Sugar dehydration to 5-hydroxymethylfurfural in mixtures of water/[Bmim]Cl catalyzed by iron sulfate

Article abstract of DOI:10.1039/d0nj03433a

Ionic liquids (ILs) as additives were used in the selective conversion of bio-based carbohydrates to 5-hydroxymethylfurfural (HMF) in this work. The effect of adding various imidazole-based ionic liquids with different anion structures on the production of HMF from fructose was firstly investigated in aqueous media. The presence of 15 wt% 1-butyl-3-methylimidazole chloride ([Bmim]Cl) ionic liquids in water with Fe2(SO4)3 as the homogeneous catalyst provided a more effective HMF synthesis compared to that without [Bmim]Cl addition. The enhanced HMF yield was mainly attributed to the fact that [Bmim]Cl might play a vital role in stabilizing the HMF molecule, which could thereby suppress side reactions involving HMF (e.g., its rehydration to levulinic acid or/and polymerization to humins). NMR and FTIR analyses suggested that such a stabilization effect stemmed from the interaction of [Bmim]Cl with the hydroxyl and aldehyde groups of HMF through hydrogen bonding. By performing the operation in a biphasic system (i.e., with the biomass-derived THF solvent as the organic phase and the addition of NaCl salt into water for improving HMF partition), the HMF yield over the Fe2(SO4)3 catalyst in the presence of the [Bmim]Cl additive could be further improved. The catalyst and ionic liquids were quite stable, and could be reused for more than five cycles with a consistent activity. A similar enhancement effect of [Bmim]Cl was also demonstrated in HMF synthesis with better yields from other biomass feedstocks or derivatives (including glucose, sucrose, cellobiose, inulin and starch) in aqueous media.