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Chinese Chemical Letters 19 (2008) 1059–1062

www.elsevier.com/locate/cclet

Coupling dehydrogenation of isobutane in the presence of carbon

dioxide over chromium oxide supported on active carbon
Jian Fei Ding a,b, Zhang Feng Qin a, Xue Kuan Li a,
Guo Fu Wang a, Jian Guo Wang a,*
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences,
P.O. Box 165, Taiyuan 030001, China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100049, China
Received 21 March 2008

Abstract
The dehydrogenation of isobutane (IB) to produce isobutene coupled with reverse water gas shift in the presence of carbon
dioxide was investigated over the catalyst Cr2O3 supported on active carbon (Cr2O3/AC). The results illustrated that isobutane
conversion and isobutene yield can be enhanced through the reaction coupling in the presence of carbon dioxide. Moreover, carbon
dioxide can partially eliminate carbonaceous deposition on the catalyst and keep the active phase (Cr2O3), which are then helpful to
alleviate the catalyst deactivation.
# 2008 Jian Guo Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Keywords: Dehydrogenation; Isobutane; Carbon dioxide; Isobutene; Reaction coupling; Cr2O3/AC

Isobutene is used in industry to produce polymers, methyl tertiary butyl ether (MTBE) and other chemicals. The
increasing demand for isobutene in recent years has drawn considerable attention to the dehydrogenation of isobutane
(IB) to isobutene. Because the direct dehydrogenation of isobutane is an endothermic and volume-expanding reaction, it
is usually performed at high temperature; hence fast catalyst deactivation due to carbonaceous deposition, poor isobutene
selectivity due to numerous side reactions, as well as high energy consumption from the high temperature operation are
crucial issues affecting the efficiency of the dehydrogenation process. Oxidative dehydrogenation is an effective way to
increase the conversion and/or lower the reaction temperature; however, the desirable dehydrogenation product is
vulnerable by deep oxidation when using oxygen as oxidant [1]. Therefore, many researchers have attempted to employ
carbon dioxide as a mild oxidant in the oxidative dehydrogenation of alkanes [2–8], where the dehydrogenation is
coupled with reverse water gas shift (RWGS). In this respect, the dehydrogenation of ethane [2,3], propane [4], isobutane
[5] and ethylbenzene [4,6–8] in the presence of carbon dioxide is believed to be an effective, energy-saving and
environmentally friendly process; however, the lack of proper catalysts of high activity and slow deactivation remains the
main obstacle to a practical process of alkane dehydrogenation with carbon dioxide.

* Corresponding author.
E-mail address: iccjgw@sxicc.ac.cn (J.G. Wang).

1001-8417/$ – see front matter # 2008 Jian Guo Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2008.05.041
1060 J.F. Ding et al. / Chinese Chemical Letters 19 (2008) 1059–1062

In this work, the dehydrogenation of isobutane to produce isobutene was carried out in the presence of carbon
dioxide over catalyst Cr2O3 supported on active carbon (Cr2O3/AC). The role of carbon dioxide in the enhancement of
isobutene yield and alleviation of catalyst deactivation was clarified.

1. Experimental

The catalyst Cr2O3/AC with a Cr loading of 3.0 mmol/g-AC was prepared by incipient wetness impregnation of the
support active carbon (40–60 mesh) with an aqueous solution of chromium nitrate. The impregnation lasted for 24 h at
room temperature and then the catalyst was dried at 110 8C in nitrogen for 12 h.
The catalytic test of isobutane dehydrogenation was carried out in a fixed bed tubular reactor (stainless steel tube
with an inner diameter of 5.0 mm) at atmospheric pressure. For each test, about 500 mg of catalyst sample was loaded
and placed in the constant temperature zone of the reactor. The catalyst was first heat-treated under an argon flow at
600 8C for 1 h; after that, the reactor was adjusted to the desired reaction temperature and the argon flow was switched
to the reaction stream (a mixture of isobutane + CO2 with the mole ratio of CO2/isobutane being 15). The volumetric
hourly space velocity (VHSV) of the gas flow for the heat treatment and the feed for the dehydrogenation was
5280 h1. The effluent was analyzed using an on-line gas chromatograph (Shimadzu GC-14C, TCD, C-18 packed
column).

