A Review on Green and Efficient Synthesis of 5-Hydroxymethylfurfural (HMF) and 2,5-Furandicarboxylic Acid (FDCA) from Sustainable Biomass

Abstract

The present work gives an overview of the approaches for green synthesis of 5-hydroxymethylfurfural (HMF) and 2,5 furan dicarboxylic acid (FDCA) focusing on reduction in the byproduct formation such as levulinic acid and humins. It was elucidated that the use of highly polar and aqueous solvents, high Brønsted acidity, high pH, reaction time, and temperature increases the levulinic acid formation in the reaction. In contrast, humin formation is increased by high basicity, temperature, and initial substrate concentration. Specific catalytic and solvent systems for minimizing the byproduct formation during HMF synthesis are also discussed along with options for use of microwave, ultrasound, and continuous processes. In terms of intensification, safety, and ease of scale-up, the use of ultrasound for HMF synthesis is promising; however, microreactors are currently a better choice for higher substrate concentration usage and higher yields. Effect of parameters like reaction time, temperature, oxidizing source, solvent, and base on FDCA synthesis is also analyzed. Depending on the reaction conditions and the reactor type, the optimum temperature typically should be between 80 and 160 °C, moderate bases, such as K2CO3 and KHCO3, are preferred to maintain a preferred pH of 7−11 and O2 is an ideal oxidizing agent. The reaction pathway for FDCA synthesis from HMF was also studied and the effect of the base and solvent elucidated. Finally, one-pot synthesis of FDCA from HMF and the strategies necessary to optimize the FDCA yield has been discussed. It was demonstrated that one-pot two-step FDCA synthesis from sugars provides enhanced FDCA yield, selectivity, and lower byproduct formation, compared to one-pot one-step synthesis.

Ecotoxicological assessment of biomass-derived furan platform chemicals using aquatic and terrestrial bioassays

“…[6][7][8] The scale up of these high yielding methodologies is feasible, reecting on the current industrialization process of HMF, more particularly of furan-2,5-dicarboxylic acid (FDCA) as polymer precursor of poly(ethylene 2,5-furandicarboxylic acid), for replacement of poly(ethylene terephthalate). [9][10][11] Furanic compounds are highly versatile biobased platform molecules produced in bioreneries as outstanding valueadded chemicals from biomass, exhibiting various applications including chemical, pharmaceutical, energy and food industries. [12][13][14] Although furans comprise undesired biorenery feedstocks for microbial fermentations, they currently attract signicant attention as green solvents, biofuels and fuel additives, lubricants, resins and plasticizers, avour enhancers in food and drink additives and intermediates in the synthesis of pharmaceuticals, chemicals and biopolymers/ biomonomers.…”

“…6–8 The scale up of these high yielding methodologies is feasible, reflecting on the current industrialization process of HMF, more particularly of furan-2,5-dicarboxylic acid (FDCA) as polymer precursor of poly(ethylene 2,5-furandicarboxylic acid), for replacement of poly(ethylene terephthalate). 9–11…”

Interaction between copper and nickel species for electrooxidation of 2,5-bis(hydroxymethyl)furan

“…10,11 Heterogeneous aerobic catalysis heavily depends on high-activity precious metal catalysts. 12,13 In contrast, green electrocatalysis, driven by an external potential, utilizes water as a mild oxidant and employs inexpensive metal catalysts, achieving efficient conversion of HMF to FDCA under ambient conditions. [14][15][16] In situ and ex situ techniques revealed that the really active phases of these inexpensive metal catalysts are their oxides, hydroxides or oxyhydroxides.…”

Highly Efficient One-Pot Conversion of Glucose to 5-Hydroxymethylfurfural over Acid–Base Bifunctional MCM-41 Mesoporous Silica under Mild Aqueous Conditions

“…Continued depletion and price hike of fossil fuel resources, coupled with the growing concerns regarding greenhouse gas emissions, has urged the manufacture of fine chemicals, energy, and biofuels using green and renewable resources. − Within the renewable sources, lignocellulosic biomass from plants has gained considerable attention over the years because of its high abundance and low price. , As one of the top value-added compounds derived from biomass, 5-hydroxymethylfurfural (HMF) can be obtained through dehydration of carbohydrates (e.g., fructose, glucose, inulin, cellobiose, and cellulose) . HMF is a viable replacement for the building block of chemical industry that is currently derived from petrochemicals . In addition, it can also be converted into a wide range of industrially important chemicals like biobased monomer 2,5-furandicarboxylic acid (FDCA), synthetic rubber material levulinic acid, and biofuel 2,5-dihydroxymethylfuran (DHMF). − Therefore, the development of efficient methods for converting carbohydrates to HMF seems to be crucial.…”

“…6 HMF is a viable replacement for the building block of chemical industry that is currently derived from petrochemicals. 7 In addition, it can also be converted into a wide range of industrially important chemicals like biobased monomer 2,5-furandicarboxylic acid (FDCA), synthetic rubber material levulinic acid, and biofuel 2,5-dihydroxymethylfuran (DHMF). 8−10 Therefore, the development of efficient methods for converting carbohydrates to HMF seems to be crucial.…”