Isobutane dehydrogenation over high-performanced sulfide V-K/γ-Al2O3 catalyst: Modulation of vanadium species and intrinsic effect of potassium

Abstract

Compared with industrial used Pt- and Cr-based catalyst in dehydrogenation (DH) of light alkanes, the sulfide V-K/γ-Al2O3 catalyst reported in this study shows lower cost and toxicity, and significant DH performance. The yield to isobutene reached as high as 52.9%, which is among the highest reported to date. We attribute such high isobutene yield to the precise modulation of polymerization degree for vanadium species via doping of potassium and indicating that the synergy between vanadium species and acid sites is critical to enhance the DH performance. Our previous work showed sulfidation promoted the increase of DH performance for vanadium-based catalyst, and we go further in this study to explore the correlation between increased range of DH performance and the added potassium. The different loaded potassium leads to variation in sulfidation degree, affecting the properties of vanadium species and acid properties consequently. The potassium was distributed uniformly on surface of the sulfide vanadium-based catalyst and was predominantly bonded with the vanadium species rather than with the γ-Al2O3 support. With increasing the potassium amount from 0 to 3 wt%, the acid amount kept decreasing, and some specific strong acid sites appeared once adequate sulfur was introduced in the V-K/γ-Al2O3 catalyst. The characterization and DFT results both revealed that the doped potassium contributes to regulating the vanadium species in the oligomeric state. The synergy between vanadium species and acid properties was regulated by the added potassium simultaneously, and thus the DH performance was enhanced. This study provides promising strategy for preparation of environment-friendly model industrial DH catalyst.