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

doi:10.11949/0438-1157.20201874

Abstract

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

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

CLC Number:

TQ 018

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.

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.

Figures/Tables 19

References 34

1	Qiu T, Guo X T, Yang J B, et al. The synthesis of biodiesel from coconut oil using novel Brønsted acidic ionic liquid as green catalyst[J]. Chemical Engineering Journal, 2016, 296: 71-78.
2	Feng Y Y, Li L, Wang X, et al. Stable poly (ionic liquid) with unique crosslinked microsphere structure as efficient catalyst for transesterification of soapberry oil to biodiesel[J]. Energy Conversion and Management, 2017, 153: 649-658.
3	Li L, Yi N, Wang X D, et al. Novel triazolium-based ionic liquids as effective catalysts for transesterification of palm oil to biodiesel[J]. Journal of Molecular Liquids, 2018, 249: 732-738.
4	Ali C H, Qureshi A S, Mbadinga S M, et al. Biodiesel production from waste cooking oil using onsite produced purified lipase from Pseudomonas aeruginosa FW_SH-1: central composite design approach[J]. Renewable Energy, 2017, 109: 93-100.
5	Pan H, Liu X F, Zhang H, et al. Multi-SO₃H functionalized mesoporous polymeric acid catalyst for biodiesel production and fructose-to-biodiesel additive conversion[J]. Renewable Energy, 2017, 107: 245-252.
6	Chang F, Zhou Q, Pan H, et al. Efficient production of biodiesel from Xanthium sibiricum Patr oil via supramolecular catalysis[J]. Renewable Energy, 2017, 111: 556-560.
7	Laesecke J, Ellis N, Production Kirchen P., analysis and combustion characterization of biomass fast pyrolysis oil - biodiesel blends for use in diesel engines[J]. Fuel, 2017, 199: 346-357.
8	Kafuku G, Mbarawa M. Biodiesel production from Croton megalocarpus oil and its process optimization[J]. Fuel, 2010, 89(9): 2556-2560.
9	Koh M Y, Mohd Ghazi T I. A review of biodiesel production from Jatropha curcas L. oil[J]. Renewable and Sustainable Energy Reviews, 2011, 15(5): 2240-2251.
10	Zhang H, Li H, Pan H, et al. Efficient production of biodiesel with promising fuel properties from Koelreuteria integrifoliola oil using a magnetically recyclable acidic ionic liquid[J]. Energy Conversion and Management, 2017, 138: 45-53.
11	Berchmans H J, Morishita K, Takarada T. Kinetic study of hydroxide-catalyzed methanolysis of Jatropha curcas-waste food oil mixture for biodiesel production[J]. Fuel, 2013, 104: 46-52.
12	Elsheikh Y A. Preparation of Citrullus colocynthis biodiesel via dual-step catalyzed process using functionalized imidazolium and pyrazolium ionic liquids for esterification step[J]. Industrial Crops and Products, 2013, 49: 822-829.
13	Olkiewicz M, Plechkova N V, Earle M J, et al. Biodiesel production from sewage sludge lipids catalysed by Brønsted acidic ionic liquids[J]. Applied Catalysis B: Environmental, 2016, 181: 738-746.
14	赵晓霞, 董振浩, 刘光斌, 等. 不同种源无患子品质差异及种籽油脂肪酸分析[J]. 江西农业大学学报, 2014, 36(3): 575-581.
	Zhao X X, Dong Z H, Liu G B, et al. Difference analysis of seed qualities and composition of fatty acid of oil of sapindus mulorossi gaertn from different provenances[J]. Acta Agriculturae Universitatis Jiangxiensis, 2014, 36(3): 575-581.
15	孙尚德, 崔龙龙, 宋范范, 等. 无患子油理化指标和甘三酯结构分析[J]. 中国油脂, 2011, 36(6): 64-67.
	Sun S D, Cui L L, Song F F, et al. Analysis of the physicochemical characteristics and triacylglycerol composition of Sapindus mukorossi Gaetrh. seed oil[J]. China Oils and Fats, 2011, 36(6): 64-67.
16	刘光斌, 赵晓霞, 胡冬南, 等. 无患子油脂的提取、理化性质及其制备生物柴油的研究[J]. 中国粮油学报, 2013, 28(3): 59-64.
