Mechanistic understanding of humin formation in the conversion of glucose and fructose to 5-hydroxymethylfurfural in [BMIM]Cl ionic liquid.

Abstract

Humin formation is one of the key issues that hinders economical 5-HMF production from hexose sugars such as glucose and fructose. In this work, the mechanism of humin formation in glucose/fructose conversion to HMF was studied in an ionic liquid system (1-butyl-3-methylimidazolium chloride, [BMIM]Cl) with CrCl3 as the catalyst. Elemental analysis, XRD, FT-IR, and TEM were applied to study the molecular structure and morphology of the solid humins. The possible intermediates to form solid humins were investigated by HPLC-MS. We synthesized furanic model compounds that mimic the experimentally identified humin intermediates to investigate the mechanism of humin growth at an early stage. The results showed that a furan compound bearing a hydroxymethyl and an electron-donating group was unstable due to three types of reactions: (1) bimolecular ether formation reactions; (2) intermolecular addition reaction; (3) furan ring opening reaction with water. The stability of a furan compound in [BMIM]Cl was increased when the hydroxymethyl group of a furan compound was protected by a methyl group, and the stability was further enhanced with an additional electron-withdrawing group (such as an aldehyde group) on the furan ring. Protecting the hydroxymethyl group of 5-HMF with a methyl group allows easy separation of the products from the [BMIM]Cl solvent through extraction.