近临界乙醇中Zr-SBA-15催化糠醛一步法制备乙酰丙酸乙酯

doi:10.11949/j.issn.0438-1157.20171463

化工学报 ›› 2018, Vol. 69 ›› Issue (6): 2488-2495.DOI: 10.11949/j.issn.0438-1157.20171463

• 催化、动力学与反应器 • 上一篇下一篇

近临界乙醇中Zr-SBA-15催化糠醛一步法制备乙酰丙酸乙酯

吕喜蕾, 阮厚航, 陈皓, 吕秀阳

浙江大学化学工程与生物工程学院, 生物质化工教育部重点实验室, 浙江杭州 310027

收稿日期:2017-11-02 修回日期:2018-01-23 出版日期:2018-06-05 发布日期:2018-06-05
通讯作者: 吕秀阳
基金资助:
国家自然科学基金项目（21676243，21476204）；中央高校基本科研业务费专项。

Single-step Zr-SBA-15 catalytic conversion of furfural to ethyl levulinate in near-critical ethanol

LÜ Xilei, RUAN Houhang, CHEN Hao, LÜ Xiuyang

Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2017-11-02 Revised:2018-01-23 Online:2018-06-05 Published:2018-06-05
Supported by:
supported by the National Natural Science Foundation of China (21676243, 21476204) and the Fundamental Research Funds for the Central Universities.

摘要/Abstract

摘要：

乙酰丙酸乙酯（ethyl levulinate，ELE）是一种用途广泛的有机化学品，可以通过糠醛先加氢再醇解制备，但存在工艺过程长、耗氢、成本高等缺点。提出了一种在近临界乙醇介质中，Zr-SBA-15催化糠醛一步法制备ELE的方法。制备了7种不同Si/Zr摩尔比的Zr-SBA-15，通过催化活性的比较优选出了Zr-SBA-15-10，并考察了催化剂量、乙醇量、反应温度和反应时间对糠醛催化转化制备ELE的影响，得到较佳的工艺条件。当糠醛量为100 mg，催化剂量为50 mg，乙醇量为7 ml，220℃下反应3 h，糠醛的转化率为99.9%，ELE的收率达47.4%。催化剂在重复使用四次之后依然保持良好的活性，通过XRD、N₂-BET、TEM等表征表明反应前后催化剂的结构没有发生明显的变化。在反应机理方面，近临界乙醇介质中Zr-SBA-15-10催化下糠醛一步法转化制备ELE的主途径可能不同于乙酰丙酸甲酯，原位氢转移路径为主反应路径。

关键词: 可持续性, 糠醛, 乙酰丙酸乙酯, 近临界乙醇, Zr-SBA-15, 反应, 优化, 一步法合成

Abstract:

Ethyl levulinate (ELE), a widely used organic chemical compound, can be produced from hydrogenation and alcoholysis of furfural (FAL). However, such processes have some shortcomings of long two-step process, large H₂ consumption, and high cost. A single-step catalytic conversion of FAL to ELE over Zr-SBA-15 in near-critical ethanol was proposed with no H₂ consumption. Among seven Zr-SBA-15 catalysts prepared with different Si/Zr molar ratios, Zr-SBA-15-10 (Si/Zr=10) exhibited best catalytic activity for FAL conversion to ELE. Further study of catalyst loading, ethanol amount, reaction temperature and time lead to an optimal operating condition, which 99.9% conversion of FAL and 47.4% yield of ELE was achieved in a mixture of 100 mg FAL and 50 mg catalyst in 7 ml ethanol at 220℃ for 3 h. The catalyst maintained good activity over four cycles of repeated use with no significant structural changes between fresh and 5th cycle used catalysts, which were characterized with XRD, N₂-BET and TEM. a two reaction pathway reaction mechanism was proposed with catalytic hydrogen transfer as the major one, which was different from that of catalytic conversion of FAL to methyl levulinate in near-critical methanol.

Key words: sustainability, furfural, ethyl levulinate, near-critical ethanol, Zr-SBA-15, reaction, optimization, single-step synthesis

中图分类号:

TQ352.2

吕喜蕾, 阮厚航, 陈皓, 吕秀阳. 近临界乙醇中Zr-SBA-15催化糠醛一步法制备乙酰丙酸乙酯[J]. 化工学报, 2018, 69(6): 2488-2495.

LÜ Xilei, RUAN Houhang, CHEN Hao, LÜ Xiuyang. Single-step Zr-SBA-15 catalytic conversion of furfural to ethyl levulinate in near-critical ethanol[J]. CIESC Journal, 2018, 69(6): 2488-2495.

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近临界乙醇中Zr-SBA-15催化糠醛一步法制备乙酰丙酸乙酯

Single-step Zr-SBA-15 catalytic conversion of furfural to ethyl levulinate in near-critical ethanol

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