Promoters for Improvement of the Catalyst Performance  in Methane Valorization Processes

I.Z. Ismagilov; A.V. Vosmerikov; L.L. Korobitsyna; E.V. Matus; M.A. Kerzhentsev; A.A. Stepanov; E.S. Mihaylova; Z.R. Ismagilov

doi:10.18321/ectj1099

Authors

I.Z. Ismagilov Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, pr. Akademika Lavrentieva, 5, Novosibirsk, Russia
A.V. Vosmerikov Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences, pr. Akademicheskiy, 4, Tomsk, Russia
L.L. Korobitsyna Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences, pr. Akademicheskiy, 4, Tomsk, Russia
E.V. Matus Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, pr. Akademika Lavrentieva, 5, Novosibirsk, Russia
M.A. Kerzhentsev Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, pr. Akademika Lavrentieva, 5, Novosibirsk, Russia
A.A. Stepanov Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences, pr. Akademicheskiy, 4, Tomsk, Russia
E.S. Mihaylova Federal Research Center of Coal and Coal Chemistry, Siberian Branch of the Russian Academy of Sciences, pr. Sovetskiy, 18, Kemerovo, Russia
Z.R. Ismagilov Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, pr. Akademika Lavrentieva, 5, Novosibirsk, Russia; Federal Research Center of Coal and Coal Chemistry, Siberian Branch of the Russian Academy of Sciences, pr. Sovetskiy, 18, Kemerovo, Russia

DOI:

https://doi.org/10.18321/ectj1099

Keywords:

catalyst, promoters, nanoparticles, methane, dehydroaromatization, autothermal reforming

Abstract

This paper is devoted to the celebration of 75 years’ jubilee of Professor Zulkhair Mansurov

In this work, the introduction of modifying additives in the composition of catalysts is considered as an effective mode of improving functional characteristics of materials for two processes of methane conversion into valuable products – methane dehydroaromatization (DHA of CH₄) into benzene and hydrogen and autothermal reforming of methane (ATR of CH₄) into synthesis gas. The effect of type and content of promoters on the structural and electronic state of the active component as well as catalyst activity and stability against deactivation is discussed. For DHA of CH₄ the operation mode of additives M = Ag, Ni, Fe in the composition of Mo-M/ZSM-5 catalysts was elucidated and correlated with the product yield and coke content. It was shown that when Ag serves as a promoter, the duration of the catalyst stable operation is enhanced due to a decrease in the rate of the coke formation. In the case of Ni and Fe additives, the Ni-Мо and Fe-Mo alloys are formed that retain the catalytic activity for a long time in spite of the carbon accumulation. For ATR of CH₄, the influence of M = Pd, Pt, Re, Mo, Sn in the composition of Ni-M catalysts supported on La₂O₃ or Ce_0.5Zr_0.5O₂/Al₂O₃ was elucidated. It was demonstrated that for Ni-M/La₂O₃ catalysts, Pd is a more efficient promoter that improves the reducibility of Ni cations and increases the content of active Nio centers. In the case of Ni-M/Ce_0.5Zr_0.5O₂/Al₂O₃ samples, Re is considered the best promoter due to the formation of an alloy with anti-coking and anti-sintering properties. The use of catalysts with optimal promoter type and its content provides high efficiency of methane valorization processes.

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