朱玉雷

摘 要：全面論述了以糖類衍生物（木糖、果糖、葡萄糖和纖維素等）為原料，水相體系中制備5-羥甲基糠醛（5-HMF）和糠醛（FFA）等生物質(zhì)平臺分子的過程。我們開發(fā)了硅酸鋁和鹽酸催化體系，研究了其在水/有機(jī)溶劑組成的雙相體系中催化葡萄糖制5-HMF路徑，發(fā)現(xiàn)葡萄糖轉(zhuǎn)化率100%，HMF收率可達(dá)61.5%。我們設(shè)計(jì)并合成了一系列不同金屬離子摻雜的介孔分子篩催化劑，實(shí)現(xiàn)了離子液體體系中高效催化葡萄糖和果糖脫水制備5-HMF。此外，我們合成了介孔分子篩催化劑，實(shí)驗(yàn)發(fā)現(xiàn)Sn-MCM-41（50）具有最好的催化效果，催化葡萄糖得到5-羥甲基糠醛的收率為51%，葡萄糖轉(zhuǎn)化率為99%。我們研制了磷酸鉭催化劑，完成了催化果糖轉(zhuǎn)化5-HMF的小試和中試研究。自行設(shè)計(jì)搭建的果糖轉(zhuǎn)化5-HMF的小試和中試裝置：5-HMF粗產(chǎn)品產(chǎn)量>250 kg/月； 果糖轉(zhuǎn)化率>95%；5-HMF收率>82%；催化劑壽命>500 h。此外，我們研究了配位不完全的鋅離子在高濃度氯化鋅溶液中催化碳水化合物轉(zhuǎn)化成5-羥甲基糠醛過程，發(fā)現(xiàn)5-HMF產(chǎn)率可達(dá)50%以上。

關(guān)鍵詞：羥甲基糠醛 糖類衍生物 新型催化劑

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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