Sunflower oil methanolysis over modified CaO catalysts Original scientific paper
Article Sidebar
Main Article Content
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 %).
Article Details
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Authors who publish with this journal agree to the following terms:Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
Authors grant to the Publisher the following rights to the manuscript, including any supplemental material, and any parts, extracts or elements thereof:
- the right to reproduce and distribute the Manuscript in printed form, including print-on-demand;
- the right to produce prepublications, reprints, and special editions of the Manuscript;
- the right to translate the Manuscript into other languages;
- the right to reproduce the Manuscript using photomechanical or similar means including, but not limited to photocopy, and the right to distribute these reproductions;
- the right to reproduce and distribute the Manuscript electronically or optically on any and all data carriers or storage media – especially in machine readable/digitalized form on data carriers such as hard drive, CD-Rom, DVD, Blu-ray Disc (BD), Mini-Disk, data tape – and the right to reproduce and distribute the Article via these data carriers;
- the right to store the Manuscript in databases, including online databases, and the right of transmission of the Manuscript in all technical systems and modes;
- the right to make the Manuscript available to the public or to closed user groups on individual demand, for use on monitors or other readers (including e-books), and in printable form for the user, either via the internet, other online services, or via internal or external networks.
How to Cite
Funding data
-
Ministarstvo Prosvete, Nauke i Tehnološkog Razvoja
Grant numbers 451-03-68/2022-14/200383;451-03-68/2022-14/200133.
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 CaOZnO. 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