Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética
Ano de defesa: | 2020 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Tecnologia |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Engenharia Química
|
Departamento: |
Engenharia Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/23283 |
Resumo: | This work proposes the use of USY zeolite activated with tungsten oxide in the esterification of oleic acid with methyl acetate. Tunguistic acid was synthesized trought the acid treatment of sodium tungstate and was used as a precursor. The characterization of the catalysts showed that the general structure of the zeolite was maintained after impregnation. However, the acidity profile of WO3/USY zeolites has been highly altered, where the strong Brønsted acid sites of the original zeolite have been blocked by tungsten oxide, allowing the reagents to have been accessed to the new Lewis acid sites and hydrogen bonds. The change of adsorption mechanism favored the conversion of oleic acid to methyl oleate. The first-order reversible pseudo-homogeneous (PH) model was able to represent the experimental data catalyzed by the USY zeolite, since the heterogeneous models (ER and LH) were classified as overparameterized and were disregarded. Kinetic and thermodynamic modeling showed that the reaction is endothermic, with change in enthalpy of 59.83 kJ mol−1 and activation energy of 41.77 kJ mol−1. The proposal of a novel kinetic model considering the active sites of the WO3/USY catalyst shown a good fit to the experimental data of the reaction catalyzed by different catalysts. The Brønsted acidic sites of the USY zeolite and the weak acidic sites of the WO3/USY zeolite showed great importance in the esterification reaction. The zeolites activated by ultrasonic method showed the greatest conversions in methyl esters. The 10% WO3/USY US catalyst presented the best performance, converting 87% of oleic acid to methyl oleate after 3 hours of reaction, at 240 °C, with a ratio of oleic acid and methyl acetate of 1:10 and 10% (w/w) of catalyst. The use of WO3/USY zeolite shows a viable and effective catalyst to esterification of oleic acid with methyl acetate, which is in accordance to prospects of free-glycerol biodiesel production. |
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2021-12-13T20:04:28Z2021-12-13T20:04:28Z2020-01-20http://repositorio.ufsm.br/handle/1/23283This work proposes the use of USY zeolite activated with tungsten oxide in the esterification of oleic acid with methyl acetate. Tunguistic acid was synthesized trought the acid treatment of sodium tungstate and was used as a precursor. The characterization of the catalysts showed that the general structure of the zeolite was maintained after impregnation. However, the acidity profile of WO3/USY zeolites has been highly altered, where the strong Brønsted acid sites of the original zeolite have been blocked by tungsten oxide, allowing the reagents to have been accessed to the new Lewis acid sites and hydrogen bonds. The change of adsorption mechanism favored the conversion of oleic acid to methyl oleate. The first-order reversible pseudo-homogeneous (PH) model was able to represent the experimental data catalyzed by the USY zeolite, since the heterogeneous models (ER and LH) were classified as overparameterized and were disregarded. Kinetic and thermodynamic modeling showed that the reaction is endothermic, with change in enthalpy of 59.83 kJ mol−1 and activation energy of 41.77 kJ mol−1. The proposal of a novel kinetic model considering the active sites of the WO3/USY catalyst shown a good fit to the experimental data of the reaction catalyzed by different catalysts. The Brønsted acidic sites of the USY zeolite and the weak acidic sites of the WO3/USY zeolite showed great importance in the esterification reaction. The zeolites activated by ultrasonic method showed the greatest conversions in methyl esters. The 10% WO3/USY US catalyst presented the best performance, converting 87% of oleic acid to methyl oleate after 3 hours of reaction, at 240 °C, with a ratio of oleic acid and methyl acetate of 1:10 and 10% (w/w) of catalyst. The use of WO3/USY zeolite shows a viable and effective catalyst to esterification of oleic acid with methyl acetate, which is in accordance to prospects of free-glycerol biodiesel production.Este trabalho propõe a utilização de zeólita USY ativada com óxido de tungstênio na reação de esterificação do ácido oleico com acetato de metila. Ácido tunguístico foi preparado a partir do tratamento ácido do tungstato de sódio e utilizado