Synthesis of 5-hydroxymethylfurfural and furfural in 1,4-dioxane versus acetone: Comparing reaction performance and solvent recyclability parameters

Research on monosaccharide dehydration primarily focuses on combining catalysts and organic solvents to maximize product yields. This study evaluates reaction performance and solvent recyclability experimentally and through process simulation, emphasizing their role in biorefinery design. Glucose and xylose, at intermediate aqueous sugar concentration, were dehydrated over aluminum chloride using 1,4-dioxane or acetone as co-solvents. Both organic systems exhibited comparable results, with 100% sugar conversion. The 5-hydroxymethylfurfural yield reached 60.9 ± 0.2% for 1,4-dioxane and 59.5 ± 0.6% for acetone systems, while the furfural yield reached 78.1 ± 0.8% and 78.9 ± 1.5%, respectively. Process simulations indicate that using acetone instead of 1,4-dioxane can significantly reduce heat duty during the solvent recovery stage by 72%, solvent loss by 60%, and catalyst loss by 48%. A multi-stage continuous distillation system was built to recover solvents from model solutions. The results highlight the advantages of using acetone instead of 1,4-dioxane, offering insights for improving energy efficiency in biorefinery processes. • The effect of solvent recyclability on biorefinery considerations is analyzed • Acetone matches dioxane in dehydration reaction at intermediate sugar concentrations • Acetone exhibits better recyclability than dioxane after monosaccharide dehydration • Using acetone in sugar dehydration can reduce overall heat demand in biorefineries • Using acetone in sugar dehydration can potentially reduce biorefinery size and OpEx