Ind. Eng. Chem. Res.

2009, 48, 75617566

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Oxidative Dehydrogenation of Ethane to Ethylene with CO2 over Fe-Cr/ZrO2

Catalysts
Shuang Deng,*,, Songgeng Li, Huiquan Li, and Yi Zhang

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Department of Chemical and Biomolecular Engineering, The Ohio State UniVersity, 140 West 19th AVenue,
Columbus, Ohio 43210, and Institute of Process Engineering, Chinese Academy of Sciences,
Beijing 10080, P. R. China

The catalytic performance of Fe-Cr/ZrO2 catalysts, prepared by two different methodsscoprecipitation and
coprecipitation-impregnation were examined in oxidative dehydrogenation of ethane to ethylene using CO2
as an oxidant. Thermogravimetric analysis and physicochemical characterization such as XPS, XRD, and
BET were performed to explore the correlation of catalytic performance with physicochemical properties of
the catalysts. Catalytic tests show that Fe-Cr/ZrO2 catalysts prepared by coprecipitation-impregnation have
higher catalytic stability, higher CO2 conversion, and lower ethylene selectivity in comparison to Fe-Cr/
ZrO2 prepared by coprecipitation. The characterization results indicate that the dehydrogenation of ethane is
activated by Cr3+ species and Fe3O4 is formed during the reaction, which can promote the reverse WGS
reaction. Coke deposition is the main reason of the deactivation of the catalysts. A possible reaction mechanism
was proposed on the basis of these results.
Introduction
Ethylene is a basic raw material in the petrol-chemical
industry. Thermal cracking of hydrocarbons (such as ethane)
in the presence of steam is currently the main source of
ethylene.1-3 However, steam cracking of ethane to ethylene is
a highly endothermic process that must be performed at high
temperatures, which consumes a great deal of energy. Moreover,
at high reaction temperatures, other unwanted reactions producing coke also occur, which can create serious problems with
reactor performance. For example, the large amount of coke
deposited on the inner walls of a tubular cracking reactor can
cause a reduction in the heat transfer rate from the walls, which
in turn requires a higher wall temperature to achieve the
desirable ethane conversion.2 Therefore, it is necessary to
develop a new technology devoted to the production of ethylene.
Oxidative dehydrogenation of ethane (ODE) by oxygen has
been proposed as an alternative route to the process of thermal
cracking of ethane because it is an exothermic process and can
be performed at lower temperatures.4-6 The low temperature
operation and exothermic reactions can significantly reduce the
external heat input to the process and lessen the coke formation.
However, the deep oxidation of ethylene could occur because
of the strong oxidation ability of oxygen, which will cause a
reduction in selectivity to ethylene. To suppress the deep
oxidation and enhance ethylene selectivity, carbon dioxide has
recently been employed as a mild oxidant for ODE instead of
oxygen.1,3,7-12
Thermodynamics analysis and experimental results10-12 have
indicated that ODE to ethylene by carbon dioxide (1) can be
described as the dehydrogenation reaction (2) coupled with
reverse water gas shift (WGS) reaction (3). The ethylene
production can be improved by the elimination of the hydrogen
produced from the dehydrogenation via the reverse WGS
reaction.
* To whom correspondence should be addressed. E-mail address:
shuang.deng@hotmail.com deng.55@osu.edu.

The Ohio State University.

Chinese Academy of Sciences.

C2H6 + CO2 T C2H4 + H2O + CO

(1)

C2H6 T C2H4 + H2

(2)

CO2 + H2 T CO + H2O

(3)