	Liu G B, Zhao X X, Hu D N, et al. Study on extraction and physiochemical properties of sapindus mukorossi seed oil and preparation of biodiesel[J]. Journal of the Chinese Cereals and Oils Association, 2013, 28(3): 59-64.
17	Ni W, Hua Y, Liu H Y, et al. Tirucallane-type triterpenoid saponins from the roots of Sapindus mukorossi[J]. Chemical & Pharmaceutical Bulletin, 2006, 54(10): 1443-1446.
18	Huang H C, Wu M D, Tsai W J, et al. Triterpenoid saponins from the fruits and galls of Sapindus mukorossi[J]. Phytochemistry, 2008, 69(7): 1609-1616.
19	Huang H C, Tsai W J, Liaw C C, et al. Anti-platelet aggregation triterpene saponins from the galls of Sapindus mukorossi[J]. Chemical & Pharmaceutical Bulletin, 2007, 55(9): 1412-1415.
20	Kuo Y H, Huang H C, Yang Kuo L M, et al. New dammarane-type saponins from the galls of sapindus mukorossi[J]. Journal of Agricultural and Food Chemistry, 2005, 53(12): 4722-4727.
21	Ullah Z, Bustam M A, Man Z. Biodiesel production from waste cooking oil by acidic ionic liquid as a catalyst[J]. Renewable Energy, 2015, 77: 521-526.
22	Yahya S, Muhamad Wahab S K, Harun F W. Optimization of biodiesel production from waste cooking oil using Fe-Montmorillonite K10 by response surface methodology[J]. Renewable Energy, 2020, 157: 164-172.
23	Jamil U, Husain Khoja A, Liaquat R, et al. Copper and calcium-based metal organic framework (MOF) catalyst for biodiesel production from waste cooking oil: a process optimization study[J]. Energy Conversion and Management, 2020, 215: 112934.
24	Sulaiman N F, Hashim A N N, Toemen S, et al. Biodiesel production from refined used cooking oil using co-metal oxide catalyzed transesterification[J]. Renewable Energy, 2020, 153: 1-11.
25	Xie W L, Wang H. Synthesis of heterogenized polyoxometalate-based ionic liquids with Brönsted-Lewis acid sites: a magnetically recyclable catalyst for biodiesel production from low-quality oils[J]. Journal of Industrial and Engineering Chemistry, 2020, 87: 162-172.
26	Guo F, Fang Z, Tian X F, et al. One-step production of biodiesel from Jatropha oil with high-acid value in ionic liquids[J]. Bioresource Technology, 2011, 102(11): 6469-6472.
27	Clark K D, Emaus M N, Varona M, et al. Ionic liquids: solvents and sorbents in sample preparation[J]. Journal of Separation Science, 2018, 41(1): 209-235.
28	Zhang Q Q, Cui X B, Feng T Y, et al. Hydrolysis of methyl acetate using ionic liquids as catalyst and solvent[J]. Molecular Catalysis, 2020, 484: 110785.
29	Ding H, Ye W, Wang Y Q, et al. Process intensification of transesterification for biodiesel production from palm oil: microwave irradiation on transesterification reaction catalyzed by acidic imidazolium ionic liquids[J]. Energy, 2018, 144: 957-967.
30	He Y F, Han X X, Chen Q, et al. Transesterification of soybean oil to biodiesel by Brønsted-type ionic liquid acid catalysts[J]. Chemical Engineering & Technology, 2013, 36(9): 1559-1567.
31	Fan P, Xing S Y, Wang J Y, et al. Sulfonated imidazolium ionic liquid-catalyzed transesterification for biodiesel synthesis[J]. Fuel, 2017, 188: 483-488.
32	Cai D R, Xie Y W, Li L, et al. Design and synthesis of novel Brønsted-Lewis acidic ionic liquid and its application in biodiesel production from soapberry oil[J]. Energy Conversion and Management, 2018, 166: 318-327.
33	Xue Z M, Qin L, Jiang J Y, et al. Thermal, electrochemical and radiolytic stabilities of ionic liquids[J]. Physical Chemistry Chemical Physics, 2018, 20(13): 8382-8402.
34	Wang B, Qin L, Mu T, et al. Are ionic liquids chemically stable?[J]. Chemical Reviews, 2017, 117(10): 7113-7131.

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