Generally, 5-hydroxymethylfurfural (HMF) is used as feedstock to produce 2,5-furandicarboxylic acid (FDCA). Whereas, its poor stability in alkaline environment results in low yield of FDCA. By contrast, 5-[(formyloxy)methyl]furfural (FMF), a novel platform compound derived from HMF, with higher thermal and alkaline stability than HMF, is more promising to replace HMF as substrate for the production of FDCA. In this study, FMF was successfully converted into FDCA over MoCuO x by using NaClO as oxidant, undergoing 2,5-diformylfuran (DFF) and 5-hydroxymethylfuran-2-carboxylic acid (HMFCA) as intermediates. Under optimization condition (30 min, 40 °C), 100% yield of FDCA was obtained. Furthermore, it was also demonstrated that the yield of FDCA up to 90% was gained in 5 wt % FMF concentration. Higher oxygen species mobility and lattice oxygen ratio endowed MoCuO x excellent catalytic activity. The synergy of Mo and Cu species in MoCuO x ensured an efficient conversion of HMF to FDCA through synergistic redox couple of Mo 6+ /Mo 5+ and Cu 2+ /Cu + .
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.
Yetao Jiang,Wei Chen,Yong Sun,Zheng Li,Xing Tang,Xianhai Zeng,Lu Lin,Shijie Liu
5-(Hydroxymethyl)furfural (HMF) is an important platform chemical, but the large scale production is limited by its instability. In this research, 5-[(formyloxy)methyl]furfural (FMF), derived from HMF, was produced directly from cellulose in formic acid reaction system with a yield of 33.4 mol% at 150 °C for 2 h. Among numerous metal salt catalysts screened in this study, alkali metal bromides were found to be effective in catalyzing cellulose conversion to FMF. Bromide anions facilitation of the esterification of HMF to form FMF was confirmed. In addition, the effects of water, acid and other reaction parameters also were investigated when NaBr was used as the catalyst. Up to 2% of water or acid in this reaction system did not impact on the FMF yield. Increasing the temperature for every 20 °C from 130 °C to 170 °C halved the reaction time but did not change the maximum yield. FMF was more hydrophobic and thermostable than HMF, which made it easier to be recovered. In a two-step process, FMF with a recovery of 29.4 mol% and purity of 97 mol% was obtained.
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