Co-production of biodiesel and methacrylated fatty acid through enzymatic catalysis with methyl methacrylate as acyl acceptor

doi:10.1016/j.cjche.2025.05.008

摘要/Abstract

摘要： Traditional biodiesel production primarily uses methanol as the acyl acceptor, but its toxicity to lipase increases process complexity and operational difficulty elevate manufacturing costs. This study aimed to explore a new method for enzymatic synthesis of biodiesel with methyl methacrylate (MMA) as acyl acceptor. Meanwhile, a 1, 3-position specific lipase Lipozyme RM IM was applied as biocatalyst, which enables simultaneous production of biodiesel (FAMEs) and methacrylate fatty acid glycerides (MFAGs) via specific sn-1, 3 transesterification of MMA with triglyceride. Under the optimal reaction conditions: temperature of 50 ℃, molar ratio of 4:1 for MMA to triglyceride, enzyme dosage of 7.5% (mass), and an extra water addition of 0.5% (mass); triglyceride conversion rate of 97%, and FAMEs yield of 65% could be obtained. Simultaneously, the multistage short-path distillation and column chromatographic method were combined used for the separation of the mixed products. Finally, the purity of FAME, MFADG, DMFAG, and MMFAG were 98%, 97.8%, 95.3%, and 81.78%, respectively. In this new approach, MMA demonstrates lower toxicity to lipases, allowing for straightforward addition of all the substrates without complex addition process, and enhancing operational feasibility. Meanwhile, the by-products of MFAGs could be applied as monomers in varnishes and protective coatings, which increased the value of the products. Thus, this investigation providing an alternative way to produce biodiesel, and providing a new pathway for the sustainable development of biodiesel.

关键词: Biodiesel, Methacrylated fatty acid, Transesterification, Enzymatic catalysis, Short-path distillation, Co-production

Abstract: Traditional biodiesel production primarily uses methanol as the acyl acceptor, but its toxicity to lipase increases process complexity and operational difficulty elevate manufacturing costs. This study aimed to explore a new method for enzymatic synthesis of biodiesel with methyl methacrylate (MMA) as acyl acceptor. Meanwhile, a 1, 3-position specific lipase Lipozyme RM IM was applied as biocatalyst, which enables simultaneous production of biodiesel (FAMEs) and methacrylate fatty acid glycerides (MFAGs) via specific sn-1, 3 transesterification of MMA with triglyceride. Under the optimal reaction conditions: temperature of 50 ℃, molar ratio of 4:1 for MMA to triglyceride, enzyme dosage of 7.5% (mass), and an extra water addition of 0.5% (mass); triglyceride conversion rate of 97%, and FAMEs yield of 65% could be obtained. Simultaneously, the multistage short-path distillation and column chromatographic method were combined used for the separation of the mixed products. Finally, the purity of FAME, MFADG, DMFAG, and MMFAG were 98%, 97.8%, 95.3%, and 81.78%, respectively. In this new approach, MMA demonstrates lower toxicity to lipases, allowing for straightforward addition of all the substrates without complex addition process, and enhancing operational feasibility. Meanwhile, the by-products of MFAGs could be applied as monomers in varnishes and protective coatings, which increased the value of the products. Thus, this investigation providing an alternative way to produce biodiesel, and providing a new pathway for the sustainable development of biodiesel.

Key words: Biodiesel, Methacrylated fatty acid, Transesterification, Enzymatic catalysis, Short-path distillation, Co-production

Dong Lu, Shuming Jin, Qiuyang Wu, Jiahao Liu, Fang Wang, Li Deng, Kaili Nie. Co-production of biodiesel and methacrylated fatty acid through enzymatic catalysis with methyl methacrylate as acyl acceptor[J]. 中国化学工程学报, 2025, 85(9): 16-24.

