Applied Catalysis A: General 196 (2000) 18

Dehydrogenation of ethane with carbon dioxide over

supported chromium oxide catalysts
Shaobin Wang , K. Murata, T. Hayakawa, S. Hamakawa, K. Suzuki
Department of Surface Chemistry, National Institute of Materials and Chemical Research, Tsukuba, Ibaraki 305-8565, Japan
Received 30 April 1999; received in revised form 12 August 1999; accepted 26 August 1999

Abstract
The oxidative dehydrogenation of ethane into ethylene by carbon dioxide over an unsupported Cr2 O3 and several supported
Cr2 O3 catalysts on metal oxides such as Al2 O3 , SiO2 , TiO2 , and ZrO2 was investigated and the effect of support on the catalytic
activity was studied. The unsupported Cr2 O3 shows medium catalytic activity in this reaction; the support will exert a quite
different effect on catalytic behavior. The catalytic activity varies with the nature of supports. Cr2 O3 /SiO2 catalysts exhibit
an excellent performance in this reaction. Cr2 O3 loading also affects the catalytic activity; 8 wt.% Cr2 O3 /SiO2 catalysts can
produce 55.5% ethylene yield at 61% ethane conversion at 650 C. Characterization indicates that the distribution of chromium
oxide on supports and surface chromium species structure are influenced by the nature of supports. The acidity/basicity and
redox property of catalysts determines the catalytic activity in the dehydrogenation of ethane by carbon dioxide. 2000
Elsevier Science B.V. All rights reserved.
Keywords: Ethane dehydrogenation; Ethylene; CO2 ; Cr2 O3 ; Support

1. Introduction vides several advantages, such as lower reaction tem-

The processes of catalytic conversion of alkanes into
their corresponding alkenes by the oxidative or nonox-
idative dehydrogenation are of increasing importance
because of growing demand for alkenes. Ethane is an
abundant component in natural gas; however, its uti-
lization by these processes receives the least atten-
tion due to the existing thermal cracking process. The
oxidative dehydrogenation of ethane by oxygen into
ethylene has been proposed as an alternative to the
process of thermal cracking of ethane because it pro-
Corresponding author. Tel.: +81-298-54-4487;
fax: +81-298-54-4487.
E-mail address: swang@nimc.go.jp (S. Wang).
perature operation and less catalyst deactivation due
to coking. In the last decade, several catalyst systems
have been developed for this reaction [14]. However,
due to the exothermic characteristic of this reaction in
the presence of oxygen, it is necessary to remove heat
and avoid over-oxidation of ethylene to carbon oxides
so as to give high selectivity towards ethylene.
Carbon dioxide as one the major greenhouse gases
has been recently considered as a source of carbon.
Catalytic hydrogenation of carbon dioxide into sev-
eral organic compounds has been intensively studied.
In fact, carbon dioxide can also act as a mild oxidant.
Utilization of carbon dioxide in some partial oxida-
tion reactions, such as CO2 reforming of methane
[5], oxidative coupling of methane [6], and oxidative

