Polymeric ionic liquids (PILs) with high acid density: Tunable catalytic performance for biodiesel production

doi:10.1016/j.cjche.2021.04.006

Chinese Journal of Chemical Engineering ›› 2021, Vol. 38 ›› Issue (10): 266-275.DOI: 10.1016/j.cjche.2021.04.006

• Materials and Product Engineering • Previous Articles Next Articles

Polymeric ionic liquids (PILs) with high acid density: Tunable catalytic performance for biodiesel production

Xiaocheng Lin¹, Youjie Huang¹, Ling Li¹, Changshen Ye¹, Jie Chen^1,2, Ting Qiu¹

1. Engineering Research Center of Reaction Distillation, Fujian Province University, College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China;
2. College of Environment and Resources, Fuzhou University, Fuzhou 350116, China

Received:2021-01-12 Revised:2021-04-08 Online:2021-12-02 Published:2021-10-28
Contact: Jie Chen, Ting Qiu
Supported by:
We acknowledged the National Natural Science Foundation of China (21878054), Project on the Integration of Industry and Education of Fujian Province (2018Y4008), Science and Technology Project of Fujian Educational Committee (JAT190051), Fuzhou University Testing Fund of precious apparatus (2020T008) and Research Initiation Funding of Fuzhou University (GXRC-19051). X. Lin also acknowledged the Award Program for Minjiang Scholar Professorship.

Polymeric ionic liquids (PILs) with high acid density: Tunable catalytic performance for biodiesel production

Xiaocheng Lin¹, Youjie Huang¹, Ling Li¹, Changshen Ye¹, Jie Chen^1,2, Ting Qiu¹

1. Engineering Research Center of Reaction Distillation, Fujian Province University, College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China;
2. College of Environment and Resources, Fuzhou University, Fuzhou 350116, China

通讯作者: Jie Chen, Ting Qiu
基金资助:
We acknowledged the National Natural Science Foundation of China (21878054), Project on the Integration of Industry and Education of Fujian Province (2018Y4008), Science and Technology Project of Fujian Educational Committee (JAT190051), Fuzhou University Testing Fund of precious apparatus (2020T008) and Research Initiation Funding of Fuzhou University (GXRC-19051). X. Lin also acknowledged the Award Program for Minjiang Scholar Professorship.

Abstract

Abstract: A series of polymeric ionic liquids (PILs) used as effective heterogeneous catalysts for biodiesel production via esterification of free fatty acids (FFAs) were effectively prepared by the reaction of poly (ethylene imine) (PEI) polymers with different molecular weight and 1,3-propanesultone, followed by the further acidification with differential effective acids, i.e. H₂SO₄, CF₃SO₃H, CH₃SO₃H or p-toluenesulfonic acid (p-TSA). Ultrahigh acidity and catalytic performance were achieved and could be fine-tuned by simply adjusting the molecular weight of PEI and by further treatment of acids. Specifically, under the optimal conditions (i.e. reaction temperature was 70 ℃, reaction time was 2.0 h, catalyst dosage was 3.15% (mass), and alcohol/acid molar ratio was 14:1) acquired through the Box-BEHNKEN response surface methodology, a high oleic acid conversion of 98.42% could be obtained over the optimal PIL, PEI(70000)-PS-p-TSA. Additionally, our PILs also showed high generality for esterification of other FFAs, with general high conversion over 90% noted in each case even under much milder reaction conditions compared to other conventional catalysts.

Key words: Catalyst, Ionic liquids, Biodiesel, Poly (ethylene imine), Esterification

摘要： A series of polymeric ionic liquids (PILs) used as effective heterogeneous catalysts for biodiesel production via esterification of free fatty acids (FFAs) were effectively prepared by the reaction of poly (ethylene imine) (PEI) polymers with different molecular weight and 1,3-propanesultone, followed by the further acidification with differential effective acids, i.e. H₂SO₄, CF₃SO₃H, CH₃SO₃H or p-toluenesulfonic acid (p-TSA). Ultrahigh acidity and catalytic performance were achieved and could be fine-tuned by simply adjusting the molecular weight of PEI and by further treatment of acids. Specifically, under the optimal conditions (i.e. reaction temperature was 70 ℃, reaction time was 2.0 h, catalyst dosage was 3.15% (mass), and alcohol/acid molar ratio was 14:1) acquired through the Box-BEHNKEN response surface methodology, a high oleic acid conversion of 98.42% could be obtained over the optimal PIL, PEI(70000)-PS-p-TSA. Additionally, our PILs also showed high generality for esterification of other FFAs, with general high conversion over 90% noted in each case even under much milder reaction conditions compared to other conventional catalysts.

