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Hydrogen‐Free Gas‐Phase Deoxydehydration of 2,3‐Butanediol to Butene on Silica‐Supported Vanadium Catalysts

The gas‐phase deoxydehydration of 2,3‐butanediol to butene was investigated in a plug flow reactor over SiO2‐supported vanadium oxide, γ‐alumina, P/ZSM‐5, and MgO catalysts with acid/base sites of varying strengths. 5 wt % vanadium on SiO2 (i.e., 5V/SiO2) showed the best performance with 100 % conversion and up to 45.2 % butene selectivity. The combination of weak acid sites and polymeric VOx surface species provided the 5V/SiO2 catalyst with bifunctional capabilities to achieve both dehydration and transfer hydrogenation, which allowed it to catalyze the deoxydehydration of 2,3‐butanediol to butene even in the absence of H2. As 2,3‐butanediol is a common yet underutilized biomass product, this reaction may provide a viable route for a biomass‐to‐chemicals application for 2,3‐butanediol.