Thermodynamic Modeling of Liquid-Liquid Equilibrium in Ternary Systems with Biodiesel and Isolated Ester (Methyl Palmitate)

Year 2022, Volume: 25 Issue: 4, 56 - 65, 01.12.2022

Jessyca Bezerra , Maria Rosiane De Alemeida Andrade , Edyjancleide Rodrigues Silva , Lindemberg De Jesus Nogueira Duarte , Gilson Gomes Medeiros , Eduardo Lins De Barros Neto

https://doi.org/10.5541/ijot.1136615

Cited By: 4

Abstract

Liquid-liquid equilibrium data were measured and analyzed for two ternary systems (biodiesel + methanol + glycerol and methyl palmitate + methanol + glycerol). Biodiesel, produced by the conventional chemical route at 60 °C for 60 min, using methanol and soybean oil at a molar rate of 10:1 and potassium hydroxide concentration (KOH) of 1 wt% exhibited thermal decomposition at temperatures between 100 and 250 ºC, reaching mass loss of approximately 98.8%, confirming soybean oil conversion into biodiesel by gas chromatography and thermogravimetry. Tie line composition quality was verified using Othmer-Tobias and Hand correlation equations. The distribution and selectivity coefficients were calculated for the immiscibility regions. The experimental tie line data exhibited good correlation in the UNIQUAC and NRTL thermodynamic models. The biodiesel system displayed deviations of 0.66 and 0.53% for the UNIQUAC and NRTL models, respectively. In addition, the methyl palmitate system showed a 1.23 and 0.48% deviation for the UNIQUAC and NRTL model, respectively. The individual behavior of the main biodiesel esters , based on the UNIQUAC model parameters, demonstrated that the type of fatty acid does not interfere in model correlation, likely due to the similarity between their composition and properties.

Keywords

Liquid-liquid equilibrium;, Metyl Palmitate;, Biodiesel;, UNIQUAC;, NRTL;, Otmer-Tobias correlation;

