Valorization of Glycerol to Glycerol Carbonate and Glycidol by Different Dialkyl Carbonates Utilizing Tricalcium Aluminate Hexahydrate as Transesterification Catalyst.

In this study, we report a base‐catalyzed transesterification reaction of glycerol, a waste product of the biodiesel industry, with various dialkyl carbonates, which act both as reactants and solvents, to convert glycerol carbonate into an industrially useful molecular building block. The catalyst, being used for the first time, is also a waste product from industry, present in bauxite residues and in the Portland cement, simply known as tricalcium aluminate. Despite being well‐known and readily available, this solid is only extremely poorly researched catalyst, nevertheless, using dimethyl and diethyl carbonate, glycerol conversion rates >80% and glycerol carbonate yields >60% could be achieved in just 1 h (under air atmosphere and reflux). In a comparison of the performance with other catalysts commonly researched today, as well as with other components of red mud and cements, the results showed that tricalcium aluminate is excellent, cheap, and largely environmentally friendly material for this purpose. Reusability studies of the catalysts have also shown that they provide high conversion and product yields even after repeated use, although different material characterization techniques showed intense glycerol‐catalyst surface interaction and intermediate product formation, the deactivating side effects of which could be avoided by catalyst regeneration steps. [ABSTRACT FROM AUTHOR]