Supercritical transesterification of vegetable oil and ethanol: temperature and residence time effects on phase formation and water content
DOI:
https://doi.org/10.18041/1900-3803/entramado.2.9807Keywords:
One-pot transesterification, Biodiesel thermal decomposition, Glycerol etherification, Catalyst-free processAbstract
Supercritical transesterification has emerged as a readily available alternative for biodiesel production since no catalyst is required, thereby generating fewer waste products. In this research, the supercritical transesterification of refined vegetable oil and aqueous ethanol was carried out at temperatures 400 to 480 °C and a 12:1 ethanol to oil molar ratio, to assess the effect of temperature and residence time in the formation of a homogeneous phase, effluent appearance and increased water content derived from glycerol etherification. The results showed that water was produced at temperatures higher than 400 °C, as expected from the occurrence of glycerol etherification, and that prolonged times resulted in gas and soot formation, indicating esters decomposition. Through water mass balances, it was possible to identify the set of operation conditions in which the water formed from glycerol etherification matched with the maximum expected according to the proposed reaction scheme.
Downloads
References
ANDREO-MARTÍNEZ, Pedro; ORTIZ-MARTÍNEZ, Víctor Manuel; GARCÍA-MARTÍNEZ, Nuria; PEREZ DE LOS RIOS, Antonia; HERNÁNDEZ-FERNÁNDEZ, Francisco José; QUESADA-MEDINA, Joaquín. Production of biodiesel under supercritical conditions: State of the art and bibliometric analysis. 2020. In: Appl. Energy. vol. 264, 114753. https://doi.org/10.1016/j.apenergy.2020.114753
CONIGLIO, Lucie; COUTINHO, João A.P.; CLAVIER, Jean-Yves; JOLIBERT, Franck; JOSE, Jacques MOKBEL, Ilham; PILLOT, Didier; PONS, Marie-Noëlle; SERGENT, Michelle; TSCHAMBER, Valérie. Biodiesel via supercritical ethanolysis within a global analysis “feedstocks-conversion-engine” for a sustainable fuel alternative. In: Prog. Energy Combust. Sci. August, 2014. vol. 43, p. 1–35. https://doi.org/10.1016/j.pecs.2014.03.001
FAROBIE, Obie; MATSUMURA, Yukihiko. A comparative study of biodiesel production using methanol, ethanol, and tert-butyl methyl ether (MTBE) under supercritical conditions. In: Bioresour. Technol. 2015. vol. 191, p. 306–311. https://doi.org/10.1016/j.biortech.2015.04.102
FENG, Li; LIU, Jiajun; LU, Haitao; LIU, Bingzhi; CHEN, Yuning. Techno-economic and profitability analysis of plant for producing biodiesel from fresh vegetable oil and waste frying oil on large-scale. In: Fuel. September, 2022. vol. 323, 124304. https://doi.org/10.1016/j.fuel.2022.124304
GARCÍA-MARTÍNEZ, Nuria; ANDREO-MARTÍNEZ, Pedro; QUESADA-MEDINA, Joaquín; PEREZ DE LOS RÍOS, Antonia; CHICA, Antonia; BENEITO-RUIZ, Ruben; CARRATALÁ-ABRIL, Juan. Optimization of non-catalytic transesterification of tobacco (Nicotiana tabacum) seed oil using supercritical methanol to biodiesel production. In: Energy Convers. Manag. 2016. Vol. 131, p. 99–108. https://doi.org/10.1016/j.enconman.2016.10.078
