Production of Hydroxymethylfurfural Derivatives From Furfural Derivatives via Hydroxymethylation.

Xianqing Lv,Li Shuai,Jing Liu,Xin Cheng,Changzhi Li,Xiaolin Luo

doi:10.3389/fbioe.2022.851668

Abstract

Hydroxymethylfurfural (HMF) derivatives such as 2,5-bis(hydroxymethyl)furan (BHMF) and furandicarboxylic acid (FDCA) are promising alternative of fossil-based diols and dicarboxylic acids for synthesis of polyesters such as polyethylene terephthalate (PET). However, high cost for preparing HMF from biomass discourages the commercialization of HMF-derived polyesters. Since producing furfural (FUR) from five-carbon sugars (e.g., xylose) via dehydration is an inexpensive and commercialized process, we herein reported a method to synthesize BHMF derivatives (5-(ethoxymethyl)furan-2-methanol (EMFM), 2,5-bis(hydroxymethyl)furan monoacetate (BHMFM) and 2,5-bis(hydroxymethyl)furan diacetate (BHMFD) from furfural derivatives, i.e., (2-(ethoxymethyl)furan (EMF) and furfuryl acetate (FA)). To avoid strong acid-induced side reactions (e.g., furan ring opening, condensation and carbonization), two reaction systems, i.e., a low-concentration HCl aqueous solution combined with formaldehyde and anhydrous acetic acid combined with paraformaldehyde, were found to be suitable for such a hydroxymethylation reaction and could lead to decent product yields. In order to improve the carbon utilization, condensed furanic byproducts were further converted into hydrocarbon fuels via a reported two-step hydrodeoxygenation (HDO) process. This study not only validates the possibility of synthesizing functional HMF derivatives (EMFM, BHMFM, and BHMFD) from commercially-available FUR derivatives (EMF and FA), but also provide a new way to transform condensed furanics to value-added hydrocarbon fuels.

Highlights

IntroductionSynthetic polymers are important material basis for promoting the development of industry and human society
Because furanics are unstable under acidic conditions, the effects of different acids such as hydrochloric acid, sulfuric acid, formic acid, acetic acid and trifluoromethanesulfonic acid on the hydroxymethylations of EMF and FA were initially investigated
The results show that the strength of the acid in the reaction system has a great influence on the reaction

Summary

Introduction

Synthetic polymers are important material basis for promoting the development of industry and human society. Most of the commercialized polymers [e.g., polyethylene terephthalate (PET)] are synthesized based on fossil-based chemicals (e.g., terephthalic acid). The extensive use of fossil-based chemicals brings about severe environmental problems such as the greenhouse effect and the shortage of nonrenewable resources. Developing alternatives of fossil-based chemicals and materials from renewable biomass is a promising way to overcome or at least alleviate these problems. 2, 5-furandicarboxylic acid (FDCA) can be used to substitute terephthalic acid for synthesis of polyesters such as polyethylene furandicarboxylate (PEF), which showed better performance (e.g., thermostability and elasticity modulus) than that of PET (Guan et al, 2021; Yang and Mu, 2021). Polyesters could be synthesized by using 2,5-bis(hydroxymethyl)furan (BHMF)

Methods

Results

Conclusion