An Efficient Heterogeneous Acid Catalyst DIC_AT-1 for One-Pot Conversion of Sucrose into 5-(Hydroxymethyl)furfural

Abstract

5-(Hydroxymethyl)­furfural (HMF) is a trending biogenic platform molecule for the production of multiple energy, fuel, and chemical products, and it can be synthesized by using C6 sugars and/or its oligomers and polymers. In the present paper, the heterogeneous solid acid catalyst DICAT-1, with characteristic properties, exhibited one-pot conversion of sucrose into 5-HMF. The DICAT-1 triggered in-situ hydrolysis, isomerization, and dehydration of sucrose to yield 5-HMF in the presence of the low boiling point (LBP) green solvent isopropyl alcohol (IPA) in combination with the cosolvent DMSO. Of the tested solvents water, IPA, DMF, DMSO, and IPA:DMSO, the use of IPA in combination with DMSO shows the profound effect on sucrose dehydration. Exploration of DICAT-1 in the presence of IPA:DMSO (70:30 v/v) resulted in a 5-HMF yield of >77%. The central composite design model (CCD) was used to find out the best operating conditions for the solvent ratio and catalyst concentration. Moreover, the process intensification study depicted the remarkable effect of solvent, reaction temperature, time, sucrose concentration, catalyst concentration, and autogenous pressure of the solvent on the yield of 5-HMF. In- process analysis was conducted by using HPLC, and the product was characterized by using HPLC, ATR-FTIR, GC-MS, and LC-MS. The plausible reaction mechanism for the DICAT-1-mediated sucrose to 5-HMF conversion was also proposed. Characteristic properties of DICAT-1 such as the porosity and presence of accessible −SO3H acid active sites favor the one-pot conversion. Moreover, the catalyst recyclability test for five consecutive runs showed consistent 5-HMF yields. Thus, DICAT-1 was found to be an efficient and robust catalyst for sucrose dehydration in the IPA:DMSO solvent mixture.

Preparation of 5-hydroxymethylfurfural using magnetic Fe3O4@SiO2@mSiO2-TaOPO4 catalyst in 2-pentanol

“…HMF could be effectively extracted into the organic layer, and the further degradation of HMF to levulinic acid and formic acid could be avoided. 59 Further increased the added water content to 40% and 60%, the yield of HMF decreased sharply at all temperatures except at 100 °C. Ulf Prüße has reported that the rehydration of HMF to levulinic acid and formic acid was favoured with increasing content of water in the low-boiling solvent HFIP.…”

“…HMF could be effectively extracted into the organic layer, and the further degradation of HMF to levulinic acid and formic acid could be avoided. 59 Further increased the added water content to 40% and 60%, the yield of HMF decreased sharply at all temperatures except at 100 C. Ulf Prüße has reported that the rehydration of HMF to levulinic acid and formic acid was favoured with increasing content of water in the low-boiling solvent HFIP. 60 Simultaneously, it was observed that the yield of HMF remained stable in a range of water content (0-20% water content) at 110 C and 120 C. Therefore, the appropriate water content was benecial for the hydrolysis of carbohydrate to HMF.…”

Hydrogen-Bond-Promoted Sucrose Conversion in a Separable Eutectic Mixture Solvent System

“…31 The carbohydrate conversion and HMF yield were calculated according to the previous report. 32 The formic acid and levulinic acid were detected by HPLC with a UV detector (210 nm) using H 2 SO 4 as a mobile phase with a flow rate of 0.8 mL•min −1 at 40 °C. The formic acid and levulinic acid were calculated based on the previous report.…”

Highly Effective Production of 5-Hydroxymethylfurfural from Fructose with a Slow-Release Effect of Proton of a Heterogeneous Catalyst

“…Currently, HMF production was achieved through the transformation of various carbohydrate sources including monosaccharides or polysaccharides (derived from the hydrolysis of biomass sources). − Fructose, one of the monosaccharides being derived from biomass, is considered to be a preferred starting feedstock for HMF synthesis via a chemical catalytic route, since its furan structure is easier to be converted with high selectivity toward HMF than the pyran structure of glucose and other polysaccharides . Conversion of fructose to HMF has thus been conducted in wide ranges of reaction solvents, such as water, organic solvent, , and aqueous–organic biphasic solvent systems. , However, HMF in acid–aqueous solutions is extremely unstable, and it can be further degraded into undesired side products such as levulinic acid (LA) and formic acid through rehydration ,, and soluble and insoluble polymers known as humins through self- or cross-polymerization. , The selectivity toward HMF can be improved in organic solvents [e.g., dimethylsulfoxide (DMSO)] or water–organic solvent biphasic systems (e.g., H 2 O/MIBK) as the results of the suppressed side reactions. However, organic solvents with a high toxicity and boiling point are disfavored for industrial HMF production, considering the energy consumption of subsequent separation of HMF and the negative environmental impact of its toxicity.…”

“…6−10 Fructose, one of the monosaccharides being derived from biomass, is considered to be a preferred starting feedstock for HMF synthesis via a chemical catalytic route, since its furan structure is easier to be converted with high selectivity toward HMF than the pyran structure of glucose and other polysaccharides. 11 Conversion of fructose to HMF has thus been conducted in wide ranges of reaction solvents, such as water, 12 organic solvent, 13,14 and aqueous−organic biphasic solvent systems. 15,16 However, HMF in acid−aqueous solutions is extremely unstable, and it can be further degraded into undesired side products such as levulinic acid (LA) and formic acid through rehydration 7,17,18 T h i s c o n t e n t i s and soluble and insoluble polymers known as humins through self-or cross-polymerization.…”