非粮生物质糖平台合成5-羟甲基糠醛的研究进展

Recent advance in synthesis of 5-hydroxymethylfurfural from non-grain biomass sugar platform

非粮生物质作为一种可再生的能源资源,其净二氧化碳排放为零,被认为是生产液体燃料、生物基化学品和聚合物最有前途的替代品之一。随着可再生能源需求的不断增加,促进了绿色合成生物基化学品的不断发展。5-羟甲基糠醛(HMF)作为一种重要的生物基平台化学品,可广泛应用于合成乙酰丙酸、2,5-呋喃二羧酸、2,5-二甲酰呋喃、2,5-双(羟甲基)-呋喃和5-羟甲基-2-呋喃胺等多种化学品,其可用于精细化工、医药中间体合成、生物可降解材料和液体燃料等领域。目前,HMF的工业生产主要是通过果糖脱除3分子水来实现的,而果糖价格高及HMF的分离效率差,导致HMF的生产成本较高,因此亟须拓展糖源和提高HMF的分离效率。非粮生物质糖平台包含葡萄糖、蔗糖、纤维素、菊粉和琼脂糖等,利用这些糖制备HMF已有广泛研究,有望在未来替代果糖。笔者从非粮生物质衍生糖平台角度出发,综述了近年来合成生物基HMF的研究及应用现状,重点介绍了均相和非均相体系催化不同糖原料合成HMF性能及机制,对比液体酸/盐及固体酸催化糖原料的差异性,分析了不同合成工艺的工业化应用前景,旨在探讨非粮生物质衍生糖平台合成HMF的应用潜力和价值,并为降低HMF及衍生化合物制备成本、合成生物基呋喃化学品的进一步发展提供理论借鉴。

To address the global energy shortage and environmental issues caused by fossil fuels,renewable energy sources are being promoted.Research in this topic is focused on converting biomass into platform chemicals instead of petroleum-based building blocks.Non-grain biomass,as a renewable energy resource with zero net CO2 emissions,is considered one of the most promising alternatives to produce liquid fuels,bio-based chemicals,and polymers.With the increasing demand for renewable energy,the continuous development of green synthetic bio-based chemicals was promoted.As an important bio-based platform chemical,5-hydroxymethylfurfural(HMF)can be widely used in the synthesis of a wide variety of chemicals such as levulinic acid,2,5-furan dicarboxylic acid,2,5-diformylfuran,2,5-bis(hydroxymethyl)-furan and 5-hydroxymethyl-2-furfurylamine,which can be used in fine chemicals,pharmaceutical intermediates synthesis,biodegradable materials,and liquid fuels.The application of HMF and its derivatives offers several solutions to the environmental and ecological problems caused by the excessive utilization of fossil fuels.However,the large-scale production of HMF is a big challenge,mainly because of the instability of HMF products and the low synthesis efficiency of carbohydrates.At present,the current industrial production of HMF is mainly attained by the dehydration of fructose that is required to eliminate three molecules of water,and the high price of fructose and the poor separation efficiency of HMF lead to the high production cost of HMF,so it is urgent to expand the sugar source and improve the separation efficiency of HMF.To prepare HMF,the utilization of the non-grain biomass sugar platforms including glucose,sucrose,cellulose,inulin,and agarose,etc.,has been extensively investigated,which is expected to replace fructose in the future.Recently,there has been an emergence of numerous researches on the carbohydrates-to-HMF process by many kinds of systems.In this study,the recent research status of synthetic and application HMF was reviewed from the perspective of different non-grain biomasses derived sugar platforms.The performance and mechanism of the homogeneous and heterogeneous systems catalyzing the synthesis of HMF from different sugar feedstocks were introduced,the difference between liquid acid/salt and solid acid catalyzed sugar feedstock was compared and the industrial application prospects of different synthesis processes were analyzed.Aiming at exploring the application potential and value of the synthesis of HMF from non-grain biomass derived sugar platform,this study provides theoretical reference for reducing the cost of HMF and its derivative compounds,and further development of synthetic biobased furan chemicals.