Tandem propane dehydrogenation and surface oxidation catalysts for selective propylene synthesis.

Wang, Wei; Chen, Sai; Pei, Chunlei; Luo, Ran; Sun, Jiachen; Song, Hongbo; Sun, Guodong; Wang, Xianhui et al. · Science · 2023

basic_science · Level V

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Abstract

Direct propane dehydrogenation (PDH) to propylene is a desirable commercial reaction but is highly endothermic and severely limited by thermodynamic equilibrium. Routes that oxidatively remove hydrogen as water have safety and cost challenges. We coupled chemical looping-selective hydrogen (H<sub>2</sub>) combustion and PDH with multifunctional ferric vanadate-vanadium oxide (FeVO<sub>4</sub>-VO<i><sub>x</sub></i>) redox catalysts. Well-dispersed VO<i><sub>x</sub></i> supported on aluminum oxide (Al<sub>2</sub>O<sub>3</sub>) provides dehydrogenation sites, and adjacent nanoscale FeVO<sub>4</sub> acts as an oxygen carrier for subsequent H<sub>2</sub> combustion. We achieved an integral performance of 81.3% propylene selectivity at 42.7% propane conversion at 550°C for 200 chemical looping cycles for the reoxidization of FeVO<sub>4</sub>. Based on catalytic experiments, spectroscopic characterization, and theory calculations, we propose a hydrogen spillover-mediated coupling mechanism. The hydrogen species generated at the VO<i><sub>x</sub></i> sites migrated to adjacent FeVO<sub>4</sub> for combustion, which shifted PDH toward propylene. This mechanism is favored by the proximity between the dehydrogenation and combustion sites.