Catalytic and selective transformation of glucose to methyl levulinate with mixed acids as catalysts

doi:10.11949/j.issn.0438-1157.20151018

Abstract

Abstract:

The efficient synthesis of methyl levulinate (MLE) from biomass feedstock using catalytic process is high economic, environment-friendly and sustainable in chemical industry. Herein, the catalytic performance of Lewis acid, Brøsted acid and mixed acid on the conversion of glucose to MLE is investigated in detail, and a satisfactory product yield is obtained. First, the different molecular sieves are combined with p-toluenesulfonic acid (PTSA) and employed as the catalysts for the direct transformation of glucose to MLE, in which the combination of Sn-β molecular sieve (being synthesized through a simple grinding method) and PTSA is the most efficient. The highest yield of MLE is about 68.3%. Furthermore, the catalyst is characterized by XRD, FT-IR and TG-DTG techniques. It is found that Sn-β can mediate the isomerization of glucose to fructose and PTSA mainly promote the alcoholysis reaction based on the experimental results and corresponding phenomena in the reaction. At last, the effects of Sn-β/PTSA ratio, reaction time and reaction temperature are studied, and the optimized conditions are obtained.

Key words: glucose, catalysis, alcoholysis, mixed-acid, methyl levulinate

摘要：

将生物质原料直接转化制备乙酰丙酸甲酯(MLE)具有经济价值高、对环境友好和可持续性强等优点。详细研究了Lewis酸(Sn-β分子筛)、Brønsted酸(对甲苯磺酸,PTSA)及混合酸(Sn-β/PTSA)在葡萄糖直接转化合成乙酰丙酸甲酯中的催化效果,取得了较高的产物收率。首先,将各种分子筛和PTSA组合成催化体系并将其应用于葡萄糖醇解合成MLE的反应过程,发现Sn-β分子筛与PTSA的混合体系效果最佳(其中,Sn-β分子筛是借助简单的研磨法制备),产物MLE的收率可达68.3%左右。进而,对分子筛催化剂进行了XRD、FT-IR和TG-DTG等表征;由实验结果可知,Sn-β分子筛的主要作用在于将葡萄糖异构生成果糖,而PTSA的催化作用是加速醇解过程;最后,针对催化剂组分的比例、反应时间和反应温度进行了优化,得到了最佳反应条件。

关键词: 葡萄糖, 催化, 醇解, 混合酸, 乙酰丙酸甲酯

CLC Number:

O643.3

ZHANG Yangyang, LUO Xuan, ZHUANG Xuli, TONG Xinli. Catalytic and selective transformation of glucose to methyl levulinate with mixed acids as catalysts[J]. CIESC Journal, 2015, 66(9): 3490-3495.

张阳阳, 罗璇, 庄绪丽, 仝新利. 混合酸催化葡萄糖选择性转化合成乙酰丙酸甲酯[J]. 化工学报, 2015, 66(9): 3490-3495.

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