参考文献

[1] I. Edeh, Biodiesel production as a renewable resource for the potential displacement of the petroleum diesel, Biorefinery Concepts, Energy and Products, IntechOpen 2020.
[2] A. Oumer, M. Hasan, A.T. Baheta, R. Mamat, A. Abdullah, Bio-based liquid fuels as a source of renewable energy: a review, Renew. Sustain. Energy Rev. 88 (2018) 82-98.
[3] A.A. Babadi, S. Rahmati, R. Fakhlaei, B. Barati, S. Wang, W. Doherty, K.K. Ostrikov, Emerging technologies for biodiesel production: processes, challenges, and opportunities, Biomass Bioenergy 163 (2022) 106521.
[4] A. Baena, A. Orjuela, S.K. Rakshit, J.H. Clark, Enzymatic hydrolysis of waste fats, oils and greases (FOGs): status, prospective, and process intensification alternatives, Chem. Eng. Process. Process Intensif. 175 (2022) 108930.
[5] D.G. Filho, A.G. Silva, C.Z. Guidini, Lipases: sources, immobilization methods, and industrial applications, Appl. Microbiol. Biotechnol. 103 (2019) 7399-7423.
[6] M. Mohtashami, J. Fooladi, A. Haddad-Mashadrizeh, M.R. Housaindokht, H. Monhemi, Molecular mechanism of enzyme tolerance against organic solvents: insights from molecular dynamics simulation, Int. J. Biol. Macromol. 122 (2019) 914-923.
[7] V. Stepankova, S. Bidmanova, T. Koudelakova, Z. Prokop, R. Chaloupkova, J. Damborsky, Strategies for stabilization of enzymes in organic solvents, ACS Catal. 3(12) (2013) 2823-2836.
[8] A.L. Serdakowski, J.S. Dordick, Enzyme activation for organic solvents made easy, Trends Biotechnol. 26(1) (2008) 48-54.
[9] J.H. Yoon, D. Mckenzie, A comparison of the activities of three β-galactosidases in aqueous-organic solvent mixtures, Enzym. Microb. Technol. 36(4) (2005) 439-446.
[10] U. Rashid, F. Anwar, B.R. Moser, S. Ashraf, Production of sunflower oil methyl esters by optimized alkali-catalyzed methanolysis, Biomass Bioenergy 32(12) (2008) 1202-1205.
[11] Z. Helwani, M. Othman, N. Aziz, J. Kim, d.W. Fernando, Solid heterogeneous catalysts for transesterification of triglycerides with methanol: a review, Appl. Catal. Gen. 363(1-2) (2009) 1-10.
[12] C. Santambrogio, F. Sasso, A. Natalello, S. Brocca, R. Grandori, S.M. Doglia, M. Lotti, Effects of methanol on a methanol-tolerant bacterial lipase, Appl. Microbiol. Biotechnol. 97 (2013) 8609-8618.
[13] K. Nie, F. Xie, F. Wang, T. Tan, Lipase catalyzed methanolysis to produce biodiesel: optimization of the biodiesel production, J. Mol. Catal. B Enzym. 43(1-4) (2006) 142-147.
[14] F. Al Basir, P.K. Roy, Study on enzyme inhibition in biodiesel synthesis: effect of stepwise addition of methanol and removal of glycerol, Energy, Ecol. Environ. 4(2) (2019) 75-84.
[15] M. Lotti, J. Pleiss, F. Valero, P.J.B.j. Ferrer, Effects of methanol on lipases: molecular, kinetic and process issues in the production of biodiesel, Biotechnol. J. 10(1) (2015) 22-30.
[16] M. Lotti, J. Pleiss, F. Valero, P.J.B.j. Ferrer, Enzymatic production of biodiesel: strategies to overcome methanol inactivation, Biotechnol. J. 13(5) (2018) 1700155.
[17] L. Brondani, J. Ribeiro, F.J.R.e. Castilhos, A New Kinetic Model for Simultaneous Interesterification and Esterification Reactions from Methyl Acetate and Highly Acidic Oil, vol. 156 (2020) 579-590.
[18] V. Makareviciene, K. Kazancev, E. Sendzikiene, M. Gumbyte, Application of simultaneous rapeseed oil extraction and interesterification with methyl formate using enzymatic catalyst, Renew. Energy 227 (2024) 120475.
[19] S. Chuepeng, C. Komintarachat, Interesterification optimization of waste cooking oil and ethyl acetate over homogeneous catalyst for biofuel production with engine validation, Appl. Energy 232 (2018) 728-739.
[20] D.-T. Tran, J.-S. Chang, D.-J.J.A.E. Lee, Recent insights into continuous-flow biodiesel production via catalytic and non-catalytic transesterification Processes, 185 (2017) 376-409.
[21] I.C. Costa, I. Itabaiana Jr, M.C. Flores, A.C. Lourenco, S.G. Leite, L.S. de M. e Miranda, I.C. Leal, R.O. de Souza, Biocatalyzed acetins production under continuous-flow conditions: valorization of glycerol derived from biodiesel industry, Journal of Flow Chemistry 3(2) (2013) 41-45.
[22] C.-H.C. Zhou, J.N. Beltramini, Y.-X. Fan, G.M. Lu, Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals, Chem. Soc. Rev. 37(3) (2008) 527-549.
