Relationship between Cr-Al Interaction and the Performance of Cr-Al2O3 Catalysts for Isobutane Dehydrogenation

Huimin  Zhang; Wanzhong  Ren; Limei  Zhang; Shang  Liu; Jinbo  Zhao; Deren  Fang

doi:10.4236/mrc.2015.42007

Deren Fang^*, Jinbo Zhao, Shang Liu, Limei Zhang, Wanzhong Ren, Huimin Zhang

Abstract: A series of catalysts were prepared using the kneading molding method and the impregnation method as well as the dry mix method by using different raw materials. By using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR) techniques, we studied the relationship between the catalyst performance and the Cr-Al interaction in the catalytic dehydrogenation of isobutane. The results demonstrated that the Cr-Al interaction in the catalyst had a direct influence on the catalytic activity and the selectivity of isobutene. The catalysts prepared using the kneading molding method had higher catalytic activity and isobutene selectivity than those prepared using the dry mix method. By comparison, XRD, XPS, and TPR results showed that the greater the Cr-Al interaction in the catalyst was, the higher the catalytic activity was. Here, we propose a mechanism of isobutane dehydrogenation.

Keywords: Isobutane Dehydrogenation, Cr/Al2O3, Cr-Al Interaction, Catalyst, Mechanism

Cite this paper: Fang, D. , Zhao, J. , Liu, S. , Zhang, L. , Ren, W. and Zhang, H. (2015) Relationship between Cr-Al Interaction and the Performance of Cr-Al₂O₃Catalysts for Isobutane Dehydrogenation. Modern Research in Catalysis, 4, 50-58. doi: 10.4236/mrc.2015.42007.

References

[1] Matsuda, T., Koike, I., Kubo, N. and Kikuchi, E. (1993) Dehydrogenation of Isobutane to Isobutene in a Palladium Membrane Reactor. Applied Catalysis A, 96, 3-13.

[2] de Rossi, S., Ferraris, G., Freminotti, S., Indovina, V. and Cimino, A. (1993) Isobutane Dehydrogenation on Chromia/Zirconia Catalysts. Applied Catalysis A, 106, 125-141.

[3] Fontfreide, J.J.H.M., Howard, M.J. and Lomas, T.A. (1989) EP Patent 0 332 289 A2.

[4] Al-Zahrani, S.M., Elbashir, N.O., Abasaeed, A.E. and Abdulwahed, M. (2000) Oxidative Dehydrogenation of Isobutane over Pyrophosphates Catalytic Systems. Catalysis Letters, 69, 65-70.

[5] Mamedov, E.A. and Corberan, V.C. (1995) Oxidative Dehydrogenation of Lower Alkanes on Vanadium Oxide-Based Catalysts. The Present State of the Art and Outlooks. Applied Catalysis A, 127, 1-40.

[6] Harrison, P.G. and Argent, A. (1986) EP Patent 189 282 A1.

[7] Yaluris, G., Rekoske, J.E., Aparicio, L.M., Madon, R.J. and Dumesic, J.A. (1995) Isobutane Cracking over Y-Zeolites: I. Development of a Kinetic-Model. Journal of Catalysis, 153, 54-64.
http://dx.doi.org/10.1006/jcat.1995.1107

[8] Mirzabekova, S.R. and Mamedov, A.Kh. (1995) Oxidation of Hydrocarbons and Alcohols by Carbon Dioxide on Oxide Catalysts. Industrial & Engineering Chemistry Research, 34, 474-482.
http://dx.doi.org/10.1021/ie00041a007

[9] Grabowski, R., Grzybowska, B., Stoczyfiski, J. and Wcisto, K. (1996) Oxidative Dehydrogenation of Isobutane on Supported Chromia Catalysts. Applied Catalysis A, 144, 335-341.

