Sunflower oil methanolysis over modified CaO catalysts Original scientific paper

Main Article Content

Marija Miladinović
https://orcid.org/0000-0001-5922-3151
Milica Z. Petković
https://orcid.org/0000-0002-1565-0298
Ivana B. Banković-Ilić
https://orcid.org/0000-0002-6304-7960
Sandra S. Konstantinović
https://orcid.org/0000-0002-3761-823X
Vlada B. Veljković
https://orcid.org/0000-0002-1671-2892

Abstract

Oil methanolysis over modified CaO catalysts was studied to assess the catalytic perfor­mance and to define an appropriate kinetic model. CaO was modified by commercial glycerol and a deep eutectic solvent (DES), choline chloride : glycerol (ChCl : Gly), to obtain cataly­tically active complexes of CaO and glycerol. The main goal was to investigate the effect of the obtained complexes on the reaction rate and fatty acid methyl ester (FAME) content and to describe the variation of the triacylglycerol (TAG) conversion degree during the reaction time. Fourier transform infrared spectroscopy (FTIR) was applied to confirm the formation of CaO complexes with glycerol or the glycerol-based DES. Different catalyst loadings (0.5, 1, and 5 % of oil weight) and methanol-to-oil molar ratios (6 : 1 and 12 : 1) were applied for inves­tigation of the sunflower oil methanolysis at 60 oC. Two kinetic models were employed yield­ing the kinetic parameters, which depended on the catalyst loading and the methanol-to-oil molar ratio. Both models showed valid applicability for describing the kinetics of the re­acti­ons catalyzed by both complexes (the mean relative percent deviation was lower than 10 %).

Downloads

Download data is not yet available.

Article Details

How to Cite
Miladinović, M. R., Petković, M. Z., Banković-Ilić, I. B., Konstantinović, S. S., & Veljković, V. . B. (2022). Sunflower oil methanolysis over modified CaO catalysts: Original scientific paper. HEMIJSKA INDUSTRIJA, 76(2), 75–85. https://doi.org/10.2298/HEMIND211125009M
Section
Chemical Engineering - General
Author Biographies

Milica Z. Petković, Tehnološki fakultet, Univerzitet u Nišu, Bulevar Oslobodjenja 124, 16000, Leskovac, Srbija

Ph.D. student

Ivana B. Banković-Ilić, Tehnološki fakultet, Univerzitet u Nišu, Bulevar Oslobodjenja 124, 16000, Leskovac, Srbija

Full professor

Sandra S. Konstantinović, Tehnološki fakultet, Univerzitet u Nišu, Bulevar Oslobodjenja 124, 16000, Leskovac, Srbija

Full professor

Funding data

References

Boocock DGB, Konar SK, Mao V, Sidi H, Fast one-phase oil-rich processes for the preparation of vegetable oil methyl esters. Biomass Bioenerg. 1996; 11: 43-50. https://doi.org/10.1016/0961-9534(95)00111-5

Sakthivel S, Halder S, Gupta PD, Influence of Co-Solvent on the Production of Biodiesel in Batch and Continuous Process. Int J Green Energy 2013; 10: 876-884. https://doi.org/10.1080/15435075.2012.727365

Zhao H, Baker GA, Ionic liquids and deep eutectic solvents for biodiesel synthesis: a review. J Chem Technol Biotechnol. 2013; 88: 3-12. https://doi.org/10.1002/jctb.3935

Todorović ZB, Stamenković OS, Stamenković IS, Avramović JM, Veličković AV, Banković-Ilić IB, Veljković VB, The effects of cosolvents on homogeneously and heterogeneously base-catalyzed methanolysis of sunflower oil. Fuel 2013; 107: 493-502. https://doi.org/10.1016/j.fuel.2012.11.049

Banković-Ilić IB, Todorović ZB, Avramović JM, Veličković AV, Veljković VB, The effect of tetrahydrofuran on the base-catalyzed sunflower oil methanolysis in a continuous reciprocating plate reactor. Fuel Process Technol. 2015;,137:,339-350. https://doi.org/10.1016/j.fuproc.2015.03.023

Huang W, Tang S, Zhao H, Tian S, Activation of Commercial CaO for Biodiesel Production from Rapeseed Oil Using a Novel Deep Eutectic Solvent. Ind Eng Chem Res. 2013; 52: 11943−47. https://doi.org/10.1021/ie401292w

Banković-Ilić IB, Miladinović MR, Stamenković OS, Veljković VB, Application of nano CaO-based catalysts in biodiesel synthesis. Renew Sustain Energy Rev. 2017; 72: 746-760. http://dx.doi.org/10.1016/j.rser.2017.01.076

Marinković DM, Stanković MV, Veličković AV, Avramović JM, Miladinović MR, Stamenković OS, Veljković VB, Jovanović DM, Calcium oxide as a promising heterogeneous catalyst for biodiesel production: Current state and perspectives. Renew Sustain Energy Rev. 2016; 56: 1387–408. https://doi.org/10.1016/j.rser.2015.12.007

Kouzu M, Kasuno T, Tajika M, Yamanaka S, Hidaka J, Active phase of calcium oxide used as solid base catalyst for transesterification of soybean oil with refluxing methanol. Appl Catal A Gen. 2008; 334: 357–65. https://doi.org/10.1016/j.apcata.2007.10.023

Kouzu M, Hidaka JS, Wakabayashi K, Tsunomori M, Solid base catalysis of calcium glyceroxide for a reaction to convert vegetable oil into its methyl esters. Appl Catal A Gen. 2010; 390: 11–8. https://doi.org/10.1016/j.apcata.2010.09.029