关键词: Catalyst, Ionic liquids, Biodiesel, Poly (ethylene imine), Esterification

Xiaocheng Lin, Youjie Huang, Ling Li, Changshen Ye, Jie Chen, Ting Qiu. Polymeric ionic liquids (PILs) with high acid density: Tunable catalytic performance for biodiesel production[J]. Chinese Journal of Chemical Engineering, 2021, 38(10): 266-275.

References

[1] S. Shah, S. Sharma, M.N. Gupta, Biodiesel preparation by lipase-catalyzed transesterification of jatropha oil, Energy Fuels 18 (1) (2004) 154-159
[2] S. Semwal, A.K. Arora, R.P. Badoni, D.K. Tuli, Biodiesel production using heterogeneous catalysts, Bioresour. Technol. 102 (3) (2011) 2151-2161
[3] S.L. Yan, C. DiMaggio, S. Mohan, M. Kim, S.O. Salley, K.Y.S. Ng, Advancements in heterogeneous catalysis for biodiesel synthesis, Top. Catal. 53 (11-12) (2010) 721-736
[4] L.L. Xu, X. Yang, X.D. Yu, Y.H. Guo, Maynurkader, Preparation of mesoporous polyoxometalate-tantalum pentoxide composite catalyst for efficient esterification of fatty acid, Catal. Commun. 9 (7) (2008) 1607-1611
[5] T. Valliyappan, N.N. Bakhshi, A.K. Dalai, Pyrolysis of glycerol for the production of hydrogen or syn gas, Bioresour. Technol. 99 (10) (2008) 4476-4483
[6] M.E. Borges, L. Díaz, Recent developments on heterogeneous catalysts for biodiesel production by oil esterification and transesterification reactions: A review, Renew. Sustain. Energy Rev. 16 (5) (2012) 2839-2849
[7] A.H. Mohammad Fauzi, N.A. Saidina Amin, Optimization of oleic acid esterification catalyzed by ionic liquid for green biodiesel synthesis, Energy Convers. Manag. 76 (2013) 818-827
[8] Z. Helwani, M.R. Othman, N. Aziz, W.J.N. Fernando, J. Kim, Technologies for production of biodiesel focusing on green catalytic techniques: A review, Fuel Process. Technol. 90 (12) (2009) 1502-1514
[9] A.S. Amarasekara, Acidic ionic liquids, Chem. Rev. 116 (10) (2016) 6133-6183
[10] M.H. Han, W.L. Yi, Q. Wu, Y. Liu, Y.C. Hong, D.Z. Wang, Preparation of biodiesel from waste oils catalyzed by a Brønsted acidic ionic liquid, Bioresour. Technol. 100 (7) (2009) 2308-2310
[11] S.Y. Gan, H.K. Ng, P.H. Chan, F.L. Leong, Heterogeneous free fatty acids esterification in waste cooking oil using ion-exchange resins, Fuel Process. Technol. 102 (2012) 67-72
[12] I. Noshadi, N.A.S. Amin, R.S. Parnas, Continuous production of biodiesel from waste cooking oil in a reactive distillation column catalyzed by solid heteropolyacid: Optimization using response surface methodology (RSM), Fuel 94 (2012) 156-164
[13] Y.A. Elsheikh, Z. Man, M.A. Bustam, S. Yusup, C.D. Wilfred, Brønsted imidazolium ionic liquids: Synthesis and comparison of their catalytic activities as pre-catalyst for biodiesel production through two stage process, Energy Convers. Manag. 52 (2) (2011) 804-809
[14] X.Z. Li, W. Eli, A green approach for the synthesis of long chain aliphatic acid esters at room temperature, J. Mol. Catal. A: Chem. 279 (2) (2008) 159-164
[15] S.K. Ritter, Alkylate rising, Chem. Eng. News 79 (40) (2001) 63-67
[16] M.A. Harmer, Q. Sun, Solid acid catalysis using ion-exchange resins, Appl. Catal. A: Gen. 221 (1-2) (2001) 45-62
[17] Y.Q. Wang, D. Zhao, L.L. Wang, X.Q. Wang, L.J. Li, Z.P. Xing, N. Ji, S.J. Liu, H. Ding, Immobilized phosphotungstic acid based ionic liquid: Application for heterogeneous esterification of palmitic acid, Fuel 216 (2018) 364-370
