Biodiesel production through ionic liquid catalysed esterification
Autor(a) principal: | |
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Data de Publicação: | 2017 |
Tipo de documento: | Dissertação |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10198/14667 |
Resumo: | Biodiesel is an alternative fuel diesel that can be produced from vegetable oils and animal fats. There is a recent growing interest in the development of alternative technologies to the oil economy, based on renewable energy sources. A possible solution is a biofuel usable in compression-ignition engines, produced from biomass rich in fats and oils. A wide range of raw materials can be used in the production of biodiesel. Nevertheless, the use of sources that do not compete with the food market like waste cooking oils, which usually feature high levels of free fatty acids (FFA’s), can put problems in the process of production of biodiesel through alkaline transesterification. These problems are partially overcome by the use of catalysts, such as ionic liquids (IL’s) that also promote reactions of esterification of FFA’s to biodiesel. Thus, the objective of this work consists in the study of the influence of IL's application in the catalysis of: esterification reactions of organic acids to the corresponding methyl esters. In the first part of the work the influence, as catalysts, of several ionic liquids in the esterification reaction of oleic acid was analyzed. The experimental conditions were as follows: reaction time 6 hours, oleic acid / methanol molar ratio = 1/10 and temperature 90 ° C. The ionic liquids evaluated were as follows: 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]), 1-butyl-3-methylimidazolium methanesulfonate ([BMIM][CH3SO3]), 1-butyl-3-methylimidazolium methylsulfate ([BMIM][CH3SO4]), 1-metylimidazolium hydrogen sulfate ([MIM][HSO4]) and tributylmethylammonium methylsulfate. The values obtained for the conversion of the oleic acid esterification reaction showed that the ionic liquid [BMIM] [HSO4] would be one of the most promising catalysts. In a second part of the work, the recovery of LI [BMIM] [HSO4] was studied and several esterification reactions of oleic acid were carried out using a quantity of catalyst of 10 wt%, 15 wt% and 20 wt% relative to the mass of oleic acid. The experimental conditions were as follows: reaction time 6 hours, oleic acid / methanol molar ratio = 1/10 and temperature 90 ° C. The reaction yield was found to be 76.6% to 10% IL, 83.3% to 15% IL and 84.8% to 20% IL. These yields decreased to 58.2% (10% IL) with 4 cycles of recycling, 75.2% (15% IL) with 5 cycles of recycling and 77.1% (20% IL) with 5 cycles of recycling. The results obtained confirm that it is possible to reuse this IL in successive reactions of esterification without great loss of yield and with this to significantly reduce the costs associated with the purchase of these compounds that are quite expensive. |
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Biodiesel production through ionic liquid catalysed esterificationBiodieselEsterificationIonic LiquidsRecoveryDomínio/Área Científica::Engenharia e Tecnologia::Engenharia QuímicaBiodiesel is an alternative fuel diesel that can be produced from vegetable oils and animal fats. There is a recent growing interest in the development of alternative technologies to the oil economy, based on renewable energy sources. A possible solution is a biofuel usable in compression-ignition engines, produced from biomass rich in fats and oils. A wide range of raw materials can be used in the production of biodiesel. Nevertheless, the use of sources that do not compete with the food market like waste cooking oils, which usually feature high levels of free fatty acids (FFA’s), can put problems in the process of production of biodiesel through alkaline transesterification. These problems are partially overcome by the use of catalysts, such as ionic liquids (IL’s) that also promote reactions