磺酸功能化离子液体的合成及催化制备生物柴油应用

doi:10.11949/0438-1157.20201874

摘要/Abstract

摘要：

基于4-甲基噻唑，采用两步法合成4种不同阴离子的磺酸功能化离子液体用于催化无患子油与甲醇酯交换反应制备生物柴油。傅里叶红外光谱、核磁共振和热重分析结果表明，离子液体被成功制备并且具备高热稳定性。其中，3-（3-磺酸基）丙基-4-甲基噻唑三氟甲烷磺酸盐（[Ps-MTH][CF₃SO₃]）在所制备的离子液体中表现出最高的催化活性。以[Ps-MTH][CF₃SO₃]为催化剂，无患子油与甲醇酯交换反应的最佳操作条件为反应温度128℃、醇油摩尔比28.10∶1、催化剂用量0.62 mmol/g（基于油的质量）、反应时间8 h，生物柴油收率高达92.78%±0.47%。此外，[Ps-MTH][CF₃SO₃]具备良好的重复使用性，在不同酯交换反应中也表现出良好的催化活性。该研究为离子液体催化无患子油制备生物柴油的工业化生产提供了基础数据。

关键词: 生物柴油, 4-甲基噻唑, 离子液体, 无患子油, 酯交换

Abstract:

Based on 4-methylthiazole, a two-step method was used to synthesize four sulfonic acid functionalized ionic liquids with different anions to catalyze the transesterification reaction of soapberry oil with methanol to produce biodiesel. The characterization results of Fourier transform infrared spectroscopy, nuclear magnetic resonance, and thermogravimetric analysis suggested that ionic liquids are successfully prepared with high thermal stability. Among the ionic liquids investigated, 3-(3-sulfonic) propyl-4-methylthiazole trifluoromethane sulfonate ([Ps-MTH][CF₃SO₃]) performs the highest catalytic activity. In particular, catalyzed by [Ps-MTH][CF₃SO₃], the optimum operating conditions of transesterification of soapberry oil and methanol are 128℃ (temperature), 28.10∶1 (molar ratio of alcohol to oil), 0.62 mmol/g (catalyst amount, based on the mass of oil) and 8 h (reaction time), leading to a high biodiesel yield of 92.78%±0.47%. Besides, [Ps-MTH][CF₃SO₃] also possesses good reusability and universality. This study will provide basic data for the industrial production of biodiesel from soapberry oil catalyzed by ionic liquids.

Key words: biodiesel, 4-methylthiazole, ionic liquids, soapberry oil, transesterification

中图分类号:

TQ 018

蔡东仁, 詹国武, 肖静冉, 邱挺. 磺酸功能化离子液体的合成及催化制备生物柴油应用[J]. 化工学报, 2021, 72(7): 3601-3612.

CAI Dongren, ZHAN Guowu, XIAO Jingran, QIU Ting. Synthesis of sulfonic acid functionalized ionic liquids for catalytic applications in biodiesel production[J]. CIESC Journal, 2021, 72(7): 3601-3612.

图/表 19

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离子液体	δ
[Ps-MTH][HSO₄]	9.81 (d, J = 2.7 Hz, 1H), 7.74 (d, J = 1.6 Hz, 1H), 4.56~4.53 (m, 2H), 2.93 (d, J = 7.2 Hz, 2H), 2.51 (d, J = 1.0 Hz, 3H), 2.31~2.28 (m, 2H)
[Ps-MTH][Tos]	9.79 (d, J = 2.7 Hz, 1H), 7.73 (d, J = 0.9 Hz, 1H), 7.59 (d, J = 8.3 Hz, 2H), 7.27 (d, J = 7.9 Hz, 2H), 4.52 (d, J = 7.7 Hz, 2H), 2.92 (d, J = 7.2 Hz, 2H), 2.50 (d, J = 0.9 Hz, 3H), 2.30 (s, 3H), 2.29~2.26 (m, 2H)
[Ps-MTH][CH₃SO₃]	9.81 (d, J = 2.7 Hz, 1H), 7.75 (d, J = 1.0 Hz, 1H), 4.56~4.53 (m, 2H), 2.94 (t, J = 7.2 Hz, 2H), 2.71 (s, 3H), 2.51 (d, J = 1.0 Hz, 3H), 2.31~2.28 (m, 2H)
[Ps-MTH][CF₃SO₃]	9.81 (d, J = 2.7 Hz, 1H), 7.75 (d, J = 1.6 Hz, 1H), 4.56~4.54 (m, 2H), 2.94 (t, J = 7.2 Hz, 2H), 2.52 (d, J = 1.0 Hz, 3H), 2.32~2.29 (m, 2H)

