Eco‐Friendly Production of 5‐Hydroxymethylfurfural from Sucrose Using Commercially Available Dihydric Phosphate as a Catalyst

Abstract

An eco‐friendly catalytic system consisted of dihydric phosphate (H2PO4—) catalyst and a methyl isobutyl ketone (MIBK)/H2O biphasic solvent has been constructed to produce 5‐hydroxymethylfurfural (HMF) from sucrose, a cheaper and more widely available feedstock than fructose. The effects of reaction conditions, viz., catalyst dosage, reaction temperature, and reaction time, on this dehydration reaction have been investigated systematically, affording more than 70% of HMF yield under the optimum conditions. This environmentally friendly system is also broadly substrate‐tolerant, high concentration of sucrose (86%), scalable catalytic system (scaled up 10 times), and sugarcane juice also give 62.5%, 70.1%, and 70.7% of HMF yield, respectively. Moreover, the function of H2PO4— containing system for isomerization of glucose into fructose has been confirmed; and the dehydration reaction has been proposed to proceed through the catalytic hydrolysis of sucrose into glucose and fructose by protons (H+), followed by the isomerization of glucose into fructose by hydrogen phosphate ions (HPO42−), and the dehydration of fructose into HMF by protons (H+), which are all from the dissociation of H2PO4— ions. Readily available and eco‐friendly catalyst, abundantly available feedstock, and simple reaction conditions could mark this process promising for HMF production in industry.

LiCl-promoted-dehydration of fructose-based carbohydrates into 5-hydroxymethylfurfural in isopropanol

“…The result could be attributed to the complexity of the reaction and high reactivity of HMF, several side reactions may occur, the most notable of which are the acidcatalyzed HMF rehydration to levulinic and formic acids, HMF self-condensation reactions, and HMF-fructose crosspolymerization, forming soluble and insoluble polymers named humins conrmed by the brown mixture aer reaction. [29][30][31]36 As known that the solvent also affected the dehydration process of fructose conspicuously through coordinating or activating intermediates. 7,[37][38][39][40] Hence, the effect of organic solvent with different structure on fructose dehydration with an aid of LiCl was investigated inevitably.…”

“…However, the HMF yield declined with increasing of initial fructose concentration, and at the 30 mmol of fructose intake, the lowest value of HMF yield of 69.9% reached frustratedly. These results could be attributed to the fact that increasing the fructose intake led to higher collision probability of fructose and generation of HMF, leading to self-or crosspolymerization and formation of humins, 31,44 and thus resulting in the low HMF yield at high fructose concentration. Nevertheless, the HMF yield is still acceptable with the moderate fructose intake, achieving 79.7% of HMF yield at a fructose intake of 10 mmol.…”

Catalytic conversion of sucrose to 5-hydroxymethylfurfural in green aqueous and organic medium

“…This is mainly attributed to the conversion of glucose to HMF needs the isomerization of glucose to fructose at the first stage and then to HMF [46]. Ma et al (2018) [6] applied verities of catalysts in a water-MIBK solvent medium. Although the addition of MIBK gave good results but MIBK has some health concerns; hence not selective.…”

“…One of the auspicious chemical, which can serve as a platform specie is 5-hydroxymethylfurfural (HMF), which is identified by the United States Department of Energy among the top 10 bio-based chemicals to produce from biorefinery carbohydrates [4,5]. Based on the following reasons it is also term as a "sleeping giant" in the field of intermediate chemicals (derivatives) from bio-based feedstock; (i) As a multifunctional molecule comprised of a furan ring with alcoholic and aldehyde group at the same time, (ii) it is a multipurpose intermediate, which could be further transformed into high value chemicals and biofuel products, such as 2,5-furan dicarboxylic acid, levulinic acid, dihydroxymethyl furan, dimethyl furan, and others, which are supposed to be favorable substitutes for corresponding petro-chemicals (Scheme 1) [6][7][8]. HMF plays a significant role among bioderivatives due to its multi-functionality to derive high-value polymer precursors and fuel additives as well as potential chemicals feedstocks [9,10].…”

“…It was observed during the glucose dehydration reaction that a high conversion (98.7%) can be achieved using pTSA and CrCl3.6H2O catalyst combination [17]. Ma et al, (2018) also achieved a complete conversion of sucrose at 150 ℃ in methyl isobutyl ketone (MIBK) with KPO4 in 3 h while increasing the temperature to 170 ℃ the conversion time was reduced to 1.0 h [6]. The superiority of pTSA is evident from the above studies that 100 % sucrose conversion could be achieved with a lower temperature than the other catalysts.…”