of esterification of FFA’s to biodiesel. Thus, the objective of this work consists in the study of the influence of IL's application in the catalysis of: esterification reactions of organic acids to the corresponding methyl esters. In the first part of the work the influence, as catalysts, of several ionic liquids in the esterification reaction of oleic acid was analyzed. The experimental conditions were as follows: reaction time 6 hours, oleic acid / methanol molar ratio = 1/10 and temperature 90 ° C. The ionic liquids evaluated were as follows: 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]), 1-butyl-3-methylimidazolium methanesulfonate ([BMIM][CH3SO3]), 1-butyl-3-methylimidazolium methylsulfate ([BMIM][CH3SO4]), 1-metylimidazolium hydrogen sulfate ([MIM][HSO4]) and tributylmethylammonium methylsulfate. The values obtained for the conversion of the oleic acid esterification reaction showed that the ionic liquid [BMIM] [HSO4] would be one of the most promising catalysts. In a second part of the work, the recovery of LI [BMIM] [HSO4] was studied and several esterification reactions of oleic acid were carried out using a quantity of catalyst of 10 wt%, 15 wt% and 20 wt% relative to the mass of oleic acid. The experimental conditions were as follows: reaction time 6 hours, oleic acid / methanol molar ratio = 1/10 and temperature 90 ° C. The reaction yield was found to be 76.6% to 10% IL, 83.3% to 15% IL and 84.8% to 20% IL. These yields decreased to 58.2% (10% IL) with 4 cycles of recycling, 75.2% (15% IL) with 5 cycles of recycling and 77.1% (20% IL) with 5 cycles of recycling. The results obtained confirm that it is possible to reuse this IL in successive reactions of esterification without great loss of yield and with this to significantly reduce the costs associated with the purchase of these compounds that are quite expensive.O biodiesel é um combustível alternativo que pode ser produzido a partir de óleos vegetais e de gorduras animais. Atualmente existe um crescente interesse no desenvolvimento de tecnologias alternativas à economia do petróleo baseadas em fontes de energia renováveis. Uma possível solução é a utilização de um biocombustível em motores de compressão-ignição, produzido a partir de biomassa rica em óleos e gorduras. Para a produção de biodiesel pode ser usada uma ampla gama de matérias-primas. No entanto, o uso de fontes que não competem com o mercado alimentar, como por exemplo os óleos alimentares usados, que geralmente têm um elevado nível de ácidos gordos livres (AGL´s), pode trazer problemas ao processo de produção de biodiesel através da transesterificação alcalina. Estes problemas são parcialmente ultrapassados usando catalisadores, tais como os líquidos iónicos (LI´s), que também promovem as reações de esterificação dos AGL´s a biodiesel. Assim, o objetivo desta dissertação de mestrado consistiu no estudo da aplicação de líquidos iónicos como catalisadores nas reações de esterificação de ácidos orgânicos aos correspondentes ésteres metílicos. Na primeira parte do trabalho analisou-se a influência, como catalisadores, de diversos líquidos iónicos na reação de esterificação do ácido oleico. Os líquidos iónicos avaliados foram os seguintes: 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]), 1-butyl-3-methylimidazolium methanesulfonate ([BMIM][CH3SO3]), 1-butyl-3-methylimidazolium methylsulfate ([BMIM][CH3SO4]), 1-metylimidazolium hydrogen sulfate ([MIM][HSO4]) and tributylmethylammonium methylsulfate. Os valores obtidos para a conversão da reação de esterificação do ácido oleico mostraram que o líquido iónico [BMIM][HSO4] seria um dos mais promissores como catalisador. Numa segunda parte do trabalho procedeu-se ao estudo da recuperação do LI [BMIM][HSO4], tendo-se realizado diversas reações de esterificação do ácido oleico usando uma quantidade de catalisador de 10%, 15% e 20% (m/m) relativamente à massa de ácido oleico. As condições experimentais foram as seguintes: tempo de reação 6 