Understanding the Deactivation of Ag−ZrO2/SiO2 Catalysts for the Single‐step Conversion of Ethanol to Butenes

Ag−ZrO2/SBA‐16 has recently been found to be efficient for catalyzing the single‐step conversion of ethanol to butene (1‐ and 2‐butene mixtures) in the presence of H2. The reaction proceeds via a cascading sequence of reactions over mixed metal and Lewis sites, with the catalyst composition tuned to selectively favor butene formation. However, the catalyst slowly deactivates when evaluated over long reaction times. In this work, we evaluated the lifetime of the Ag−ZrO2/SBA‐16 catalyst system for ethanol‐to‐butene conversion at 325 °C for up to 800 hours on stream. Several characterization techniques were used to elucidate the mechanism(s) by which catalyst deactivation occurs. Coke deposition, Ag particle sintering, and Ag0‐to‐Ag+ oxidation state change were identified to be the major causes of catalyst deactivation. Coke deposits cover primarily Lewis acid sites which are responsible for aldol condensation, Meerwein‐Ponndorf‐Verley (MPV) reduction, and dehydration reactions. Ag particle sintering and Ag oxidation state change leads to a reduction in the number of metallic Ag sites responsible for the dehydrogenation/hydrogenation steps. The fresh catalyst likely experiences hydrothermal sintering in the early stage of reaction and permanently loses some active Lewis acid sites before reaching a new structural steady state. The deactivation of Lewis acid sites leads to a decrease in overall ethanol conversion, whereas the deactivation of the metallic Ag sites decreases the butene selectivity. For catalyst regeneration, oxidative calcination (at 500 °C) followed by reduction (at 325 °C) successfully removes all the coke species on the catalyst surface and restores the metallic Ag particles of the 4Ag−4ZrO2/SBA‐16 catalysts.