The key to promoting the reaction toward the desired reaction

pathway is the development of a catalyst with desirable
behaviors. A variety of catalysts have been examined in
ODE with carbon dioxide as an oxidant.1,3,4,7-13 Among these
catalysts, Cr-based catalysts have proven to be very effective
catalysts for this reaction.13,14 Various promoters have been used
to further improve catalytic performance. In our prior work,14-16
it has been demonstrated that Fe-promoted Cr2O3/ZrO2 catalysts
exhibit high catalytic activity.
It is known that the performance of a catalyst depends on its
physical-chemical properties, which are strongly affected by
the synthetic technique of the catalyst. In the research described
here, two different methodsscoprecipitation and coprecipitation-impregnation were adopted to prepare Fe-Cr/ZrO2
catalysts for the comparison. Various characterization techniques
including TEM, X-ray photoelectron spectroscopy (XPS), X-ray
diffraction (XRD), and thermogravimetric analysis were used
to examine the chemical and texture properties of the catalysts
before and after reaction aiming at understanding the activity
of Fe-Cr/ZrO2 catalysts in ODE to ethylene with CO2.
Experimental Section
Catalyst Preparation. Fe-Cr/ZrO2 catalysts were synthesized by two different techniques: coprecipitation and
coprecipitation-impregnation. The coprecipitation method has
been described in a previous paper.14 For the coprecipitationimpregnation method, Fe was added to the support of zirconium
using the coprecipitation method. After vacuum drying at 80
C for 8 h, the obtained precipitate was further impregnated
with aqueous solutions of the appropriate amount of
Cr(NO3)3 9H2O and stirred for 6 h at 40 C. The carefully stirred
paste was then vacuum-dried at 60 C overnight. All the dried
samples were calcined at 600 C for 4 h, and then pressed,

10.1021/ie9007387 CCC: $40.75 2009 American Chemical Society

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Figure 1. Catalytic activity and stability of Fe-Cr/ZrO2 catalysts.

crushed, and sieved into catalysts of 20-40 meshes. The

catalysts, which were prepared by the coprecipitation and
coprecipitation-impregnation methods, have the same loadings
of Fe and Cr (5 wt % of Fe and 10 wt % of Cr). Hereafter,
Fe-Cr/ZrO2(C) denotes the catalyst prepared by coprecipitation,
and Fe-Cr/ZrO2 (CI) stands for the catalyst prepared by
coprecipitation-impregnation.
Material Characterization Techniques. Specific surface
areas (SBET), pore sizes, and pore volumes of the catalysts were
measured by N2 adsorption-desorption isotherms at -196 C
on an Autosorb-1 physisorb analyzer. TEM images were taken
on a HITACHI H-8100 microscope. X-ray photoelectron
spectroscopy (XPS) was performed on a PHI 5300/ESCA
system (Perkin-Elmer) at 25 mA under the vacuum of 2.9
10-7 Pa. The X-ray source was AL Ka radiation. All binding
energies were referenced to C1s of 284.6 eV. X-ray diffraction
(XRD) patterns of the catalysts were obtained on a Rigaku
D/max-2400 X-ray diffractometer, operated at 40 kV and 120
mA with Ni filtered Cu Ka radiation. Thermogravimetric studies
of the catalysts were conducted on a Netzsch STA449C
thermobalance in a synthetic air oxidant atmosphere by elevating
the temperature from room temperature to 800 C at a heating
rate of 15 C /min.
Catalytic Tests. The catalytic tests were performed in a fixedbed flow type quartz reactor packed with 0.2 g of the catalyst
and 1 g of quartz sand at atmospheric pressure. The reactant
stream consisting of 20% ethane, 60% carbon dioxide, and 20%
Ar was introduced into the reactor at a flow rate of 15 mL/min.
The reaction temperature was controlled at 650 C. The products
were analyzed on line by a gas chromatograph (Shimadzu GC
14B) with a Porapak QS column and a 5A molecular sieve
column. After reaction, the reactor was cooled with pure Ar
until it cooled to room temperature. The used catalysts were
taken out from the reactor and placed in sealed sample bags,
which were stored in a desiccator before characterization.
Results and Discussion
Catalytic Performance. The blank test (the reactor contains only quartz particles) was performed first to verify that
the reactor material is inert in this reaction. The result shows

Table 1. Structural Properties of Fresh Fe-Cr/ZrO2 (C) and

Fe-Cr/ZrO2 (CI) Catalysts
catalysts

SBET (m2/g)

pore volume
(cm3/g)

average pore
size (nm)

