A Comparative Study of Basic, Amphoteric, and Acidic Catalysts in the Oxidative Coupling of Methanol and Ethanol for Acrolein Production.

The impact of acid/base properties (determined by adsorption microcalorimetry) of various catalysts on the cross-aldolization of acetaldehyde and formaldehyde leading to acrolein was methodically studied in oxidizing conditions starting from a mixture of methanol and ethanol. The aldol condensation and further dehydration to acrolein were carried out on catalysts presenting various acid/base properties (MgO, Mg-Al oxides, Mg/SiO2 , NbP, and heteropolyanions on silica, HPA/SiO2 ). Thermodynamic calculations revealed that cross-aldolization is always favored compared with self-aldolization of acetaldehyde, which leads to crotonaldehyde formation. The presence of strong basic sites is shown to be necessary, but a too high amount drastically increases COx production. On strong acid sites, production of acrolein and carbon oxides (COx ) does not increase with temperature. The optimal catalyst for this process should be amphoteric with a balanced acid/base cooperation of medium strength sites and a small amount (<100 μmol g-1 ) of very strong basic sites (Qdiff >150 kJ mol-1 ).