新型催化剂实现糖类衍生物脱水合成5—羟甲基糠醛研究

朱玉雷

摘 要：全面论述了以糖类衍生物（木糖、果糖、葡萄糖和纤维素等）为原料，水相体系中制备5-羟甲基糠醛（5-HMF）和糠醛（FFA）等生物质平台分子的过程。我们开发了硅酸铝和盐酸催化体系，研究了其在水/有机溶剂组成的双相体系中催化葡萄糖制5-HMF路径，发现葡萄糖转化率100%，HMF收率可达61.5%。我们设计并合成了一系列不同金属离子掺杂的介孔分子筛催化剂，实现了离子液体体系中高效催化葡萄糖和果糖脱水制备5-HMF。此外，我们合成了介孔分子筛催化剂，实验发现Sn-MCM-41（50）具有最好的催化效果，催化葡萄糖得到5-羟甲基糠醛的收率为51%，葡萄糖转化率为99%。我们研制了磷酸钽催化剂，完成了催化果糖转化5-HMF的小试和中试研究。自行设计搭建的果糖转化5-HMF的小试和中试装置：5-HMF粗产品产量>250 kg/月； 果糖转化率>95%；5-HMF收率>82%；催化剂寿命>500 h。此外，我们研究了配位不完全的锌离子在高浓度氯化锌溶液中催化碳水化合物转化成5-羟甲基糠醛过程，发现5-HMF产率可达50%以上。

关键词：羟甲基糠醛 糖类衍生物 新型催化剂

Abstract：In this report，the preparation of platform molecular， such as 5-hydroxymethylfurfural （5-HMF） and furfural （FFA） in the aqueous-phase system from saccharide derivatives （xylose， fructose， glucose and cellulose） are summarized. The catalyst system contained silicate and hydrochloric acid was developed， and then the 5-HMF preparation with glucose as substrate was examined in aqueous/organic biphasic solvent system.The obtained glucose conversion rate was 100%， and HMF yield was 61.5%. We also designed and synthesized a series of metal ions doped mesoporous molecular sieve， experimental results shown that these catalysts exhibited effective capability for dehydration of glucose and fructose to 5-HMF in ionic liquid. In addition， we also synthesized mesoporous molecular sieve catalyst， Sn-MCM-41 （50）， which was found with excellent catalytic effect for glucose to 5-HMF conversion. The obtained 5-HMF yield was 51%， and glucose conversion was 99%. Furthermore， we prepared tantalum phosphate catalyst， and fructose converted to 5-HMF in small-scale and pilot plant was examined. The experimental results demonstrated that 5-HMF produce ability is > 250 kg/month； fructose conversion rate > 95%； 5-HMF yield>82%； catalyst life > 500h. Moreover， the incompletely coordinated zinc ions in the concentrated aqueous ZnCl2 solution catalyze the direct conversion of carbohydrates into 5-HMF was studied， and a moderate 5-HMF yield up to 50% can be accomplished.

Key Words：HMF；Sugar derivatives；Novel catalyst

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