0926-860X/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 9 9 ) 0 0 4 5 0 - 0
2 S. Wang et al. / Applied Catalysis A: General 196 (2000) 18
dehydrogenations of ethane [7], propane [8], and
isobutane [9], has been reported. Nakagawa et al.
[7] studied the dehydrogenation of ethane by carbon
dioxide over several oxides and found that gallium
oxide is an effective catalyst for this reaction, giving
18.6% ethylene yield with a selectivity of 94.5% at
650 C. Takahara and Saito [8] reported the promot-
ing effect of carbon dioxide on dehydrogenation of
propane over supported Cr2 O3 catalysts. They found
that carbon dioxide exerted a promoting effect only
on SiO2 -supported Cr2 O3 catalysts. Shimada et al. [9]
found that iron loaded on activated carbon produced
isobutane conversion of 48% with 80% isobutene se-
lectivity at 600 C in the oxidative dehydrogenation
of isobutane by CO2 .
Supported chromium oxides are well known to be
active catalysts for hydrogenation, isomerization of
olefins, and dehydrogenation of alkanes [10,11]. In
recent years, several researchers have explored the
application of chromium-based catalysts in the oxida-
tive dehydrogenations of ethane [12], propane [13]
and butane [1416] in the presence of oxygen. We in-
vestigated the catalytic activity of zirconia-supported
chromium oxide catalysts in the oxidative dehydro-
genation of ethane, to find that this catalyst system
showed high conversion but low selectivity to ethy-
lene. In order to enhance the ethylene selectivity, it
is interesting to study the same reaction by replacing
oxygen with carbon dioxide. In this investigation, we
prepared several oxide-supported Cr2 O3 catalysts and
studied the effect of support on catalytic behavior in
the oxidative dehydrogenation of ethane with carbon
dioxide over Cr2 O3 -based catalysts.
2. Experimental
2.1. Catalyst preparation
Three commercial catalyst supports: -Al2 O3 , SiO2
and TiO2 , were obtained from Wako Chemicals. An
amorphous ZrO2 support was prepared by precipita-
tion of a ZrO(NO3 )2 (Wako Chemicals) solution by
drop-wise adding NH3 H2 O. The deposits were then
filtered, dried at 105 C overnight and calcinated at
300 C for 3 h. The Cr2 O3 -based catalysts were pre-
pared by the wetness impregnation method. Chromium
nitrate (Wako Chemicals) solution at various concen-
trations was mixed with the supports, followed by
evaporation under constant stirring and then calcina-
tion at 700 C for 3 h. A chromium oxide sample ob-
tained from Soekawa Chemicals was also employed
as a catalyst in this investigation.
2.2. Catalyst characterization
BET surface areas of the supports and catalysts
were measured by nitrogen adsorption at 196 C on a
Micromeritics volumetric instrument provided by Shi-
madzu. XRD patterns of the prepared catalysts were
determined on a Philips PW 1800 X-ray diffractometer
at 40 kV and 40 mA. The radiation source was Cu K
with a Ni filter. XPS measurements were carried out
on a PHI 5500 ESCA system (Perkin-Elmer) with Mg
K as a radiation source. Data were acquired at 14 kV
and 30 mA under the vacuum of 9.4 1010 Torr.
The temperature-programmed reduction (TPR) ex-
periments were conducted in a fixed-bed reactor.
0.5 g samples were loaded in the reactor and were
heat-treated under Ar gas flow of 30 ml/min to 700 C
at a heating rate of 5 C/min. After being maintained
at 700 C for 30 min, the temperature was reduced
to the ambient temperature under the same gas flow.
Then 10% H2 /Ar flow at a rate of 30 ml/min was in-
troduced into the reactor and a heating program was
started to raise the temperature to 700 C at a heat-
ing rate of 3 C/min. The concentrations of H2 were
determined by a GC-8A equipped with a TCD.
2.3. Catalytic performance
The selective oxidative dehydrogenation of ethane
by carbon dioxide was performed at atmospheric pres-
sure in a fixed-bed vertical-flow reactor constructed
from a high-purity alumina tube (i.d. = 6 mm) packed
with 1 g of catalyst and 2 g of quartz sand and mounted
inside a tube furnace. The reactant stream, consisting
of 10% ethane, 50% carbon dioxide and 40% nitro-
gen, was introduced into the reactor at a flow rate of
60 ml/min. The reaction temperature ranged between
500 and 650 C. The products were analyzed by two
gas chromatographs (Shimadzu, GC-8A) equipped
with a Porapak Q column using a FID for hydrocar-
bons and a 5A molecular sieve column for CO, CO2 ,
CH4 , O2 , N2 , and H2 using a TCD, respectively.
 S. Wang et al. / Applied Catalysis A: General 196 (2000) 18 3

Table 1
Catalytic activities of various supported Cr2 O3 catalysts at 650 Ca
Catalyst T ( C) Conversion (%) Selectivity (%) Yield (%)

