Synthesis and Optimization of Methyl Laurate Using Sulfonated Pyrrolidonium Ionic Liquid as a Catalyst
-
Benyong Han
, Fang Yin
, Shiqing Liu
, Xingling Zhao , Jing Liu , Changmei Wang , Hong Yang and Wudi Zhang
Abstract
Methyl laurate was synthesized from lauric acid and methanol using Brønsted acid ionic liquids as catalysts, by an esterification reaction. The efficiencies of four different catalysts, 1-methylimidazolium hydrogen sulfate ([Hmim]HSO4), 2-pyrrolidonium hydrogen sulfate ([Hnhp]HSO4), 1-(3-sulfonic acid) propyl-2-pyrrolidonium hydrogen sulfate ([C3SO3Hnhp]HSO4) and H2SO4 were compared. The effect of the methanol/lauric acid molar ratio, reaction temperature, reaction time, and catalyst dosage on the lauric acid conversion was investigated by single-factor experiments. On the basis of single-factor experiments, the esterification of lauric acid and methanol was optimized using response surface methodology (RSM) based on central composite design (CCD). The results showed that the most effective catalyst was the ionic liquid [C3SO3Hnhp]HSO4. The optimal conditions were as follows: [C3SO3Hnhp]HSO4 dosage of 10 % (based on the mass of lauric acid), methanol/lauric acid molar ratio of 9:1, reaction time of 1 h and reaction temperature of 70 °C. Under these conditions, the lauric acid conversion reached 95.33 %. The catalytic activity of [C3SO3Hnhp]HSO4 still remained high after 5 cycles.
Acknowledgements
This study was supported by the National Natural Science Foundation of China (51366015), the Yunnan Provincial Sciences and Technology Platform Promotion Plan (2013DH041), the Specialized Research Fund for Doctoral Program of Universities (20135303110001), Yunnan Province Key Fund of Applied Basic Research (2014FA030), and Open Fund from Yunnan Key Laboratory of Rural Energy Engineering (2017KF03).
References
Aghabarari, B., M. Ghiaci, S. G. Amini, E. Rahimi, and M. V. Martinez-Huerta. 2014. “Esterification of Fatty Acids by New Ionic Liquids as Acid Catalysts.” Journal of the Taiwan Institute of Chemical Engineers 45 (2): 431–35.10.1016/j.jtice.2013.08.003Search in Google Scholar
Alegría, A., and J. Cuellar. 2015. “Esterification of Oleic Acid for Biodiesel Production Catalyzed by 4-Dodecylbenzenesulfonic Acid.” Applied Catalysis B-Environmental 179: 530–41.10.1016/j.apcatb.2015.05.057Search in Google Scholar
American Oil Chemists' Society. 2005. Official methods and recommended practices of the American Oil Chemists' Society,Urbana.Search in Google Scholar
Boey, P. L., G. P. Maniam, and S. A. Hamid. 2011. “Performance of Calcium Oxide as a Heterogeneous Catalyst in Biodiesel Production: A Review.” Chemical Engineering Jouranl 168 (1): 15–22.10.1016/j.cej.2011.01.009Search in Google Scholar
Cao, Z. J., X. Zhao, F. Q. He, Y. Zhou, K. Huang, A. M. Zheng, and D. J. Tao. 2018. “Highly Efficient Indirect Hydration of Olefins to Alcohols Using Superacidic Polyoxometalate-Based Ionic Hybrids Catalysts.” Industrial & Engineering Chemistry Research 57 (19): 6654–63.10.1021/acs.iecr.8b00535Search in Google Scholar
Carmo, A. C., L. K. de Souza, C. E. Da Costa, E. Longo, J. R. Zamian, and G. N. Da Rocha Filho. 2009. “Production of Biodiesel by Esterification of Palmitic Acid over Mesoporous Aluminosilicate Al-MCM-41.” Fuel 88 (3): 461–68.10.1016/j.fuel.2008.10.007Search in Google Scholar
Che, R., L. Huang, and X. Yu. 2015. “Enhanced Biomass Production, Lipid Yield and Sedimentation Efficiency by Iron Ion.” Bioresource Technology 192: 795–98.10.1016/j.biortech.2015.05.009Search in Google Scholar PubMed
