An ionic liquid–organics–water ternary biphasic system enhances the 5-hydroxymethylfurfural yield in catalytic conversion of glucose at high concentrations

Abstract

Increasing the glucose loading in the 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid containing a dissolved CrCl₃ catalyst system led to excessive formation of humins and a serious decrease in the 5-hydroxymethylfurfural (5-HMF) yield. A biphasic system containing glycol dimethyl ether (GDE) as the extraction phase, and [BMIM]Cl/CrCl₃/glucose in combination with a partitioned amount of GDE and an appropriate amount of water as the reaction phase was found to be highly efficient for the reaction; CrCl₃ catalyzed the formation of 5-HMF in 64.5 mol% yield from a very high glucose concentration (80 wt% with respect to the ionic liquid) at 108 °C. This 5-HMF yield in the [BMIM]Cl–GDE–H₂O ternary biphasic system nearly doubled that obtained in the single [BMIM]Cl/CrCl₃/glucose reaction phase. Importantly, the GDE phase contained about 56% of the generated 5-HMF without detectable contamination by the ionic liquid or carbohydrates. GDE served multiple functions: as a hydrogen-bond acceptor, it exhibited excellent extraction performance for 5-HMF; due to its low boiling point and suitable solubility saturation point in the ionic liquid, a sustained GDE bubbling phenomenon in the ionic liquid phase was observed that promoted the rate of inter-phase mass-transfer of 5-HMF in reactions; and GDE mediated the [BMIM]Cl phase to a reduced viscosity. In addition, an appropriate amount of water in the ternary system promoted the extraction efficiency of 5-HMF and also lowered the viscosity of [BMIM]Cl/glucose. The ionic liquid–organics–water ternary biphasic system has been demonstrated for high 5-HMF productivity and separation efficiency.