Catalyst-free production of fatty acid ethyl esters (FAEE) from macauba pulp oil




Acrocomia aculeate, Catalyst-free, Continuous, Ethanol


In this study, the production of fatty acid ethyl esters (FAEE) from macauba pulp oil and pressurized ethanol was investigated. The experiments were conducted without the addition of catalyst, at 20 MPa, to determine the effect of temperature (200 to 300 °C) and the oil to ethanol mass ratio (1:1 and 1:2) on the FAEE content and different residence times (10 to 45 min). The effect of the addition of n-hexane to the oil (20 wt%) as a co-solvent was also evaluated. The use of high temperatures (275 and 300 °C) resulted in high FAEE content (∼90%). Increasing the amount of ethanol in the reaction medium contributed to the formation of esters only at operating temperatures of 200 to 250 °C. It was also observed that with the addition of co-solvent (in the oil) it was possible to obtain high amounts of FAEE in a shorter reaction time. In addition, a low content of unreacted compounds (∼8.0%) and the conversion of ∼90 and 99% of the free fatty acids and triglycerides were observed, respectively.


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Abbaszaadeh A, Ghobadian B, Omidkhah MR, Najafi G. 2012. Current biodiesel production technologies : A comparative review. Energ. Convers. and Manage. 63, 138-148.

Abdala ACDA, Colonelli TADS, Trentini CP, Oliveira JV, Cardozo-Filho L, Silva EA, Silva C. 2014a. Effect of additives in the reaction medium on noncatalytic ester production from used frying oil with supercritical ethanol. Ener. Fuels 283122-3128.

Abdala AC, Garcia VA, Trentini CP, Cardozo- Filho L, Silva EA, Silva C. 2014b. Continuous Catalyst-Free Esterification of Oleic Acid in Compressed Ethanol. Int. J. Chem. Eng. 2014, 1-5.

Akkarawatkhoosith N, Kaewchada A, Jaree A. 2019a. Enhancement of continuous supercritical biodiesel production : influence of co-solvent types. Enrgy Proced. 156, 48-52.

Akkarawatkhoosith N, Kaewchada A, Jaree A. 2019b. Production of Biodiesel from Palm Oil under Supercritical Ethanol in the Presence of Ethyl Acetate. Energ. Fuel 33, 5322-5331. research-article.

Akkarawatkhoosith N, Kaewchada A, Jaree A. 2019c. Simultaneous development of biodiesel synthesis and fuel quality via continuous supercritical process with reactive co-solvent. Fuel 237, 117-125.

American Oil Chemists’ Society. Standard Methods for the Analysis of Oils, Fats and Derivatives, International Union of Pure and Applied Chemistry Commission on Oils, Fats and Derivatives § (1990).

Bezerra FWF, Costa WA, Oliveira MS, Andrade HÁ, Carvalho JRN. 2018. Transesterification of palm pressed-fibers (Elaeis guineensis Jacq.) oil bysupercriticalfluid carbon dioxide with entrainer ethanol. J. Supercrit. Fluids 136, 136-143.

Colonelli TADS, Trentini CP, Santos KA, Oliveira JV, Cardozo-Filho L, Silva EA, Silva C. 2017. Assessment of process variables on the use of macauba pulp oil as feedstock for the continuous production of ethyl esters under pressurized conditions. Braz. J. Che. Eng. 34, 831-839.

Costa WA, Bezerra FWF, Oliveira MS, Andrade HA, Santos APM, Cunha VMB, Junior RN. 2019. Supercritical CO2 extraction and transesterification of the residual oil from

industrial palm kernel cake with supercritical methanol. J. Supercrit. Fluids, 147, 179-187.

Demirbas A. 2002. Biodiesel from vegetable oils via transesterification in supercritical methanol. Energ. Convers. and Manage. 43, 2349-2356.

Đokić-Stojanović1 DR, Todorović ZB, Troter DZ, Stamenković OS, Veselinović LM, Zdujić MV, Manojlović DD, Veljković VB. 2019. Influence of various co-solvents on the calcium oxide-catalyzed ethanolysis of sunflower oil. J. Serbian Chem. Soc. 84, 253-265.

Doná G, Cardozo-Filho L, Silva C, Castilhos F. 2013. Biodiesel production using supercritical methyl acetate in a tubular packed bed reactor. Fuel Process. Technol. 106, 605-610.

Evaristo AB, Grossi JAS, Pimentel LD, Goulart SDM, Martins AD, Santos VL, Motoike S. 2016. Harvest and post-harvest conditions influencing macauba (Acrocomia aculeata) oil quality attributes. Ind. Crops. Prod. 85, 63-73.

