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

A wide overview of the biphasic production of 5-hydroxymethylfurfural and furfural from lignocellulosic sugars is presented together with a screening of solvents following a methodology based on COSMO-RS and section guides.

A divergent approach for the synthesis of (hydroxymethyl)furfural (HMF) from spent aromatic biomass-derived (chloromethyl)furfural (CMF) as a renewable feedstock

“…[9][10][11][12] Conventionally, CMF is prepared by the treatment of HMF or cellulose with dry hydrogen halide, wherein, the hydroxyl group in HMF undergoes substitution by a halogen atom. [13][14][15] Other methods involve, treatment of carbohydrate with HCl-LiCl, 11,16 deep eutectic solvents (such as choline chloride), 17,18 HCl-H 3 PO 4 in presence of CHCl 3 under biphasic condition, 19 and metal chlorides (such as CrCl 3 , AlCl 3 and ZnCl 2 ) or mixed metal chlorides (CrCl 3 -ZnCl 2 ). 20 Notwithstanding the numerous efforts depicted above, each of them suffers from at least one of the following limitations: low product selectivity, formation of by-products, low conversion efficacy and product yield, harsh reaction conditions, requirement of costly reagents, prolonged reaction times and tedious operations with complex setups (facility for continuous extraction).…”

Impact of Thermal Treatment of Nb2O5 on Its Performance in Glucose Dehydration to 5-Hydroxymethylfurfural in Water

“…The dehydration of carbohydrates is significantly influenced by the temperature, which affects the yield and selectivity to HMF [ 65 , 66 ]. A thorough review of the literature on the subject displayed a broad range of conditions employed in the dehydration reactions, with the most frequently applied temperatures in the range of 120 to 200 °C [ 26 ] and different reaction times between 15 min and 24 h [ 65 ]. Thus, prior to testing the prepared catalysts, the influence of the temperature and reaction time was studied using Nb 2 O 5 _SA.…”

“…Most importantly, when the reaction is carried out in water, the negative impact of these side reactions on the yield of HMF is more significant [ 11 , 21 , 23 ]. Hence, the process is normally carried out in ionic liquids [ 24 , 25 ], high boiling point organic solvents such as dimethyl sulfoxide DMSO [ 16 ], or biphasic systems [ 26 , 27 , 28 ]. However, more restrictive regulations, such as REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) in the European Union (EU), are strong incentive for careful consideration to select the most appropriate alternative solvent in terms of performance, availability and price, taking into account the health and safety as well as environmental impacts [ 26 ].…”

Applied biocatalysis beyond just buffers – from aqueous to unconventional media. Options and guidelines

“…biocatalytical methods to create these compounds are currently under investigation. Some hydrophobic solvents can be obtained from dehydration of sugars 128 or citrus waste. 129,130 Despite the growing amount of more sustainable options, all combinations with proton donating or accepting abilities and polarity are not yet available.…”