Production of 4‑Hydroxymethylfurfural from Derivatives of Biomass-Derived Glycerol for Chemicals and Polymers

Replacing petroleum feedstocks by sustainable resources requires new and efficient methods to convert simple biomass-derived compounds to functionally useful and versatile chemicals. We discovered a new path for potential industrial-scale conversion of glycerol, a voluminously available byproduct from worldwide biodiesel production, to 5- and 4-hydroxymethylfurfurals through a cost-effective process. Staring from glycerol derivatives, glyceraldehyde (GLYD) or dihydroxyacetone (DHA), 5-HMF or 4-HMF could be obtained through base-catalyzed condensation and acid-catalyzed dehydration steps in the batch process. Effects of reaction temperature, base, and acid effectively demonstrate the product distribution. To promote this process into commercial-scale application, we also performed the two-step conversion in continuous process. Under optimal conditions, 4-HMF could be obtained in 80% isolated yield. To interpret the potential utilization of 4-HMF, we also explored the application of 4-HMF and synthesized several functional molecules for both pharmaceutical and material sciences.