Fe-Cr/ZrO2(C)
Fe-Cr/ZrO2 (CI)

172.1
181.7

0.51
0.61

11.79
13.44

that the ethane conversion is 1.10% at 650 C, which is

considered to be negligible in this reaction.
Figure 1 presents the catalytic activity and stability of Fe-Cr/
ZrO2 (C) and Fe-Cr/ZrO2 (CI) catalysts, respectively. The
ethylene yield on Fe-Cr/ZrO2 (C) dramatically drops from 50%
to 38% over the time on stream. However, the ethylene yield
on Fe-Cr/ZrO2 (CI) varies little. The ethylene selectivity over
Fe-Cr/ZrO2 (C) is higher than that over Fe-Cr/ZrO2 (CI) while
its CO2 conversion is lower. The selectivity toward ethylene
on both catalysts shows a slight increase at the initial reaction
stage and then gains level off. These results indicate that the
preparation methods significantly affect catalytic activity and
stability of Fe-Cr/ZrO2 catalysts. The Fe-Cr/ZrO2(CI) catalyst
exhibits high catalytic stability in comparison to the Fe-Cr/
ZrO2(C) catalyst. It is worth pointing out that the magnitude of
variation in the CO2 conversion is less than that in the
corresponding ethane conversion for the Fe-Cr/ZrO2(C). The
main reason is that the content of CO2 is higher than that of
the ethane in the feed gas where the mole ratio of CO2 to ethane
is 3:1.
Textural and Structural Properties. The BET surface area,
average pore size, and pore volume of the Fe-Cr/ZrO2 catalysts
are given in Table 1. The values of both catalysts are
comparable, which indicates that the structures of the Fe-Cr/
ZrO2 catalysts are not strongly affected by the preparation
methods. This similarity may be explained by the fact that the
Fe-Cr/ZrO2 (CI) catalyst is made from the impregnation of Cr
onto the surface of Fe/ZrO2, and thus, its structure is largely
determined by the Fe/ZrO2 structure, which is prepared with
the coprecipitation method as well.
Figure 2 shows the TEM images of the Fe-Cr/ZrO2(C) and
Fe-Cr/ZrO2 (CI) catalysts before and after reaction, which
provides visual examination for the catalysts. All of the fresh
catalysts investigated are regularly spherical in shape and exhibit

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Figure 2. TEM images of (a) fresh Fe-Cr/ZrO2 (C), (b) used Fe-Cr/ZrO2 (C), (c) fresh Fe-Cr/ZrO2 (CI), and (d) used Fe-Cr/ZrO2 (CI) catalysts.

Figure 3. XRD patterns of (a) fresh Fe-Cr/ZrO2 (CI), (b) used Fe-Cr/
ZrO2 (CI), (c) fresh Fe-Cr/ZrO2 (C), and (d) used Fe-Cr/ZrO2 (C) catalysts.