C2 H6 CO2 C2 H4 CH4 C3 H 8 CO/H2 C2 H 4

Quartz 550 0.08 0.01 91.4 8.6 0 0.07

600 0.4 0.08 95.5 4.5 0 0.4
650 5.0 1.4 97.6 2.4 0 4.9
Cr2 O3 500 1.1 4.5 94.4 5.6 0 19.2 1.0
550 6.2 9.5 97.7 2.3 0 9.9 6.0
600 12.1 16.8 95.4 4.6 0.03 4.8 11.6
650 22.5 29.4 87.0 12.9 0.06 3.2 19.6
5 wt.% Cr2 O3 /SiO2 500 13.0 3.2 98.0 1.95 0.05 1.1 12.7
550 23.9 5.9 96.7 3.3 0.07 1.2 23.1
600 38.8 9.6 95.7 4.2 0.1 1.4 37.1
650 56.1 14.6 92.9 6.8 0.2 1.8 52.1
5 wt.% Cr2 O3 /Al2 O3 500 1.4 1.4 89.8 10.2 7.9 1.2
550 6.6 1.3 94.8 5.2 0.04 6.6 6.2
600 12.6 4.9 97.6 2.3 0.06 5.6 12.3
650 19.2 5.5 96.5 3.4 0.09 4.1 18.5
5 wt.% Cr2 O3 /TiO2 500 0.1 0.1 90.3 9.6 6.1 0.1
550 0.3 0.3 92.2 7.8 6.4 0.3
600 0.9 0.8 93.7 6.3 4.2 0.8
650 5.9 1.6 97.1 2.6 0.3 0.8 5.8
5 wt.% Cr2 O3 /ZrO2 500 10.3 4.6 95.3 4.6 0.03 7.3 9.8
550 22.9 10.2 87.2 12.7 0.05 3.9 20.0
600 37.9 19.2 74.6 25.3 0.09 3.2 28.3
650 57.3 29.1 60.4 39.4 0.10 2.8 34.6
a Reaction conditions: CO2 : C2 H6 = 5 : 1, flow rate = 60 ml/min, 1 g catalysts.

3. Results and discussion
3.1. Catalytic performance of various supported
Cr2 O3 catalysts
Table 1 lists the catalytic conversions and product
distributions over Cr2 O3 and all supported Cr2 O3 cat-
alysts at various temperatures. It is seen that catalytic
conversion increases with the increasing temperature;
however, the tested catalysts still exhibit varying activ-
ities depending on the nature of supports. Quartz sand
shows little activity in CO2 dehydrogenation of ethane
below 600 C. It exhibits only 5% ethane conversion at
650 C, indicating that the homogeneous reaction and
quartz sand will not make significant contributions to
the heterogeneous reaction. The unsupported Cr2 O3
shows activity at temperatures over 550 C. Ethane
conversion of 22% with 87% ethylene selectivity can
be obtained at 650 C. It is noted that CO2 conver-
sions are always higher than those of ethane conver-
sions at all temperatures over Cr2 O3 . This seems to
suggest that Cr2 O3 is more active in activation of
CO2 , which is probably due to the redox property of
Cr2 O3 .
The supported Cr2 O3 catalysts exhibit quite dif-
ferent activities for this reaction. Cr2 O3 /SiO2 shows
the highest ethane conversion, while Cr2 O3 /TiO2
demonstrates the lowest activity, even lower than
that of the unsupported Cr2 O3 catalyst. Cr2 O3 /SiO2
also exhibits the highest ethylene selectivity, whereas
Cr2 O3 /ZrO2 gives the lowest selectivity to ethylene.
However, Cr2 O3 /ZrO2 shows higher methane selec-
tivity, suggesting that it favors the cracking of ethane.
This is probably due to its reducibility, which will
be shown later (Fig. 5). The reduction of Cr species
may involve Cr6+ Cr3+ and further reduction to
Cr2+ or Cr metal. These two species will cause the
cracking process of ethane to methane at high temper-
4 S. Wang et al. / Applied Catalysis A: General 196 (2000) 18

