Conversion of Cellulose from Plant Biomass to 5-(hydroxymethyl)furfural (HMF) and its Derivatives in Ionic Liquid Media

In this study, the main goal is introducing a new method for the production of 5-(hydroxymethyl)furfural (HMF) and its derivatives. I propose an integrated process with low energy input for high-yield production of hydroxymethyl furfural (HMF) from glucose in biomass hydrolysates. Due to the prevalent recognition that HMF is a versatile platform molecule for fuels and chemicals, there is a critical need for economically viable technologies for its production from biomass hydrolysates. Previous attempts to generate HMF in aqueous media (either from untreated biomass or from hydrolysates) have not resulted in high yields due to loss of product to humins and inability to prevent hydrolysis of HMF to levulinic and formic acids. Although biomass hydrolysates typically contain glucose, it is now broadly recognized that the best yields can be obtained by dehydration of the corresponding keto-isomer, fructose, and by executing the reactions in non aqueous reaction media (e.g. DMSO and ionic liquids (ILs)). The challenge then, for cost-effective and high-yield HMF production, is to devise a cohesive pathway to efficiently transfer glucose from biomass hydrolysate into the non-aqueous reaction media; produce HMF in high yield; and isolate it for downstream processing, all with low energy input and recycling of process streams.;The technology addresses this challenge and we propose a hybrid enzyme- and chemo-catalytic process that first converts hydrolysate glucose to its more reactive ketose form and subsequently integrates with a downstream catalytic dehydration step that achieves high yields of HMF. The conversion of hydrolysate glucose to fructose and its near-complete recovery is accomplished through a novel enzyme-based simultaneous-isomerization-and-reactive-extraction (SIRE) process. The recovered fructose is then dehydrated to HMF in an acidic ionic liquid (IL) reaction medium and simultaneously extracted into low-boiling tetrahydrofuran (THF) solvent to prevent side reactions, increase process yields and facilitate easy product recovery. Conversion of fructose to HMF in IL-media results in superior yields than in aqueous solutions and also occurs at mild operating conditions (IL rxn T ~ 50 °C; aqueous rxn T >160 °C). Finally, a key feature of this technology is that it permits recycling and reuse of the catalysts, solvents and reaction media. This method also is proven to be an ideal pathway to produce furfural and HMF simultaneously from mixed C5 and C6 sugars stream. In addition, for the important HMF derivatives namely 5-ethoxy methyl furfural (EMF), levulinic acid and 5-acetoxymethyl furfural (AMF) production this method has modified and successfully applied.