uniform particle size distribution. Coke can readily be observed

on the surface of the Fe-Cr/ZrO2 (C) catalyst after reaction,
and the boundaries between particles become blurry compared
with those before reaction. In contrast, much less coke was found
on surface of the Fe-Cr/ZrO2 (CI) catalyst after reaction. This
phenomenon has been confirmed by the TGA results, which
will be discussed in a later section.
XRD patterns of Fe-Cr/ZrO2(C) and Fe-Cr/ZrO2 (CI)
catalysts before and after reaction are presented in Figure 3.
Only tetragonal ZrO2 diffraction peaks can be observed on their
XRD spectra. No diffraction peaks corresponding to crystalline
Cr and Fe appear, suggesting that Cr and Fe active species were
highly dispersed in the catalysts and did not sinter after the high
temperature reaction. It should be noted that there is no obvious
change in the width and height of the diffraction peaks before
and after reaction for both catalysts. This means that there is
no appreciable growth of particles. The coke on the Fe-Cr/
ZrO2(C) and Fe-Cr/ZrO2 (CI) catalysts is considered amorphous
carbon since there are no diffraction peaks of crystal carbon on
their XRD patterns.
XPS Results. Surface Cr species on Fe-Cr/ZrO2(C) and
Fe-Cr/ZrO2 (CI) catalysts were examined with XPS before and
after reaction as shown in Figure 4. Two peaks appear on all
the fresh catalysts: one at 576 eV and the other at 579 eV,
which can be assigned to Cr3+ and Cr6+, respectively.1,17 After
reaction, the peak at 579 eV disappeared, suggesting that most
of Cr6+ species have been reduced to Cr3+ in the reaction.
There is a general consensus that the catalytic activity of Crbased dehydrogenation catalysts is strongly dependent on the
Cr species.3,17,18 However, there is a controversy on the
oxidation state of the active species of Cr. Wang et al.17
investigated the dehydrogenation of ethane with CO2 over
supported Cr-based catalysts and proposed that surface Cr3+

Figure 4. XPS spectra of Cr 2p on (a) fresh Fe-Cr/ZrO2 (CI), (b) used

Fe-Cr/ZrO2 (CI), (c) fresh Fe-Cr/ZrO2 (C), and (d) used Fe-Cr/ZrO2 (C)
catalysts.
Table 2. Analysis of Cr Species on Fresh Fe-Cr/ZrO2 (C) and
Fe-Cr/ZrO2 (CI) Catalysts
catalyst

Cr3+BE (eV)

Cr6+BE (eV)

Cr6+/Cr3+

Fe-Cr/ZrO2 (C)
Fe-Cr/ZrO2 (CI)

576.2
576.3

578.9
579.0

2.70
1.73

species and Cr6+/Cr3+ couples are the active sites for the
dehydrogenation of ethane. Ge et al.19 used ESR and UV-DRS
to probe the active site for ODE with CO2 over silica-supported
chromium oxide catalysts. They found that species with a high
valence state (Cr5+ or Cr6+) are important for the reaction. In
our work, Cr3+ ions are considered the active species for
dehydrogenation, with the argument that only Cr3+ species has
been detected by XPS on the used catalysts and there is no
obvious deactivation of Fe-Cr/ZrO2 (CI) catalysts in the
stability test. (The degradation of Fe-Cr/ZrO2(C) catalysts is
caused by coke deposition, which is to be discussed in a later
section). The increase of ethylene selectivity in the beginning
of ODE can be attributed to the reduction of Cr6+ to Cr3+.
The Cr6+/Cr3+ ratio over the Fe-Cr/ZrO2(C) is higher than
the ratio over the Fe-Cr/ZrO2 (CI) as shown in Table 2, which
may indicate that Cr6+ ions have an effect on the dehydrogenation of ethane. Weckhuysen et al.18 research shows that Cr6+
ions are the precursors for the Cr3+ dehydrogenation centers.
Based on this finding, we speculate that there are more Cr6+
ions over the Fe-Cr/ZrO2 (C), which results in its high
selectivity toward ethylene (as indicated in Figure 1b), and its
high ethylene yield as well as ethane conversion in the beginning
of the reaction (shown in Figure 1a and Figure 1d, respectively).

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Table 3. Analysis of O 1s on the Used Fe-Cr/ZrO2 (C) and
Fe-Cr/ZrO2 (CI) Catalysts
OI

OII

OIII

binding percent binding percent binding percent

catalysts energy (eV) (%) energy (eV) (%) energy (eV) (%)

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Fe-Cr/
ZrO2 (C)
Fe-Cr/
ZrO2(CI)

Figure 5. XPS spectra of Fe 2p on (a) fresh Fe-Cr/ZrO2 (CI), (b) used

Fe-Cr/ZrO2 (CI), (c) fresh Fe-Cr/ZrO2 (C), and (d) used Fe-Cr/ZrO2 (C)
catalysts.

