Production of 5-Hydroxymethylfurfural (Hmf) via Fructose Dehydration: Effect of Solvent and Salting-Out

Abstract

-5-Hydroxymethylfurfural (HMF) is a key renewable platform compound for production of fuels and chemical intermediates. The production of 5-hydroxymethylfurfural (HMF) from fructose dehydration was studied using H 3 PO 4 as catalyst, in organic/water system with different solvents (acetone, 2-butanol and ethyl ether). The effect of fructose concentration, temperature and acid concentration was investigated in acetone/water medium. The increase in fructose concentration favors the formation of condensation products and rehydration products are favored at high acid concentration. The solvents exhibited similar performance when the volume ratio of organic to aqueous phase was 1:1, but when this ratio increases to 2:1, the HMF yield obtained with ether was much lower. NaCl addition to the aqueous phase promoted the extraction of HMF to the organic phase, with an HMF yield of 80% in the case of 2:1 acetone/water medium.

New Frontiers in the Catalytic Synthesis of Levulinic Acid: From Sugars to Raw and Waste Biomass as Starting Feedstock

“…Brasholz et al investigated the conversion of fructose to LA with HCl in the 1:2 mixture of H 2 O:CH 3 OH achieving after 1.33 h at 140 • C the LA yield of 46.4 wt % [35]. The majority of protic solvents, such as ethanol and butanol or mixtures of them with water, have been tested for the dehydration of fructose to 5-HMF [86,87]. On the other hand, protic solvents and in particular alcohols have been extensively employed for levulinate esters production, through the direct conversion from biomass by alcoholysis under acidic conditions.…”

Catalytic dehydration of hexose sugars to 5‐hydroxymethylfural

“…It was found that the cyclic C4‐ethers (e.g., tetrahydrofuran) correspond to the largest partition coefficient (R) and therefore the highest HMF selectivity (83%). Gomes et al . investigated the effects of organic solvents such as acetone, 2‐butanol and ethyl ether and found that the biphasic systems obtained higher HMF yields than water media and the 1:2 water:actone biphasic system containing NaCl achieved the highest HMF yield (80%, see Table ).…”

“…143 It was found that the cyclic C4-ethers (e.g., tetrahydrofuran) correspond to the largest partition coefficient (R) and therefore the highest HMF selectivity (83%). Gomes et al 107 investigated the effects of organic solvents such as acetone, 2-butanol and ethyl ether and found that the biphasic systems obtained higher HMF yields than water media and the 1:2 water:actone biphasic system containing NaCl achieved the highest HMF yield (80%, see Table 2). The R value of acetone equals 3.4, and 2-butanol has a larger R value (4.4), while the dehydration of fructose in the water/2-butanol biphasic system corresponds to the lower HMF yield (64%), which seems to contradict the general predictions.…”

Production of 5-(Hydroxymethyl)furfural from Biomass: Synthetic Challenges and Applications as Building Block in Polymers and Liquid Fuel Production

“…Por exemplo, Souza e colaboradores mostraram os atrativos efeitos da adição de NaCl para extração de 5-HMF formado no meio reacional a partir da frutose utilizando água/acetona como solvente e H 3 PO 4 como catalisador. 53 É importante destacar que a extensão do efeito salting-out depende da natureza das interações iônicas entre todos os componentes e alguns desses fatores incluem a natureza dos sais, concentrações, temperatura e pressão. 54 Nesse contexto, diversos estudos vêm utilizando diferentes sais (NaCl, NaBr, KCl, KBr, KI, KNO 3 , K 2 SO 4 , MgCl 2 , AlCl 3 , FeCl 3 , CH 3 COONa, NaNO 3 , Na 2 SO 4 , LiCl, LiBr CH 3 COOLi, LiNO 3 , Li 2 SO 4 e KCl) e solventes orgânicos em sistemas bifásicos para preparação de 5-HMF a partir de carboidratos.…”