离子液体	δ
[Ps-MTH][HSO₄]	9.81 (d, J = 2.7 Hz, 1H), 7.74 (d, J = 1.6 Hz, 1H), 4.56~4.53 (m, 2H), 2.93 (d, J = 7.2 Hz, 2H), 2.51 (d, J = 1.0 Hz, 3H), 2.31~2.28 (m, 2H)
[Ps-MTH][Tos]	9.79 (d, J = 2.7 Hz, 1H), 7.73 (d, J = 0.9 Hz, 1H), 7.59 (d, J = 8.3 Hz, 2H), 7.27 (d, J = 7.9 Hz, 2H), 4.52 (d, J = 7.7 Hz, 2H), 2.92 (d, J = 7.2 Hz, 2H), 2.50 (d, J = 0.9 Hz, 3H), 2.30 (s, 3H), 2.29~2.26 (m, 2H)
[Ps-MTH][CH₃SO₃]	9.81 (d, J = 2.7 Hz, 1H), 7.75 (d, J = 1.0 Hz, 1H), 4.56~4.53 (m, 2H), 2.94 (t, J = 7.2 Hz, 2H), 2.71 (s, 3H), 2.51 (d, J = 1.0 Hz, 3H), 2.31~2.28 (m, 2H)
[Ps-MTH][CF₃SO₃]	9.81 (d, J = 2.7 Hz, 1H), 7.75 (d, J = 1.6 Hz, 1H), 4.56~4.54 (m, 2H), 2.94 (t, J = 7.2 Hz, 2H), 2.52 (d, J = 1.0 Hz, 3H), 2.32~2.29 (m, 2H)

离子液体	δ
[Ps-MTH][HSO₄]	157.13, 146.27, 120.64, 50.73, 46.65, 24.01, 11.98
[Ps-MTH][Tos]	157.09, 146.24, 141.98, 138.95, 128.95, 124.87, 120.64, 50.71, 46.64, 24.01, 19.99, 11.97
[Ps-MTH][CH₃SO₃]	157.13, 146.28, 120.64, 50.73, 46.65, 37.96, 24.01, 11.98
[Ps-MTH][CF₃SO₃]	157.12, 146.28, 120.64, 118.11, 50.73, 46.65, 24.01, 11.98

离子液体	δ
[Ps-MTH][HSO₄]	157.13, 146.27, 120.64, 50.73, 46.65, 24.01, 11.98
[Ps-MTH][Tos]	157.09, 146.24, 141.98, 138.95, 128.95, 124.87, 120.64, 50.71, 46.64, 24.01, 19.99, 11.97
[Ps-MTH][CH₃SO₃]	157.13, 146.28, 120.64, 50.73, 46.65, 37.96, 24.01, 11.98
[Ps-MTH][CF₃SO₃]	157.12, 146.28, 120.64, 118.11, 50.73, 46.65, 24.01, 11.98

序号	离子液体	收率 / %
1	[Ps-MIH][CF₃SO₃]	83.85±0.39
2	[Ps-MPH][CF₃SO₃]	84.92±0.75
3	[Ps-MTH][CF₃SO₃]	87.28±0.83
4	[Ps-MTH][HSO₄]	84.28±0.58
5	[Ps-MTH][Tos]	84.50±0.46
6	[Ps-MTH][CH₃SO₃]	81.62±0.29