Figure 6. XPS spectra of O 1s on (a) used Fe-Cr/ZrO2 (C) and (b) used
Fe-Cr/ZrO2 (CI) catalysts.

Figure 5 shows the XPS spectra of Fe 2p on the fresh and

used Fe-Cr/ZrO2(C) and Fe-Cr/ZrO2 (CI) catalysts. As shown
in Figure 5, the Fe 2p3/2 peaks for all the fresh catalysts are
located at 711.2 eV, which implies that the dominant phase on
the surface is Fe2O3.20,21 It is worth noting that the Fe 2p3/2
peaks on the examined used catalysts are shifted to the 710.7
eV, which is indicative of magnetite (Fe3O4) phase.20,21 It has
been reported that there exists a satellite peak for Fe 2p3/2 of
Fe2O3 located at 719 eV while there is no satellite peak for Fe
2p3/2 of Fe3O4.20 The absence of the satellite peak associated
with Fe 2p3/2 on the used catalysts further confirms the existence
of Fe3O4. Fe3O4 has an inverse spinal structure, which can
readily undergo rapid electron exchange between Fe3+ and Fe2+.
The electron hopping between Fe3+ and Fe2+ can facilitate the
proceeding of reaction 3.21,22
On the basis of the above analysis, it may be concluded that
for the ODE to ethylene using CO2 as an oxidant over Fe-Cr/
ZrO2 catalysts, Cr3+ species takes the role of the dehydrogenation of ethane and Fe promotes the CO2 hydrogenation
(reverse WGS reaction) through the redox cycle of Fe3+ and
Fe2+.
The O 1s XPS spectra of the used Fe-Cr/ZrO2(C) and
Fe-Cr/ZrO2 (CI) catalysts are depicted in Figure 6. The O 1s
XPS spectra are wide and unsymmetrical, which can be
deconvoluted into three components with different banding
energy values of 529.5, 531, and 532 eV. The peak at the
lower binding energy is assigned to surface lattice oxygen O2(hereafter denoted as O1).23,24 The peak at the higher binding
energy (531 eV) can be attributed to carbonates or adsorbed
CO2 (hereafter denoted as OII).24 The peak at the highest binding

529.74

68.38

531.38

6.48

532.37

24.78

529.51

82.64

531.35

11.10

532.19

6.25

energy (532 eV) is defined to be adsorbed oxygen species

(O-, O2) and/or surface hydroxyls (OH) (hereafter denoted as
OIII).23,24
Table 3 gives the proportions of these oxygen species on the
catalysts obtained by the fitting program. The Fe-Cr/ZrO2 (CI)
catalyst has a higher proportion of oxygen species in adsorbed
CO2 (OII) than the Fe-Cr/ZrO2 (C) catalyst, which means that
there are more active sites for CO2 on its surface. Therefore,
the Fe-Cr/ZrO2 (CI) catalyst exhibits higher CO2 conversion
as indicated in the catalytic performance experiment. Previous
research14,25,26 show that CO2 can be activated by basic sites.
For this reason, the number of adsorbed CO2 (OII) could be
related to the number of basic sites. It is conceivable that OIII
is highly relevant to oxygen vacancies present in the samples.24
The higher proportion of OIII sites on Fe-Cr/ZrO2 (C) catalyst
imply that a larger amount of oxygen vacancies were created
by the coprecipitation method. Research has indicated that
oxygen vacancies benefit WGS reaction.21,27 For example,
Zhang et al.21 compared three different preparation methods for
catalysts in WGS reaction, which shows that sol-gel provides
the highest catalytic performance because there are more oxygen
vacancies created during sol-gel process. From this perspective,
it is reasonable that the Fe-Cr/ZrO2(C) catalyst has higher
ethylene selectivity than Fe-Cr/ZrO2 (CI).
Reaction Mechanism. In consideration of the roles of Cr,
Fe, and O species in the ODE to ethylene over the Fe-Cr/
ZrO2 catalysts in the presence of CO2, the following reaction
mechanism was proposed (shown in Figure 7). Ethane is
activated by Cr3+ species to generate ethylene and H atom. Some
of the H atoms recombine to form H2. Other atoms combine
with lattice oxygen to produce H2O, simultaneously reducing
Fe3+ to Fe2+. CO2 dissociates on the active site (denoted as [ ])
to produce CO and active oxygen species (O*). The active
oxygen species (O*) are absorbed by oxygen vacancies (denoted
as 0) to form adsorbed oxygen species (Oad). Then, these
adsorbed oxygen species (Oad) diffuse into the crystal to create
lattice oxygen, which supplements the reduced lattice oxygen
that is used to produce H2O. At the same time, the active oxygen
species (O*) reoxidize Fe2+ to Fe3+, which forms the reductionoxidation cycle.
Catalyst Deactivation. In general, coke deposition, thermal
degradation, and the transformation of an active phase are key

