Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2
Autor(a) principal: | |
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Data de Publicação: | 2008 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da Universidade Federal Fluminense (RIUFF) |
Texto Completo: | https://app.uff.br/riuff/handle/1/17101 |
Resumo: | Hydrogen in the main fuel for fuel cells. The lack of hydrogen infrastructure and the problem of dissolved hydrogen storage had stimulated the development of compact fuel reformers, which are able to produce a rich hydrogen gas mixture from fuels such as the hydrocarbons. Due to its abundance and high ratio H: C, methane (CH4) in an ideal hydrogen source. The process of partial oxidation of the methane is one of the known methods for hydrogen production. In this process the fuel reacts with a limited amount of oxygen to produce hydrogen, purification is required later. The partial oxidation can be applied in different types of hydrocarbons, including heavy fuel and solid hydrocarbons. The present work has investigated the catalytic activity of rhodium supported on γ-Al2O3, CeO2, ZrO2 and Ce-ZrO2, with the purpose to evaluate the influence of the support in the activity of these catalysers in the reaction of partial oxidation of the methane. Al physical-chemistry characterization techniques were used as X ray diffraction (XRD), Difuse reflectance spectroscopy ultraviolet-visible (DRS-UV-vis), temperature programmed reduction (TPR), chemissortion, the model reaction of ciclohexane dehydrogenation and temperature programmed surface reaction (TPSR). TPSR allowed to evaluate the mechanism of CH4 conversion. The analysis of the TPR profiles allowed to conclude that the addition of the metal to the Ce-ZrO2 supports promotes the reduction of the solid solution at lower temperatures than the ones verified in the absence of rhodium. The chemisorption analysis, and the TPSR results, showed that the catalytic activity is related to the amount of metallic sites on the surface. Regarding of the activity test, all the catalysts showed an initial induction time, except for 1.5% Rh/Al2O3. After this induction time, the catalysts kept stable during 24 hours of reaction. In general, it was verified that the catalytic activity increases with the dispersion for all the catalysts. |
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Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2Partial Oxidation of Methane in catalysts Rh/Ce-ZrO2Oxidação parcialMetanoCatalisadorMetano - PropriedadesOxidaçãoasCatalytic converterMethane - PropertiesOxidationCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICAHydrogen in the main fuel for fuel cells. The lack of hydrogen infrastructure and the problem of dissolved hydrogen storage had stimulated the development of compact fuel reformers, which are able to produce a rich hydrogen gas mixture from fuels such as the hydrocarbons. Due to its abundance and high ratio H: C, methane (CH4) in an ideal hydrogen source. The process of partial oxidation of the methane is one of the known methods for hydrogen production. In this process the fuel reacts with a limited amount of oxygen to produce hydrogen, purification is required later. The partial oxidation can be applied in different types of hydrocarbons, including heavy fuel and solid hydrocarbons. The present work has investigated the catalytic activity of rhodium supported on γ-Al2O3, CeO2, ZrO2 and Ce-ZrO2, with the purpose to evaluate the influence of the support in the activity of these catalysers in the reaction of partial oxidation of the methane. Al physical-chemistry characterization techniques were used as X ray diffraction (XRD), Difuse reflectance spectroscopy ultraviolet-visible (DRS-UV-vis), temperature programmed reduction (TPR), chemissortion, the model reaction of ciclohexane dehydrogenation and temperature programmed surface reaction (TPSR). TPSR allowed to evaluate the mechanism of CH4 conversion. The analysis of the TPR profiles allowed to conclude that the addition of the metal to the Ce-ZrO2 supports promotes the reduction of the solid solution at lower temperatures than the ones verified in the absence of rhodium. The chemisorption analysis, and the TPSR results, showed that the catalytic activity is related to the amount of metallic sites on the surface. Regarding