Catalyst and Process Design for the Continuous Manufacture of Rare Sugar Alcohols by Epimerization– Hydrogenation of Aldoses

Abstract

Sugar alcohols are applied in the food, pharmaceutical, poly- mer, and fuel industries and are commonly obtained by reduc- tion of the corresponding saccharides. In view of the rarity of some sugar substrates, epimerization of a readily available monosaccharide has been proposed as a solution, but an effi- cient catalytic system has not yet been identified. Herein, a mo- lybdenum heteropolyacid-based catalyst is developed to trans- form glucose, arabinose, and xylose into less-abundant man- nose, ribose, and lyxose, respectively. Adsorption of molybdic acid onto activated carbon followed by ion exchange to the cesium form limits leaching of the active phase, which greatly improves the catalyst stability over 24 h on stream. The hydro- genation of mixtures of epimers is studied over ruthenium cat- alysts, and it is found that the precursor to the desired polyol is advantageously converted with faster kinetics. This is ex- plained by density functional theory on the basis of its more favorable adsorption on the metal surface and the lower energy barrier for the addition of a hydrogen atom to the pri- mary carbon atom. Finally, different designs for a continuous process for the conversion of glucose into mannitol are stud- ied, and it is uncovered that two reactors in series with one containing the epimerization catalyst and the other containing a mixture of the epimerization and hydrogenation catalysts in- creases the mannitol/sorbitol ratio to 1.5 from 1 for a single mixed-bed reactor. This opens a prospective route to the effi- cient valorization of renewables to added-value chemicals.