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A Pd/Al 2 O 3  catalyst (Pd = 0.1 wt%) for ethanol conversion to butanol deactivates within 10 h of service, despiteits high initial activity at 275°C. Probable deactivation mechanisms wereexplored, including poisoning ofPd/Al 2 O 3  due to adsorption ofby-products on Pd, sintering of Pd phases, leaching of Pd from the catalyst,changes in the Pd electronic state, changes in the catalyst’s porous structure,and blockage of Al 2 O 3  activesites. The Pd/Al 2 O 3  deactivationwas found to be mainly caused by CO molecules that evolved during sidereactions. These molecules can either block Pd active sites due to the formationof strong Pd–CO complexes, or enter a CO disproportionation reaction to formcarbon deposits on Pd phases. The knowledge gained from this study can be usedfor the targeted modification ofPd/Al 2 O 3  and the creation ofselective systems operating stably in the presence of by-products.

Deactivation Mechanism of Palladium Catalysts for Ethanol Conversion to Butanol