Chowdhury, S., R. S. Mohan, and J. L Scott. 2007. “Reactivity of Ionic Liquids.” Tetrahedron 63 (11): 2363–89.10.1016/j.tet.2006.11.001Search in Google Scholar
Costa, A. A., P. R. Braga, J. L. de Macedo, J. A. Dias, and S. C. Dias. 2012. “Structural Effects of WO3 Incorporation on USY Zeolite and Application to Free Fatty Acids Esterification.” Microporous and Mesoporous Materials 147 (1): 142–48.10.1016/j.micromeso.2011.06.008Search in Google Scholar
Fan, P., S. Xing, J. Wang, J. Fu, L. Yang, G. Yang, and P. Lv. 2017. “Sulfonated Imidazolium Ionic Liquid-Catalyzed Transesterification for Biodiesel Synthesis.” Fuel 188: 483–88.10.1016/j.fuel.2016.10.068Search in Google Scholar
Fan, X., F. Chen, and X. Wang. 2010. “Ultrasound-Assisted Synthesis of Biodiesel from Crude Cottonseed Oil Using Response Surface Methodology.” Journal of Oleo Science 59 (5): 235–41.10.5650/jos.59.235Search in Google Scholar PubMed
Fang, D., J. Yang, and C. Jiao. 2011. “Dicationic Ionic Liquids as Environmentally Benign Catalysts for Biodiesel Synthesis.” Acs Catalysis 1 (1): 42–47.10.1021/cs100026qSearch in Google Scholar
Fauzi, A. H. M., and N. A. S. Amin. 2013. “Optimization of Oleic Acid Esterification Catalyzed by Ionic Liquid for Green Biodiesel Synthesis.” Energy Conversion and Management 76: 818–27.10.1016/j.enconman.2013.08.029Search in Google Scholar
Fauzi, A. H. M., N. A. S. Amin, and R. Mat. 2014. “Esterification of Oleic Acid to Biodiesel Using Magnetic Ionic Liquid: Multi-Objective Optimization and Kinetic Study.” Apply Energy 114: 809–18.10.1016/j.apenergy.2013.10.011Search in Google Scholar
Han, B., W. Zhang, Y. Chen, F. Yin, S. Liu, X. Zhao, and H. Yang. 2014. “Synthesis of Methyl Laurate Catalyzed by Brønsted Acid Ionic Liquids.” Journal of Chemical and Pharmaceutical Research 6: 435–40.Search in Google Scholar
Han, M., W. Yi, Q. Wu, Y. Liu, Y. Hong, and D. Wang. 2009. “Preparation of Biodiesel from Waste Oils Catalyzed by a Brønsted Acidic Ionic Liquid.” Bioresource Technology 100 (7): 2308–10.10.1016/j.biortech.2008.10.046Search in Google Scholar
Han, X., K. Chen, H. Du, X. J. Tang, C. T. Hung, K. C. Lin, and S. B. Liu. 2016. “Novel Keggin-Type H4PVMo11O40-based Ionic Liquid Catalysts for N-Caprylic Acid Esterification.” Journal of the Taiwan Institute of Chemical Engineers 58: 203–09.10.1016/j.jtice.2015.07.005Search in Google Scholar
Han, X. X., Y. F. He, C. T. Hung, L. L. Liu, S. J. Huang, and S. B. Liu. 2013. “Efficient and Reusable Polyoxometalate-Based Sulfonated Ionic Liquid Catalysts for Palmitic Acid Esterification to Biodiesel.” Chemical Engineering Science 104: 64–72.10.1016/j.ces.2013.08.059Search in Google Scholar
He, Q., Y. Xu, Y. Teng, and D. Wang. 2008. “Biodiesel Production Catalyzed by Whole-Cell Lipase from Rhizopus Chinensis.” Chinese Journal of Catalysis 29 (1): 41–46.10.1016/S1872-2067(08)60015-7Search in Google Scholar
Huang, B., Y. Wang, K. Zhang, Y. Fang, and B. Zhou. 2007. “Synthesis of Pyrrolidonium Acidic Ionic Liquids and Their Catalytic Activity for Esterification of Acetic Acid and Butanol.” Chinese Journal of Catalysis 28 (8): 743–48.Search in Google Scholar
Karimi, B., and M. Vafaeezadeh. 2012. “SBA-15-functionalized Sulfonic Acid Confined Acidic Ionic Liquid: A Powerful and Water-Tolerant Catalyst for Solvent-Free Esterifications.” Chemical Communications 48 (27): 3327–29.10.1039/c2cc17702aSearch in Google Scholar