atures. Cr2 O3 /ZrO2 exhibits similar activity to that of

Cr2 O3 /SiO2 , but the selectivity is lower than that of
Cr2 O3 /SiO2 . Cr2 O3 /Al2 O3 shows a medium ethane
conversion, close to that of Cr2 O3 at each temperature.
For all supported Cr2 O3 catalysts, CO2 conversions
are always lower than the values of ethane conversion,
unlike the behavior of Cr2 O3 . Based on the ethane
conversion and ethylene yield, the catalytic activity
of Cr2 O3 and the supported catalysts follows the
order of Cr2 O3 /SiO2 > 5 wt.% Cr2 O3 /ZrO2 > 5 wt.%
Cr2 O3 /Al2 O3 Cr2 O3 > 5 wt.% Cr2 O3 /TiO2 .
The catalytic properties of the supported chromium
catalysts are strongly affected by the acidity/basicity
of the oxide support. Lugo and Lunsford [10] studied
the effect of support on chromium catalysts in dehy-
drogenation of ethane and found that the catalytic ac-
tivity in terms of turnover frequency decreased in the
order Cr2 O3 /Al2 O3 > Cr2 O3 /SiO2 > Cr2 O3 > Cr2 O3 /Y-
zeolite. The different order in activity for silica- Fig. 1. Effect of Cr2 O3 loading in Cr2 O3 /SiO2 system on catalytic
and alumina-supported Cr2 O3 catalysts in Lugo and activity. Reaction conditions: 1 g catalyst, C2 H6 : CO2 = 1 : 5, flow
rate = 60 ml/min, T = 550 C.
Lunsfords work and this investigation is probably
due to the different reaction systems and the supports
employed. Mentasty et al. [13] have reported that the
texture of different aluminas had an effect on catalytic
behavior in dehydrogenation of propane. Takahara The effect of Cr2 O3 loading in Cr2 O3 /SiO2 system
and Saito [8] investigated the dehydrogenation of on catalytic activity was investigated; the results are
propane in the presence of CO2 over Cr2 O3 /Al2 O3 , shown in Fig. 1. As seen, ethane conversion increases
Cr2 O3 /SiO2 and Cr2 O3 /C and reported that CO2 ex- as Cr2 O3 content increases and it reaches the maxi-
hibited a promoting effect on Cr2 O3 /SiO2 while CO2 mum value at 8 wt.% Cr2 O3 . CO2 conversion achieves
showed no or poisonous influence on Cr2 O3 /C and the highest value at 5 wt.% Cr2 O3 . Ethylene selectiv-
Cr2 O3 /Al2 O3 catalysts. It has been also proposed ity over Cr2 O3 /SiO2 catalysts is higher than that of
that CO2 would exert a adverse effect on activity the support; however, it shows little difference among
for those strong basic catalysts in the oxidative de- Cr2 O3 /SiO2 catalysts with the varying Cr2 O3 content.
hydrogenation of ethane [17,18]. We also found that The catalytic stability of Cr2 O3 /SiO2 catalysts
acidic ions promoted catalytic activity, while basic was also investigated at 650 C. Fig. 2 shows the
ions suppressed the activity in dehydrogenation of catalytic performance of 5 wt.% Cr2 O3 /SiO2 and
ethane [19]. Therefore, it is believed that the lower 8 wt.% Cr2 O3 /SiO2 catalysts as a function of time.
catalytic activity of Cr2 O3 /Al2 O3 observed in this It is seen that the two catalysts exhibit deactivation
work is due to the strong basicity of Al2 O3 . Rossi et at different rates, which can be ascribed to the car-
al. [14] investigated isobutane dehydrogenation over bon deposition. 8 wt.% Cr2 O3 /SiO2 shows a higher
Al2 O3 -, SiO2 - and ZrO2 -supported Cr2 O3 catalysts. deactivation rate. For both catalysts, as the ethane
They found that zirconia-supported Cr2 O3 catalysts conversion decreases, ethylene selectivity increases.
showed higher activity than those over Cr2 O3 /Al2 O3 Ethane conversion and ethylene yield decrease from
and Cr2 O3 /SiO2 . Sloczynski et al. [20] reported a 56.1% and 52.1% to 45.4% and 43.5%, respectively,
sequence of activity in the oxidative dehydrogena- over 5 wt.% Cr2 O3 /SiO2 after about 6 h reaction. For
tion of isobutane to be Cr2 O3 > 2 O3 /Al2 O3 > 8 wt.% Cr2 O3 /SiO2 , ethane conversion and ethylene
Cr2 O3 /TiO2 . This order is similar to the result in this yield change from 61.4% and 55.5% to 52.7% and
investigation. 49.7%, respectively, after about 4 h.
 S. Wang et al. / Applied Catalysis A: General 196 (2000) 18 5

