the pre-treatment in H2 atmosphere at 1000 8C, no
(4) reaction could be continued since the reactor was quickly
plugged by significant coke formation (Table 4). In the XRD
the reduction of Mg1xFexO4 to metallic Fe0 (5). The of the sample after the reduction (Fig. 1d), the lines of
reductions of Fe3+ to Fe2+ and Fe0 Mg(Al)O were sharpened while the lines of Fe metal
Mg1x FeIIx O þ H2 ! a-Fe þ H2 O þ MgO (5) appeared, indicating that periclase Mg(Fe, Al)O was
reductively decomposed to Mg(Al)O and Fe metal. When
were confirmed by both XRD and Mössbauer spectroscopy the reduced sample was used in the dehydrogenation
[42]. In the present work, the temperatures of both TPR reaction, the lines of MgO were further sharpened and, at the
peaks varied depending on the ratio of Mg/Fe/Al; the first same time, many reflection lines of Fe3C carbide appeared
peak significantly moved between 456 and 552 8C. Similar together with those of graphite and MgAl2O4 spinel in the
results were obtained for Mg–Fe mixed oxides prepared XRD (Fig. 1f). These results indicate that periclase Mg(Al)O
from HT precursors [29]. It is therefore possible that Fe3+ in was decomposed into MgO and MgAl2O4 spinel and,
Mg3Fe0.5Al0.5 mixed oxide was reduced to Fe2+ or Fe0 by H2 moreover, that Fe metal was converted into Fe3C carbide by
formed during the dehydrogenation reaction at 550 8C. coke deposited on it during the reaction.
Effects of the conditions of pre-treatment of Mg3Fe0.5Al0.5
mixed oxide on the activity in the dehydrogenation reaction 3.6. Possible active phase on Mg3Fe0.5Al0.5
are shown in Table 4. The pre-treatment in H2 atmosphere was
carried out under the same conditions as that of TPR to exactly The time course of the dehydrogenation reaction is shown
follow the effect of the reduction of Fe3+ to Fe2+ or Fe0. in Fig. 10. After the pre-treatment of Mg3Fe0.5Al0.5 mixed
Sometimes the reduction treatment with H2 brought over- oxide in N2 atmosphere (Fig. 10, full line), a short induction
reduction to the catalyst, resulting in the formation of metallic period of 20 min was observed, i.e., the conversion of
Fe. As a result, coking became significant on the metallic Fe ethylbenzene started at a low value and increased during
and the reaction was finally suppressed (vide infra). In the 20 min to reach a steady state value. The selectivity to
XRD of the samples, reflection lines of periclase Mg(Fe, Al)O styrene gradually increased while that to benzene decreased
were observed in all samples treated at 550 8C (Fig. 1a–c). A during the reaction for 3 h. When the mixed oxide was pre-
weak reflection of Mg(Fe, Al)2O4 spinel was observed for the treated in H2 atmosphere, the induction period almost
samples treated in both N2 and O2 atmospheres (Fig. 1a and b), disappeared and both conversion and selectivity showed
whereas no such reflection was observed for the sample high values, close to those of the steady state, even at the
treated in H2 atmosphere (Fig. 1c). Even with such changes in beginning of the reaction (Fig. 10, dotted line). After the
the XRD, no significant effect of pre-treatments in N2, H2, and reaction reached steady state, the reaction profiles were
O2 atmosphere at 550 8C was observed in the reaction results. almost the same as those obtained after the pre-treatment in
The pre-treatments in both N2 and H2 atmosphere at 550 8C N2 atmosphere. It was thus clearly confirmed that the
resulted in a similar high activity, whereas that in O2 reduction pre-treatment brought a favorable effect to the
atmosphere at 550 8C caused a little decrease in the activity. catalytic activity of Mg3Fe0.5Al0.5 catalyst.