References

• T. Güney, "Renewable energy, non-renewable energy and sustainable development," Int. J. Sustain. Dev. World Ecol., 26, 389–397, 2019, https://doi.org/10.1080/13504509.2019.1595214.
• P. Mukhopadhyay, R. Chakraborty, "LCA of sustainable biodiesel production from fried Borassus flabellifer oil in energy-proficient reactors: Impact assessment of multi fuel-additives on pour point, NOx and engine performance," Sustain. Energy Technol. Assessments., 44, 100994, 2021, https://doi.org/10.1016/j.seta.2021.100994.
• J.A. Okolie, A. Mukherjee, S. Nanda, A.K. Dalai, J.A. Kozinski, "Next-generation biofuels and platform biochemicals from lignocellulosic biomass," Int. J. Energy Res., 45, 14145–14169, 2021, https://doi.org/10.1002/er.6697.
• M. Viccaro, D. Caniani, S. Masi, S. Romano, M. Cozzi, "Biofuels or not biofuels? The “Nexus Thinking” in land suitability analysis for energy crops," Renew. Energy., 187, 1050–1064, 2022, https://doi.org/10.1016/j.renene.2022.02.008.
• F. Fangfang, A. Alagumalai, O. Mahian, "Sustainable biodiesel production from waste cooking oil: ANN modeling and environmental factor assessment," Sustain. Energy Technol. Assessments., 46, 101265, 2021, https://doi.org/10.1016/j.seta.2021.101265.
• M.M. Hasan, M.M. Rahman, "Performance and emission characteristics of biodiesel–diesel blend and environmental and economic impacts of biodiesel production: A review," Renew. Sustain. Energy Rev., 74, 938–948, 2017, https://doi.org/10.1016/j.rser.2017.03.045.
• A. Asoodeh, F. Eslami, S.M. Sadrameli, "Liquid–liquid equilibria of systems containing linseed oil biodiesel + methanol + glycerol: Experimental data and thermodynamic modeling," Fuel., 253, 460–473, 2019, https://doi.org/10.1016/j.fuel.2019.04.170.
• M. Hashemzadeh Gargari, S.M. Sadrameli, "Investigating continuous biodiesel production from linseed oil in the presence of a Co-solvent and a heterogeneous based catalyst in a packed bed reactor," Energy., 148, 888–895, 2018, https://doi.org/10.1016/j.energy.2018.01.105.
• J.C. Ge, S.K. Yoon, "Combustion and Emission Characteristics of a Diesel Engine Fueled with Crude Palm Oil Blends at Various Idling Speeds," Applied Sciences, 12(13), 6294, 2022.
• S.M. Rasulov, I.M. Abdulagatov, "PVT, saturated liquid density and vapor-pressure measurements of main components of the biofuels at high temperatures and high pressures: Methyl palmitate," Fuel., 218, 282–294, 2018, https://doi.org/10.1016/j.fuel.2018.01.039.
• F. Yang, M.A. Hanna, R. Sun, "Value-added uses for crude glycerol - A byproduct of biodiesel production," Biotechnol. Biofuels., 5, 1–10, 2012, https://doi.org/10.1186/1754-6834-5-1322413907.
• T. Zhang, C. Liu, Y. Gu, F. Jérôme, "Glycerol in energy transportation: A state-of-the-art review," Green Chem., 23, 7865–7889, 2021, https://doi.org/10.1039/d1gc02597j.
• Y. Wang, Y. Muhammad, S. Yu, T. Fu, K. Liu, Z. Tong, X. Hu, H. Zhang, "Preparation of Ca-and Na-Modified Activated Clay as a Promising Heterogeneous Catalyst for Biodiesel Production via Transesterification," Appl. Sci., 12, 2022, https://doi.org/10.3390/app12094667.
• C.S. Osorio-González, N. Gómez-Falcon, F. Sandoval-Salas, R. Saini, S.K. Brar, A.A. Ramírez, "Production of biodiesel from castor oil: A review," Energies., 13, 1–22, 2020, https://doi.org/10.3390/en13102467.
