Statistical Analysis of Enzymatic Reaction Parameters for Biolubricant Synthesis via Response Surface Methodology (RSM)

Document Type : Research Article


Kocaeli University, Chemical Engineering Department, Kocaeli, TURKEY


Recently, the synthesis of biolubricants has been the focus of researchers because of their good lubricating properties and environmentally friendly products. This study was performed to optimize reaction parameters for the enzymatic transesterification reaction between waste edible oil methyl ester (biodiesel, FAME) and trimethylolpropane (TMP) by using Response Surface Methodology (RSM). The parameters that affect the enzymatic transesterification reaction were chosen as temperature (35–55°C), amount of catalyst (0–10 %wt. of mixture), TMP-to-FAME molar ratio (0.17-0.33), and reaction time (0–96 h), to produce TMP triester (biolubricant). Response surface methodology (RSM) and three-level–four-factor Central Composite Design (CCD) were employed to evaluate the effects of these synthesis parameters on the percentage conversion of FAME by transesterification. Enzyme amount and reaction time were the most important variables. The optimum reaction conditions were determined to be the temperature at 50°C; the amount of catalyst, 5%wt; molar ratio, 0.25 and 48 h of reaction time, under these conditions 91% TMP ester's yield was obtained. The interaction parameter of the lipase quantity with the FAME to TMP molar ratio was found to be the most important among all of the other parameters.