These results suggest that the surface of Mg3Fe0.5Al0.5 mixed Many papers suggest that the active phase in iron oxide
oxide was almost same after 1 h of the dehydrogenation catalyst is Fe3+. Ranke co-workers [14] reported that
reaction, i.e., the surface was reduced by H2 produced during unpromoted Fe2O3 was much more active than Fe3O4 and
the reaction. This was actually seen in the facts that the that KFeO2 is the active species for K-promoted iron oxide
reflection line of Mg(Fe, Al)2O4 spinel disappeared (Fig. 1e) catalyst in the dehydrogenation of ethylbenzene. KFeO2 as
Table 4
Effect of pre-treatment of Mg3Fe0.5Al0.5 mixed oxide catalyst
Condition of pre-treatment Conversion (%) of ethylbenzene Selectivity (%)
Styrene Benzene Toluene Hydrogena
N2b 60.0 91.7 4.7 3.6 92.0
O2c 58.5 91.2 5.0 3.7 86.4
H2d 59.1 93.2 4.0 2.8 92.0
H2e – – – – –
a
Calculated based on the stoichiometry of ethylbenzene dehydrogenation to styrene.
b
With N2 (20 ml min1) at 550 8C for 1 h.
c
With O2/N2 (10/10 ml min1) at 550 8C for 1 h.
d
With H2/Ar (5/95 ml min1) from room temperature to 550 8C at a rate of 10 8C min1.
e
With H2/Ar (5/95 ml min1) from room temperature to 1000 8C at a rate of 10 8C min1.
Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231 229
the active phase was also identified using SEM and Auger gave clear evidence of the fact that defective surfaces are
microscopy by Lundin et al. [7]. Moreover, a study on K- more active than well-ordered ones [13]. Also, the in situ
promoted iron oxide catalyst films prepared on Ru(0 0 0 1) study of MCM-41-supported iron oxide by XANES and
as a model catalyst reported that the KFeO2 shell around a EXAFS showed that a distorted form of iron oxide species is
K2Fe22O34 core was identified for the active phase [50]. In metastable and contains labile surface oxide anions, which
the ethylbenzene dehydrogenation over K-promoted iron are probably responsible for the high initial catalytic activity
oxide catalyst, the fully oxidized iron phases containing Fe3+ during ethylbenzene dehydrogenation reaction at 500 8C
ions are responsible for high catalytic activity; their partial [56]. Such effects of reduced iron species or defect structure
reductions by generated H2 caused a deactivation, and the due to the partial reduction on the catalyst surface are likely
treatment with steam leads to a partial re-oxidation, resulting in the present work.
in the re-activation of the catalyst [51]. It was also reported
that the activity losses over the Fe-Mg-Al catalysts with 3.7. Possible roles of Mg and Al
time-on-stream were completely restored by oxygen pulses
[34]. The addition of Mg as well as Al will be also important in
Fe K-edge XANES spectra of Mg3Fe0.5Al0.5 after the the high activity of Mg–Fe–Al mixed oxides. A high
reaction, along with that before the reaction and that of stability was observed by the addition of Mg on K-promoted
Fe(II)O as control, are shown in Fig. 11. The iron species iron oxide catalyst; it was attributed to the fact that MgO
was slightly reduced after the reaction; the charge of iron is prevented the pore destruction of the catalyst [19]. By the
considered to be between Fe2+ and Fe3+ judging from the process of supporting promoted iron oxide catalyst on MgO,
location of the absorbance curve of Mg3Fe0.5Al0.5 after the coke formation was limited because the catalyst was
reaction in the spectra. In the present work, it must be subjected to a suitable pre-treatment [20]. Aluminum was
emphasized that the reduced iron species is active as well as proved to be an excellent promoter, preventing sintering in
stable in the ethylbenzene dehydrogenation (Figs. 10 and iron-oxide catalysts [17,18]. The supported system can
11). It is noteworthy that H2 is formed during the prevent the physical degradation of the catalyst particles.
dehydrogenation and reduces the surface of catalyst [52]. In the present work, the surface area of Mg3Fe0.5Al0.5
Reports also suggest the possibility of Fe2+ as the active was 169.0 m2 g1 cat before the reaction, and it decreased
species. Lee [53] observed that a-Fe2O3 (hematite) as a main to 152.4 and 147.1 m2 g1 cat after the reaction for 1 and 3 h,
component in the catalyst is reduced to Fe3O4 (magnetite) respectively, suggesting that the surface area was somewhat
during the reaction and that the latter is more selective. stabilized during the reaction.
