An overview of the biphasic dehydration of sugars to 5-hydroxymethylfurfural and furfural: a rational selection of solvents using COSMO-RS and selection guides

Abstract

The valorization of sugars from lignocellulosic biomass has attracted much interest for the production of chemicals and fuels. From the dehydration of glucose or fructose and xylose, 5-hydroxymethylfurfural (5-HMF) and furfural can be obtained, respectively, which are highly praised chemicals used as building blocks. To increase the productivity of the process avoiding undesired side reactions that furans may undergo in the reaction phase, many authors follow a liquid–liquid approach. This way, an in situ extraction of the dehydration products occurs from the reaction phase (usually aqueous) to an organic solvent phase. Solvent selection is a matter of interest in Green Chemistry; therefore, careful consideration must be given to select the most appropriate alternatives in terms of performance, environmental, health and safety (EHS) impacts and subsequent downstream processing. For performance, the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) has emerged as a tool to screen among different candidates based on structural information of the molecules. For EHS considerations, different solvent guides assist in the assessment of the most favourable alternatives. This review provides a comprehensive survey of the solvents and operational conditions employed in the biphasic dehydration of sugars to 5-HMF and furfural, followed by an account of the selection guides and methods for the evaluation of solvents, including COSMO-RS. Finally, to contrast with the most commonly selected solvents, such as methyl isobutyl ketone, a rational screening is presented here for the biphasic production of furans based on COSMO-RS predictions and the assessment of the selection guides. Predictions and further validation of the distribution coefficients show that ethyl acetate and methyl propionate are promising solvents for the in situ extraction of 5-HMF and furfural from aqueous media whilst being ranked as recommended green solvents by most solvent selection guides available in literature.