[23] P. Mukhopadhyay, R. Chakraborty, S. Singh, Triacetin additive in biodiesel to reduce air pollution: a review, Environ. Chem. Lett. 20(2) (2022) 1193-1224.
[24] A.O. Esan, A.D. Adeyemi, S. Ganesan, A review on the recent application of dimethyl carbonate in sustainable biodiesel production, J. Clean. Prod. 257 (2020) 120561.
[25] M. Sponchioni, S. Altinok, Poly (methyl methacrylate): market trends and recycling, Adv. Chem. Eng., Elsevier 2022, pp. 269-287.
[26] M.J.D. Mahboub, J.-L. Dubois, F. Cavani, M. Rostamizadeh, G.S. Patience, Catalysis for the synthesis of methacrylic acid and methyl methacrylate, Chem. Soc. Rev. 47(20) (2018) 7703-7738.
[27] T. Akbas, U. Beker, F. Guner, A. Erciyes, Y. Yagci, Drying and semidrying oil macromonomers. III. Styrenation of sunflower and linseed oils, J. Appl. Polym. Sci. 88(10) (2003) 2373-2376.
[28] G. Capiel, E. Hernandez, N.E. Marcovich, M.A. Mosiewicki, Stress relaxation behavior of weldable crosslinked polymers based on methacrylated oleic and lauric acids, Eur. Polym. J. 132 (2020) 109740.
[29] A. Campanella, M. Zhan, P. Watt, A.T. Grous, C. Shen, R.P. Wool, Triglyceride-based thermosetting resins with different reactive diluents and fiber reinforced composite applications, Composites Part A: Applied Science Manufacturing 72 (2015) 192-199.
[30] J.J. La Scala, J.A. Orlicki, R. Jain, C.A. Ulven, G.R. Palmese, U.K. Vaidya, J.M. Sands, Emission modeling of styrene from vinyl ester resins with low hazardous air pollutant contents, Clean Technol. Environ. Policy 11 (2009) 283-292.
[31] G. Capiel, N.E. Marcovich, M.A. Mosiewicki, From the synthesis and characterization of methacrylated fatty acid based precursors to shape memory polymers, Polym. Int. 68(3) (2019) 546-554.
[32] G. Capiel, N.E. Marcovich, M.A. Mosiewicki, Shape memory polymer networks based on methacrylated fatty acids, Eur. Polym. J. 116 (2019) 321-329.
[33] J.J. La Scala, J.M. Sands, J.A. Orlicki, E.J. Robinette, G.R. Palmese, Fatty acid-based monomers as styrene replacements for liquid molding resins, Polymer 45(22) (2004) 7729-7737.
[34] Y. Lv, S. Sun, J.J.A.o. Liu, Biodiesel production catalyzed by a methanol-tolerant lipase A from Candida Antarctica in the presence of excess water, ACS Omega 4(22) (2019) 20064-20071.
[35] T. Tan, K. Nie, F. Wang, Production of biodiesel by immobilized Candida sp. lipase at high water content, Appl. Biochem. Biotechnol. 128 (2006) 109-116.
[36] X.-G. Gaoa, S.-G. Cao, K.-C. Zhang, Production, properties and application to nonaqueous enzymatic catalysis of lipase from a newly isolated Pseudomonas strain, Enzym. Microb. Technol. 27(1-2) (2000) 74-82.
[37] M. Noel, D. Combes, Effects of temperature and pressure on Rhizomucor miehei lipase stability, J. Biotechnol. 102(1) (2003) 23-32.
[38] D.M. Cetina, G.I. Giraldo, C.E. Orrego, Application of response surface design to solvent, temperature and lipase selection for optimal monoglyceride production, J. Mol. Catal. B Enzym. 72(1-2) (2011) 13-19.
[39] M.M. Soumanou, M. Perignon, P. Villeneuve, Lipase-catalyzed interesterification reactions for human milk fat substitutes production: a review, Eur. J. Lipid Sci. Technol. 115(3) (2013) 270-285.
[40] M. Hajar, S. Shokrollahzadeh, F. Vahabzadeh, A. Monazzami, Solvent-free methanolysis of canola oil in a packed-bed reactor with use of Novozym 435 plus loofa, Enzym. Microb. Technol. 45(3) (2009) 188-194.
[41] N. Dizge, B. Keskinler, A. Tanriseven, Biodiesel production from canola oil by using lipase immobilized onto hydrophobic microporous styrene-divinylbenzene copolymer, Biochem. Eng. J. 44(2-3) (2009) 220-225.
[42] S.-M. Jung, Y.-C. Park, K. Park, Effects of environmental conditions and methanol feeding strategy on lipase-mediated biodiesel production using soybean oil, Biotechnol. Bioproc. Eng. 15 (2010) 614-619.
[43] R.C. Rodrigues, B.C. Pessela, G. Volpato, R. Fernandez-Lafuente, J.M. Guisan, M.A. Ayub, Two step ethanolysis: a simple and efficient way to improve the enzymatic biodiesel synthesis catalyzed by an immobilized-stabilized lipase from Thermomyces lanuginosus, Process Biochem. 45(8) (2010) 1268-1273.