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Zhihao Si,Xin Zhang,Miao Zuo,Tao Wang,Yong Sun,Xing Tang,Xianhai Zeng,Lu Lin 한국화학공학회 2020 Korean Journal of Chemical Engineering Vol.37 No.2
2, 5-furandicarboxylic acid (FDCA) is a one of the most promising biomass-derived chemicals to substitute the non-renewable terephthalic acid as the monomer for producing polyethyleneterephthalate. At present, the oxidation of HMF is regarded as a prevalent way to prepare FDCA. Nevertheless, the isolation and storage of HMF is still a challenge. Herein, based on the higher stability of 5-formyloxymethylfurfural (FMF) than 5-hydroxymethylfurfural (HMF), we present an effective preparation route to prepare FDCA by substituting HMF with FMF as feedstock. A complete conversion of FMF and a 93.55% selectivity of FDCA were obtained in the mixed solvent of water and 1, 2- dioxane using Ru/C as catalyst and O2 as oxidant. An improved process was developed for preparing FDCA using FMF as feedstock. The investigation of conversion pathway showed that FMF and HMF were simultaneously oxidized to 2, 5-diformylfuran (DFF) in a case of the existence of the reversible equilibrium between FMF and HMF. Then DFF was oxidized to 5-formyl-2-furancarboxylic acid (FFCA). Subsequently, FFCA was oxidized to FDCA. In this process, the oxidation of FFCA to FDCA was determined as the rate-determining step. Furthermore, appropriate alkalinity favored the selectivity of FDCA and the conversion of FMF.
Caixia Xiong,Yong Sun,Juan Du,Wei Chen,Zhihao Si,He Gao,Xing Tang,Xianhai Zeng 한국화학공학회 2018 Korean Journal of Chemical Engineering Vol.35 No.6
5-[(Formyloxy)methyl]furfural (FMF), an analogue of 5-(hydroxymethyl)furfural (HMF) is becoming more attractive due to its superior stability and hydrophobicity, which make it easier to refineand store. In the present study, FMF was produced from fructose by one-pot approach in pure formic acid media or by a two-step approach via HMF in choline chloride (ChCl)/fructose deep eutectic solvents (DES) system. A favorable FMF yield of 63.22% was reached by two-step approach. In addition, the effects of reaction parameters, such as temperature and acidity, on preparation of FMF from fructose were systematically investigated. The dehydration of fructose into HMF was confirmed as the rate-controlling step in the consecutive reaction. Ultimately, the separation and purification procedures of FMF were put forward. The FMF with a purity of 98.8% was obtained finally. Meanwhile, the FMF purified by saturated sodium bicarbonate solution showed an excelled storage stability.