胆碱基碱性离子液体催化合成仲丁醇性能研究

doi:10.11949/0438-1157.20230548

摘要/Abstract

摘要：

利用碱性催化剂催化乙酸仲丁酯与甲醇酯交换制备仲丁醇已成为化工领域的研究热点。相较于传统催化剂，碱性离子液体具有更高效的催化效率和稳定循环使用特性，是一种具有发展潜力的新型绿色催化剂。为此，设计合成了五种基于胆碱的碱性离子液体，通过表征与实验证实阴离子的碱性是影响其催化活性的关键因素。运用适宜催化剂咪唑化胆碱[Ch][IM]经响应面曲线法获得较适宜的催化反应条件：反应温度为45℃，醇酯比为4.42∶1，催化剂投加量为8.91%，其乙酸仲丁酯的转化率达到93.95%，高于醇钠等传统催化剂，展现出在酯交换反应体系中的高效性与在仲丁醇工业化生产过程中应用的可能性。

关键词: 催化剂, 化学反应, 离子液体, 仲丁醇, 酯交换

Abstract:

The use of basic catalysts to catalyze the transesterification of sec-butyl acetate and methanol to prepare sec-butanol has become a research hotspot in the chemical industry. Compared to traditional basic catalysts, basic ionic liquids have more efficient catalytic efficiency and robust reusability, making them a new class of green catalysts with development potentials. Therefore, this study designed and synthesized five choline-based basic ionic liquids, and confirmed through characterization and experiments that the basicity of anions is a key factor affecting their catalytic activity. The results from the response surface method (RSM) analysis showed that suitable reaction conditions of imidazolized choline [Ch][IM] were as follows: the reaction temperature was 45℃, the alcohol ester ratio was 4.42∶1, and the catalyst dosage was 8.91%, the conversion rate of sec-butyl acetate reached 93.95%, which was much higher than that of traditional catalysts such as sodium alcohol, thus confirming its high catalytic efficiency in the transesterification reaction and the possibility of application in the industrial production of sec-butanol.

Key words: catalyst, chemical reaction, ionic liquids, sec-butanol, transesterification

中图分类号:

TQ 426.94

陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.

Jie CHEN, Yongsheng LIN, Kai XIAO, Chen YANG, Ting QIU. Study on catalytic synthesis of sec-butanol by tunable choline-based basic ionic liquids[J]. CIESC Journal, 2023, 74(9): 3716-3730.

图/表 16

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离子液体	核磁数据
[Ch][IM]	7.11 (s, 1H, CH), 6.68 (s, 2H, CH₂), 3.85 (m, J = 5.3, 2.6 Hz, 2H, CH₂), 3.39~3.37 (m, 2H, CH₂), 3.12 (s, 9H, CH₃)
[Ch][OH]	5.74 (t, J = 5.2 Hz, 1H, OH), 3.87~3.74 (m, 2H, CH₂), 3.48~3.42 (m, 2H, CH₂), 3.17 (s, 9H, CH₃)
[Ch][CH₃O]	3.84 (s, 2H, CH₂), 3.38~3.27 (m, 2H, CH₂), 3.15 (d, J = 11.5 Hz, 12H, CH₃)
[Ch][1,2,4-Triz]	6.80 (t, J = 7.7 Hz, 2H, CH), 6.24 (d, J = 8.0 Hz, 2H, CH), 6.06 (t, J = 7.0 Hz, 1H, CH), 3.81 (dt, J = 5.3, 2.6 Hz, 2H, CH₂), 3.41~3.28 (m, 2H, CH₂), 3.11 (s, 9H, CH₃)
[Ch][2-PyO]	7.65 (s, 2H, CH), 3.86 (m, J = 5.5, 2.7 Hz, 2H, CH₂), 3.40 (dd, J = 4.3, 2.6 Hz, 2H, CH₂), 3.13 (s, 9H, CH₃)

离子液体	核磁数据
[Ch][IM]	7.11 (s, 1H, CH), 6.68 (s, 2H, CH₂), 3.85 (m, J = 5.3, 2.6 Hz, 2H, CH₂), 3.39~3.37 (m, 2H, CH₂), 3.12 (s, 9H, CH₃)
[Ch][OH]	5.74 (t, J = 5.2 Hz, 1H, OH), 3.87~3.74 (m, 2H, CH₂), 3.48~3.42 (m, 2H, CH₂), 3.17 (s, 9H, CH₃)
[Ch][CH₃O]	3.84 (s, 2H, CH₂), 3.38~3.27 (m, 2H, CH₂), 3.15 (d, J = 11.5 Hz, 12H, CH₃)
[Ch][1,2,4-Triz]	6.80 (t, J = 7.7 Hz, 2H, CH), 6.24 (d, J = 8.0 Hz, 2H, CH), 6.06 (t, J = 7.0 Hz, 1H, CH), 3.81 (dt, J = 5.3, 2.6 Hz, 2H, CH₂), 3.41~3.28 (m, 2H, CH₂), 3.11 (s, 9H, CH₃)
[Ch][2-PyO]	7.65 (s, 2H, CH), 3.86 (m, J = 5.5, 2.7 Hz, 2H, CH₂), 3.40 (dd, J = 4.3, 2.6 Hz, 2H, CH₂), 3.13 (s, 9H, CH₃)

催化剂	转化率/%^①	pH（水）^②	pH（甲醇）^②
氯化胆碱	0	0	0
CH₃ONa	84.75	12.14	11.21
[Ch][IM]	90.35	12.80	11.36
[Ch][OH]	83.12	12.54	11.05
[Ch][CH₃O]	62.35	11.65	10.67
[Ch][2-PyO]	56.25	11.55	10.49
[Ch][1,2,4-Triz]	48.78	11.36	10.29

催化剂	转化率/%^①	pH（水）^②	pH（甲醇）^②
氯化胆碱	0	0	0
CH₃ONa	84.75	12.14	11.21
[Ch][IM]	90.35	12.80	11.36
[Ch][OH]	83.12	12.54	11.05
[Ch][CH₃O]	62.35	11.65	10.67
[Ch][2-PyO]	56.25	11.55	10.49
[Ch][1,2,4-Triz]	48.78	11.36	10.29

影响因素	水平及范围
影响因素	-1	0	1
反应温度(A)/℃	30	50	70
醇酯比(B)	1∶1	3∶1	5∶1
催化剂投加量(C)/%	1	5	9