Courty and Le Page [54] mentioned that the catalyst is more The pore-size of Mg3Fe0.5Al0.5 showed a wide distribu-
stable after a reduction of Fe2O3 to Fe3O4 after the first 200 h tion from 2 nm to above 25 nm as well as an increasing
operation. Yang et al. [55], using Mössbauer spectroscopy distribution with an increase in radius (Rp). The lowest limit
on K-promoted iron oxide catalyst, suggested that the active of pore radius detectable in the present method is 2 nm, and
site contained no K and was promoted by a rapid electron therefore no information concerning micropores smaller
exchange between Fe2+ and Fe3+ catalyzed by K. Use of than 2 nm could be obtained. However, no significant
unpromoted Fe2O3 in the ethylbenzene dehydrogenation distribution less than 5 nm was observed on Mg3Fe0.5Al0.5.
230 Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231
Mg3Fe0.5Al0.5 calcined at 850 8C showed a sharp distribu- processes. The high catalytic performance is due to the
tion at less than 5 nm, together with a broad distribution formation of partially reduced iron oxides on the surface of
around 20 nm in radius. When the calcination temperature catalyst, together with the high surface area along with the
was increased, the pores with large size diminished and the porosity. All these characters are owing to the fact that
pore-size distribution tended to converge to the small values. catalysts were prepared via periclase Mg(Al, Fe)O as solid
Mg–Al(3/1) hydrotalcite showed a peak around 2–3 nm solutions intermediate starting from Mg–Fe–Al hydrotalcite
together with a wide distribution up to 20 nm in radius. The as the precursors.
former pore-sizes are probably related to the layered
structure, while the latter is due to a ‘‘card house’’ structure
consisting of many small plates. We calculated the basal References
interlayer spacing from the strong symmetric (0 0 3)
reflection (2u = 13.48) of Mg–Al(3/1) hydrotalcite. If the [1] E.H. Lee, Catal. Rev. Eng. Sci. 8 (1973) 285.
thickness of the brucite-like layer is assumed to be 4.8 Å [2] K. Kochloefl, in: G. Ertl, H. Knözinger, J. Weitkamp (Eds.),
Handbook of Heterogeneous Catalysis, vol. 5, VCH, Weinheim,
[57], the interlayer distance corresponds to 2.9 Å. The high 1998, p. 2151.
surface area of Mg3Fe0.5Al0.5 is probably due to the presence [3] T. Hirano, Appl. Catal. 26 (1986) 65.
of meso- and macro-pores in the catalyst. The pore-size [4] T. Hirano, Appl. Catal. 28 (1986) 119.
distribution of Mg3Fe0.5Al0.5 showed no substantial change [5] M. Muhler, J. Schütze, M. Wesemann, T. Rayment, A. Dent, R.
from before to after the reaction. Schlögl, G. Ertl, J. Catal. 126 (1990) 339.
[6] M. Muhler, R. Schlögl, G. Ertl, J. Catal. 138 (1992) 413.
The amounts of coke deposited on the catalyst were 15.7 [7] J. Lundin, L. Holmlid, P.G. Menon, L. Nyberg, Ind. Eng. Chem. Res.
and 22.5 mg g1 cat after 1 h of reaction in CO2 and Ar, 32 (1993) 2500.
respectively; these amounts were far larger than the values, [8] K. Coulter, D.W. Goodman, R.G. Moore, Catal. Lett. 31 (1995) 1.
i.e., 1.83 and 0.60 mg g1 cat , observed after 5 h of reaction
[9] S.C. Ndlela, B.H. Shanks, Ind. Eng. Chem. Res. 42 (2003) 2112.