Farobie O, Matsumura Y. 2017. State of the art of biodiesel production under supercritical conditions. Prog. Energy. Combust. Sci. 63, 173-203.

Go AW, Sutanto S, NguyenThi BT, Cabatingan LK, Ismadji S, Ju Y. 2014. Transesterification of soybean oil with methanol and acetic acid at lower reaction severity under subcritical conditions. Energ. Convers. Manag. 88, 1159-1166.

Jesus AA, Souza DF, Oliveira JA, Deus MS, Silva MG, Franceschi E, Dariva C. 2018. Mathematical modeling and experimental esterification at supercritical conditions for biodiesel production in a tubular reactor. Energ. Convers. Manag. 171, 1697-1703.

Kusdiana D, Saka S. 2004. Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresour. Technol. 91, 289-295.

Lescano CH, Oliveira IP, Silva LR, Baldivia DS, Sanjinez-Argandonã, EJ, Arruda EJ, Lima FF. 2015. Nutrients content, characterization and oil extraction from Acrocomia aculeata (Jacq.) Lodd . fruits. Afr. J. Food Sci. 9, 113-119.

Lim S, Lee K. 2013. Influences of different cosolvents in simultaneous supercritical extraction and transesterification of Jatropha curcas L . seeds for the production of biodiesel. Chem. Eng. J. 221, 436-445.

Liu J, Nan Y, Huang X, Bond JQ, Tavlarides LL. 2018. Applied Catalysis B: Environmental Continuous esteri fi cation of oleic acid to ethyl oleate under sub / supercritical conditions over γ-Al2O3. Appl. Catal. B 232, 155-163.

Maçaira J, Santana A, Costa A, Ramirez E, Larrayoz MA. 2014. Process Intensification Using CO2 As Cosolvent under Supercritical Conditions Applied to the Design of Biodiesel Production. Ind. Eng. Chem. Res. 5 3, 3985-3995.

Mardhiah HH, Chyuan H, Masjuki HH, Lim S, Pang YL. 2017. Investigation of carbon-based solid acid catalyst from Jatropha curcas biomass in biodiesel production. Energ. Convers. and Manage. 144, 10-17.

Mello BTF, Gonçalves JE, Rodrigues GM, Cardozo-Filho L, Silva C. 2017. Hydroesterification of crambe oil (Crambe abyssinica H.) under pressurized conditions. Ind. Crops Prod. 97, 110-119.

Muppaneni T, Reddy HK, Ponnusamy S, Patil PD, Sun Y, Dailey P, Deng S. 2013. Optimization of biodiesel production from palm oil under supercritical ethanol conditions using hexane as co-solvent : A response surface methodology approach. Fuel 107, 633-640.

Musa IA. 2016. The effects of alcohol to oil molar ratios and the type of alcohol on biodiesel production using transesterification process. Egypt. J. Pet. 25, 21-31.

Nan Y, Liu J, Lin R, Tavlarides LL. 2015. Production of biodiesel from microalgae oil (Chlorella protothecoides) by non-catalytic transesterification in supercritical methanol and ethanol: Process optimization. J. Supercrit. Fluids 97, 174-182.

Nunes ÂA, Buccini DF, Jaques JAS, Portugal LC, Guimarães RCA, Favaro SP, Carvalho CME. 2018. Effect of Acrocomia aculeata Kernel Oil on Adiposity in Type 2 Diabetic Rats. Plant. Foods Hum. Nutr. 73, 61-67.

Ortiz-Martínez VM, Salar-García MJ, Palacios-Nereo FJ, Olivares-Carrillo P, Quesada-Medina J, Ríos APDL, Hernández-Fernández FJ. 2016. In-depth study of the transesterification reaction of Pongamia pinnata oil for biodiesel production using catalyst-free supercritical methanol process. J. Supercrit. Fluids 113, 23-30.

Osmieri L, Esfahani RAM, Recasens F. 2017. Continuous biodiesel production in supercritical two-step process: phase equilibrium and process design. J. Supercrit. Fluids 124, 57-71.

Patil PD, Deng S. 2009. Optimization of biodiesel production from edible and non-edible vegetable oils. Fuel 88, 1302-1306.

Pinnarat T, Savage PE. 2010. Noncatalytic esterification of oleic acid in ethanol. J. Supercrit. Fluids, 53, 53-59.

Postaue N, Trentini CP, Mello BTF, Cardozo- Filho L, Silva C. 2019. Continuous catalystfree interesterification of crambe oil using methyl acetate under pressurized conditions.