IZQUIERDO, J.; MONTIEL, Manuel; PALÉS, I.; OUTÓN, Pablo; GALÁN, María-Isabel; JUTGLAR, L.; VILLARRUBIA, M.; IZQUIERDO, María; HERMO, M.P.; ARIZA, Xavier. Fuel additives from glycerol etherification with light olefins: State of the art. In. Renew. Sustain. Energy Rev. 2012. vol. 16, p. 6717–6724. https://doi.org/10.1016/j.rser.2012.08.005
KRISHNA, Sachin-Muralee; ABDUL-SALAM, P.; TONGROON, Manida; CHOLLACOOP, Nuwong. Performance and emission assessment of optimally blended biodiesel-diesel-ethanol in diesel engine generator. In: Appl. Therm. Eng. 2019. vol.155, p. 525–533. https://doi.org/10.1016/j.applthermaleng.2019.04.012
KUSDIANA, Dadan; SAKA, Shiro. Effects of water on biodiesel fuel production by supercritical methanol treatment. In: Bioresour. Technol. 2004. vol. 91, p. 289–295. https://doi.org/10.1016/S0960-8524(03)00201-3
LEE, Wen-Jhy; LIU, Yi-Cheng; MWANGI, Francis-Kimani; CHEN, Wei-Sin; LIN, Sheng-Lun; FUKUSHIMA, Yasuhiro; LIAO, Chao-Ning; Wang, Lin-Chi. Assessment of energy performance and air pollutant emissions in a diesel engine generator fueled with water-containing ethanol-biodiesel-diesel blend of fuels. In: Energy. September, 2011. vol. 36, p. 5591–5599. https://doi.org/10.1016/j.energy.2011.07.012
LIU, Jiuxu; SHEN, Yujie; NAN, Yue; TAVLARIDES, Lawrence. Thermal decomposition of ethanol-based biodiesel: Mechanism, kinetics, and effect on viscosity and cold flow property. Fuel. August, 2016. vol. 178, p. 23–36. https://doi.org/10.1016/j.fuel.2016.03.033
MARULANDA-BUITRAGO, Paola-Andrea; MARULANDA-CARDONA, Víctor-Fernando. Supercritical transesterification of beef tallow for biodiesel production in a batch reactor. In: CTyF - Ciencia, Tecnol. y Futur. 2015. vol. 6, p. 57–68. https://doi.org/10.29047/01225383.20
MARULANDA, Víctor-Fernando. Biodiesel production by supercritical methanol transesterification: Process simulation and potential environmental impact assessment. In: J. Clean. Prod. 2012. vol. 33, p. 109–116. https://doi.org/10.1016/j.jclepro.2012.04.022
MARULANDA, Víctor-Fernando; ANITESCU, George; TAVLARIDES, Lawrence. Biodiesel fuels through a continuous flow process of chicken fat supercritical transesterification. In: Energy and Fuels. 2010. vol. 24, p. 253–260. https://doi.org/10.1021/ef900782v
MENDOW, G., VEIZAGA, N.S., SÁNCHEZ, B.S., QUERINI, C. a. Biodiesel production by two-stage transesterification with ethanol. In: Bioresour. Technol. 2011. vol. 102, p. 10407–10413. https://doi.org/10.1016/j.biortech.2011.08.052
QI, D.H., CHEN, Hao, MATTHEWS, R.D., BIAN, Y.Z. Combustion and emission characteristics of ethanol-biodiesel-water micro-emulsions used in a direct injection compression ignition engine. In: Fuel. 2010. vol. 89, p. 958–964. https://doi.org/10.1016/j.fuel.2009.06.029
QUESADA-MEDINA, Joaquín; OLIVARES-CARRILLO, Pilar. Evidence of thermal decomposition of fatty acid methyl esters during the synthesis of biodiesel with supercritical methanol. In: J. Supercrit. Fluids. 2011. vol. 56, p. 56–63. https://doi.org/10.1016/j.supflu.2010.11.016
SAKDASRI, Winatta; NGAMPRASERTSITH, Somkiat; SAENGSUK, Pongrawee; SAWANGKEAW, Ruengwit. Supercritical reaction between methanol and glycerol: The effects of reaction products on biodiesel properties. In: Energy Convers. Manag. X. 2021. vol. 12, 100145. https://doi.org/10.1016/j.ecmx.2021.100145