2. Results and discussion

Through the similar procedures of the thermodynamic calculation as reported previously [8], equilibrium
conversion of isobutane under different atmospheres and temperatures can be obtained, as shown in Fig. 1. It suggests
obviously that the equilibrium conversion of isobutane can be enhanced considerably at a certain temperature or the
reaction temperature can be reduced at a certain isobutene yield by coupling the isobutane dehydrogenation (Eq. (1))
with the RWGS (Eq. (2)):

ðCH3 Þ3 CH ¼ ðCH3 Þ2 CCH2 þ H2 (1)

CO2 þ H2 ¼ CO þ H2 O (2)
For example, at 550 8C, the equilibrium conversion of isobutane increases from 82.1% in an inert atmosphere (Ar/
IB = 9) to 94.4% in the presence of CO2 (CO2/IB = 9); alternatively, to achieve an equilibrium conversion of isobutane
of 85.0%, the reaction temperature can be decreased from 562 8C in the inert atmosphere (Ar/IB = 9) to 503 8C in the
presence of CO2 (CO2/IB = 9).

Fig. 1. Reaction coupling of isobutane (IB) dehydrogenation to isobutene with RWGS: the effects of the initial feed composition (in mole ratio) and
temperature on the equilibrium conversion of isobutane at 0.1 MPa.
 J.F. Ding et al. / Chinese Chemical Letters 19 (2008) 1059–1062 1061

Fig. 2. A comparison of isobutane (IB) dehydrogenation over Cr2O3/AC in the presence of CO2 and inert atmosphere argon (reaction conditions:
650 8C, 0.1 MPa, VHSV = 5280 h1, the initial mole ratio of CO2 (or Ar) to IB = 15).

A comparison of isobutane dehydrogenation over Cr2O3/AC in the presence of CO2 and in the presence of the inert
atmosphere argon is shown in Fig. 2. It illustrates that isobutane conversion in the presence of carbon dioxide is much
higher than that in the inert atmosphere. Isobutene selectivity in carbon dioxide is also some higher than that in argon;
this is probably due to the partial removal of hydrogen from the dehydrogenation in the reacting system by the RWGS
(Eq. (2)), which can suppress the side-reactions like hydroisomerization and hydrogenolysis [5]. All these indicate that
carbon dioxide is effective to enhance the dehydrogenation of isobutane through the reaction coupling.
Fig. 2 also suggests that the deactivation rate of catalyst Cr2O3/AC in the presence of carbon dioxide is slower than
that in the presence of an inert atmosphere. At 650 8C, isobutane conversion decreased from 50.3% to 41.6% in 6 h in
the presence of carbon dioxide; while it decreased from 29.8% to 10.2% in 6 h in the argon atmosphere. These may
suggest that carbon dioxide can partially eliminate carbonaceous deposition on the catalyst and then alleviate the
catalyst deactivation [5]:
Cs þ CO2 ! 2CO (3)

XRD patterns of the fresh and used Cr2O3/AC catalysts are shown in Fig. 3. Cr2O3 phase is present in all the
catalysts and the catalyst structure changes little after the reaction. However, in comparison with the diffraction peaks
for the catalyst after reaction in carbon dioxide, the intensity of diffraction for the catalyst after the reaction in argon
decreases to some extent. These then suggest that Cr2O3 is an active phase for the dehydrogenation of isobutane over
Cr2O3/AC catalyst and carbon dioxide is helpful to keep the Cr2O3 phase.

Fig. 3. XRD patterns of Cr2O3/AC catalysts before and after isobutane dehydrogenation: (a) before reaction, calcined in argon at 600 8C for 1 h; (b)
after reaction at 650 8C for 6 h, in carbon dioxide; (c) after reaction at 650 8C for 6 h, in argon.
1062 J.F. Ding et al. / Chinese Chemical Letters 19 (2008) 1059–1062

In conclusion, the dehydrogenation of isobutane to produce isobutene coupled with the RWGS over the catalyst
Cr2O3/AC in the presence of carbon dioxide exhibits significant superiority over that in the presence of an inert
atmosphere. These may be attributed to that carbon dioxide as a weak oxidant can eliminate hydrogen produced during
the dehydrogenation and alleviate the catalyst deactivation by partially removing the carbonaceous deposition and
keeping the active Cr2O3 phase.

Acknowledgments

The authors are grateful for the financial support of the State Key Fundamental Research Project (2006CB202504)
and the National Natural Science Foundation of China (No. 20676140) and Natural Science Foundation of Shanxi
Province.

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