化工学报 ›› 2021, Vol. 72 ›› Issue (7): 3601-3612.doi: 10.11949/0438-1157.20201874

• 催化、动力学与反应器 • 上一篇    下一篇

磺酸功能化离子液体的合成及催化制备生物柴油应用

蔡东仁1(),詹国武1(),肖静冉1,邱挺2()   

  1. 1.华侨大学化工学院,福建 厦门 361021
    2.福州大学石油化工学院,福建 福州 350108
  • 收稿日期:2020-12-20 修回日期:2021-03-28 出版日期:2021-07-05 发布日期:2021-07-19
  • 通讯作者: 詹国武,邱挺 E-mail:15506@hqu.edu.cn;gwzhan@hqu.edu.cn;tingqiu@fzu.edu.cn
  • 作者简介:蔡东仁(1990—),男,博士,讲师,15506@hqu.edu.cn
  • 基金资助:
    国家自然科学基金项目(21878054)

Synthesis of sulfonic acid functionalized ionic liquids for catalytic applications in biodiesel production

CAI Dongren1(),ZHAN Guowu1(),XIAO Jingran1,QIU Ting2()   

  1. 1.College of Chemical Engineering, Huaqiao University, Xiamen 361021, Fujian, China
    2.College of Chemical Engineering, Fuzhou University, Fuzhou 350108, Fujian, China
  • Received:2020-12-20 Revised:2021-03-28 Online:2021-07-05 Published:2021-07-19
  • Contact: ZHAN Guowu,QIU Ting E-mail:15506@hqu.edu.cn;gwzhan@hqu.edu.cn;tingqiu@fzu.edu.cn

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

图1

磺酸功能化离子液体合成示意图"

图2

微型磁力高压反应釜1—电加热套;2—磁转子;3—热电偶;4—压力表;5—取样口;6—充气口;7—氮气钢瓶"

图3

甘油与醋酸的酯化反应"

图4

4种磺酸功能化离子液体的FT-IR谱图"

图5

4种磺酸功能化离子液体的1H NMR谱图"

图6

4种磺酸功能化离子液体的13C NMR谱图"

表1

4种磺酸功能化离子液体1H NMR数据"

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)

表2

4种磺酸功能化离子液体的13C NMR数据"

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

图7

4种磺酸功能化离子液体的TGA"

表3

4种噻唑型离子液体的催化活性"

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

图8

[Ps-MTH][CF3SO3]催化酯交换反应机理"

图9

单因素实验结果"

表4

响应面分析的因素及水平"

编码水平

X1

反应温度/℃

X2

醇油摩尔比

X3

催化剂用量/(mmol/g)

-1110150.34
0120230.54
1130310.74

表5

响应面分析的实验值和预测值"

序号工艺条件收率 / %
X1X2X3实验值预测值
100087.80±0.3687.23
200087.67±0.4787.23
31-1077.03±0.3377.12
411089.45±0.5888.95
5-10-169.02±0.6168.45
6-11079.16±0.5579.07
700087.02±0.5287.23
810-179.02±0.1978.86
9-1-1064.32±0.8364.82
1010184.60±0.3685.17
1100087.05±0.4987.23
12-10173.24±0.3573.40
130-1165.26±0.6864.60
1401-171.35±0.2572.01
1500086.63±0.7387.23
1601187.82±0.2887.76
170-1-169.04±0.4469.10

表6

BBD模型的方差及显著性"

来源方差和自由度均方F

P

Prob > F

模型1253.599139.29319.77< 0.0001
X1245.981245.98564.69< 0.0001
X2339.691339.69779.84< 0.0001
X363.23163.23145.15< 0.0001
X1X21.4611.463.360.1094
X1X30.4610.461.060.3371
X2X3102.521102.52235.35< 0.0001
X1246.43146.43106.59< 0.0001
X22173.721173.72398.81< 0.0001
X32233.271233.27535.53< 0.0001
残差3.0570.44
失拟项2.0930.702.920.1634
纯误差0.9540.24
离散系数R2校正R2预测R2方差精密度
0.660.99760.99450.972179.1548.097

表7

无患子生物柴油的理化性质"

性质数值ASTM D6751标准
密度(20℃)/(kg/m3)869.43
运动黏度(40℃)/(mm2/s)6.341.9~6.0
酸值/(mg/g)0.37≤0.50
含水量/(mg/kg)94≤500
闪点/℃170.5≥130
铜片腐蚀度1a≤3
十六烷值60.9≥47

图10

[Ps-MTH][CF3SO3]的重复使用性能"

图11

新鲜[Ps-MTH][CF3SO3]与回收[Ps-MTH][CF3SO3]的FT-IR谱图比较"

表8

[Ps-MTH][CF3SO3]在不同酯交换反应中的催化活性"

序号原料低碳醇催化剂收率 / %
1无患子油甲醇0
2无患子油甲醇H2SO491.26±0.34
3无患子油甲醇[Ps-MTH][CF3SO3]92.78±0.47
4无患子油乙醇[Ps-MTH][CF3SO3]83.17±0.28
5无患子油丙醇[Ps-MTH][CF3SO3]74.19±0.32
6煎炸废油甲醇[Ps-MTH][CF3SO3]76.77±0.61
7棕榈油甲醇[Ps-MTH][CF3SO3]84.59±0.54
8椰子油甲醇[Ps-MTH][CF3SO3]92.90±0.44
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