Esipovich A, Danov S, Belousov A, Rogozhin A, Improving methods of CaO transesterification activity. J Mol Catal A Chem. 2014; 395: 225–233. http://dx.doi.org/10.1016/j.molcata.2014.08.011

Ranjan A, Dawn SS, Nirmala N, Santhosh A, Arun J, Application of deep eutectic solvent in biodiesel reaction: RSM optimization, CI engine test, cost analysis and research dynamics. Fuel. 2022; 307: 121933. https://doi.org/10.1016/j.fuel.2021.121933

Troter DZ, Todorović ZB, Đokić-Stojanović DR, Stamenković OS, Veljković VB, Application of ionic liquids and deep eutectic solvents in biodiesel production: A review. Renew Sustain Energy Rev. 2016; 61: 473–500. https://doi.org/10.1016/j.rser.2016.04.011

Gu L, Huang W, Tang S, Tian S, Zhang X, A novel deep eutectic solvent for biodiesel preparation using a homogeneous base catalyst. Chem Eng J. 2015; 259:647–52. https://doi.org/10.1016/j.cej.2014.08.026

Manurung R, Ramadhani DR, Maisarah S, One step transesterification process of sludge palm oil (SPO) by using deep eutectic solvent (DES) in biodiesel production. AIP Conf Proceed. 2017a; 1855: 070004. https://doi.org/10.1063/1.4985531

Manurung R, Winarta A, Taslim, IL, Biodiesel production from ethanolysis of palm oil using deep eutectic solvent (DES) as co-solvent. Mater Sci Eng. 2017b; 206: 012023. https://doi.org/10.1088/1757-899X/206/1/012023

Troter DZ, Todorović ZB, Đokić-Stojanović DR, VeselinovićLjM, Zdujić MV, Veljković VB, Choline chloride-based deep eutectic solvents in CaO-catalyzed ethanolysis of expired sunflower oil. J Mol Liq. 2018; 266: 557-67. https://doi.org/10.1016/j.molliq.2018.06.106

León-Reina L, Cabeza A, Maireles-Torres JRP, Alba-Rubio AC, Granados ML, Structural and surface study of calcium glyceroxide, an active phase for biodiesel production under heterogeneous catalysis. J Catal. 2013; 300: 30–36. https://doi.org/10.1016/j.jcat.2012.12.016

Sánchez-Cantú M, Reyes-Cruz FM, Rubio-Rosas E, Pérez-Díaz LM, Ramírez E, Valente JS, Direct synthesis of calcium diglyceroxide from hydrated lime and glycerol and its evaluation in the transesterification reaction. Fuel 2014; 138: 126–133. https://doi.org/10.1016/j.fuel.2014.08.006

Reyero I, Arzamendi G, Gandía LM, Heterogenization of the biodiesel synthesis catalysis: CaO and novel calcium compounds as transesterification catalysts. Chem Eng Res Des 2014; 92: 1519–30. https://doi.org/10.1016/j.cherd.2013.11.017

Ferrero GO, Almeida MF, Alvim-Ferraz MCM, Dias JM, Glycerol-enriched heterogeneous catalyst for biodiesel production from soybean oil and waste frying oil. Energy Convers Manag. 2015; 89:665–71. http://dx.doi.org/10.1016/j.enconman.2014.10.032

Lukić I, Kesić Ž, Zdujić M, Skala D, Calcium diglyceroxide synthesized by mechanochemical treatment, its characterization and application as catalyst for fatty acid methyl esters production. Fuel 2016; 165: 159–65. http://dx.doi.org/10.1016/j.fuel.2015.10.063

Miladinović MR, Krstić JB, Tasić MB, Stamenković OS, Velјković VB, А kinetic study of quicklime-catalyzed sunflower oil methanolysis. Chem Eng Res Des. 2014; 92: 1740-52. https://doi.org/10.1016/j.cherd.2013.11.023

Miladinović MR, Stamenković OS, Veljković VB, Skala UD, Continuous sunflower oil methanolysis over quicklime in a packed-bed tubular reactor. Fuel 2015;.154:.301-307. https://doi.org/10.1016/j.fuel.2015.03.057

Lukić I, Kesić Ž, Maksimović S, Zdujić M, Liu H, Krstić J, Skala D, Kinetics of sunflower and used vegetable oil methanolysis catalyzed by CaOZnO. Fuel 2013; 113: 367–78. https://doi.org/10.1016/j.fuel.2013.05.093

Chen X, Li Z, Chun Y, Yang F, Xu H, Wu X, Effect of the formation of diglycerides/monoglycerides on the kinetic curve in oil transesterification with methanol catalyzed by calcium oxide. ACS Omega. 2020; 5: 4646−4656. https://doi.org/10.1021/acsomega.9b04431

Miladinović MR, Tasić MB, Stamenković OS, Veljković VB, Skala DU, Further study on kinetic modeling of sunflower oil methanolysis catalyzed by calcium-based catalysts. Chem Ind Chem Eng Q. 2016; 22: 137−144 https://doi.org/10.2298/CICEQ150618027M

Tasić MB, Miladinović MR, Stamenković OS, Veljković VB, Skala DU, Kinetic modeling of sunflower oil methanolysis catalyzed by calcium-based catalysts. Chem EngTechol. 2015; 38(9): 1550-56. https://doi.org/10.1002/ceat.201500076

Most read articles by the same author(s)