on the ZrO2 -supported catalyst, the reduction in sur-

Fig. 2. Stability of 5 wt.% Cr2 O3 /SiO2 and 8 wt.%
Cr2 O3 /SiO2 catalysts at 650 C. Reaction conditions: 1 g catalyst,
C2 H6 : CO2 = 1:5, flow rate = 60 ml/min.
3.2. Catalyst characterization
BET surface areas of the supports and their sup-
ported Cr2 O3 catalysts are given in Table 2. Impreg-
nation of chromium oxide on the supports reduces the
surface area of the corresponding support, as expected;
however, the reduction extent differs among the cat-
alysts. Impregnation of Cr2 O3 on SiO2 has little in-
fluence on the reduction in surface area, while for the
other three catalysts, the surface areas are significantly
reduced. Due to the phase transformation occurring
face area shows the greatest extent. XRD measure-
ments indicate that the ZrO2 support presents an amor-
phous phase, while crystalline tetragonal ZrO2 exists
in Cr2 O3 /ZrO2 catalysts (Fig. 3a). It is well known
that heat-treatment will induce the transformation of
amorphous ZrO2 to crystalline ZrO2 .
The XRD patterns of all Cr2 O3 -based catalysts are
presented in Fig. 3a. One can see that Cr2 O3 diffrac-
tion peaks only appear in TPR profile of Cr2 O3 /SiO2
catalysts, while no peaks can be observed in the XRD
spectra of other three supported catalysts, probably
due to Cr2 O3 in amorphous phase or well dispersed
on the supports. This suggests that the phase and dis-
persion of Cr2 O3 strongly depend on the nature of
the support. TiO2 , Al2 O3 and ZrO2 favor the distri-
bution of Cr2 O3 on the support surface. Rossi et al.
[14] reported that crystallite Cr2 O3 is only present in
the concentrated loading of Cr2 O3 in supported Cr2 O3
samples (Al2 O3 , SiO2 and ZrO2 ). The Cr loading at
which Cr2 O3 started to appear greatly depended on the
support, silica being the one on which this loading is
the lowest. In another research project on Cr2 O3 /TiO2
catalysts in the oxidative dehydrogenation of ethane,
El-Idrissi et al. [12] found that no Cr2 O3 crystallites
could be detected in XRD patterns of Cr2 O3 /TiO2 cat-
alysts. Such findings are similar to the results obtained
in this investigation.
It has been found that the molecular structure of Cr
on oxides is strongly dependent on the environmental
conditions and the type and composition of the sup-
port. The acidbase property of supports plays an im-
portant role in Cr anchorage and dispersion on oxide
supports [11]. The anchorage process is pronounced
on the more basic support. It has been proposed that
the water molecules adsorbed on the support and
around Cr are removed upon heating in air, while
Cr3+ ions are oxidized to Cr6+ . The formed dehy-
drated chromium oxide species do not decompose

Table 2
Physico-chemical properties of the various supports and catalysts
Catalyst SBET (m2 /g) Support SBET (m2 /g) PZC of support [1] Cr3+ BE (eV) Cr6+ BE (eV) Cr6+ /Cr3+
5 wt.% Cr2 O3 /SiO2 334 338 1.02.0 576.8 579.3 0.54
5 wt.% Cr2 O3 /Al2 O3 115 181 7.09.0 577.0 580.0 0.43
5 wt.% Cr2 O3 /TiO2 7.8 8.8 6.0 576.4 579.2 0.44
5 wt.% Cr2 O3 /ZrO2 62 122 6.7 576.7 579.1 1.35
6 S. Wang et al. / Applied Catalysis A: General 196 (2000) 18