Figure 7. Possible reaction mechanism of the oxidative dehydrogenation

of ethane by CO2 over Fe-Cr/ZrO2 catalysts.

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7565

Acknowledgment
This research was supported by the National Science Foundation of China (Gant No. 20436050), and National 863 Program
Youth Foundation (Grant No. 2004AA649230).
Literature Cited

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Figure 8. TG-DTG profiles of used Fe-Cr/ZrO2 (C) and Fe-Cr/ZrO2 (CI)

catalysts.

factors that lead to the deactivation of catalysts in dehydrogenation reactions.18 The thermal degradation and transformation
of an active phase can be excluded from the causes of catalyst
deactivation in our work since there was no substantial evidence
found.
TEM results indicate there is coke on surface of the
catalysts, particular on Fe-Cr/ZrO2(C) catalyst. To evaluate
the content of the carbon deposition, thermogravimetric
analyses were performed for the used catalysts in oxidant
atmosphere (shown in Figure 8). The peak at 360 C on
the derived thermogravimetric profile (DTG) is related to the
burning of coke.28 It was found that there was obvious weight
loss of the Fe-Cr/ZrO2 (C) catalyst compared with that of
the Fe-Cr/ZrO2 (CI) due to the burning of the coke. The
percentage of coke per weight of catalysts is 9.64% for the
used Fe-Cr/ZrO2 (C) and 1.13% for the used Fe-Cr/ZrO2
(CI). The relatively high coke deposition on Fe-Cr/ZrO2 (C)
catalyst gives an explanation for its dramatic decrease in the
production of ethylene over the time on stream. It is
speculated that more CO2 was involved in the decoking
reaction 4 over the Fe-Cr/ZrO2 (CI) catalyst
C + CO2 f 2CO

(4)

after considering its higher CO2 conversion and higher

stability in comparison to these catalytic properties over the
Fe-Cr/ZrO2(C) catalyst. Further investigation should be
conducted to confirm this speculation.
Conclusions
Fe-Cr/ZrO2 catalysts prepared by different methods have
been examined in ODE to ethylene in the presence of
CO2.The catalyst prepared by the coprecipitation-impregnation method exhibits stable catalytic performance during the
time on stream. In contrast, there is obvious deactivation
(ethylene yield and ethane conversion) for the catalyst
prepared by the coprecipitation method, which can be
attributed to coke deposition during the reaction. The catalyst
prepared by the coprecipiation method gives higher ethylene
selectivity and lower CO2 conversion. The high ethylene
selectivity could be explained by its larger amount of oxygen
vacancies (OIII). Less adsorbed CO2 (OII) on the catalyst may
cause its low CO2 conversion. The characterization results
indicate that Cr3+ species are the active sites for the
dehydrogenation of ethane and Fe2O3 is reduced to Fe3O4
during the reaction, which may enhance the reverse WGS
reaction.

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Ind. Eng. Chem. Res., Vol. 48, No. 16, 2009

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Publication Date (Web): July 2, 2009 | doi: 10.1021/ie9007387

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ReceiVed for reView May 6, 2009

ReVised manuscript receiVed June 7, 2009
Accepted June 19, 2009
IE9007387