[18] J.M. Miao, H. Wan, G.F. Guan, Synthesis of immobilized Brønsted acidic ionic liquid on silica gel as heterogeneous catalyst for esterification, Catal. Commun. 12 (5) (2011) 353-356
[19] X.Z. Liang, H.Q. Xiao, C.Z. Qi, Efficient procedure for biodiesel synthesis from waste oils using novel solid acidic ionic liquid polymer as catalysts, Fuel Process. Technol. 110 (2013) 109-113
[20] T.T. Liu, Z.L. Li, W. Li, C.J. Shi, Y. Wang, Preparation and characterization of biomass carbon-based solid acid catalyst for the esterification of oleic acid with methanol, Bioresour. Technol. 133 (2013) 618-621
[21] C. Thomazeau, H. Olivier-Bourbigou, L. Magna, S. Luts, B. Gilbert, Determination of an acidic scale in room temperature ionic liquids, J. Am. Chem. Soc. 125 (18) (2003) 5264-5265
[22] Y.L. Gu, J. Zhang, Z.Y. Duan, Y.Q. Deng, Pechmann reaction in non-chloroaluminate acidic ionic liquids under solvent-free conditions, Adv. Synth. Catal. 347 (4) (2005) 512-516
[23] R. Kore, R. Srivastava, Synthesis and applications of highly efficient, reusable, sulfonic acid group functionalized Brönsted acidic ionic liquid catalysts, Catal. Commun. 12 (15) (2011) 1420-1424
[24] X.C. Lin, X.M. Ling, J.Y. Chen, M.C. Li, T.W. Xu, T. Qiu, Self-solidification ionic liquids as heterogeneous catalysts for biodiesel production, Green Chem. 21 (11) (2019) 3182-3189
[25] G.E.P. Box, K.B. Wilson, On the experimental attainment of optimum conditions, J. R. Stat. Soc. B 13 (1951) 1-38
[26] J. Chen, Y.B. Wang, C.S. Ye, W. Lyu, J.W. Zhu, W. Yan, T. Qiu, Self-reducible conjugated microporous polyaniline for long-term selective Cr(VI) detoxication driven by tunable pore dimension, ACS Appl. Mater. Interfaces 12 (25) (2020) 28681-28691
[27] J. Chen, T. Qiu, W. Yan, C.F.J. Faul, Exploiting Hansen solubility parameters to tune porosity and function in conjugated microporous polymers, J. Mater. Chem. A 8 (43) (2020) 22657-22665
[28] J. Chen, W. Yan, E.J. Townsend, J.T. Feng, L. Pan, V. Del Angel Hernandez, C.F.J. Faul, Tunable surface area, porosity, and function in conjugated microporous polymers, Angew. Chem. Int. Ed. 58 (34) (2019) 11715-11719
[29] S.R. Lowry, K.A. Mauritz, An investigation of ionic hydration effects in perfluorosulfonate ionomers by Fourier transform infrared spectroscopy, J. Am. Chem. Soc. 102 (14) (1980) 4665-4667
[30] J. Zhao, J.X. Yang, P.F. Sun, Y.H. Xu, Sodium sulfonate groups substituted anthraquinone as an organic cathode for potassium batteries, Electrochem. Commun. 86 (2018) 34-37
[31] J. Lu, J. Wang, S. Rohani, Preparation and characterization of amorphous, I and II forms of clopidogrel hydrogen sulfate, Cryst. Res. Technol. 47 (5) (2012) 505-510
[32] J. Chen, J.W. Zhu, N. Wang, J.T. Feng, W. Yan, Hydrophilic polythiophene/SiO₂ composite for adsorption engineering: Green synthesis in aqueous medium and its synergistic and specific adsorption for heavy metals from wastewater, Chem. Eng. J. 360 (2019) 1486-1497
[33] X.M. Liu, H.Y. Ma, Y. Wu, C. Wang, M. Yang, P.F. Yan, U. Welz-Biermann, Esterification of glycerol with acetic acid using double SO₃H-functionalized ionic liquids as recoverable catalysts, Green Chem. 13 (3) (2011) 697
