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

Abstract

We report for the first time the direct conversion of raw grape berry biomass to hydroxymethylfurfural (HMF) using ionic liquid solvents with metal chloride catalysts. Exploiting raw plant biomass as a biorefinery feedstock is innovative for sustainable chemical industry. The use of the raw biomass to synthesize compounds can indeed lead to less energy consumption and less CO 2 emissions. Using raw plant biomass skips pretreatment steps that are required to produce biomaterials such as carbohydrates or cellulosic biomass. Here, grape berry biomass was used as a raw chemical feedstock for the production of hydroxymethylfurfural, a key platform intermediate for syntheses of future renewable biofuels. We examined 3 ionic liquid solvents, 3 reaction temperatures, 5 chloride catalysts, and 5 concentrations of HCl. We found an increasing HMF yields depending on reaction conditions. 1-octyl-3-methylimidazolium chloride was most effective for HMF synthesis. Addition of HCl or metal chlorides alone showed little improvement. The highest HMF yield of about 100 mg HMF per mL of grape biomass extract was obtained using 0.3 M HCl, [OMIM]Cl, and CrCl 2 at 100°C for 3 h. Our study provides a model system of sustainable production of valuable compounds from raw plant biomass.

Review: Sustainable production of hydroxymethylfurfural and levulinic acid: Challenges and opportunities

“…Some biomass containing a high amount of soluble sugars, such as grapes, can be readily converted to HMF without pretreatment [54]. However, sustainability concerns and commercial scale applicability dictate that efforts should focus on the production of HMF from untreated lignocellulosic biomass rather than edible crops-derived carbohydrates [55].…”

5-Hydroxymethylfurfural (HMF) Production from Real Biomasses

“…It has been reported that also crop plants containing a high amount of soluble sugars, such as grapes, can be a good source of raw biomass materials for HMF production [ 37 ]. In fact, the high amounts of soluble sugars which are present in grapes, are more quickly converted to HMF than other plant biomass.…”

“…The positive effect of HCl has been attributed to a combined role of HCl as a Brønsted catalyst and the dual property as cation and anion of ILs. The highest HMF yield (about 100 mg HMF/mL of grape biomass extract) was obtained using 0.3 M HCl, [OMIM]Cl, and CrCl 2 at 100 °C for 3 h [ 37 ]. Grape berries are an interesting biomass because their sugars, mainly fructose and glucose, are quickly converted to HMF without a depolymerization process.…”

Bioderived furanic compounds as replacements for BTX in chemical intermediate applications

“…Other reports have studied combinations of Brønsted and Lewis acids. 227–230 Acid functionalized ionic liquid cations including 1-(4-sulfonic acid) butyl-3-methylimidazolium perform better compared with inorganic acids or [HSO 4 ] − ionic liquids when combined with a Lewis acid, increasing the yield by 20% with MnCl 2 . 231 Based on this observation, a metallic bifunctional ionic liquid by substituting the hydrogen in the 1-(3-sulfonic acid) propane-3-methylimidazole hydrosulfate with Cr was reported.…”