Calcium additives enhance coke migration and catalyst stability for Pt-based catalysts in ethane dehydrogenation

Understanding and mitigating catalyst deactivation in high-temperature alkane dehydrogenation reactions is critical toward improving their energy and atom efficiency. In this work, we show that a partial overcoat of calcium oxide on a Pt-In alloy catalyst reduces the rate of catalyst deactivation by 10-fold during the non-oxidative dehydrogenation of ethane to ethylene. During 20 h of time-on-stream at 600 °C in 5 % C2H6, the Ca-doped PtIn2 catalyst retains >85 % of its initial activity while the undoped PtIn2 deactivates to <20 %. Temperature-programmed oxidation and spatially-resolved Raman spectroscopy reveal that the improved catalyst stability stems from enhanced migration of coke precursors away from the catalytically-relevant Pt sites to the silica support. Strikingly, the Ca overcoat does not alter the inherent rate and selectivity of coke formation but rather its crystallinity and localization, which nonetheless has a dramatic impact on the long-term performance of the catalyst.