[10] W.D. Mross, Catal. Rev.-Sci. Eng. 24 (1983) 591.
over Cr-MCM-41-DHT catalysts in CO2 and He, respec-
[11] R.L. Hirsch, J.E. Gallagher, R.R. Lessard, R.D. Wesselhoft, Science
tively [58]. These values suggest that the coking was not 215 (1982) 121.
main reason of the catalyst deactivation, since no deactiva- [12] W.P. Addiego, C.A. Estrada, D.W. Goodman, M.P. Rosynek, R.G.
tion was observed over Mg3Fe0.5Al0.5 catalyst while a clear Windham, J. Catal. 146 (1994) 407.
deactivation took place over Cr-MCM-41-DHT catalysts [13] W. Weiss, D. Zscherpel, R. Schlögl, Catal. Lett. 52 (1998) 215.
[58], and, moreover, the deactivation of Mg3Fe0.5Al0.5 [14] O. Shekhah, W. Ranke, R. Schlögl, J. Catal. 225 (2004) 56.
[15] B.D. Herzog, H.F. Raso, Ind. Eng. Chem. Prod. Res. Dev. 23 (1984)
catalyst occurred in CO2 but was not observed in Ar 187.
atmosphere. The porous structure with the high surface area [16] A.B. Styles, in: B.E. Leach (Ed.), Applied Industrial Catalysis, Aca-
was sufficiently preserved and no remarkable deactivation demic Press, New York, 1983, p. 137.
was observed on Mg3Fe0.5Al0.5 during the reaction for 3 h. [17] G.C. Araújo, M.C. Rangel, Catal. Today 62 (2000) 201.
These stabilizing effects on the catalytic activity are [18] H. Topsoe, J.A. Dumesic, M. Boudart, J. Catal. 28 (1978) 477.
[19] T. Hirano, Bull. Chem. Soc. Jpn. 59 (1986) 2672.
probably due to the fact that catalyst was prepared via [20] D.E. Stobbe, F.R. van Buren, A.W. Stobbe-Kreemers, A.J. van Dillen,
solid solutions, i.e., periclase Mg(Fe, Al)O, starting from J.W. Geus, J. Chem. Soc., Faraday Trans. 87 (1991) 1631.
Mg–Fe–Al hydrotalcite as the precursors. [21] A.C. Oliveira, A. Valentini, P.S.S. Nobre, M.C. Rangel, React. Kinet.
Catal. Lett. 75 (2002) 135.
[22] F. Cavani, F. Trifiro, A. Vaccari, Catal. Today 11 (1991) 173.
[23] O. Clause, M. Gazzano, F. Trifiro, A. Vaccari, L. Zatorski, Appl. Catal.
4. Conclusion 73 (1991) 217.
[24] E.C. Kruissink, L.L. Van Reijen, J.R.H. Ross, J. Chem. Soc., Faraday
Mg-Fe-Al mixed oxide catalysts prepared from the Trans. 177 (1991) 649.
corresponding layered double hydroxides as the precursors [25] K. Takehira, T. Shishido, P. Wang, T. Kosaka, K. Takaki, Phys. Chem.
were successfully applied for the ethylbenzene dehydro- Chem. Phys. 5 (2003) 3801.
[26] K. Takehira, T. Shishido, P. Wang, T. Kosaka, K. Takaki, J. Catal. 221
genation to styrene. By calcining the precursors, we (2004) 43.
obtained the mixed oxides with a high surface area and a [27] G. Carja, R. Nakamura, T. Aida, H. Niiyama, J. Catal. 218 (2003)
mesoporous character, where periclase Mg(Fe, Al)O was 104.
mainly detected by the XRD analysis. During the reaction, [28] F. Malherbe, C. Forano, B. Sharma, M.P. Atkins, J.P. Besse, Appl. Clay
Sci. 13 (1998) 381.
the iron species on the catalyst surface was partially reduced
[29] J. Shen, B. Guang, M. Tu, Y. Chen, Catal. Today 30 (1996) 77.
to the valence state between Fe2+ and Fe3+, and the partially [30] M. Tu, J. Shen, Y. Chen, J. Solid State Chem. 128 (1997) 73.
reduced iron species were effective for the dehydrogenation. [31] P.S. Kumbhar, J. Sanchez-Valente, F. Figueras, Tetrahedron Lett. 39
Neither CO2 nor O2 showed any favorable effect as the (1998) 2573.
additive in the reaction medium in the dehydrogenation [32] S.M. Auer, J.-D. Grunwaldt, R.A. Köppel, A. Baiker, J. Mol. Catal. A
reaction. The ethylbenzene conversion of 60% and the 139 (1999) 305.