[34] W. Li, Y. Wang, Z.Z. Wang, L.Y. Dai, Y.Y. Wang, Novel SO₃H-functionalized ionic liquids based on benzimidazolium cation: Efficient and recyclable catalysts for one-pot synthesis of biscoumarin derivatives, Catal. Lett. 141 (11) (2011) 1651-1658
[35] J. Chen, M.T. Yu, C.Y. Wang, J.T. Feng, W. Yan, Insight into the synergistic effect on selective adsorption for heavy metal ions by a polypyrrole/TiO₂ composite, Langmuir 34 (34) (2018) 10187-10196
[36] S.P. Satasia, P.N. Kalaria, D.K. Raval, Acidic ionic liquid immobilized on cellulose: An efficient and recyclable heterogeneous catalyst for the solvent-free synthesis of hydroxylated trisubstituted pyridines, RSC Adv. 3 (10) (2013) 3184
[37] A.M.M. Ali, M.Z.A. Yahya, H. Bahron, R.H.Y. Subban, M.K. Harun, I. Atan, Impedance studies on plasticized PMMA-LiX [X: CF₃SO₃-, N(CF₃SO₂)₂-] polymer electrolytes, Mater. Lett. 61 (10) (2007) 2026-2029
[38] G.Q. Guan, K. Kusakabe, N. Sakurai, K. Moriyama, Transesterification of vegetable oil to biodiesel fuel using acid catalysts in the presence of dimethyl ether, Fuel 88 (1) (2009) 81-86
[39] A. Alegría, J. Cuellar, Esterification of oleic acid for biodiesel production catalyzed by 4-dodecylbenzenesulfonic acid, Appl. Catal. B: Environ. 179 (2015) 530-541
[40] D. Lu, J.W. Zhao, Y. Leng, P.P. Jiang, C.J. Zhang, Novel porous and hydrophobic POSS-ionic liquid polymeric hybrid as highly efficient solid acid catalyst for synthesis of oleate, Catal. Commun. 83 (2016) 27-30
[41] A.H. Mohammad Fauzi, N.A.S. Amin, R. Mat, Esterification of oleic acid to biodiesel using magnetic ionic liquid: Multi-objective optimization and kinetic study, Appl. Energy 114 (2014) 809-818
[42] C.F. Oliveira, L.M. Dezaneti, F.A.C. Garcia, J.L. de Macedo, J.A. Dias, S.C.L. Dias, K.S.P. Alvim, Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on zirconia, Appl. Catal. A: Gen. 372 (2) (2010) 153-161
[43] P. Yin, L. Chen, Z. Wang, R.J. Qu, X.G. Liu, Q. Xu, S.H. Ren, Biodiesel production from esterification of oleic acid over aminophosphonic acid resin D418, Fuel 102 (2012) 499-505
[44] Y.W. Zhao, J.X. Long, F.G. Deng, X.F. Liu, Z. Li, C.G. Xia, J.J. Peng, Catalytic amounts of Brønsted acidic ionic liquids promoted esterification: Study of acidity-activity relationship, Catal. Commun. 10 (5) (2009) 732-736
[45] H.P. Zhu, F. Yang, J. Tang, M.Y. He, Brønsted acidic ionic liquid 1-methylimidazolium tetrafluoroborate: A green catalyst and recyclable medium for esterification, Green Chem. 5 (1) (2003) 38
[46] H.N. Lim, A. Kassim, N.M. Huang, M.A. Yarmo, P.S. Khiew, W.S. Chiu, Preparation and characterization of brushite crystals using high internal phase emulsion, Colloid J. 71 (6) (2009) 793-802
[47] K. Saravanan, B. Tyagi, R.S. Shukla, H.C. Bajaj, Esterification of palmitic acid with methanol over template-assisted mesoporous sulfated zirconia solid acid catalyst, Appl. Catal. B: Environ. 172-173 (2015) 108-115
[48] X.X. Han, H. Du, C.T. Hung, L.L. Liu, P.H. Wu, D.H. Ren, S.J. Huang, S.B. Liu, Syntheses of novel halogen-free Brønsted-Lewis acidic ionic liquid catalysts and their applications for synthesis of methyl caprylate, Green Chem. 17 (1) (2015) 499-508

