Abstract
The objective of this chapter is to place in the proper perspective the effect of gas-phase reactions in the oxidative dimerization of methane. Obviously this concerns mainly the cofeed operation because gas-phase oxygen is not present in the cyclic mode in order to avoid extensive oxidation of the products. Furthermore, by gas-phase reactions we understand the homogeneous reactions that occur in the absence of a catalyst, because it has been proven convincingly by Lunsford’s group (Ito et al. 1987; Campbell, Morales, and Lunsford 1987) and by many others, that the dimerization reaction indeed occurs in the gas phase via surface-initiated methyl radicals. Lane and Wolf (Lane and Wolf 1988) were among the first to study systematically the homogeneous gas-phase dimerization of methane. Prior to our work, most reports were concerned with catalytic effects and very little had been reported regarding homogeneous reactions in the absence of catalysts. At about the same time that our results were published, two other reports appeared in the literature confirming that, indeed, gas-phase reactions were relevant (Asami et al. 1987; Hutchings, Scurrell, and Woodhouse 1988). Thereafter, the gas-phase work has been repeated in many laboratories and the results of our earlier report have been confirmed (van der Wiele, Geerts, and van Kasteren 1990; Hatano et al. 1990). Unfortunately, the effect of the gas-phase reactions has been misinterpreted by many authors and is now seen as the limiting factor in the yield that can be attained in this process. This is only partially true because the real limiting factor is the lack of selective low-temperature catalysts that can operate under conditions in which gas-phase reactions are not significant.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Aika, K.-I., T. Moriyama, N. Takasaki, and E. Iwamatsu. 1986. Oxidative dimerization over BaCO3, SrCO3 and these catalysts promoted with alkali. J. Chem. Soc. , Chem. Commun. 1210.
Asami, K., S.S. Hashimoto, T. Shikada, K. Fujimoto, and H.-O. Tominaga. 1986. Selective oxidative coupling of methane over supported lead oxide catalyst. Chem. Lett. 1233.
Asami, K., F. Omata, K. Fujimoto, and H.-O. Tominaga. 1987. Oxidative coupling of methane in the homogeneous gas phase under pressure. J. Chem. Soc. , Chem. Commun. 1287.
Bytyn, W., and M. Beams. 1986. Supported PbO catalysts for the oxidative coupling of methane—The effect of surface acidity of the support on C2+ selectivity. J. Appl. Catal. 28: 199.
Campbell, K.D., E. Morales, and J.H. Lunsford. 1987. Gas phase coupling of methyl radicals during the catalytic partial oxidation of methane. J. Am. Chem. Soc. 109: 7900–901.
Driscoll, D.J., W. Martir, J.-X. Wang, and J.H. Lunsford. 1985. Formation of gas-phase methyl radicals over MgO. J. Am. Chem. Soc. 107: 58–63.
Emesh Ali, I.T., and Y. Amenomiya. 1986. Oxidative coupling of methane over the oxides of group IIIA, IVA, and VA metals. J. Phys. Chem. 90: 4785.
Feng, Y., J. Niiranen, and D. Gutman. 1991. Kinetic studies of the catalytic oxidation of methane, I: Methyl radical production on 1% Sr/Al2O3. J. Phys. Chem. 95: 6558–63.
Geisbrecht, R.A., and T.E. Daubert. 1975. Chemical and physical processes of hydrocarbon combustion: Chemical processes. Ind. Eng. Chem. Process Des. Dey. 14: 159.
Hatano, M., P.G. Hinson, K.S. Vines, and J.H. Lunsford. 1990. Comments on “Blank reactor corrections in studies of the oxidative dehydrogenation of methane” by D.J.C. Yates and N. E. Zlotin. J. Catal. 124: 557.
Hinsen, W., W. Bytyn, and M. Baerns. 1984. Oxidative dehydrogenation and coupling of methane. In Proceedings of the 8th International Congress on Catalysis, Berlin, 1984, Vol. III, pp. 581–592.
Hutchings, G.J., M.S. Scurrell, and J.R. Woodhouse. 1988. The role of gas phase reaction in the selective oxidation of methane. J. Chem. Soc. , Chem. Commun. 253.
