The vanadium-based dehydrogenation (DH) catalyst is becoming a promise alternative to the industrial used Pt- and Cr-based catalysts, due to lower cost and less environmental threat. However, the low DH activity hampered the industrial application of vanadium-based catalysts. Herein, for the first time, we introduce a method to prepare high-efficiency vanadium-based catalyst by constructing pure V3+ species on γ-Al2O3 through treatment of as-prepared thiovanadate. The V3+ species contributes to not only enhancing the DH activity, but also fabricating the V3+-O/S acid-base pair with ideal strength and stability. The isobutene yield can reach as high as 56.9 wt%. Only Lewis acid is recognized on V3+/Al2O3 catalyst, while no Brønsted acid remains. The side-reactions are consequently inhibited, and the selectivity to isobutene is improved. Besides, with the increase of vanadium loadings, the Lewis acid content increases at first and then decreases, and the content of acid sites in middle strength keeps decreasing. Though the deposited coke on V3+/Al2O3 was just 2.5 wt% during 8.5 h consecutive DH reaction, the valence state of vanadium was still influenced and the fraction of inert V4+ species increased steadily. This study will improve the potential for industrial application of vanadium-based DH catalyst, and offer theoretical guidance for optimization of ideal DH catalysts.
Keywords: Deactivation process; High-efficiency vanadium-based catalyst; Isobutane non-oxidative dehydrogenation; Pure V(3+) species.
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