Catalytic production of hydroxymethylfurfural from sucrose using 1-methyl-3-octylimidazolium chloride ionic liquid

Abstract

Hydroxymethylfurfural (HMF) is an important chemical intermediate, but it has not been widely used because of low yields and high production costs. Sucrose is available at lower costs than other sugars and thus could be a biomass-derived abundant source for HMF production. In this study, a catalytic process for efficiently producing HMF from sucrose was scrutinized using 1-methyl-3-octylimidazolium chloride ([MOIM]Cl) as a reaction solvent, and HCl and metal chlorides (CrCl 2 and Zncl 2 ) as a catalyst. The rate of sucrose hydrolysis was relatively much faster in the reactions with HCl than without it. The hydrolysis of sucrose to fructose and glucose was affected by its reaction time. The mixed solvent of 50% [MOIM]Cl and 50% sucrose solution with HCl was more effective in HMF synthesis than single solvent alone. The addition of ZnCl 2 and CrCl 2 increased HMF yields by approximately 1.2-1.8-fold and its higher yield was found in the latter. The highest yield (82.0±3.9 wt%) in HMF production was achieved in the reaction mixture containing 5 g [MOIM]Cl and 5 mL of 20% sucrose solution with 0.5 M HCl plus CrCl 2 at 30 min reaction time. However, 0.3 M HCl was more effective for the HMF productivity than 0.5 M HCl.

Synthesis of 5‐(Hydroxymethyl)furfural in Ionic Liquids: Paving the Way to Renewable Chemicals

“…[51] Notably, a significant difference between CrCl 2 and CrCl 3 was observed, with HMF yields of 62 % and 43 %, respectively. Chromium chloride was also used as a catalyst in the investigation by Chun et al [67] using HCl/[ OMIm]Cl/EtOAc mixtures, in which the best results were obtained with a sucrose concentration of 50 wt % and an HCl concentration of 0.3 m. Outstanding results were reported by Lima et al, [42] who claimed quantitative HMF yield when using a [BMIm]Cl/MIBK/CrCl 3 system (MIBK: methyl iso-butyl ketone), which is surprising since their results for fructose and glucose alone were only 88 % and 79 %, respectively, under the same reaction conditions. Good results were further attained in the SnCl 4 /[EMIm][BF 4 ] system where 17 wt % solution of sucrose was converted to HMF with a yield of 65 %.…”

Direct production of hydroxymethylfurfural from raw grape berry biomass using ionic liquids and metal chlorides

“…Our data also identified the possibility of high yield of HMF from grape biomass extract containing ionic liquid solvents and HCl. In addition, our result suggests that raw grape berry biomaterials can be a more favorable biomass compared with other ones because the sugars (mainly fructose and glucose) present in grape berry biomass are more quickly converted to HMF without depolymerization process, and thus, their reaction process for the synthesis of HMF is much simpler and easier than that of other ones (Antal et al 1990;Chun et al 2010a). The chemical structure of HMF synthesized in the reaction mixture was confirmed by GC-mass analysis (Fig.…”

“…Other recent studies demonstrated that imidazolium-based ionic liquids could enhance the HMF yields by facilitating the coordination between the sugars and metal chloride catalysts (Zhao et al 2007). Until now, some imidazolium-based ionic liquid solvents have been introduced for enhanced synthesis of HMF in the presence of certain metal chloride catalysts using some simple sugars (Chun et al 2010a;Moreau et al 2006;Zhao et al 2007). The ionic liquids have some properties favorable to synthetic processes.…”

“…These properties include high thermal stability, wide solvating properties in the solution, low melting points, and dual properties of cation and anion (Olivier-Bourbigou et al 2010). Some workers demonstrated that the combination of some imidazolium-based ionic liquids and metal halide catalysts was very effective for the synthesis of HMF from various carbohydrate sources such as lignocellulose, cellulose, starch, and other sugars (Chun et al 2010a, b;Lee et al 2011;Qi et al 2009;Su et al 2009;Yi et al 2011). Their findings have suggested the feasibility of utilizing raw biomass with high sugars in synthesizing HMF.…”

Ionic Liquids as Tools for the Acid‐Catalyzed Hydrolysis/Dehydration of Saccharides to Furanic Aldehydes

“…% in the IL), giving an outstanding result of 98 % Y Hmf (99 % C) in the case of 12-MPA/( [bmim]Cl or [emim]Cl) at 120 8C/3 h. [89] Pure ACN as solvent gave only 7 % C of glucose. %) at 120 8C/1.5 h, using 0.3 m HCl in [omim]Cl (IL purity 98 %); [86] and 30 wt. [89] On the other hand, non-protic solvents.…”