Propane dehydrogenation (PDH) is a commercial propylene production technology of great interest, but the high reaction temperature is a challenge for the stability of the catalyst. In this paper, a Ca-stabilized sub-nanometer (~0.8 nm in diameter) platinum-tin cluster catalyst was designed and prepared for efficient propane dehydrogenation with a deactivation rate of only 0.0098 h-1 at 600 °C, a propylene selectivity of &gt;96%, a propylene production rate of 24 mol C3H6 /(gPt*h), and only ~1% activity loss after regeneration under air atmosphere. The effect of calcium introduction on the catalyst structure was clarified based on the characterization of 27Al NMR, H2-TPR, H2-TPD, NH3-TPD, XPS, CO-DRIFT and TG. The results show that calcium prefers to land on the penta-coordinated Al3+ sites on the alumina surface and makes the tin oxide more reducible by forming Sn-O-Ca bonds with tin oxide, which in turn promotes the alloying of platinum and tin and improves the propylene selectivity and catalyst stability. The corresponding kinetic modeling of carbon accumulation as well as the intrinsic kinetic modeling revealed that the introduction of calcium changed the rate-determining step of the Pt-Sn catalyst in the process of propane dehydrogenation.

Alkaline earth ions stabilized sub-nano platinum tin clusters for propane dehydrogenation

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ACS Fall 2022

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