SAKDASRI, Winatta; SAWANGKEAW, Ruengwit, NGAMPRASERTSITH, Somkiat, 2015. Continuous production of biofuel from refined and used palm olein oil with supercritical methanol at a low molar ratio. In: Energy Convers. Manag. vol.103, p. 934–942. https://doi.org/10.1016/j.enconman.2015.07.027
SAWANGKEAW, Ruengwit; SATAYANON, Witsanee; BUNYAKIAT, Kunchana; CAMY, Séverine; CONDORET, Jean-Stéphane; NGAMPRASERTSITH, Somkiat. Continuous production of biodiesel with Sspercritical methanol: a simple compressible flow model for tubular eactors. In: Int. J. Chem. React. Eng. 2011. vol. 9. https://doi.org/10.2202/1542-6580.2758
SIDHU, Manpreet-Singh; ROY, Murari-Mohon; WANG, Wilson. Glycerine emulsions of diesel-biodiesel blends and their performance and emissions in a diesel engine. In. Appl. Energy. November, 2018. vol. 230, p. 148–159. https://doi.org/10.1016/j.apenergy.2018.08.103
STAMENKOVIĆ, Olivera; VELIČKOVIĆ, Ana; VELJKOVIĆ, Vlada. The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives. In: Fuel. 2011. vol. 90, p. 3141–3155. https://doi.org/10.1016/j.fuel.2011.06.049
TAN, Kok-Tat; LEE, Keat-Teong. A review on supercritical fluids (SCF) technology in sustainable biodiesel production: Potential and challenges. In: Renew. Sustain. Energy Rev. 2011. vol.15, p. 2452–2456. https://doi.org/10.1016/j.rser.2011.02.012
TONGROON, Manida; SAISIRIRAT, Peerawat; SUEBWONG, Amornpoth; AUNCHAISRI, Jirasak; KANANONT, Mongkon; CHOLLACOOP, Nuwong. Combustion and emission characteristics investigation of diesel-ethanol-biodiesel blended fuels in a compression-ignition engine and benefit analysis. In: Fuel. 2019. Vol. 255, 115728. https://doi.org/10.1016/j.fuel.2019.115728
VIEITEZ, Ignacio; DA SILVA, Camila; ALCKMIN, Isabella; BORGES, Gustavo; CORAZZA, Fernanda; OLIVEIRA, Vladimir,; GROMPONE, Maria; JACHMANIÁN, Iván. Continuous catalyst-free methanolysis and ethanolysis of soybean oil under supercritical alcohol/water mixtures. In. Renew. Energy. 2010. vol. 35, p. 1976–1981. https://doi.org/10.1016/j.renene.2010.01.027
VEGA-GUERRERO, Diana-Berenice; GÓMEZ-CASTRO, Fernando-Israel; LÓPEZ-MOLINA, Antioco. Production of biodiesel with supercritical ethanol: Compromise between safety and costs. In: Chem. Eng. Res. Des. 2022. vol. 184, p. 79-89.
https://doi.org/10.1016/j.cherd.2022.05.055
VIEITEZ, Ignacio; DA SILVA, Camila; BORGES, Gustavo; CORAZZA, Fernanda; OLIVEIRA, Vladimir; GROMPONE, Maria, JACHMANIÁN, Ivan. 2008. Continuous production of soybean biodiesel in supercritical ethanol-water mixtures. In: Energy and Fuels. 2008. vol. 22, p. 2805–2809. https://doi.org/10.1021/ef800175e
WAN-YING, Wong; STEVEN, Lim; YEAN-LING, Pang; SIEW-HOONG, Shuit; MAN-KEE, Lam; INN-SHI, Tan; WEI-HSIN, Chen. A comprehensive review of the production methods and effect of parameters for glycerol-free biodiesel production. In: Renew. Sustain. Energy Rev. 2023. vol 182, 113397.
Published
Issue
Section
License
Copyright (c) 2023 Entramado
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