basic property. Silica surfaces contain more acidic

hydroxyl groups which will prevent the penetration of
hydrate chromate and have, therefore, a poor capacity
for Cr anchoring. Consequently, Cr2 O3 particles are
frequently encountered on the silica surface, even at
very low Cr loadings.
The XRD patterns of Cr2 O3 /SiO2 at different Cr2 O3
loading are shown in Fig. 3b. SiO2 is present in amor-
phous phase. Weak Cr2 O3 peaks can be seen in the
XRD profile of 2 wt.% Cr2 O3 /SiO2 catalyst. The more
Cr2 O3 loading on catalysts, the stronger the Cr2 O3
diffraction peaks are.
The surface Cr species on all supported catalysts
were examined by XPS measurements. The XPS spec-
tra of Cr 2p over Cr2 O3 -based catalysts are shown in
Fig. 4. One can see that two peaks occur for Cr 2p3/2
spectra over all catalysts: one is appearing around
576 eV and the other at 579 eV. Those two species can
be assigned to Cr3+ and Cr6+ , respectively [11,15,16].
Table 2 presents the binding energy values (BE) of
the peaks observed for Cr 2p3/2 spectra over the sup-
ported Cr2 O3 catalysts. The BE values of Cr 2p3/2
peaks were obtained by applying a fitting program. It
is seen that the binding energies for Cr3+ and Cr6+
differ between catalysts, showing values ranging from
576.4 and 579.1 to 577.0 and 580.0 eV. It is noted that
the binding energies for Cr3+ and Cr6+ exhibit the

Fig. 3. XRD patterns of various Cr2 O3 /oxide catalysts. (a)

Cr2 O3 /oxide catalysts, (b) Cr2 O3 /SiO2 catalysts with different
Cr2 O3 loading.