horas, razão molar ácido oleico/metanol = 1/10 e temperatura 90 °C. Verificou-se que o rendimento da reação foi de 76,6 % para 10% de LI, 83,3% para 15% de LI e 84,8% para 20% de LI. Estes rendimentos diminuíram para 58,2% (10% de LI) com 4 atapas de reciclagem, 75,2% (15% de LI) com 5 etapas de reciclagem e 77,1% (20% de LI) com 5 etapas de reciclagem. Os resultados obtidos permitem confirmar que é possível reutilizar este LI em reações sucessivas de esterificação sem grande perda de rendimento e com isso diminuir significativamente os custos associados à compra destes compostos que são bastante caros.Կենսադիզելն այլընտրանքային դիզելային վառելիք է, որն ստացվում է բուսական յուղերից և կենդանական ճարպերից: Վերջին շրջանում աճում է հետաքրքրությունն այլընտրանքային տեխնոլոգիաների` նավթային տնտեսության, հիմականում վերականգնվող էներգիայի աղբյուրների նկատմամբ: Հնարավոր լուծում է ներքին այրման շարժիչներում կենսավառելիքի օգտագործումը, որն արտադրված է ճարպերով և յուղերով հարուստ կենսազանգվածից: Կենսադիզելի արտադրության մեջ հնարավոր է օգտագործել հումքի լայն ընտրանի: Օգտագործվող հումքի աղբյուրները չեն մասնակցում պարենային շուկայի մրցակցությանը: Այդպիսիք են` խոհանոցային թափոններ հանդիսացող յուղերը, որոնք հիմնականում բնորոշվում են խնդրահարույց ազատ ճարպային թթուների (ԱՃԹ) մեծ պարունակությամբ: Այս խնդիրը մասամբ հաղթահարվել է` օգտագործելով կատալիզատորներ, ինչպիսիք են իոնային հեղուկները (ԻՀ), որոնք նույնպես նպաստում են կենսադիզելում ԱՃԹ-ի եթերացմանը: Այսպիսով, այս աշխատանքի նպատակն է ուսումնասիրել իոնային հեղուկ կատալիզատորների ազդեցությունը համապատասխան մեթիլեթերների հետ օրգանական թթուների եթերացման ռեակցիաներում: Աշխատանքի առաջին մասում հետազոտվել է մի քանի իոնային հեղուկների ազդեցությունն օլեինաթթվի եթերացման ռեակցիայում: Փորձի պայմանները հետևյալն են. ռեակցիայի ժամանակը ` 6 ժամ, օլեինաթթու / մեթանոլ մոլային հարաբերակցությունը` 1/10, ջերմաստիճանը 90°C: Հետազոտվող իոնային հեղուկները հետևյալն են. 1-բութիլ-3-մեթիլիմիդազոլիումի հիդրոսուլֆատ ([BMIM][HSO4]), 1-բութիլ-3-մեթիլիմիդազոլիումի մեթանսուլֆոնատ ([BMIM][CH3SO3]), 1-բութիլ-3-մեթիլիմիդազոլիումի մեթիլսուլֆատ ([BMIM][CH3SO4]), 1-մեթիլիմիդազոլիումի հիդրոսուլֆատ ([MIM][HSO4]) և տրիբութիլմեթիլամոնիումի մեթիլսուլֆատ: Օլեինաթթվի եթերացման ռեակցիայի արդյունքները ցույց տվեցին, որ [BMIM][HSO4] իոնային հեղուկն ամենախոստումալից կատալիզատրներից մեկն է: Աշխատանքի երկրորդ մասում ուսումնասիրվել են [BMIM][HSO4] իոնային հեղուկի վերականգնումը և օլեինաթթվի եթերացման մի քանի ռեակցիաներ, որոնցում օգտագործված կատալիզատորի զանգվածը եղել է օլեինաթթվի զանգվածի 10%, 15%, 20%-ը: Փորձի պայմանները հետևյալն են. ռեակցիայի ժամանակը ` 6 ժամ, օլեինաթթու / մեթանոլ մոլային հարաբերակցությունը` 1/10, ջերմաստիճանը 90°C: Ռեակցիայի ելքը կազմել է 76.6% ԻՀ-ի 10%-ի դեպքում, 83.3% ` ԻՀ-ի 15%-ի դեպքում և 84.8%` ԻՀ-ի 20%-ի դեպքում: Այս ելքերը նվազել են մինչև 58.2% (10% ԻՀ)` վերամշակման 4 ցիկլից հետո, 75.2% (15% ԻՀ)` վերամշակման 5 ցիկլից հետո, 77.1% (20% ԻՀ)` վերամշակման 5 ցիկլից հետո: Ստացված արդյունքները հաստատում են, որ հնարավոր է այս ԻՀ-ի վերաօգտագործումը եթերացման հաջորդական ռեակցիաներում` առանց ելքի մեծ կորստի, և զգալիորեն նվազեցնել այդ, բավականին թանկ, միացությունների գնման հետQueiroz, AnaRibeiro, António E.Brito, PauloHovhannisyan, NellyBiblioteca Digital do IPBTadevosyan, Arevik2017-11-28T17:09:30Z20172017-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfhttp://hdl.handle.net/10198/14667TID:201784564enginfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-11-21T10:34:27Zoai:bibliotecadigital.ipb.pt:10198/14667Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T23:04:28.270611Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Biodiesel production through ionic liquid catalysed esterification |
title |
Biodiesel production through ionic liquid catalysed esterification |
spellingShingle |
Biodiesel production through ionic liquid catalysed esterification Tadevosyan, Arevik Biodiesel Esterification Ionic Liquids Recovery Domínio/Área Científica::Engenharia e Tecnologia::Engenharia Química |
title_short |
