Mixed manganese ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof

Abstract

The present invention provides a method of producing a mixed manganese ferrite catalyst, and a method of preparing 1,3 -butadiene using the mixed manganese ferrite catalyst. Specifically, the present invention provides a method of producing a mixed manganese ferrite catalyst through a coprecipitation method which is performed at a temperature of 10 - 40 DEG C, and to a method of preparing 1,3 -butadiene using the mixed manganese ferrite catalyst through an oxidative dehydrogenation reaction, in which a C4 mixture containing n-butene, n-butane and other impurities is directly used as reactants without performing additional n-butane separation process or n-butene extraction. The present invention is advantageous in that 1,3-butadiene can be prepared directly using a C4 mixture including n-butane at a high concentration as a reactant through an oxidative hydrogenation reaction without performing an additional n-butane separation process, and 1,3-butadiene, having high activity, can be also obtained in high yield for a long period of time.

Description

technical field [0001] The invention relates to a mixed manganese ferrite catalyst, a preparation method thereof, and a method for preparing 1,3-butadiene by using the catalyst. Specifically, the present invention relates to a method for preparing a mixed manganese ferrite catalyst by co-precipitation (the method is carried out at a temperature of 10°C to 40°C); and a method for using the mixed manganese ferrite catalyst and a process for the preparation of 1,3-butadiene by oxidative dehydrogenation, in which inexpensive C4 mixtures containing n-butene, n-butane and other impurities are used directly as reactants without additional n-butane separation process or n-butene extraction process. Background technique [0002] 1,3-butadiene, which is increasingly in demand in the petrochemical market, is obtained by naphtha cracking process, direct dehydrogenation of n-butene, or oxidative dehydrogenation of n-butene, and then the 1,3-butadiene 3-Butadiene is supplied to the petr...

AI Technical Summary

Problems solved by technology

Among them, the naphtha cracking process accounts for more than 90% of the supply of butadiene, but there is such a problem in this process that new naphtha cracking centers (NCCs) must be established to meet the growing demand for butadiene , and because the naphtha cracking process does not produce butadiene alone, other essential petrochemical feedstocks are produced in excess in addition to butadiene

In addition, the direct dehydrogenation reaction of n-butene has such a problem that the reaction is unfavorable in terms of thermodynamics, and since the reaction is an endothermic reaction, high temperature and low pressure conditions are required, so that the yield is low, so This reaction is not suitable as a commercial process (L.M. Madeira, M.F. Portela, Catal. Rev., Vol. 44, p. 247 (2002))

[0009] In the oxidative dehydrogenation of n-butene, the above-mentioned zinc ferrite catalyst has such problems that metal oxide must be added to prevent deactivation, acid treatment must be carried out and complicated post-treatment procedures are required, while the manganese ferrite The catalyst has the problem that high temperature must be maintained in the co-precipitation process to prepare a manganese ferrite catalyst with a pure spinel structure, and the yield of 1,3-butadiene obtained using this manganese ferrite catalyst is lower than Productivity when using a zinc ferrite catalyst (see H.E.Manning, U.S. Patent Document No. 3,671,606 (1972); T.Kodama, M.Ookubo, S.Miura, Y.Kitayama, Mater.Res.Bull. 1,501 pages (1996); Z.J. Zhang, Z.L. Wang, B.C. Chakoumakos, J.S. Yin, J.Am.Chem.Soc., Vol. 120, 1,800 pages (1998)

[0010] There is another problem in the oxidative dehydrogenation of n-butene: when the reactant contains a predetermined amount or more of n-butane, the yield of 1,3-butadiene decreases (L.M. Welch, L.J.Croce, H.F.Christmann , Hydrocarbon Processing, 131 pages (1978))

As disclosed in the above patent documents, in the catalytic process for producing 1,3-butadiene from n-butene by oxidative dehydrogenation reaction, since pure n-butene is used as a reactant, an additional process is required to separate pure n-butene from the C4 mixture, which inevitably reduces the economic efficiency

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