into O2 and Cr2 O3 , at least for low Cr loadings, but

are anchored by an esterification reaction with the
hydroxyl group of the inorganic oxide, resulting in
the formation of surface Cr species. The point of
zero charge (PZC) of four supports is given in Table
1. It is seen that silica shows acidic property, while
the other three supports exhibit weak acidity and Fig. 4. XPS spectra of Cr 2p on various supported Cr2 O3 catalysts.
 S. Wang et al. / Applied Catalysis A: General 196 (2000) 18
Fig. 5. TPR profiles of various Cr2 O3 -based catalysts.
highest values over Cr2 O3 /Al2 O3 catalyst. From Ta-
ble 2, it is also seen that the Cr6+ /Cr3+ ratios were
also different for all catalysts. Cr2 O3 /ZrO2 shows the
greatest value, while Cr2 O3 /Al2 O3 and Cr2 O3 /TiO2
show the lowest Cr6+ /Cr3+ ratios.
Fig. 5 shows the TPR profiles of Cr2 O3 and
the supported Cr2 O3 catalysts. It is shown that all
Cr2 O3 -based catalysts present varying TPR patterns,
suggesting different interactions between the sup-
port and Cr2 O3 . Two weak reduction peaks occur in
Cr2 O3 TPR profile at temperatures of 150350 and
400600 C, respectively. One weak peak appears in
Cr2 O3 /TiO2 TPR spectrum between 400 and 650 C
centered at 550 C (in an expanded scale). For the
Cr2 O3 /SiO2 catalyst, a strong reduction peak can be
observed at ca. 450 C. For Cr2 O3 /Al2 O3 , a weak
peak and a very strong peak were detected at 350 C
and 700 C, respectively. Mentasty et al. [13] inves-
tigated the reducibility of Cr2 O3 /Al2 O3 catalysts by
the TPR technique and reported a reduction peak at
250400 C, which is similar to observation in this
investigation. Compared with the above catalysts, the
Cr2 O3 /ZrO2 sample exhibits a quite different reduc-
tion behavior. It can be reduced from 200 C at a
larger extent. The reducibility will decrease around
400 C and then it will increase again from 500 to
700 C.
7
It has been proposed that the active species for
dehydrogenation in Cr2 O3 -based catalysts are Cr3+
or/and Cr2+ ions [10,21,22]. Ashmawy [21] evaluated
ethane dehydrogenation over Cr2 O3 /Al2 O3 catalysts
and proposed that both Cr2+ and Cr3+ are active for
the reaction and Cr2+ is the more active ion. Konig and
Tetenyi [19] studied the dehydrogenation of ethane
on -Cr2 O3 and identified coordinatively unsaturated
Cr3+ ions as the active sites. Lugo and Lunsford
[10] investigated the oxidative dehydrogenation of
ethane over -Cr2 O3 , Cr2 O3 /Al2 O3 , Cr2 O3 /SiO2
and Cr2 O3 /Y-zeolite catalysts and found that Cr2+
ions acted as active sites. In this investigation, we
found that two Cr species, Cr3+ and Cr6+ , coexist
on the catalyst surface. These catalysts exhibit dif-
ferent reduction extent due to the varying Cr6+ /Cr3+
ratios. Thus, we believe that surface Cr3+ species and
Cr6+ /Cr3+ couples will be the active sites for dehy-
drogenation of ethane, based on XPS and TPR mea-
surements. The catalytic activity is dependent on the
redox property of catalysts. Therefore, it is believed
that a redox mechanism will play an important role
in the reaction. The dehydrogenation and oxidative
dehydrogenation due to the introduction of CO2 and
its decomposition to produce surface oxygen species
will be the parallel reaction paths in the dehydrogena-
tion of ethane by carbon dioxide. In this reaction, CO,
H2 and water were also detected. Based on those re-
sults, the possible reactions occurring are proposed as
follows:
C2 H6 C2 H4 + H2 (1)
2C2 H6 + 2CrO3 2C2 H4 + Cr 2 O3 + 3H2 O (2)
Cr 2 O3 + 2CO2 2CO + 2CrO3 (3)
H2 + CO2 CO + H2 O (4)
C2 H6 + 2CO2 4CO + 3H2 (5)
C2 H6 + H2 2CH4 (6)
In Table 2, it has been shown that Cr6+ /Cr3+ ratios are
high over Cr2 O3 /ZrO2 and Cr2 O3 /SiO2 . TPR results
also demonstrate that Cr2 O3 /ZrO2 can be reduced be-
tween 200 and 700 C with the greatest extent of reduc-
tion. However, due to the strong ability to give oxygen
species from CrO3 on Cr2 O3 /ZrO2 this catalyst ex-
hibits larger ethane and CO2 conversions but the low-
est ethylene selectivity. Cr2 O3 /SiO2 shows a medium
8 S. Wang et al. / Applied Catalysis A: General 196 (2000) 18
Cr6+ /Cr3+ couple site and reduction extent, leading
to the similar activity to that of Cr2 O3 /ZrO2 but with
higher ethylene selectivity. Although Cr2 O3 /Al2 O3
shows a weak reduction peak between 300 and 400 C,
earlier than the one that occurred on Cr2 O3 /SiO2 , the
stronger reduction process only occurred after 550 C.
The surface redox sites are lower, resulting in less
activity than that of the Cr2 O3 /SiO2 catalyst. In addi-
tion, strong basicity of support Al2 O3 will also have
a negative effect on activity. The higher activity of
Cr2 O3 than that of Cr2 O3 /TiO2 can be also ascribed
to the high reducibility of Cr2 O3 revealed by TPR
results.
4. Conclusions
In this investigation it is found that supported
Cr2 O3 catalysts exhibit varying activities in the de-
hydrogenation of ethane by carbon dioxide, depend-
ing on the interaction between Cr2 O3 and the sup-
port. Among catalysts prepared in this investigation,
Cr2 O3 /SiO2 exhibits higher conversion, ethylene se-
lectivity and stability. The order of activity follows
Cr2 O3 /SiO2 > Cr2 O3 /ZrO2 > Cr2 O3 /Al2 O3 > Cr2 O3 /
TiO2 . The loading of Cr2 O3 also affects the activ-
ity with the optimal amount of 8 wt.%. The nature
of the support exerts an influence upon chromium
species and redox properties, which in return deter-
mine the catalytic behavior of the supported Cr2 O3
catalysts.
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