Page 98 - 《精细化工》2020年第11期

·2244· 精细化工 FINE CHEMICALS 第 37 卷

的多层鳞片型结构具有非常低的表面积，并研究了 of Chemical Engineering, 2018, 2018: 2316939.
在二硫化钨催化下微波辅助合成 5-EMF 和 EL。以 [5] ALIPOUR S, OMIDVARBORNA H, KIM D S. A review on
synthesis of alkoxymethyl furfural, a biofuel candidate[J]. Renewable
果糖为底物，在 160 ℃、15 min 下，果糖转化率为
& Sustainable Energy Reviews. 2017, 71: 908-926.
100.0%，5-EMF 的产率为 62.0%。从机理层面分析， [6] HU L, LIN L, WU Z, et al. Recent advances in catalytic
二硫化钨催化剂同时具备 Brønsted 酸位点和 Lewis transformation of biomass-derived 5-hydroxymethylfurfural into the
酸位点，该催化剂能有效地将碳水化合物转化为 innovative fuels and chemicals[J]. Renewable & Sustainable Energy
5-EMF。YANG 等 [15] 制备了层状钼酸铌固体酸催化 Reviews, 2017, 74: 230-257.
[7] CHEN B L, XU G Z, ZHENG Z B, et al. Efficient conversion of
剂，通过改变元素 Mo 和 Nb 的比例来调控 Brønsted
corn stover into 5-ethoxymethylfurfural catalyzed by zeolite USY in
酸量和层间结构，结果表明，增加 Nb 含量可提高 ethanol/THF medium[J]. Industrial Crops & Products, 2019, 129:
酸催化效果。在 100 ℃、1 h 下，将 5-HMF 与乙醇 503-511.
醚化，5-HMF 完全转化，5-EMF 选择性大于 99.0%， [8] GUO H X, DUEREH A, SU Y Q, et al. Mechanistic role of
产率较高，具有巨大的工业应用前景。以果糖为底物 protonated polar additives in ethanol for selective transformation of
biomass-related compounds[J]. Applied Catalysis B: Environmental,
时，100 ℃、12 h 下，获得了 67.0%的产率。相比其
2020, 264: 188509.
他类型酸催化剂，该催化剂具有优异的催化 5-HMF [9] MASCAL M, NIKITIN E B. Direct, high-yield conversion of
生产 5-EMF 的催化性能，且结构简单、制备方法 cellulose into biofuel[J]. Angewandte Chemie-International Edition,
简易。 2008, 47: 7924-7926.
[10] RAVEENDRA G, RAJASEKHAR A, SRINIVAS M, et al. Selective
3 结束语 etherification of hydroxymethylfurfural to biofuel additives over Cs
containing silicotungstic acid catalysts[J]. Applied Catalysis A:
由生物质可再生资源合成生物燃料 5-EMF 对可 General, 2016, 520: 105-113.
[11] LI H, SARAVANAMURUGAN S, YANG S, et al. Direct
持续发展具有深远的意义。总结了由生物质原料合
transformation of carbohydrates to the biofuel 5-ethoxymethylfurfural by
成 5-EMF 的反应路径和形成机理，综述了近 5 年来 solid acid catalysts[J]. Green Chemistry, 2016, 18(3): 726-734.
各类多相酸性催化剂制备 5-EMF 的催化特点和最新 [12] MA Y, WANG J X, TAN W H, et al. Directional liquefaction of
进展。针对均相催化剂存在的问题，对多相酸催化 lignocellulosic biomass for value added monosaccharides and aromatic
compounds[J]. Industrial Crop & Products, 2019, 135: 251-259.
剂的制备和发展进行了总结，得到以下结论：
[13] GAWADE A B, YADAV G D. Microwave assisted synthesis of
（1）近年来，从原料的使用、催化剂载体的制 5-ethoxymethylfurfural in one pot from D-fructose by using deep
备都逐渐向环境友好化、资源可持续利用化的方向 eutectic solvent as catalyst under mild condition[J]. Biomass and
发展。催化转化 5-EMF 的催化条件需反应时间长或 Bioenergy, 2018, 117: 38-43.
[14] CHEN B L, XU G Z, ZHENG Z B, et al. Efficient one-pot
温度高，未来催化体系的研究应以高效的催化活性、
production of biofuel 5-ethoxymethylfurfural from corn stover:
温和的反应条件、环境友好的溶剂体系为目标开展。
Optimization and kinetics[J]. Energy Fuels, 2019, 33: 4310-4321.
（2）目前，由多糖或农林废弃物转化为 5-EMF [15] YANG F, TANG J J, OU R, et al. Fully catalytic upgrading synthesis
的产率仍较低，以 5-HMF 和果糖为原料转化为 of 5-ethoxymethylfurfural from biomass-derived 5-hydroxymethylfurfural
5-EMF 的研究较多，产率相对较高，但成本也高。 over recyclable layered-niobium-molybdate solid acid[J]. Applied
Catalysis B: Environmental, 2019, 256: 117786.
未来的研究方向应着力于由生物质一步转化为
[16] YAO Y, GU Z, WANG Y, et al. Magnetically-recoverable
5-EMF，实现生物质资源化利用。 carbonaceous material: An efficient catalyst for the synthesis of
5-hydroxymethylfurfural and 5-ethoxymethylfurfural from
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