The products produced by hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) are potential sustainable substitutes for petroleum-based building blocks used in the production of chemicals. We have studied the hydrogenation of HMF over supported Ru, Pd, and Pt catalysts in monophasic and biphasic reactor systems to determine the effects of the metal, support, solution phase acidity, and the solvent to elucidate the factors that determine the selectivity for hydrogenation of HMF to its fully hydrogenated form of 2,5-di-hydroxy-methyl-tetrahydrofuran (DHMTHF). We show that the selectivity to DHMTHF is affected by the acidity of the aqueous solution containing HMF. The major by-products observed are C6-polyols formed from the acid-catalyzed degradation and subsequent hydrogenation of 2,5-dihydroxymethylfuran (DHMF), an intermediate hydrogenation product of HMF to DHMTHF. The highest yields (88–91%) to DHMTHF are achieved using Ru supported on materials with high isoelectric points, such as ceria, magnesia–zirconia, and γ-alumina. Supported catalysts containing Pt and Pd at the same weight percent as Ru are not as active for the selective hydrogenation to DHMTHF.
Conversions of various pentoses and hexoses into methyl lactate has been demonstrated for the Sn-Beta catalyst. It is found that pentoses are converted to methyl lactate in slightly lower yields (∼40%) than what is obtained for hexoses (∼50%), but higher yields of glycolaldehyde dimethyl acetal are observed for the pentoses. This finding is in accordance to a reaction pathway that involves the retro aldol condensation of the sugars to form a triose and glycolaldehyde for the pentoses, and two trioses for hexoses. When reacting glycolaldehyde (formally a C2-sugar) in the presence of Sn-Beta, aldol condensation occurs, leading to the formation of methyl lactate, methyl vinylglycolate and methyl 2-hydroxy-4-methoxybutanoate. In contrast, when converting the sugars in water at low temperatures (100 °C), Sn-Beta catalyses the isomerisation of sugars (ketose–aldose epimers), rather than the formation of lactates.