Oxidação Parcial do Metano em catalisadores Rh/Ce-ZrO2

Detalhes bibliográficos
Autor(a) principal: Oliveira, Raquel Lima
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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spelling 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:21202021-03-10T19:09:35Repositório 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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