Conversion of Polysaccharides to Sugar Alcohols: A Modeling Approach Based on Oligosaccharides

We extend our former kinetic and experimental study of hydrogenolysis of di‐ and trisaccharides using Ru/C in combination with a molecular acid as a catalyst system, to longer oligosaccharides up to heptasaccharide. The extended kinetics, despite the considerably more complex reaction network, reconfirms our previous hypothesis that reactions of oligosaccharides proceed through two competing reaction pathways, namely hydrolysis of oligosaccharides and their hydrogenation to a reduced form. This challenges the widely accepted supposition that conversion of polysaccharides to sorbitol passes consecutively through hydrolysis to monosaccharides followed by hydrogenation to sorbitol. This works also sets forth the hypothesis that hydrogenation of long‐chain oligosaccharides increases the rate of hydrolysis to a considerable extent and presents a significant alternative pathway in sorbitol formation.