Production of 5-hydroxymethylfurfural in a eutectic mixture of citric acid and choline chloride and its extractive recovery

Abstract

Please cite this article as: T. Kobayashi, M. Yoshino, Y. Miyagawa, S. Adachi, Production of 5-hydroxymethylfurfural in a eutectic mixture of citric acid and choline chloride and its extractive recovery, Separation and Purification Technology (2015), doi: http://dx. AbstractSynthesis of 5-hydroxymethylfurfural (HMF 1 ) from D-fructose was analyzed from the kinetic and equilibrium points of view in a eutectic mixture of citric acid and choline chloride (CA/CC) or in [Bmim]Cl to achieve an efficient production of HMF in a biphasic reaction system. The partition coefficient of HMF between an organic solvent and the ionic liquid phases was measured using various organic solvents. Among these solvents, ethyl acetate was found to exhibit the best performance for the extractive recovery of HMF. The stability of HMF was also evaluated in CA/CC at 70-120 ºC, and HMF was found to be stable below 80 ºC. Kinetic analysis of the formation of HMF was performed under the assumption that fructose was converted into HMF through parallel and consecutive reactions. The kinetically calculated results matched well with the experimental ones. The reaction behaviors were different at low and high (over 20% (kg/kg of IL)) initial fructose concentrations. At high initial fructose concentrations, the equilibrium yield of HMF decreased with increasing initial fructose concentration. The addition of ethyl acetate to the CA/CC phase (biphasic reaction) was effective in improving the HMF yield, especially when the fructose concentration was high.

Decomposition Kinetics of Glucose and Fructose in Subcritical Water Containing Sodium Chloride

“…6 , Arrhenius plot), and the plots yielded straight lines with similar slopes. The activation energies ranged from 112 to 144 kJ/mol, similar to the results obtained for the decomposition of saccharides in other subcritical fluids 17) and ionic liquids, 23) and somewhat higher than in supercritical water. 24) …”

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

“…95 Finally, a mixture of ChCl with citric acid as HBD acted simultaneously as RP and catalyst with EtOAc forming the biphasic system where the activity was the highest compared to THF, 2-BuOH and MIBK, reaching yields of 92%. 96 Other substrates for 5-hydroxymethylfurfural production in biphasic systems. Finally, Table 3 provides a similar summary for further studies where 5-HMF was obtained as the main product from other carbohydrate sources from which the corresponding dehydration can occur.…”

“…The use of EtOAc has previously been acknowledged, although not to extract the products from a strictly aqueous phase: it has been described its use to separate 5-HMF from reacting media consisting of H 2 O-acetone 81 or DESs like ChCl : citric acid 96 or ChCl : oxalic acid. 97 In this cases, the conversion of the corresponding substrates attained were high and the selectivities ranged from 50 to 98%.…”

Green Processing of Lignocellulosic Biomass and Its Derivatives in Deep Eutectic Solvents

“…The relatively low extraction of HMF and its stability in the DES are primarily ascribed to the strong interaction between HMF and ChCl . Notably, HMF recovery would dramatically decrease because of the formation of humins in the DES at temperatures higher than 100 °C . On the other hand, the strong interaction between HMF and ChCl would, in turn, make the separation of HMF from its derivatives, such as 2,5‐diformylfuran (DFF) and HMF esters, facile through DES extraction…”