Li, Y., S. Hu, J. Cheng, and W. Lou. 2014. “Acidic Ionic Liquid-Catalyzed Esterification of Oleic Acid for Biodiesel Synthesis.” Chinese Journal of Catalysis 35 (3): 396–406.10.1016/S1872-2067(14)60005-XSearch in Google Scholar
Liu, W., P. Yin, X. Liu, S. Zhang, and R. Qu. 2015. “Biodiesel Production from the Esterification of Fatty Acid over Organophosphonic Acid.” Journal of Industrial and Engineering Chemistry 21: 893–99.10.1016/j.jiec.2014.04.029Search in Google Scholar
Liu, Y., Y. T. Wang, T. Liu, and D. J. Tao. 2014. “Facile Synthesis of Fructone from Ethyl Acetoacetate and Ethylene Glycol Catalyzed by SO3H-functionalized Brønsted Acidic Ionic Liquids.” RSC Advances 4 (43): 22520–25.10.1039/c4ra01708kSearch in Google Scholar
Lokman, I. M., U. Rashid, Z. Zainal, R. Yunus, and Y. H. Taufiq-Yap. 2014. “Microwave-Assisted Biodiesel Production by Esterification of Palm Fatty Acid Distillate.” Journal of Oleo Science 63 (9): 849–55.10.5650/jos.ess14068Search in Google Scholar PubMed
Lourinho, G., and P. Brito. 2015. “Advanced Biodiesel Production Technologies: Novel Developments.” Reviews in Environmental Science and Bio/Technology 14 (2): 287–316.10.1007/s11157-014-9359-xSearch in Google Scholar
Meng, L, and Z. Tian. 2011. “Synthesis of Methyllaurate over SO42-/SnO2-SiO2 as Catalyst.” Chemical Industry Times 25: 17–19.Search in Google Scholar
Meziant, L., Y. Benchikh, and H. Louaileche. 2014. “Deployment of Response Surface Methodology to Optimize Recovery of Dark Fresh Fig (Ficus Carica L., Var. Azenjar) Total Phenolic Compounds and Antioxidant Activity.” Food Chemistry 162: 277–82.10.1016/j.foodchem.2014.04.054Search in Google Scholar PubMed
Muhammad, N., Y. A. Elsheikh, M. I. A. Mutalib, A. A. Bazmi, R. A. Khan, H. Khan, and Z. Man. 2015. “An Overview of the Role of Ionic Liquids in Biodiesel Reactions.” Journal of Industrial and Engineering Chemistry 21: 1–10.10.1016/j.jiec.2014.01.046Search in Google Scholar
Olkiewicz, M., N. V. Plechkova, M. J. Earle, A. Fabregat, F. Stüber, A. Fortuny, and C. Bengoa. 2016. “Biodiesel Production from Sewage Sludge Lipids Catalysed by Brønsted Acidic Ionic Liquids.” Applied Catalysis B: Environmental 181: 738–46.10.1016/j.apcatb.2015.08.039Search in Google Scholar
Ramachandran, K., T. Suganya, N. N. Gandhi, and S. Renganathan. 2013. “Recent Developments for Biodiesel Production by Ultrasonic Assist Transesterification Using Different Heterogeneous Catalyst: A Review.” Renewable and Sustainable Energy Reviews 22: 410–18.10.1016/j.rser.2013.01.057Search in Google Scholar
Saravanan, K., B. Tyagi, and H. C. Bajaj. 2012. “Esterification of Caprylic Acid with Alcohol over Nano-Crystalline Sulfated Zirconia.” Journal of Sol-Gel Science and Technology 62 (1): 13–17.10.1007/s10971-011-2671-9Search in Google Scholar
Souza, B. S., D. M. Pinho, E. C. Leopoldino, P. A. Suarez, and F. Nome. 2012. “Selective Partial Biodiesel Hydrogenation Using Highly Active Supported Palladium Nanoparticles in Imidazolium-Based Ionic Liquid.” Applied Catalysis A: General 433: 109–14.10.1016/j.apcata.2012.05.006Search in Google Scholar
Suhendra, D., E. R. Gunawan, A. D. Nurita, D. Komalasari, and T. Ardianto. 2017. “Optimization of the Enzymatic Synthesis of Biodiesel from Terminalia Cattapa L. Kernel Oil Using Response Surface Methodology.” Journal of Oleo Science 66 (3): 209–15.10.5650/jos.ess16167Search in Google Scholar PubMed