• D.S. Negi, F. Sobotka, T. Kimmel, R. Schoma, "Liquid - Liquid Phase Equilibrium in Glycerol - Methanol - Methyl Oleate and Glycerol - Monoolein - Methyl Oleate Ternary Systems," Ind. Eng. Chem. Res., 3693–3696, 2006.
• I.E.P. Toledo, L. Ferreira-Pinto, F.A.P. Voll, L. Cardozo-Filho, L. Meili, D.D.G. Coêlho, S.H.V. De Carvalho, J.I. Soletti, "Liquid-Liquid Equilibrium of the System {Peanut Biodiesel + Glycerol + Ethanol} at Atmospheric Pressure," J. Chem. Eng. Data., 64, 2207–2212, 2019, https://doi.org/10.1021/acs.jced.8b01185.
• J.R.F. Silva, M.A. Mazutti, F.A.P. Voll, L. Cardozo-Filho, M.L. Corazza, M. Lanza, W.L. Priamo, J. Vladimir Oliveira, "Thermophysical properties of biodiesel and related systems: (Liquid + liquid) equilibrium data for Jatropha curcas biodiesel," J. Chem. Thermodyn., 58, 467–475, 2013, https://doi.org/10.1016/j.jct.2012.10.006.
• T. Wannachod, M. Hronec, T. Soták, K. Fulajtárová, U. Pancharoen, A. Arpornwichanop, "Effects of salt on the LLE and tie-line data for furfuryl alcohol - N-butanol-water at T = 298.15 K," J. Mol. Liq., 218, 50–58, 2016, https://doi.org/10.1016/j.molliq.2016.02.027.
• M. Maghami, J. Yousefi Seyf, S.M. Sadrameli, A. Haghtalab, "Liquid-liquid phase equilibrium in ternary mixture of waste fish oil biodiesel-methanol-glycerol: Experimental data and thermodynamic modeling," Fluid Phase Equilib., 409, 124–130, 2016, https://doi.org/10.1016/j.fluid.2015.09.046.
• J.C. Nunes, J.J.P. Nascimento, A.S. Peiter, L. Ferreira-Pinto, J.I. Soletti, S.H.V. De Carvalho, J.J.N. Alves, A.C.B. De Araujo, "Experimental Data and Phase Equilibrium Modeling in Ternary and Pseudoquaternary Systems of Sunflower Oil for Biodiesel Production," J. Chem. Eng. Data., 64, 412–420, 2019, https://doi.org/10.1021/acs.jced.8b00276.
• B. Bazooyar, F. Shaahmadi, M.A. Anbaz, A. Jomekian, "Intelligent modelling and analysis of biodiesel/alcohol/glycerol liquid-liquid equilibria," J. Mol. Liq., 322, 114972, 2021, https://doi.org/10.1016/j.molliq.2020.114972.
• M.A. Noriega, P.C. Narváez, "UNIFAC correlated parameters for liquid-liquid equilibrium prediction of ternary systems related to biodiesel production process," Fuel., 249, 365–378, 2019, https://doi.org/10.1016/j.fuel.2019.03.124.
• L.A. Follegatti-Romero, M.B. Oliveira, F.R.M. Batista, E.A.C. Batista, J.A.P. Coutinho, A.J.A. Meirelles, "Liquid-liquid equilibria for ternary systems containing ethyl esters, ethanol and glycerol at 323.15 and 353.15 K," Fuel., 94, 386–394, 2012, https://doi.org/10.1016/j.fuel.2011.09.020.
• M. Toikka, P. Kuzmenko, A. Samarov, M. Trofimova, "Phase behavior of the oleic acid – methanol – methyl oleate – water mixture as a promising model system for biodiesel production: Brief data review and new results at 303.15 K and atmospheric pressure," Fuel., 319, 2022, https://doi.org/10.1016/j.fuel.2022.123730.
• R.N. Cavalcanti, M.B. Oliveira, A.J.A. Meirelles, "Liquid-liquid equilibria for systems containing fatty acid ethyl esters, ethanol and glycerol at 333.15 and 343.15 K: Experimental data, thermodynamic and artificial neural network modeling," Brazilian J. Chem. Eng., 35, 819–834, 2018, https://doi.org/10.1590/0104-6632.20180352s20160267.
• D.F. Othmer, E. Tobias, "Tie Line Correlation," Industrial and Engineering Chemistry, 34, 6, 1942, https://doi.org/https://doi-org.ez18.periodicos.capes.gov.br/10.1021/ie50390a600.
• D.B. Hand, Dineric distribution, 1930, https://doi.org/https://doi.org/10.1021/j150315a009.
