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

doi:10.11949/j.issn.0438-1157.20171463

Abstract

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

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

CLC Number:

TQ352.2

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.

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.

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