Triethanolamine as an efficient cosolvent for biodiesel production by CaO-catalyzed sunflower oil ethanolysis: An optimization study

Dušica R. Đokić-Stojanović, Zoran B. Todorović, Dragan Z. Troter, Olivera S. Stamenković, Ljiljana M. Veselinović, Miodrag V. Zdujić, Dragan D. Manojlović, Vlada B. Veljković

Abstract


Triethanolamine was applied as an efficient „green“ cosolvent for biodiesel production by CaO-catalyzed ethanolysis of sunflower oil. The reaction was conducted in a batch stirred reactor and optimized with respect to the reaction temperature (61.6-78.4 °C), the ethanol-to-oil molar ratio (7:1-17:1) and the cosolvent loading (3-36 % of the oil weight) by using a rotatable central composite design (RCCD) combined with the response surface methodology (RSM). The optimal reaction conditions were found to be: the ethanol-to-oil molar ratio of 9:1, the reaction temperature of 75 °C and the cosolvent loading of 30 % to oil weight, which resulted in the predicted and actual fatty acid ethyl ester (FAEE) contents of 98.8 % and 97.9±1.3 %, respectively, achieved within only 20 min of the reaction. Also, high FAEE contents were obtained with expired sunflower oil, hempseed oil and waste lard. X-ray diffraction analysis (XRD) was used to understand the changes in the CaO phase. The CaO catalyst can be used without any treatment in two consecutive cycles. Due to the calcium leaching into the product, an additional purification stage must be included in the overall process.


Keywords


biodiesel; heterogeneous catalysis; transesterification; XRD

References


Veljković VB, Veličković AV, Avramović JM, Stamenković OS. Modeling of biodiesel production: Performance comparison of Box–Behnken, face central composite and full factorial design. Chin J Chem Eng. 2019; 27: 1690–1698.

Stamenković OS, Veličković AV, Veljković VB. The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives. Fuel. 2011; 90: 3141–3155.

Li Q, Xu J, Du W, Li Y, Liu D. Ethanol as the acyl acceptor for biodiesel production. Renew Sustain Energy Rev. 2013; 25: 742–748.

Betiku E, Okeleye AA, Ishola NB, Osunleke AS, Ojumu TV. Development of a novel mesoporous biocatalyst derived from kola nut pod husk for conversion of Kariya seed oil to methyl esters: A case of synthesis, modeling and optimization studies. Catal Lett. 2019; 149: 1772–1787.

Chingakham C, Tiwary C, Sajith V. Waste animal bone as a novel layered heterogeneous catalyst for the transesterification of biodiesel. Catal Lett. 2019; 149: 1100–1110.

Kesić Ž, Lukić I, Zdujić M, Mojović Lj, Skala D. Calcium oxide based catalysts for biodiesel production: A review. Chem Ind Chem Eng Q. 2016; 22: 391−408.

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: 1387−1408.

Troter DZ, Todorović ZB, Đokić-Stojanović DR, Veselinović LjM, Zdujić MV, Veljković VB. Choline chloride-based deep eutectic solvents in CaO-catalyzed ethanolysis of expired sunflower oil. J Mol Liq. 2018; 266: 557−567.

Chueluecha N, Kaewchada A, Jaree A. Enhancement of biodiesel synthesis using co-solvent in a packed-microchannel. J Ind Eng Chem. 2017; 51: 162–171.

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.

Kouzu M, Fujimori A, Suzuki T, Koshi K, Moriyasu H. Industrial feasibility of powdery CaO catalyst for production of biodiesel. Fuel Process Technol. 2017; 165: 94–101.

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.

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.

Trentin CM, Lima AP, Alkimim IP, da Silva C, de Castilhos F, Mazutti MA, Oliveira JV. Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor using carbon dioxide as co-solvent. Fuel Process Technol. 2011; 92: 952–958.

Kang K-H, Lee D-K. Synthesis of magnesium oxysulfate whiskers using triethanolamine as a morphology control agent. J Ind Eng Chem. 2014; 20: 2580–2583.

Kumar A, Kumar P, Aathira MS, Singh DP, Behera B, Jain SL. A bridged ruthenium dimer (Ru–Ru) for photoreduction of CO2 under visible light irradiation. J Ind Eng Chem. 2018; 61: 381–387.

Ying A, Li Z, Ni Y, Xu S, Hou H, Hu H. Novel multiple-acidic ionic liquids: Green and efficient catalysts for the synthesis of bis-indolylmethanes under solvent-free conditions. J Ind Eng Chem. 2015; 24: 127–131.

AOCS. Official and tentative methods. Chicago, USA: American Oil Chemistsʼ Society; 1980.

Veličković AV, Avramović JM, Stamenković OS, Veljković VB. Kinetics of the sunflower oil ethanolysis using CaO as catalyst. Chem Ind Chem Eng Q. 2016; 22: 409−418.

Veličković AV, Stamenković OS, Todorović ZB, Veljković VB. Application of the full factorial design to optimization of base-catalyzed sunflower oil ethanolysis. Fuel. 2013; 104: 433–442.

http://cran.us.r-project.org

López Granados M, Martín Alonso D, Alba-Rubio AC, Mariscal R, Ojeda M, Brettes P. Transesterification of triglycerides by CaO: Increase of the reaction rate by biodiesel addition. Energy Fuel. 2009; 23: 2259–2263.

Avramović J, Veličković A, Stamenković O, Rajković K, Milić P, Veljković V. Optimization of sunflower oil ethanolysis catalyzed by calcium oxide: RSM versus ANN-GA. Energy Convers Manage. 2015; 105: 1149−1156.

Đokić-Stojanović DR, Todorović ZB, Troter DZ, Stamenković OS, Veselinović LjM, Zdujić MV, Manojlović DD, Veljković VB. Influence of various cosolvents on the calcium oxide-catalyzed ethanolysis of sunflower oil. J Serb Chem Soc. 2019; 84: 253–265.

Todorović ZB, Troter DZ, Đokić-Stojanović DR, Veličković AV, Avramović JM, Stamenković OS, Veselinović LjM, Veljković VB. Optimization of CaO-catalyzed sunflower oil methanolysis with crude biodiesel as a cosolvent. Fuel. 2019; 237: 903–910.

Lam MK, Lee KT. Accelerating transesterification reaction with biodiesel as cosolvent: A case study for solid acid sulfated tin oxide catalyst. Fuel. 2010; 89: 3866–3870.

Shu Q, Zhang Q, Xu G, Nawaz Z, Wang D, Wang J. Synthesis of biodiesel from cottonseed oil and methanol using a carbon-based solid acid catalyst. Fuel Process Technol. 2009; 90: 1002–1008.

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: 357–365.

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.

Roschat W, Siritanon T, Kaewpuang T, Yoosuk B, Promarak V. Economical and green biodiesel production process using river snail shells-derived heterogeneous catalyst and co-solvent method. Bioresour Technol. 2016; 209: 343−350.

Kostić MD, Bazargan A, Stamenković OS, Veljković VB, McKay G. Optimization and kinetics of sunflower oil methanolysis catalyzed by calcium oxide-based catalyst derived from palm kernel shell biochar. Fuel. 2016; 163: 304–313.




DOI: https://doi.org/10.2298/HEMIND190822033D

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