• M.R. de Almeida Andrade, C.B. Silva, T.K.O. Costa, E.L. de Barros Neto, J.M. Lavoie, "An experimental investigation on the effect of surfactant for the transesterification of soybean oil over eggshell-derived CaO catalysts", Energy Convers. Manag. X., 11, 2021, https://doi.org/10.1016/j.ecmx.2021.100094.
• A.A. Evangelista Neto, J.C.C. Sobrinho, H.N.M. Oliveira, H.F.S. Freitas, F.F.M. Silva, E.L. Barros Neto, "Liquid-Liquid Equilibrium Data for the Pseudo-Ternary Biodiesel of Chicken Fat + Methanol + Glycerol," Brazilian J. Pet. Gas., 12, 123–133, 2018, https://doi.org/10.5419/bjpg2018-0012.
• C.. Sena, S.R.C; Pereira, "Melon Seed Oil Utilization for Biodiesel Production and Analysis of Liquid-Liquid Equilibrium for the System Biodiesel+Methanol+Glycerin," Environ. Prog. Sustain. Energy., 33, 676–680, 2014, https://doi.org/10.1002/ep.
• L. Stragevitch, Equilíbrio Líquido-Líquido de Misturas de Não Eletrólitos, 1997.
• B.E. Reid, Robert C.; Prausnitz, John M.; Poling, The Properties of Gases and Liquids, 4th ed., New York, 1987.
• L.M.S. Freire, T.C. Bicudo, R. Rosenhaim, F.S.M. Sinfrônio, J.R. Botelho, J.R. Carvalho Filho, I.M.G. Santos, V.J. Fernandes, N.R. Antoniosi Filho, A.G. Souza, "Thermal investigation of oil and biodiesel from jatropha curcas L.," J. Therm. Anal. Calorim., 96, 1029–1033, 2009, https://doi.org/10.1007/s10973-009-0055-y.
• V. Kumbhar, A. Pandey, C.R. Sonawane, A.S. El-Shafay, H. Panchal, A.J. Chamkha, "Statistical analysis on prediction of biodiesel properties from its fatty acid composition," Case Stud. Therm. Eng., 30, 2022, https://doi.org/10.1016/j.csite.2022.101775.
• A. Alcántara-Carmona, F.J. López-Giménez, M.P. Dorado, "Compatibility studies between an indirect injection diesel injector and biodiesel with different composition: Stationary tests," Fuel., 307, 2022, https://doi.org/10.1016/j.fuel.2021.121788.
• A. Ghanadzadeh Gilani, A. Najafgholizadeh, B. Mohammadi khanghah, M. Nasouri Gazani, "Experimental and correlational study of phase equilibria in aqueous solutions of phosphoric acid with alcohols at different temperatures," J. Mol. Liq., 268, 553–560, 2018, https://doi.org/10.1016/j.molliq.2018.06.115.
• J.C.G. Filho, F.B. Bispo, M.L. Corazza, P.F. Arce, F.A.P. Voll, D. De Gusmão Coêlho, L. Ferreira-Pinto, S.H.V. De Carvalho, J.I. Soletti, "Liquid-Liquid Equilibrium Measurement and Thermodynamic Modeling of the { Sterculia striata Biodiesel + Glycerol + Ethanol} System," J. Chem. Eng. Data., 66, 3293–3299, 2021, https://doi.org/10.1021/acs.jced.1c00341.
• Y. Jiang, S. Lin, H. Yan, H. Guo, Q. Li, "Liquid-liquid equilibrium data measurement and thermodynamic modelling for ternary mixtures composed of water, diethylene glycol dimethyl ether and different solvents at 298.2 K," J. Chem. Thermodyn., 165, 0–7, 2020, https://doi.org/10.1016/j.jct.2021.106669.
• A.L. Esipovich, A.E. Rogozhin, A.S. Belousov, E.A. Kanakov, K. V. Otopkova, S.M. Danov, "Liquid–liquid equilibrium in the systems FAMEs + vegetable oil + methyl alcohol and FAMEs + glycerol + methyl alcohol," Fuel., 217, 31–37, 2018, https://doi.org/10.1016/j.fuel.2017.12.083.
• A. Ghanadzadeh Gilani, J. Jahanbin sardroodi, F. Verpoort, S. Rahmdel, "Experimental study and thermodynamic modeling of phase equilibria of systems containing cyclohexane, alcohols (C4 and C5), and deep eutectic solvents," J. Mol. Liq., 340, 2021, https://doi.org/10.1016/j.molliq.2021.117196.