Biodiesel production through ionic liquid catalysed esterification |
title_full |
Biodiesel production through ionic liquid catalysed esterification |
title_fullStr |
Biodiesel production through ionic liquid catalysed esterification |
title_full_unstemmed |
Biodiesel production through ionic liquid catalysed esterification |
title_sort |
Biodiesel production through ionic liquid catalysed esterification |
author |
Tadevosyan, Arevik |
author_facet |
Tadevosyan, Arevik |
author_role |
author |
dc.contributor.none.fl_str_mv |
Queiroz, Ana Ribeiro, António E. Brito, Paulo Hovhannisyan, Nelly Biblioteca Digital do IPB |
dc.contributor.author.fl_str_mv |
Tadevosyan, Arevik |
dc.subject.por.fl_str_mv |
Biodiesel Esterification Ionic Liquids Recovery Domínio/Área Científica::Engenharia e Tecnologia::Engenharia Química |
topic |
Biodiesel Esterification Ionic Liquids Recovery Domínio/Área Científica::Engenharia e Tecnologia::Engenharia Química |
description |
Biodiesel is an alternative fuel diesel that can be produced from vegetable oils and animal fats. There is a recent growing interest in the development of alternative technologies to the oil economy, based on renewable energy sources. A possible solution is a biofuel usable in compression-ignition engines, produced from biomass rich in fats and oils. A wide range of raw materials can be used in the production of biodiesel. Nevertheless, the use of sources that do not compete with the food market like waste cooking oils, which usually feature high levels of free fatty acids (FFA’s), can put problems in the process of production of biodiesel through alkaline transesterification. These problems are partially overcome by the use of catalysts, such as ionic liquids (IL’s) that also promote reactions of esterification of FFA’s to biodiesel. Thus, the objective of this work consists in the study of the influence of IL's application in the catalysis of: esterification reactions of organic acids to the corresponding methyl esters. In the first part of the work the influence, as catalysts, of several ionic liquids in the esterification reaction of oleic acid was analyzed. The experimental conditions were as follows: reaction time 6 hours, oleic acid / methanol molar ratio = 1/10 and temperature 90 ° C. The ionic liquids evaluated were as follows: 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]), 1-butyl-3-methylimidazolium methanesulfonate ([BMIM][CH3SO3]), 1-butyl-3-methylimidazolium methylsulfate ([BMIM][CH3SO4]), 1-metylimidazolium hydrogen sulfate ([MIM][HSO4]) and tributylmethylammonium methylsulfate. The values obtained for the conversion of the oleic acid esterification reaction showed that the ionic liquid [BMIM] [HSO4] would be one of the most promising catalysts. In a second part of the work, the recovery of LI [BMIM] [HSO4] was studied and several esterification reactions of oleic acid were carried out using a quantity of catalyst of 10 wt%, 15 wt% and 20 wt% relative to the mass of oleic acid. The experimental conditions were as follows: reaction time 6 hours, oleic acid / methanol molar ratio = 1/10 and temperature 90 ° C. The reaction yield was found to be 76.6% to 10% IL, 83.3% to 15% IL and 84.8% to 20% IL. These yields decreased to 58.2% (10% IL) with 4 cycles of recycling, 75.2% (15% IL) with 5 cycles of recycling and 77.1% (20% IL) with 5 cycles of recycling. The results obtained confirm that it is possible to reuse this IL in successive reactions of esterification without great loss of yield and with this to significantly reduce the costs associated with the purchase of these compounds that are quite expensive. |
publishDate |
2017 |
dc.date.none.fl_str_mv |
2017-11-28T17:09:30Z 2017 2017-01-01T00:00:00Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10198/14667 TID:201784564 |
url |
http://hdl.handle.net/10198/14667 |
identifier_str_mv |
TID:201784564 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
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1799135292277391360 |