Energ. Convers. and Manage. 187, 398-406.

Santos KC, Hamerski F, Voll FAP, Corazza ML. 2018. Experimental and kinetic modeling of acid oil (trans)esterification in supercritical ethanol. Fuel 224, 489-498.

Santos PR, Pedersen FA, Ramos LP, Corazza ML. 2017. Esterification of fatty acids with supercritical ethanol in a continuous tubular reactor. J. Supercrit. Fluids 126, 25-36.

Sawangkeaw R, Bunyakiat K, Ngamprasertsith S. 2011. Continuous production of biodiesel with supercritical methanol : Optimization of a scale-up plug fl ow reactor by response surface methodology. Fuel Process. Technol. 92, 2285-2292.

Silva C, Castilhos F, Oliveira JV, Cardozo-Filho L, Trentin CM, Lima AP, Oliveira JV. 2010. Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor. Fuel Process. Technol. 91, 1274-1281.

Silva C, Colonelli TAS, Silva EA, Cabral VF, Oliveira JV, Cardozo-Filho L. 2014. Continuous catalyst-free production of esters from Jatropha curcas L. oil under supercritical ethanol. Braz. J. Chem. Eng. 31727-735.

Silva C, Oliveira JV. 2014. Biodiesel production through non-catalytic supercritical transesterification: Current state and perspectives. Braz. J. Chem. Eng. 31, 271-285.

Silva C, Weschenfelder T, Rovani S, Corazza FC, Corazza ML, Dariva C, Oliveira JV. 2007. Continuous Production of Fatty Acid Ethyl Esters from Soybean Oil in Compressed Ethanol. Ind. Eng. Chem. Res. 46, 5304-5309.

Soto G, Hegel P, Pereda S. 2014. Supercritical production and fractionation of fatty acid esters and acylglycerols. J. Supercrit. Fluids 93, 74-81.

Standard UNE-EN 14105. 2003. Determinación de los contenidos de glicerol libre y total y de mono-, di- y triglicéridos. Madrid, Spain. Srivastava G, Paul AK, Goud VV. 2018. Optimization of non-catalytic transesterification of microalgae oil to biodiesel under supercritical methanol condition. Energy. Conver. Manag. 156, 269-278.

Tobar M, Núñez GA. 2018. Supercritical transeterification of microalgae triglycerides for biodiesel production: Effect of alcohol type and co-solvent. J. Supercrit. Fluids 137, 50-56.

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

Trentini CP, Fonseca JM, Cardozo-Filho L, Reis R, Sampaio SC, Silva C. 2018. Assessment of continuous catalyst-free production of ethyl esters from grease trap waste. J. Supercrit. Fluids 136, 157-163.

Trentini CP, Postaue N, Cardozo-Filho L, Reis RR, Sampaio SC, Silva C. 2019. Production of esters from grease trap waste lipids under supercritical conditins: Effect of water addition on ethanol. J. Supercrit. Fluids 147, 16.

Vieitez I, Irigaray B, Casullo P, Pardo MJ, Grompone MA, Jachmanián I. 2012. Effect of free fatty acids on the efficiency of the supercritical ethanolysis of vegetable oils from different origins. Energy. and Fuels 26, 1946-1951.

Vieitez I, Silva C, Alckmin I, Borges GR, Corazza FC, Oliveira JV, Jachmanián, I. 2010. Continuous catalyst-free methanolysis and ethanolysis of soybean oil under supercritical

alcohol/water mixtures. Renew. Energ. 35, 1976-1981.

Visioli LJ, Castilhos F, Cardozo-Filho L, Mello BTF, Silva C. 2016. Production of esters from soybean oil deodorizer distillate in pressurized ethanol. Fuel Process. Technol. 149, 326-331.

Visioli LJ, Trentini CP, Castilhos F, Silva C. 2018. Esters production in continuous reactor from macauba pulp oil using methyl acetate in pressurized conditions. J. Supercrit. Fluids 140, 238-247.

Zhou D, Qiao B, Li G, Xue S, Yin J. 2017. Continuous production of biodiesel from microalgae by extraction coupling with transesterification under supercritical conditions. Bioresour. Technol. 238, 609-615.



How to Cite

Silva C, Colonelli T, Trentini C, Postaue N, Zempulski D, Cardozo-Filho L, Silva E. Catalyst-free production of fatty acid ethyl esters (FAEE) from macauba pulp oil. grasasaceites [Internet]. 2021Mar.3 [cited 2021Apr.20];72(1):e398. Available from: