Study of the operational conditions for ethyl esters production using residual frying oil and KF/clay catalyst in a continuous system

Authors

DOI:

https://doi.org/10.3989/gya.0322211

Keywords:

Ethyl esters, Heterogeneous catalyst, Residual frying oil

Abstract


The transesterification of residual frying oil (RFO) with pressurized ethanol was carried out in a continuous reactor containing KF/clay as a heterogeneous catalyst. In the experiments, different oil:ethanol mass ratios were evaluated at 275 and 300 ºC and 20 MPa. In the sequence, the operational stability of the catalyst was evaluated for 8 hours, as well as the conduct of the reaction in two steps (testing new and recycled catalyst). An esters yield of ~90% was achieve at 275 ºC, for15 min and at 1:1.5 oil:ethanol mass ratio. Under these conditions, the catalyst provided a stable yield in the first 3 hours of operation, and a total decrease of 29% after 8 hours. This result can be attributed mainly to the leaching of the K+ cations for the reactions in which the catalyst was exposed to long operating times. The two-step reaction served to increase the RFO conversion to esters, with low thermal decomposition.

Downloads

Download data is not yet available.

References

Abdala ACA, Colonelli TAS, Trentini CP, Oliveira JV, Cardozo-Filho L, Silva EA, Silva C. 2014. Effect of additives in the reaction medium on noncatalytic ester production from used frying oil with supercritical ethanol. Energy Fuels 28, 3122-3128. https://doi.org/10.1021/ef402253e

Alves HJ, Rocha AM, Monteiro MR, Morwtti C, Cabrelon MD, Schwengber CA, Milinsk MC. 2014. Treatment of clay with KF: New solid catalyst for biodiesel production. Appl. Clay Sci. 91-92, 98-104. https://doi.org/10.1016/j.clay.2014.02.004

Álvarez-Mateos P, García-Martín JF, Guerrero-Vacas FJ, Naranjo-Calderón C, Barrios-Sánchez CC, Pérez-Camino MC. 2019. Valorization of a high-acidity residual oil generation in the waste cooking oils recycling industries. Grasas Aceites 70, 1-9. https://doi.org/10.3989/gya.1179182

Andreo-Martínez P, Ortiz-Martínez VM, García-Martínez N, Ríos AP, Hernández-Fernández FJ, Quesada-Medina J. 2020. Production of biodiesel under supercritical conditions: State of the art and bibliometric analysis. Appl. Energy 264, 114753. https://doi.org/10.1016/j.apenergy.2020.114753

ANP. 2014. Agência Nacional do Petróleo. Resolução ANP No 45, DE 25.8.2014 - DOU 26.8.2014.

Aprobio. 2018. Matérias-primas alternativas batem recorde de participação no biodiesel. Assoc. dos Prod. do Bras. Available at: https://aprobio.com.br/noticia/materias-primas-alternativas-batem-recorde-de-participacao-no-biodiesel

Biktashev AS, Usmanov RA, Gabitov RR, Gazizov RA, Gumerov FM, Abdulagatov IM, Yarullin RS, Yakushev, IA. 2011. Transesterification of rapeseed and palm oils in supercritical methanol and ethanol. Biomass Bioener. 35, 2999-3011. https://doi.org/10.1016/j.biombioe.2011.03.038

Boz N, Degirmenbasi N, Kalyon DM. 2009. Conversion of biomass to fuel: Transesterification of vegetable oil to biodiesel using KF loaded nano-γ-Al2O3 as catalyst. Appl. Catal. B Environ. 89, 590-596. https://doi.org/10.1016/j.apcatb.2009.01.026

Bunyakiat K, Makmee S, Sawangkeaw R, Ngamprasertsith S. 2006. Continuous production of biodiesel via transesterification from vegetable oils in supercritical methanol. Energy Fuels 20, 812-817. https://doi.org/10.1021/ef050329b

Campanelli P, Banchero M, Manna L. 2010. Synthesis of biodiesel from edible, non-edible and waste cooking oils via supercritical methyl acetate transesterification. Fuel 89, 3675-3682. https://doi.org/10.1016/j.fuel.2010.07.033

Centi G, Perathoner S. 2008. Catalysis by layered materials: A review. Microporous Mesoporous Mater. 107, 3-15. https://doi.org/10.1016/j.micromeso.2007.03.011

Endalew AK, Kiros Y, Zanzi R. 2011. Heterogeneous catalysis for biodiesel production from Jatropha curcas oil (JCO). Energy 36, 2693-2700. https://doi.org/10.1016/j.energy.2011.02.010

Fonseca JM, Cardozo-Filho L,Teleken LG, Silva C. 2018. Ethyl esters from waste oil: Reaction data of non-catalytic hydroesterification at pressurized conditions and purification with sugarcane bagasse ash. J. Environ. Chem. Eng. 6, 4988-4996. https://doi.org/10.1016/j.jece.2018.07.044

Gonzalez SL, Sychoski MM, Navarro-Díaz, HJ, Callejas N, Sainebe M, Vieitez I, Jachmanián I, Silva C, Hense H, Oliveira JV. 2013. Continuous catalyst-free production of biodiesel through transesterification of soybean fried oil in supercritical methanol and ethanol. Energy Fuels 27, 5253-5259. https://doi.org/10.1021/ef400869y

Hajjari M, Tabatabaei M, Aghbashlo M, Ghanavati, H. 2017. A review on the prospects of sustainable biodiesel production: A global scenario with an emphasis on waste-oil biodiesel utilization. Renew. Sustain. Energy Rev. 72, 445-464. https://doi.org/10.1016/j.rser.2017.01.034

He H, Wang T, Zhu S. 2007. Continuous production of biodiesel fuel from vegetable oil using supercritical methanol process. Fuel 86, 442-447. https://doi.org/10.1016/j.fuel.2006.07.035

Hegel P, Andreatta A, Pereda S, Bottini S, Brignole EA. 2008. High pressure phase equilibria of supercritical alcohols with triglycerides, fatty esters and cosolvents. Fluid Phase Equilib. 266, 31-37. https://doi.org/10.1016/j.fluid.2008.01.016

Jesus AA. 2010. Síntese de biodiesel em meio contínuo pressurizado empregando hidrotalcitas como catalisadores heterogêneos. Aracaju: Universidade Tiradentes.

Krohn BJ, McNeff CV, Yan B, Nowlan D. 2011. Production of algae-based biodiesel using the continuous catalytic Mcgyan® process. Bioresour. Technol. 102, 94-100. https://doi.org/10.1016/j.biortech.2010.05.035 PMid:20561783

Kusdiana D, Saka S. 2004. Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresour. Technol. 91, 289-295. https://doi.org/10.1016/S0960-8524(03)00201-3

Lin HC, Tan CS. 2014. Continuous transesterification of coconut oil with pressurized methanol in the presence of a heterogeneous catalyst. J. Taiwan Inst. Chem. Eng. 45, 495-503. https://doi.org/10.1016/j.jtice.2013.06.015

Liu J, Shen Y, Nan Y, Tavlarides LL. 2016. Thermal decomposition of ethanol-based biodiesel: Mechanism, kinetics, and effect on viscosity and cold flow property. Fuel 178, 23-36. https://doi.org/10.1016/j.fuel.2016.03.033

Lokman IM, Goto M, Rashid U, Taufiq-Yap YH. 2016. Sub- and supercritical esterification of palm fatty acid distillate with carbohydrate-derived solid acid catalyst. Chem. Eng. J. 284, 872-878. https://doi.org/10.1016/j.cej.2015.08.102

Maçaira J, Santana A, Recasens F, Larrayoz MA. 2011. Biodiesel production using supercritical methanol/carbon dioxide mixtures in a continuous reactor. Fuel 90, 2280-2288. https://doi.org/10.1016/j.fuel.2011.02.017

Mahlia TMI, Syazmi ZAHS, Mofijur M, Abas AEP, Bilad MR, Ong HC, Silitonga AS. 2020. Patent landscape review on biodiesel production : Technology updates. Renew. Sustain. Energy Rev. 118, 109526. https://doi.org/10.1016/j.rser.2019.109526

Mazanov SV, Gabitova AR, Usmanov RA, Gumerov, FM, Labidi S, Amar MB, Passarello JP, Kanaev A, Volle F, Neindre BL. 2016. Continuous production of biodiesel from rapeseed oil by ultrasonic assist transesterification in supercritical ethanol. J. Supercrit. Fluids 118, 107-118. https://doi.org/10.1016/j.supflu.2016.07.009

McNeff CV, McNeff LC, Yan B, Nowlan DT,Rasmussen M, Gyberg AE, Krohn BJ, Fedie RL, Hoye TR. 2008. A continuous catalytic system for biodiesel production. Appl. Catal. A Gen. 343, 39-48. https://doi.org/10.1016/j.apcata.2008.03.019

Nagendrappa G. 2011. Organic synthesis using clay and clay-supported catalysts. Appl. Clay Sci. 53, 106-138. https://doi.org/10.1016/j.clay.2010.09.016

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. https://doi.org/10.1016/j.supflu.2017.01.010

Ouanji F, Khachani M, Boualag M, Kacini M, Ziyad M. 2016. Large-scale biodiesel production from Moroccan used frying oil. Int. J. Hydrogen Energy 41, 21022-21029. https://doi.org/10.1016/j.ijhydene.2016.05.236

Quesada-Medina J, Olivares-Carrillo P. 2011. Evidence of thermal decomposition of fatty acid methyl esters during the synthesis of biodiesel with supercritical methanol. J. Supercrit. Fluids 56, 56-63. https://doi.org/10.1016/j.supflu.2010.11.016

Ribeiro JS, Celante D, Brondani LN, Trojahn DO, Silva C, Castilhos F. 2018. Synthesis of methyl esters and triacetin from macaw oil (Acrocomia aculeata) and methyl acetate over γ-alumina. Ind. Crops Prod. 124, 84-90. https://doi.org/10.1016/j.indcrop.2018.07.062