Imai, H., and T. Tagawa. 1986. Oxidative coupling of methane over LaA1O3. J. Chem. Soc. , Chem. Commun. 52.
Ito, T., and J.H. Lunsford. 1985. Synthesis of ethylene and ethane by partial oxidation of methane over lithium-doped magnesium oxide. Nature (London) 314: 721–722.
Ito, T., J.-X. Wang, C.-H. Lin, and J.H. Lunsford. 1987. Oxidative dimerization of methane over a lithium-promoted magnesium oxide catalyst. J. Am. Chem. Soc. 107: 5062.
Iwamatsu, E., T. Moriyama, N. Takasaki, and K.-I. Aika. 1987. Importance of the specific surface area of the catalyst in oxidative dimerization of methane over promoted magnesium oxide. J. Chem. Soc. , Chem. Commun. 19.
Kalenik, Z., E.E. Miro, J. Santamaria, and E.E. Wolf. 1989. Transient and steady state studies of the gas phase and catalytic oxidative coupling of methane. Preprints of 3B Symposium on Methane Activation, 1989 Pacifichem Meeting, Honolulu, HI, p. 109.
Kalenik, Z., and E.E. Wolf. 1990a. Comments on the effect of gas phase reactions on oxidative coupling of methane. J. Catal. 124: 566.
Kalenik, Z., and E.E. Wolf. 1991. Methane Oxidative Coupling over Lithium Promoted Lanthanum-Titanate Oxide. Natural Gas Conversion. Amsterdam: Elsevier Science Publishers, pp. 97–105.
Kimble, J.B., and J.H. Kolts. 1986. Oxidative coupling of methane to higher hydrocarbons. Energy Prog. 6: 226.
Labinger, J.A., and K.C. Ott. 1987. Mechanistic studies on the oxidative coupling of methane. J. Phys. Chem. 91: 2682.
Lane, G.S., Z. Kalenik, and E.E. Wolf. 1989. Methane oxidative coupling over titanate catalysts. J. Appl. Catal. 53: 183.
Lane, G.S., E.E. Miro, and E.E. Wolf. 1989. Methane oxidative coupling. II. A study of lithium-titania-catalyzed reactions of methane. J. Catal. 119: 161.
Lane, G.S., and E.E. Wolf. 1988. Methane utilization by oxidative coupling. I. A study of reactions in the gas phase during the cofeeding of methane and oxygen. J. Catal. 113: 144.
Lin, C.-H., K.D. Campbell, J.-X. Wang, and J.H. Lunsford. 1986. Oxidative dimerization of methane over lanthanum oxide. J. Phys. Chem. 90: 534–7.
Lin, C.-H., T. Ito, J.-X. Wang, and J.H. Lunsford. 1987. Oxidative dimerization of methane over magnesium and calcium oxide catalysts promoted with group IA ions: The role of [M+O-] centers. J. Am. Chem. Soc. 109: 4808.
Martin, G.A., A. Bates, V. Ducarme, and C. Mirodatos. 1989. Oxidative conversion of methane and C2 hydrocarbons on oxides: Homogeneous versus heterogeneous process. Appl. Catal. 47: 287.
Matsuura, I., Y. Utsumi, M. Nakai, and T. Doi. Chem. Lett. 1986. Oxidative coupling of methane over lithium-promoted zinc oxide catalyst. 1981.
Miro, E.E. Z. Kalenik, J. Santamaria, and E.E. Wolf. 1990a. Transient studies on methane oxidative coupling over alkali-metal promoted titanate catalysts. Catal. Today 6: 511.
Miro, E.E., J. Santamaria, and E.E. Wolf. 1990a. Oxidative coupling of methane on alkali metal-promoted nickel titanate. I. Catalyst characterization and transient studies. J. Catal. 124: 451.
Miro, E.E., J. Santamaria, and E.E. Wolf. 1990b. Oxidative coupling of methane on alkali metal-promoted nickel titanate. II. Kinetic studies. J. Catal. 124: 465.
Moriyama, T., N. Takasaki, E. Iwamatsu, and K.-I. Aika. 1986. Oxidative dimerization of methane over promoted magnesium oxide catalysts. Important factors. Chem. Lett. 1165.