[10] Iannazzo, V., Neri, G., Galvagno, S., Serio, M.D., Tesser, R. and Santacesaria, E. (2003) Oxidative Dehydrogenation of Isobutane over V2O5-Based Catalysts Prepared by Grafting Vanadyl Alkoxides on TiO2-SiO2 Supports. Applied Catalysis A, 246, 49-68.

[11] Moriceau, P., Grzybowska, B., Gengembre, L. and Barbaux, Y. (2000) Oxidative Dehydrogenation of Isobutane on Cr-Ce-O Oxide II: Physical Characterizations and Determination of the Chromium Active Species. Applied Catalysis A, 199, 73-82.

[12] Moriceau, P., Grzybowska, B., Barbaux, Y., Wrobel, G. and Hecquet, G. (1998) Oxidative Dehydrogenation of Isobutane on Cr-Ce-0 Oxide: I. Effect of the Preparation Method and of the Cr Content. Applied Catalysis A, 68, 269-277.

[13] Al-Zahrani, S.M., Elbashir, N.O., Abasaeed, A.E. and Abdulwahed, M. (2001) Catalytic Performance of Chromium Oxide Supported on Al2O3 in Oxidative Dehydrogenation of Isobutane to Isobutene. Industrial & Engineering Chemistry Research, 40, 781-784.
http://dx.doi.org/10.1021/ie000334x

[14] Karamullaoglu, G., Onen, S. and Dogu, T. (2002) Oxidative Dehydrogenation of Ethane and Isobutane with Chromium-Vanadium-Niobium Mixed Oxide Catalysts. Chemical Engineering and Processing, 41, 337-347.
http://dx.doi.org/10.1016/S0255-2701(01)00150-7

[15] Elbashir, N.O., Al-Zahrani, S.M., Abasaeed, A.E. and Abdulwahed, M. (2003) Alumina-Supported Chromium-Based Mixed-Oxide Catalysts in Oxidative Dehydrogenation of Isobutane to Isobutene. Chemical Engineering and Processing, 42, 817-823.
http://dx.doi.org/10.1016/S0255-2701(02)00108-3

[16] Airaksinen, S.M.K., Harlin, M.E. and Krause, A.O.I. (2002) Kinetic Modeling of Dehydrogenation of Isobutane on Chromia/Alumina Catalyst. Industrial & Engineering Chemistry Research, 41, 5619-5626.
http://dx.doi.org/10.1021/ie020371j

[17] Pinard, L., Bichon, P., Popov, A., Lemberton, J.L., Canaff, C., Mauge, F., et al. (2011) Identification of the Carbonaceous Compounds Present on a Deactivated Cobalt Based Fischer-Trospch Catalyst Resistant to “Rejuvenation Treatment”. Applied Catalysis A, 406, 73-80.

[18] Fang, D.R., Zhao, J.B., Li, W.J., Fang, X., Yang, X., Ren, W.Z. and Zhang, H.M. (2015) Investigation of the Characteristics and Deactivation of Catalytic Active Center of Cr-Al2O3 Catalysts for Isobutane Dehydrogenation. Journal of Energy Chemistry, 24, 101-107.
http://dx.doi.org/10.1016/S2095-4956(15)60290-X

[19] Wang, S.B., Murata, K., Hayakawa, T., Hamakawa, S. and Suzuki, K. (2000) Dehydrogenation of Ethane with Carbon Dioxide over Supported Chromium Oxide Catalysts. Applied Catalysis A, 196, 1-8.

[20] Deng, S., Li, H.Q. and Zhang, Y. (2003) Oxidative Dehydrogenation of Ethane with Carbon Dioxide to Ethylene over Nanosized Cr2O3 Catalysts. Chinese Journal of Catalysis, 24, 744-750.

[21] Zhao, H.H., Song, H.L., Miao, Z.C. and Chou, L.J. (2014) Isobutane Dehydrogenation over Chromia Alumina Catalysts Prepared from MIL-101: Insight into Chromium Species on Activity and Selectivity. Journal of Energy Chemistry, 23, 708-716.
http://dx.doi.org/10.1016/S2095-4956(14)60203-5