of the activity test, all the catalysts showed an initial induction time, except for 1.5% Rh/Al2O3. After this induction time, the catalysts kept stable during 24 hours of reaction. In general, it was verified that the catalytic activity increases with the dispersion for all the catalysts.Conselho Nacional de Desenvolvimento Cientifico e TecnológicoO principal combustível para células a combustível é o hidrogênio. A falta de infraestrutura de hidrogênio e o problema de armazenamento de hidrogênio incentivaram o desenvolvimento de reformadores de combustível compactos, os quais são capazes de produzir um gás rico em hidrogênio a partir de combustíveis como os hidrocarbonetos. Metano (CH4), devido à sua abundância e alta vazão H:C torna-o uma fonte ideal de hidrogênio. O processo de oxidação parcial do metano é um dos métodos mais conhecidos e antigos de produção de hidrogênio. Neste processo o combustível reage com uma quantidade limitada de oxigênio para produzir o hidrogênio, que depois é purificado. A oxidação parcial do metano pode ser aplicada em diferentes tipos de hidrocarbonetos, incluindo combustíveis pesados e hidrocarbonetos sólidos. No presente trabalho foram investigados catalisadores de ródio suportados em γ-Al2O3, CeO2, ZrO2 e Ce-ZrO2, com a finalidade de avaliar a influência do suporte na atividade destes catalisadores na reação de oxidação parcial do metano. Foram utilizadas técnicas de caracterização físico-químicas como difração de raios X (DRX), espectroscopia no ultra-violeta visível com reflectância difusa (DRS), redução à temperatura programada (TPR), quimissorção e a reação modelo de desidrogenação do cicloexano. Foram realizados ainda, experimentos de reação superficial a temperatura programada (TPSR) que permitiram avaliar o mecanismo de conversão do metano. A análise dos perfis de TPR permitiu concluir que a adição do metal aos suportes Ce- ZrO2 promove a redução da solução sólida em temperaturas inferiores às verificadas na ausência do ródio. Os ensaios de quimissorção, em conjunto com os resultados de TPSR, mostraram que a atividade catalítica está diretamente relacionada com a quantidade de sítios metálicos presentes na superfície. Com relação ao teste de atividade, todos os catalisadores apresentaram um tempo de indução inicial, exceto o catalisador 1,5% Rh/Al2O3. Após esse tempo de indução foi verificado que os catalisadores se mantiveram estáveis durante 24 h de reação. E, de modo geral, verificouse que a atividade aumenta com a dispersão para todos os catalisadores.Programa de Pós-graduação em QuímicaQuímicaPassos, Fabio BarbozaCPF:84590628737http://genos.cnpq.br:12010/dwlattes/owa/prc_imp_cv_int?f_cod=K4784205D6Carvalho, Carlos Eduardo MartinsCPF:76859587522http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782395D8&dataRevisao=nullCarneiro, José Walkimar de MesquitaCPF:45657447857http://genos.cnpq.br:12010/dwlattes/owa/prc_imp_cv_int?f_cod=K4781147U4Mattos, Lisiane VeigaCPF:00505053422http://lattes.cnpq.br/9588738213862295Oliveira, Raquel Lima2021-03-10T19:09:35Z2008-02-292021-03-10T19:09:35Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfapplication/pdfhttps://app.uff.br/riuff/handle/1/17101porCC-BY-SAinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Federal Fluminense (RIUFF)instname:Universidade Federal Fluminense (UFF)instacron:UFF2021-03-10T19:09:35Zoai:app.uff.br:1/17101Repositório InstitucionalPUBhttps://app.uff.br/oai/requestriuff@id.uff.bropendoar:21202024-08-19T11:15:16.262076Repositório Institucional da Universidade Federal Fluminense (RIUFF) - Universidade Federal Fluminense (UFF)false |
dc.title.none.fl_str_mv |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 Partial Oxidation of Methane in catalysts Rh/Ce-ZrO2 |
title |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 |
spellingShingle |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 Oliveira, Raquel Lima Oxidação parcial Metano Catalisador Metano - Propriedades Oxidação as Catalytic converter Methane - Properties Oxidation CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
title_short |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 |
title_full |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 |
title_fullStr |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 |
title_full_unstemmed |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 |