• X. Meng, X. Liu, J. Gao, D. Xu, L. Zhang, Y. Wang, "Liquid-Liquid Equilibrium of Isobutyl Acetate + Isobutyl Alcohol + Imidazolium-Based Ionic Liquids at 298.15 and 308.15 K," J. Chem. Eng. Data. 64, 778–783, 2019, https://doi.org/10.1021/acs.jced.8b01045.
• M.P. Cumplido, A. Cháfer, J.I. Guayazan-Jaimes, J. de la Torre, J.D. Badia, "Potential of phosphonium-based ionic liquids to purify 1-propanol from water by liquid–liquid extraction at mild conditions," J. Chem. Thermodyn., 165, 2022, https://doi.org/10.1016/j.jct.2021.106588.
• S. Shiozawa, D. Gonçalves, M.C. Ferreira, A.J.A. Meirelles, E.A.C. Batista, "Liquid-liquid equilibrium data and thermodynamic modeling of systems involved in the biodiesel production in terms of acylglycerols, free fatty acids, ethyl esters, and ethanol at 303.2 and 318.2 K and local pressure," Fluid Phase Equilib., 507 112431, 2020, https://doi.org/10.1016/j.fluid.2019.112431.
• H. Liu, B. Jia, W. Sun, S. Dong, "Measurement and Thermodynamic Modeling of Ternary (Liquid + Liquid) Equilibrium for Extraction of 2-Methyl-3-buten-2-ol from Aqueous Solution with Different Solvents," J. Chem. Eng. Data., 65, 5030–5036, 2020, https://doi.org/10.1021/acs.jced.0c00667.
• H. Shekaari, M.T. Zafarani-Moattar, B. Mohammadi, "Effective extraction of benzene and thiophene by novel deep eutectic solvents from hexane / aromatic mixture at different temperatures," Fluid Phase Equilib., 484, 38–52, 2019, https://doi.org/10.1016/j.fluid.2018.11.025.
• K.R.B. De Melo, G.C. Lopes, D.D.G. Coêlho, J.I. Soletti, "Liquid-liquid equilibrium for systems composed by biodiesel from catolé oil (Syagrus cearensis), methanol and glycerol," Chem. Ind. Chem. Eng. Q., 26, 21–29, 2020, https://doi.org/10.2298/CICEQ190508021B.
• H.S. Mousavi, M. Rahimi, M. Mohadesi, "Experimental Investigation and Thermodynamic Modeling of Glycerin/Methanol/Organic Solvent Systems," Chem. Eng. Technol., 42, 628–636, 2019, https://doi.org/10.1002/ceat.201800356.
• L.R. Kanda, F.A.P. Voll, M.L. Corazza, "LLE for the systems ethyl palmitate (palmitic acid)(1)+ethanol(2)+glycerol (water)(3)," Fluid Phase Equilib. 354, 147–155, 2013, https://doi.org/10.1016/j.fluid.2013.06.027.
• E.G.D.A. Rocha, L.A. Follegatti-Romero, S. Duvoisin, M. Aznar, "Liquid-liquid equilibria for ternary systems containing ethylic palm oil biodiesel + ethanol + glycerol/water: Experimental data at 298.15 and 323.15 K and thermodynamic modeling," Fuel., 128, 356–365, 2014, https://doi.org/10.1016/j.fuel.2014.01.074.
• F.R. Do Carmo, N.S. Evangelista, R.S. De Santiago-Aguiar, F.A.N. Fernandes, H.B. De Sant’Ana, "Evaluation of optimal activity coefficient models for modeling and simulation of liquid-liquid equilibrium of biodiesel + glycerol + alcohol systems," Fuel. 125, 57–65, 2014, https://doi.org/10.1016/j.fuel.2014.01.108.
• M.J. Lee, Y.C. Lo, H.M. Lin, "Liquid-liquid equilibria for mixtures containing water, methanol, fatty acid methyl esters, and glycerol," Fluid Phase Equilib., 299 180–190, 2010, https://doi.org/10.1016/j.fluid.2010.10.010.
• M. Mohadesi, "Liquid-Liquid Equilibrium for Ternary Systems Containing Biodiesel + Glycerol + Alcohol ( Ethanol or Methanol ): Thermodynamic Modeling," Journal of Chemical and Petroleum Engineering, 54, 285–295, 2020, https://doi.org/10.22059/jchpe.20 20.299983.1309.