Sun, S., and X. Li. 2016. “Functional Ionic Liquids Catalyzed the Esterification of Ricinoleic Acid with Methanol to Prepare Biodiesel: Optimization by Response Surface Methodology.” Journal of the American Oil Chemists' Society 93 (6): 757–64.10.1007/s11746-016-2826-5Search in Google Scholar
Talebian-Kiakalaieh, A., N. A. S. Amin, A. Zarei, and I. Noshadi. 2013. “Transesterification of Waste Cooking Oil by Heteropoly Acid (HPA) Catalyst: Optimization and Kinetic Model.” Applied Energy 102: 283–92.10.1016/j.apenergy.2012.07.018Search in Google Scholar
Tao, D. J., Y. Dong, Z. J. Cao, F. F. Chen, X. S. Chen, and K. Huang. 2016. “Tuning the Acidity of Sulfonic Functionalized Ionic Liquids for Highly Efficient and Selective Synthesis of Terpene Esters.” Journal of Industrial and Engineering Chemistry 41: 122–29.10.1016/j.jiec.2016.07.014Search in Google Scholar
Tao, D. J., Z. M. Li, Z. Cheng, N. Hu, and X. S. Chen. 2012. “Kinetics Study of the Ketalization Reaction of Cyclohexanone with Glycol Using Brønsted Acidic Ionic Liquids as Catalysts.” Industrial & Engineering Chemistry Research 51 (50): 16263–69.10.1021/ie302089sSearch in Google Scholar
Trinh, H., S. Yusup, and Y. Uemura. 2018. “Optimization and Kinetic Study of Ultrasonic Assisted Esterification Process from Rubber Seed Oil.” Bioresource Technology 247: 51–57.10.1016/j.biortech.2017.09.075Search in Google Scholar PubMed
Ullah, Z., M. A. Bustam, and Z. Man. 2015. “Biodiesel Production from Waste Cooking Oil by Acidic Ionic Liquid as a Catalyst.” Renewable Energy 77: 521–26.10.1016/j.renene.2014.12.040Search in Google Scholar
Vitiello, R., C. Li, V. Russo, R. Tesser, R. Turco, and M. Di Serio. 2017. “Catalysis for Esterification Reactions: A Key Step in the Biodiesel Production from Waste Oils.” Rendiconti Lincei 28 (1): 117–23.10.1007/s12210-016-0570-2Search in Google Scholar
Welton, T. 1999. “Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis.” Chemical Reviews 99 (8): 2071–84.10.1021/cr980032tSearch in Google Scholar PubMed
Zhang, H., F. Xu, X. Zhou, G. Zhang, and C. Wang. 2007. “A Brønsted Acidic Ionic Liquid as an Efficient and Reusable Catalyst System for Esterification.” Green Chemistry 9 (11): 1208–11.10.1039/b705480gSearch in Google Scholar
Zhang, L., M. Xian, Y. He, L. Li, J. Yang, S. Yu, and X. Xu. 2009. “A Brønsted Acidic Ionic Liquid as an Efficient and Environmentally Benign Catalyst for Biodiesel Synthesis from Free Fatty Acids and Alcohols.” Bioresource Technology 100 (19): 4368–73.10.1016/j.biortech.2009.04.012Search in Google Scholar PubMed
Zhao, H., and G. A. Baker. 2013. “Ionic Liquids and Deep Eutectic Solvents for Biodiesel Synthesis: A Review.” Journal of Chemical Technology & Biotechnology 88 (1): 3–12.10.1002/jctb.3935Search in Google Scholar
Zhao, Y., J. Long, F. Deng, X. Liu, Z. Li, C. Xia, and J. Peng. 2009. “Catalytic Amounts of Brønsted Acidic Ionic Liquids Promoted Esterification: Study of Acidity-Activity Relationship.” Catalysis Communications 10 (5): 732–36.10.1016/j.catcom.2008.11.030Search in Google Scholar
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Articles in the same Issue
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- A Study on the Role of Clostridium Saccharoperbutylacetonicum N1-4 (ATCC 13564) in Producing Fermentative Hydrogen
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- Immobilization of Fructofuranosidase from Aureobasidium sp. Onto TiO2 and Its Encapsulation on Gellan Gum for FOS Production
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