Dehydration of Methanol to Dimethyl Ether over Heteropoly Acid Catalysts: The Relationship between Reaction Rate and Catalyst Acid Strength

Dehydration of methanol to dimethyl ether (DME) was studied at a gas/solid interface over a wide range of bulk and supported Brønsted acid catalysts based on tungsten Keggin heteropoly acids (HPA) and compared with the reaction over HZSM-5 zeolites (Si/Al = 10–120). Turnover rates for these catalysts were measured under zero-order reaction conditions. The HPA catalysts were demonstrated to have much higher catalytic activities than the HZSM-5 zeolites. A good correlation between the turnover rates and catalyst acid strengths, represented by the initial enthalpies of ammonia adsorption, was established. This correlation holds for the HPA and HZSM-5 catalysts studied, which indicates that the methanol-to-DME dehydration with both HPA and HZSM-5 catalysts occurs via the same (or similar) mechanism and the turnover rate of methanol dehydration for both catalysts is primarily determined by the strength of catalyst acid sites, regardless of the catalyst pore geometry.