como precursor. A caracterização dos catalisadores mostrou que a estrutura geral da zeólita foi mantida após a impregnação. No entanto, o perfil de acidez das zeólitas WO3/USY foi fortemente alterado, onde os sítios fortes ácidos de Brønsted da zeólita original foram bloqueados pelo óxido de tungstênio, possibilitando o acesso dos reagentes a novos sítios ácidos de Lewis e ligações de hidrogênio. Esta alteração do mecanismo de adsorção favoreceu a conversão de ácido oleico em oleato de metila. O modelo pseudo-homogêneo (PH) reversível de primeira ordem foi capaz de representar os dados experimentais da reação catalisada pela zeólita USY, ao passo que os modelos heterogêneos (ER e LH) foram classificados como sobreparametrizados e, por isso, desconsiderados. A modelagem cinética e termodinâmica mostrou que a reação é endotérmica, com variação de entalpia de 59,83 kJ mol−1 e energia de ativação de 41,77 kJ mol−1. Um novo modelo cinético considerando os sítios ativos do catalisador WO3/USY se ajustou bem aos dados experimentais da reação catalisada por diferentes catalisadores. Os sítios ácidos de Brønsted da zeólita USY e os sítios ácidos fracos da zeólita WO3/USY apresentaram grande importância na reação de esterificação. As zeólitas ativadas pela via ultrassônica apresentaram as maiores conversões na obtenção de ésteres metílicos. O catalisador 10% WO3/USY US obteve o melhor desempenho, convertendo 87% do ácido oleico em metil oleato após 3 horas de reação, a 240°C, com proporção de ácido oleico e acetato de metila de 1:10 e 10% (m/m) de catalisador. Desta maneira, a zeólita WO3/USY se apresenta como uma forma viável e eficaz para a esterificação do ácido oleico com acetato de metila, que está alinhada à perspectiva de produção de biodiesel sem glicerol.porUniversidade Federal de Santa MariaCentro de TecnologiaPrograma de Pós-Graduação em Engenharia QuímicaUFSMBrasilEngenharia QuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessOleato de metilaPseudo-homogêneoEstimação de parâmetrosBiodieselGlicerolMethyl oleatePseudo-homogeneousParameter estimationBiodieselGlycerolCNPQ::ENGENHARIAS::ENGENHARIA QUIMICAEsterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinéticaEsterification of oleic acid and methyl acetate with WO3/USY: catalyst impregnation effects and kinetic modelinginfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisCastilhos, Fernanda dehttp://lattes.cnpq.br/4590978604104577Salau, Nina Paula GonçalvesDotto, Guilherme LuizEnzweiler, HevelineSilva, Willian Leonardo dahttp://lattes.cnpq.br/8067428535204228Ketzer, Felipe300600000006600600600600600340e815f-99e3-423d-b9d8-4333d082cb0f9b38b514-eb80-4764-a3a9-317425937f1ff6584a8d-b792-472e-b9cc-78d2529681e6ce06dd92-4d22-48c9-8063-6c0dc6c33b8e0a068f94-1d92-4b36-b0bb-50d4063c2e39ab4e5bdf-591c-436a-96d2-c6cb93dcac6ereponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGEQ_2020_KETZER_FELIPE.pdfTES_PPGEQ_2020_KETZER_FELIPE.pdfTese de Doutoradoapplication/pdf3514976http://repositorio.ufsm.br/bitstream/1/23283/1/TES_PPGEQ_2020_KETZER_FELIPE.pdf6767bd7ce61506c0e040e1a9a62a932dMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.ufsm.br/bitstream/1/23283/2/license_rdf4460e5956bc1d1639be9ae6146a50347MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-816http://repositorio.ufsm.br/bitstream/1/23283/3/license.txtf8fcb28efb1c8cf0dc096bec902bf4c4MD53TEXTTES_PPGEQ_2020_KETZER_FELIPE.pdf.txtTES_PPGEQ_2020_KETZER_FELIPE.pdf.txtExtracted texttext/plain335970http://repositorio.ufsm.br/bitstream/1/23283/4/TES_PPGEQ_2020_KETZER_FELIPE.pdf.txt6f797a2931ab8519edfa760fe7fa0fc0MD54THUMBNAILTES_PPGEQ_2020_KETZER_FELIPE.pdf.jpgTES_PPGEQ_2020_KETZER_FELIPE.pdf.jpgIM Thumbnailimage/jpeg4495http://repositorio.ufsm.br/bitstream/1/23283/5/TES_PPGEQ_2020_KETZER_FELIPE.pdf.jpgc825ef35b89f148e8b9d0bb930a8966aMD551/232832021-12-30 09:13:39.213oai:repositorio.ufsm.br:1/23283Q3JlYXRpdmUgQ29tbW9ucw==Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2021-12-30T12:13:39Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética |
dc.title.alternative.eng.fl_str_mv |
Esterification of oleic acid and methyl acetate with WO3/USY: catalyst impregnation effects and kinetic modeling |
title |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética |
spellingShingle |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética Ketzer, Felipe Oleato de metila Pseudo-homogêneo Estimação de parâmetros Biodiesel Glicerol Methyl oleate Pseudo-homogeneous Parameter estimation Biodiesel Glycerol CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética |
title_full |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética |
title_fullStr |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética |
title_full_unstemmed |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética |
title_sort |
Esterificação do ácido oleico e acetato de metila com zeólita WO3/USY: efeitos da impregnação do catalisador e modelagem cinética |
author |
Ketzer, Felipe |
author_facet |
Ketzer, Felipe |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Castilhos, Fernanda de |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/4590978604104577 |
dc.contributor.referee1.fl_str_mv |
Salau, Nina Paula Gonçalves |
dc.contributor.referee2.fl_str_mv |
Dotto, Guilherme Luiz |
dc.contributor.referee3.fl_str_mv |
Enzweiler, Heveline |
dc.contributor.referee4.fl_str_mv |
Silva, Willian Leonardo da |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/8067428535204228 |
dc.contributor.author.fl_str_mv |
Ketzer, Felipe |
contributor_str_mv |
Castilhos, Fernanda de Salau, Nina Paula Gonçalves Dotto, Guilherme Luiz Enzweiler, Heveline Silva, Willian Leonardo da |
dc.subject.por.fl_str_mv |
Oleato de metila Pseudo-homogêneo Estimação de parâmetros Biodiesel Glicerol |
topic |
Oleato de metila Pseudo-homogêneo Estimação de parâmetros Biodiesel Glicerol Methyl oleate Pseudo-homogeneous Parameter estimation Biodiesel Glycerol CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Methyl oleate Pseudo-homogeneous Parameter estimation Biodiesel Glycerol |
dc.subject.cnpq.fl_str_mv |
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA |
description |
This work proposes the use of USY zeolite activated with tungsten oxide in the esterification of oleic acid with methyl acetate. Tunguistic acid was synthesized trought the acid treatment of sodium tungstate and was used as a precursor. The characterization of the catalysts showed that the general structure of the zeolite was maintained after impregnation. However, the acidity profile of WO3/USY zeolites has been highly altered, where the strong Brønsted acid sites of the original zeolite have been blocked by tungsten oxide, allowing the reagents to have been accessed to the new Lewis acid sites and hydrogen bonds. The change of adsorption mechanism favored the conversion of oleic acid to methyl oleate. The first-order reversible pseudo-homogeneous (PH) model was able to represent the experimental data catalyzed by the USY zeolite, since the heterogeneous models (ER and LH) were classified as overparameterized and were disregarded. Kinetic and thermodynamic modeling showed that the reaction is endothermic, with change in enthalpy of 59.83 kJ mol−1 and activation energy of 41.77 kJ mol−1. The proposal of a novel kinetic model considering the active sites of the WO3/USY catalyst shown a good fit to the experimental data of the reaction catalyzed by different catalysts. The Brønsted acidic sites of the USY zeolite and the weak acidic sites of the WO3/USY zeolite showed great importance in the esterification reaction. The zeolites activated by ultrasonic method showed the greatest conversions in methyl esters. The 10% WO3/USY US catalyst presented the best performance, converting 87% of oleic acid to methyl oleate after 3 hours of reaction, at 240 °C, with a ratio of oleic acid and methyl acetate of 1:10 and 10% (w/w) of catalyst. The use of WO3/USY zeolite shows a viable and effective catalyst to esterification of oleic acid with methyl acetate, which is in accordance to prospects of free-glycerol biodiesel production. |
publishDate |
2020 |
dc.date.issued.fl_str_mv |
2020-01-20 |
dc.date.accessioned.fl_str_mv |
2021-12-13T20:04:28Z |
dc.date.available.fl_str_mv |
2021-12-13T20:04:28Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/23283 |
url |
http://repositorio.ufsm.br/handle/1/23283 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
300600000006 |
dc.relation.confidence.fl_str_mv |
600 600 600 600 600 |
dc.relation.authority.fl_str_mv |
340e815f-99e3-423d-b9d8-4333d082cb0f 9b38b514-eb80-4764-a3a9-317425937f1f f6584a8d-b792-472e-b9cc-78d2529681e6 ce06dd92-4d22-48c9-8063-6c0dc6c33b8e 0a068f94-1d92-4b36-b0bb-50d4063c2e39 ab4e5bdf-591c-436a-96d2-c6cb93dcac6e |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
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openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Tecnologia |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Engenharia Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Engenharia Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Tecnologia |
dc.source.none.fl_str_mv |
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