[33] P.S. Kumbhar, J. Sanchez-Valente, J.M.M. Millet, F. Figueras, J. Catal.
styrene selectivity of 95% were stably observed over 191 (2000) 467.
Mg3Fe0.5Al0.5 catalyst at the optimum temperature of [34] P. Kuśtrowski, A. Rafalska-Łasocha, D. Majda, D. Tomaszewska, R.
550 8C, which was lower than that employed in commercial Dziembaj, Solid State Ionics 141–142 (2001) 237.
Y. Ohishi et al. / Applied Catalysis A: General 288 (2005) 220–231 231
[35] X. Ye, N. Ma, W. Hua, Y. Yue, C. Miao, Z. Xie, Z. Gao, J. Mol. Catal. [47] S.A. Axon, K.K. Fox, S.W. Carr, J. Klinowski, Chem. Phys. Lett. 189
A 217 (2004) 103. (1992) 1.
[36] N. Mimura, I. Takahara, M. Saito, Y. Sasaki, K. Murata, Catal. Lett. 78 [48] Y. Ma, S.L. Suib, Chem. Mater. 11 (1999) 3545.
(2002) 125. [49] Y. Ohishi, T. Kawabata, T. Shishido, K. Takaki, Q. Zhang, Y. Wang, K.
[37] M. Miyata, A. Okada, Clays Clay Miner. 25 (1977) 14. Takehira, J. Mol. Catal. A 230 (2005) 49.
[38] K. Tanaka, H. Yamashita, R. Tsuchitani, T. Funabiki, T. Yoshida, J. [50] G. Ketteler, W. Ranke, R. Schlögl, J. Catal. 212 (2002) 104.
Chem. Soc., Faraday Trans. 84 (1988) 2987. [51] X.M. Zhu, M. Shön, U. Bartmann, A.C. van Veen, M. Muhler, Appl.
[39] D. Dollimore, G.R. Heal, J. Appl. Chem. 14 (1964) 109. Catal. A 266 (2004) 99.
[40] A. Drits, T.N. Sokolova, G.V. Sokolova, V.I. Cherkashin, Clays Clay [52] G.R. Meima, P.G. Menon, Appl. Catal. A 212 (2001) 239.
Miner. 35 (1987) 401. [53] E.H. Lee, Catal. Rev. 8 (1973) 285.
[41] R.D. Shannon, Acta Crystallogr. A 32 (1976) 751. [54] Ph. Courty, J.F. Le Page, Stud. Surf. Sci. Catal. 3 (1979) 293.
[42] L.A. Boot, A.J. van Dillen, J.W. Geus, A.M. van der Kraan, A.A. vand [55] X. Yang, S. Weng, K. Jiang, L. Mao, Y. Euong, K. Jing, Hyperfine
der Horst, F.R. van Buren, Appl. Catal. A 145 (1996) 389. Interact. 69 (1991) 863.
[43] X. Ge, M. Li, J. Shen, J. Solid State Chem. 161 (2001) 38. [56] S.-T. Wong, J.-F. Lee, S. Cheng, C.-Y. Mou, Appl. Catal. A 198 (2000)
[44] P. Ratnasami, R. Kumar, Catal. Today 9 (1991) 329. 115.
[45] G. Centi, F. Vazzana, Catal. Today 53 (1999) 683. [57] M.A. Drezdon, Inorg. Chem. 37 (1988) 4628.
[46] D.W. Lewis, G. Sanker, C.R.A. Catlow, S.W. Carr, J.M. Thomas, Nucl. [58] K. Takehira, Y. Ohishi, T. Shishido, T. Kawabata, K. Takaki, Q. Zhang,
Instrum. Methods Phys. Res. B 97 (1995) 44. Y. Wang, J. Catal. 224 (2004) 404.