Nelson, P.F., and N.W. Cant. 1990. Isotopic labelling studies of the mechanism of the catalytic oxidative coupling of methane. Preprints of 9th International Symposium on Natural Gas Conversion, 1990 Oslo Meeting, Oslo, Norway, p. 35.
Otsuka, K., and K. Jinno. Inorg. Chim. Acta 1986. Kinetic studies on partial oxidation of methane over samarium oxides. 121: 237.
Otsuka, K., K. Jinno, and A. Morikawa, 1986. Active and selective catalysts for the synthesis of C2H4 and C2H6 via oxidative coupling of methane. J. Catal. 100: 353.
Otsuka, K., and T. Komatsu. 1986. Conversion of methane to aromatic hydrocarbons by combination of catalysts. Chem. Lett., 1955.
Otsuka, K., and T. Komatsu. 1987a. High catalytic activity of Sm2O3 for oxidative coupling of methane into ethane and ethylene. Chem. Lett. 483–484.
Otsuka, K., and T. Komatsu. 1987b. Active catalysts in oxidative coupling of methane. J. Chem. Soc., Chem. Commun. 388.
Otsuka, K., Q. Liu, M. Hatano, and A. Morikawa. 1986. Synthesis of ethylene by partial oxidation of methane over the oxides of transition elements with LiCI. Chem. Lett. 903.
Otsuka, K., Q. Liu, and A. Morikawa. 1986. Active and selective catalysts in oxidative coupling of methane. Nickel oxides with salts of alkali metals. Inorg. Chim. Acta 118: L23.
Roos, J.A., S.J. Korf, R.H.J. Veehof, J.G. Van Ommen, and J.R.H. Ross. 1989. Reaction path of the oxidative coupling of methane over a lithium-doped magnesium oxide catalyst: Factors affecting the rate of total oxidation of ethane and ethylene. Appl. Catal. 52: 147.
Santamaria, J., Miro, E.E., and E.E. Wolf. 1991. Reactor simulation studies of methane oxidative coupling on a Na/NItiO3 catalyst. Ind. Eng. Chem. Res. 30: 1157–65.
Sofranko, J.A., J.J. Leonard, and C.A. Jones. 1987. The oxidative conversion of methane to higher hydrocarbons. J. Catal. 103: 302.
Tong, Y., M.P. Rosynek, and J.H. Lunsford. 1990. The role of sodium carbonate and oxides supported on lanthanide oxides in the oxidative dimerization of methane. J. Catal. 126: 291.
Tsang, W., and R.F. Hampson. 1986. Chemical kinetic data base for combustion chemistry. Part I. Methane and related compounds. J. Phys. Chem. Ref. Data 15: 1087.
van der Wiele, K., J.W.M.H. Geerts, and J.M.N. van Kasteren. 1990. The role of heterogeneous reactions during the oxidative coupling of methane over Li/MgO catalysts. Catal. Today 6: 497.
Yamagata, N., S.S. Tanaka, S. Sasaki, and S. Okazaki. 1987. Oxidative coupling of methane over BaO mixed with CaO and MgO. Chem. Lett. 81.
Yates, D.J., and N.E. Zlotin. 1990. Reply to Hatano, Hinson, Vines, and Lunsford’s comments on “Blank reactor correactions in Studies of the Oxidative Dehydrogenation of Methane.” J. Catal. 124: 562.
Yates, D.J., and N.E. Zlotin. 1988. Blank reactor coreactions in studies of the oxidative dehydrogenation of methane. J. Catal. 111: 317.
Author information
Authors and Affiliations
Editor information
Rights and permissions
Copyright information
© 1992 Springer Science+Business Media New York
About this chapter
Cite this chapter
Kalenik, Z., Wolf, E.E. (1992). The Role of Gas-Phase Reactions during Methane Oxidative Coupling. In: Wolf, E.E. (eds) Methane Conversion by Oxidative Processes. Van Nostrand Reinhold Catalysis Series. Springer, Dordrecht. https://doi.org/10.1007/978-94-015-7449-5_2
Download citation
DOI: https://doi.org/10.1007/978-94-015-7449-5_2
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-015-7451-8
Online ISBN: 978-94-015-7449-5
eBook Packages: Springer Book Archive