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. https://doi.org/10.1016/j.fuel.2018.03.102

Shehata MS. 2013. Emissions , performance and cylinder pressure of diesel engine fuelled by biodiesel fuel. Fuel 112, 513-522. https://doi.org/10.1016/j.fuel.2013.02.056

Silva C, Castilhos F, Oliveira JV, Cardozo Filho L. 2010. Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor. Fuel Process. Technol. 91, 1274-1281. https://doi.org/10.1016/j.fuproc.2010.04.009

Silva C, Oliveira JV. 2014. Biodiesel production through non-catalytic supercritical transesterification: Current state and perspectives. Brazilian J. Chem. Eng. 31, 271-285. https://doi.org/10.1590/0104-6632.20140312s00002616

Simões SS, Ribeiro JS, Celante D, Brondani LN, Castilhos F. 2020. Heterogeneous catalyst screening for fatty acid methyl esters production through interesterification reaction. Renew. Energy 146, 719-726. https://doi.org/10.1016/j.renene.2019.07.023

Soares DZ, Andreozzi SL. 2011. Reflexões sobre o etanol e o biodiesel na matriz energética brasileira. Rev. Geográfica América Cent. 2, 1-17.

Tan KT, Lee KT, Mohamed AR. 2010. Effects of free fatty acids , water content and co-solvent on biodiesel production by supercritical methanol reaction. J. Supercrit. Fluids 53, 88-91. https://doi.org/10.1016/j.supflu.2010.01.012

Teo SH, Goto M, Taufiq-Yap YH. 2015. Biodiesel production from Jatropha curcas L. oil with Ca and La mixed oxide catalyst in near supercritical methanol conditions. J. Supercrit. Fluids 104, 243-250. https://doi.org/10.1016/j.supflu.2015.06.023

Trentini CP, Fonseca JM, Cardozo Filho L., Reis RR, Sampaio SC, Silva C. 2018. Assessment of continuous catalyst-free production of ethyl esters from grease trap waste. J. Supercrit. Fluids 136, 157-163. https://doi.org/10.1016/j.supflu.2018.02.018

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, 9-16. https://doi.org/10.1016/j.supflu.2019.02.008

Trentini CP, Postaue N, Cardozo-Filho L, Silva C. 2020. Waste oil/crambe oil blends for ethyl ester production under supercritical conditions. J. Supercrit. Fluids 163, 104889. https://doi.org/10.1016/j.supflu.2020.104889

Vieitez I, Silva C, Alckmin I, Borges GR, Corazza FC, Oliveira JV, Grompone MA, Jachmanián I. 2009. Effect of temperature on the continuous synthesis of soybean esters under supercritical ethanol. Energy Fuels 23, 558-563. https://doi.org/10.1021/ef800640t

Visioli LJ, Castilhos F, Silva C. 2019. Use of heterogeneous acid catalyst combined with pressurized conditions for esters production from macauba pulp oil and methyl acetate. J. Supercrit. Fluids 150, 65-74. https://doi.org/10.1016/j.supflu.2019.03.023

Wang L, Yang J. 2007. Transesterification of soybean oil with nano-MgO or not in supercritical and subcritical methanol. Fuel 86, 328-333. https://doi.org/10.1016/j.fuel.2006.07.022

Xu QQ, Li Q, Yin JZ, Guo D, Qiao BQ. 2016. Continuous production of biodiesel from soybean flakes by extraction coupling with transesterification under supercritical conditions. Fuel Process. Technol. 144, 37-41. https://doi.org/10.1016/j.fuproc.2015.12.018

Zempulski DA, CP, Milinsk MC, Alves HJ, Silva C. 2020. Continuous transesterification reaction of residual frying oil with pressurized ethanol using KF/Clay as catalyst. Eur. J. Lipid Sci. Technol. 122, 1900315. https://doi.org/10.1002/ejlt.201900315

Zeng D, Yang L, Fang T. 2017. Process optimization, kinetic and thermodynamic studies on biodiesel production by supercritical methanol transesterification with CH3ONa catalyst. Fuel 203, 739-748. https://doi.org/10.1016/j.fuel.2017.05.019

Zhang Y, Liu H, Zhu X, Lukic I, Zdujic M, Shen X, Shala D. 2018. Biodiesel synthesis and kinetic analysis based on MnCO3/Na silicate as heterogeneous catalyst. J. Serbian Chem. Soc. 83, 345-365. https://doi.org/10.2298/JSC170612005Z

Published

2022-06-13

How to Cite

1.
Zempulski D, Postaue N, Stevanato N, Alves H, Silva C. Study of the operational conditions for ethyl esters production using residual frying oil and KF/clay catalyst in a continuous system. Grasas aceites [Internet]. 2022Jun.13 [cited 2024Mar.28];73(2):e453. Available from: https://grasasyaceites.revistas.csic.es/index.php/grasasyaceites/article/view/1930

Issue

Section

Research

Funding data

Conselho Nacional de Desenvolvimento Científico e Tecnológico
Grant numbers 141798/2016-5;141810/2020-3