Main Subjects

[1] Unugul T., Kutluk T., Kutluk B.G., Kapucu N., Environmentally Friendly Processes from Coffee Wastes to Trimethylolpropane Esters to be Considered Biolubricants, J. Air & Waste Man. Assoc., 70(11): 1198-1215 (2020).
[2] Salimon J., Salih N., Yousif E., Review article-Biolubricants: Raw Materials, Chemical Modifications, and Environmental Benefits, E. J. of Lipid Sci. Tech., 112(5): 519-530 (2010).
[3]  Gunam-Resul M.F.M., Ghazi T.I.M., Idris, A., Kinetic Study of Jatropha Biolubricant from Transesterification of Jatropha Curcas Oil with Trimethylolpropane: Effects of Temperature, In. Crops and Prod., 38: 87-92 (2021).
[4] Nagendramma P., Kaul S., Development of eco-Friendly/Biodegradable Lubricants: An Overview, Ren. and Sus. En. Rev.,16 (1): 764-774 (2012).
[5] Samidin S., Salihn., Salimon J., Synthesis And Characterization Of Trimethylolpropane Based Esters As Green Biolubricant Basestock, Bio. Res. in App. Chem., 11(5): 13638-13651 (2021).
[6] Appiah G., Tulashie S.K., Akpari E.E.A., Rene E.R., Dodoo D., Biolubricant Production via Esterification and Transesterification Processes: Current Updates
and Perspectives
, Int. J. En. Res.,46(4): 1-31. (2021).
[7]  Hájek M., Vávra A., de Paz Carmona H., Kocík J., The Catalysed Transformation of Vegetable Oils or Animal Fats to Biofuels and Biolubricants: A Review, Catalysts,11(9): 1118-1128 (2021).
[8] Kibar, M.E., Akin A.N., Optimization of Carbon Dioxide Capture Process Parameters in Sodium Metaborate SolutionIran. J. Chem. Chem. Eng. (IJCCE), 40(5): 1554-1565(2021).
[9] Kutluk T., Kutluk B.G., Lipase Catalysis: an Environmentally Friendly Production for Polyol Esters (Biolubricant) from Microalgae Oil, Environ. Tech.,
1-24 (2022).
[10] Aziz N.A.M, Yunus R, Rashid U., Syam A.M., Application of Response Surface Methodology (RSM) for Optimizing the Palm-Based Pentaerythritol Ester Synthesis, Ind. Crops and Prod.,62: 305-312 (2014).
[12] Somidi Asish K.R., Das U., Dalai Ajay K., One-pot Synthesis of Canola Oil-Based Biolubricants Catalyzed by MoO3/Al2O3 and Process Optimization Study, Chem. Eng. J., 293: 293-272 (2016).
[13] Somidi Asish, K.R., Roayapalley P.K., Dalai A.K., Synthesis of O-propylated Canola Oil Derivatives Using Al-SBA-15 Catalyst and Study on Their Application as a Fuel Additive, Cat. Today, 291: 204-212 (2017).
[15] Wang E., Ma X., Tang Z., Yan R., Wang Y., Riley W.W., Reaney M. J. T., Synthesis and Oxidative Stability of Trimethylolpropane Fatty Acid Triester as a Biolubricant Base Oil from Waste Cooking Oil, Biomass Bioeng., 66: 371-378 (2014).
[16] Chowdhury A., Mitra D., Biswas D., Biolubricant Synthesis from Waste Cooking Oil via Enzymatic Hydrolysis Followed by Chemical Esterification,
J. Chem. Technol. Biotechnol., 88(1): 139-144 (2013).
[18] Chowdhury A., Mitra D., Biswas D., Synthesis of Biolubricant Components from Waste Cooking Oil Using a Biocatalytic Route, Env. Prog. Sustain., 33(3): 933-940 (2014).
[19] de Lima R., Bento H.B.S., Reis C.E.R. Boas R.N.V., de Feriatas L., Carvalho A.K.F., de Castro H.F.,  Biolubricant Production from Stearic Acid and Residual Secondary Alcohols: System and Reaction Design for Lipase-Catalyzed Batch and Continuous Processes, Catal. Lett.,152: 547–558 (2022)
[21] Almasi S., Ghobadian B., Najafi G., Soufi M.D., A Novel Approach for Biolubricant Production from Rapeseed Oil-Based Biodiesel using Ultrasound Irradiation: Multi-Objective Optimization, Sus. Eng. Tech. Ass.,43: 100960 (2021).
[22] Bolina I.C.A., Gomes R.A.B., Mendes A.A., Biolubricant Production from Several Oleaginous Feedstocks Using Lipases as Catalysts: Current Scenario and Future Perspectives, BioEng. Res.,14: 1039–1057 (2021).
[23] Linko Y.Y., Tervakangas T., Lämsä M., Linko P., Production of Trimethylolpropane Esters of Rapeseed Oil Fatty Acids by Immobilized Lipase, Biotech. Tech., 11: 889–892 (1997).
[24] Uosukainen E., Linko Y.Y., Lämsä M., Tervakangas T., Linko P., Transesterification of Trimethylolpropane and Rapeseed Oil Methyl Ester to Environmentally Acceptable Lubricants, J. Am. Oil Chem. Soc., 75: 1557–1563 (1998).
[26] Greco-Duarte J., Oliveira E.D.C., Da Silva J.A.C., Lafuente R.F., Freire D.M.G., Two-Step Enzymatic Production of Environmentally Friendly Biolubricants Using Castor Oil: Enzyme Selection and Product Characterization, Fuel, 202: 196–205 (2017).
[27] Cerón A. A., Boas R. N. V., Biaggio C. F., Castro H. F., Synthesis of Biolubricant by Transesterification of Palm Kernel Oil with Simulated Fusel Oil: Batch and Continuous Processes, Bio. and Bioen., 119: 166–172 (2018).
[28] Zhang W., Ji H., Song Y., Ma S., Xiong W., Chen C., Chen B., Zhang X., Green Preparation of Branched Biolubricant by Chemically Modifying Waste Cooking Oil with Lipase and Ionic Liquid, J. Clean.Prod., 274: 122918 (2020).
[30] Angulo B., Fraile J.M., Gil L., Herrerías C.I., Comparison of Chemical and Enzymatic Methods for the Transesterification of Waste Fish Oil Fatty Ethyl Esters with Different Alcohols, ACS Om., 5 (3): 1479-1487 (2020).
[31] Aguieiras E.C.G., Cavalcanti E.D.C., Silva P.R., Soares V.F., Lafuente R.F., Assunçao C. L. B., Silva J.A.C., Freire D.M.G., Enzymatic Synthesis of Neopentyl Glycol-Bases Biolubricants Using Biodiesel from Soybean and Castor Bean as Raw Materials, Ren. Eng., 148: 689-696 (2020).
[33] Cavalcanti E.D.C., Aguieiras E.C.G., Silva P.R., Duarte J.G., Cipolatti E.P., Lafuente R.F.,  Silva J.A.C., Freire D. M.G., Improved Production Of Biolubricants from Soybean Oil and Different Polyols via Esterification Reaction Catalyzed by Immobilized Lipase from Candida Rugosa, Fuel,  215: 705–713 (2018).