title_sort |
Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2 |
author |
Oliveira, Raquel Lima |
author_facet |
Oliveira, Raquel Lima |
author_role |
author |
dc.contributor.none.fl_str_mv |
Passos, Fabio Barboza CPF:84590628737 http://genos.cnpq.br:12010/dwlattes/owa/prc_imp_cv_int?f_cod=K4784205D6 Carvalho, Carlos Eduardo Martins CPF:76859587522 http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782395D8&dataRevisao=null Carneiro, José Walkimar de Mesquita CPF:45657447857 http://genos.cnpq.br:12010/dwlattes/owa/prc_imp_cv_int?f_cod=K4781147U4 Mattos, Lisiane Veiga CPF:00505053422 http://lattes.cnpq.br/9588738213862295 |
dc.contributor.author.fl_str_mv |
Oliveira, Raquel Lima |
dc.subject.por.fl_str_mv |
Oxidação parcial Metano Catalisador Metano - Propriedades Oxidação as Catalytic converter Methane - Properties Oxidation CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
topic |
Oxidação parcial Metano Catalisador Metano - Propriedades Oxidação as Catalytic converter Methane - Properties Oxidation CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
description |
Hydrogen in the main fuel for fuel cells. The lack of hydrogen infrastructure and the problem of dissolved hydrogen storage had stimulated the development of compact fuel reformers, which are able to produce a rich hydrogen gas mixture from fuels such as the hydrocarbons. Due to its abundance and high ratio H: C, methane (CH4) in an ideal hydrogen source. The process of partial oxidation of the methane is one of the known methods for hydrogen production. In this process the fuel reacts with a limited amount of oxygen to produce hydrogen, purification is required later. The partial oxidation can be applied in different types of hydrocarbons, including heavy fuel and solid hydrocarbons. The present work has investigated the catalytic activity of rhodium supported on γ-Al2O3, CeO2, ZrO2 and Ce-ZrO2, with the purpose to evaluate the influence of the support in the activity of these catalysers in the reaction of partial oxidation of the methane. Al physical-chemistry characterization techniques were used as X ray diffraction (XRD), Difuse reflectance spectroscopy ultraviolet-visible (DRS-UV-vis), temperature programmed reduction (TPR), chemissortion, the model reaction of ciclohexane dehydrogenation and temperature programmed surface reaction (TPSR). TPSR allowed to evaluate the mechanism of CH4 conversion. The analysis of the TPR profiles allowed to conclude that the addition of the metal to the Ce-ZrO2 supports promotes the reduction of the solid solution at lower temperatures than the ones verified in the absence of rhodium. The chemisorption analysis, and the TPSR results, showed that the catalytic activity is related to the amount of metallic sites on the surface. Regarding of the activity test, all the catalysts showed an initial induction time, except for 1.5% Rh/Al2O3. After this induction time, the catalysts kept stable during 24 hours of reaction. In general, it was verified that the catalytic activity increases with the dispersion for all the catalysts. |
publishDate |
2008 |
dc.date.none.fl_str_mv |
2008-02-29 2021-03-10T19:09:35Z 2021-03-10T19:09:35Z |
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 |
https://app.uff.br/riuff/handle/1/17101 |
url |
https://app.uff.br/riuff/handle/1/17101 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
CC-BY-SA info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
CC-BY-SA |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Programa de Pós-graduação em Química Química |
publisher.none.fl_str_mv |
Programa de Pós-graduação em Química Química |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da Universidade Federal Fluminense (RIUFF) instname:Universidade Federal Fluminense (UFF) instacron:UFF |
instname_str |
Universidade Federal Fluminense (UFF) |
instacron_str |
UFF |
institution |
UFF |
reponame_str |
Repositório Institucional da Universidade Federal Fluminense (RIUFF) |
collection |
Repositório Institucional da Universidade Federal Fluminense (RIUFF) |
repository.name.fl_str_mv |
Repositório Institucional da Universidade Federal Fluminense (RIUFF) - Universidade Federal Fluminense (UFF) |
repository.mail.fl_str_mv |
riuff@id.uff.br |
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1811823703259873280 |