Polymeric ionic liquids (PILs) with high acid density: Tunable catalytic performance for biodiesel production

Polymeric ionic liquids (PILs) with high acid density: Tunable catalytic performance for biodiesel production

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jinlong Liu, Chenye Wang, Xingrui Wang, Chen Zhao, Huiquan Li, Ganyu Zhu, Jianbo Zhang. Reconstruction and recovery of anatase TiO₂ from spent selective catalytic reduction catalyst by NaOH hydrothermal method [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 53-60.
[2]	Eileen Katherine Coronado-Aldana, Cindy Lizeth Ferreira-Salazar, Nubia Yineth Piñeros-Castro, Rubén Vázquez-Medina, Felipe A. Perdomo. Thermodynamic analysis, synthesis, characterization, and evaluation of 1-ethyl-3-methylimidazolium chloride: Study of its effect on pretreated rice husk [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 143-154.
[3]	Yifan Jiang, Bingqi Xie, Jisong Zhang. Highly reactive and reusable heterogeneous activated carbons-based palladium catalysts for Suzuki-Miyaura reaction [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 165-172.
[4]	Peipei Ai, Huiqing Jin, Jie Li, Xiaodong Wang, Wei Huang. Ultra-stable Cu-based catalyst for dimethyl oxalate hydrogenation to ethylene glycol [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 186-193.
[5]	Yuehua Liu, Lili Chen, Shoujun Liu, Song Yang, Ju Shangguan. Role of iron-based catalysts in reducing NO_x emissions from coal combustion [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 1-8.
[6]	Fei Li, Xuemei Wang, Pengze Zhang, Qinqin Wang, Mingyuan Zhu, Bin Dai. Nitrogen and phosphorus co-doped activated carbon induces high density Cu⁺ active center for acetylene hydrochlorination [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 193-199.
[7]	Zhonghao Li, Yuanyuan Yang, Huanong Cheng, Yun Teng, Chao Li, Kangkang Li, Zhou Feng, Hongwei Jin, Xinshun Tan, Shiqing Zheng. Measurement and model of density, viscosity, and hydrogen sulfide solubility in ferric chloride/trioctylmethylammonium chloride ionic liquid [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 210-221.
[8]	Junyang Liu, Luming Wang, Yuhang Bian, Chunshan Li, Zengxi Li, Jie Li. Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor: Experimental and kinetic studies [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 1-10.
[9]	Chen Chen, Qiong Tang, Hong Xu, Mingxing Tang, Xuekuan Li, Lei Liu, Jinxiang Dong. Alkyl-tetralin base oils synthesized from coal-based chemicals and evaluation of their lubricating properties [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 20-28.
[10]	Qunfeng Zhang, Bingcheng Li, Yuan Zhou, Deshuo Zhang, Chunshan Lu, Feng Feng, Jinghui Lv, Qingtao Wang, Xiaonian Li. Regulation of the selective hydrogenation performance of sulfur-doped carbon-supported palladium on chloronitrobenzene [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 69-75.
[11]	Yutong Jiang, Yifeng Chen, Fuliu Yang, Jixue Fan, Jun Li, Zhuhong Yang, Xiaoyan Ji. Efficient SO₂ removal using aqueous ionic liquid at low partial pressure [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 355-363.
[12]	Jiajia Chen, Xinyu Lu, Dandan Wang, Pengcheng Xiu, Xiaoli Gu. Effective depolymerization of alkali lignin using an attapulgite-Ce_0.75Zr_0.25O₂(ATP-CZO)-supported cobalt catalyst in ethanol/isopropanol media [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 50-62.
[13]	Linlin Su, Meijun Chen, Li Gong, Hua Yang, Chao Chen, Jun Wu, Ling Luo, Gang Yang, Lulu Long. Boost activation of peroxymonosulfate by iron doped K_2-xMn₈O₁₆: Mechanism and properties [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 88-97.
[14]	Bingxiao Feng, Lining Hao, Chaoting Deng, Jiaqiang Wang, Hongbing Song, Meng Xiao, Tingting Huang, Quanhong Zhu, Hengjun Gai. A highly hydrothermal stable copper-based catalyst for catalytic wet air oxidation of m-cresol in coal chemical wastewater [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 338-348.
[15]	Shujun Peng, Song Lei, Sisi Wen, Jian Xue, Haihui Wang. A Ruddlesden–Popper oxide as a carbon dioxide tolerant cathode for solid oxide fuel cells that operate at intermediate temperatures [J]. Chinese Journal of Chemical Engineering, 2023, 56(4): 25-32.