Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério

Detalhes bibliográficos
Autor(a) principal: Xavier, Thiago Padovani
Data de Publicação: 2011
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Repositório Institucional da UFU
Texto Completo: https://repositorio.ufu.br/handle/123456789/15208
https://doi.org/10.14393/ufu.di.2011.79
Resumo: In the present study, the behavior of La1-xCexNiO3 (x = 0; 0.05 and 0.10) perovskite-type oxides catalysts was investigated, acting as catalysts, in reactions of dry reforming of methane (DRM) and biogas reforming (BR). The catalysts were synthesized by sol-gel method (or citrate) and by combustion with urea. Later, they were structurally evaluated and studied on the catalytic performance. The synthesized perovskite-type oxides were characterized by X-ray diffraction, nitrogen adsorption temperature programmed reduction and thermal gravimetric analysis. The catalysts showed low values of specific area (< 10 m2 g-1). The LaNiO3 phase present in all the calcined samples was converted into La2O3, Ni0 and La(OH)3 after reduction, keeping the phase CeO2 in the doped samples with cerium. It was observed more evident La(OH)3 phase in the samples synthesized by combustion method. The average crystallite sizes, on the main stage LaNiO3, remained between 13 to 17 nm. La0,90Ce0,10NiO3 synthesized by combustion had the lowest average crystallite size whereas La0, 95Ce0,05NiO3 and La0,90Ce0,10NiO3 synthesized by sol-gel method has the highest value. The sol-gel method produced NiO grains (20-25 nm) smaller than those produced by the combustion method (31 - 38 nm). But for all samples is observed a decrease in average Ni0 grain sizes after reduction. In the samples synthesized by combustion method the mean Ni0 crystallite size were similar (20, 19 and 21 nm), whereas the values increased with Ce addition (13 21 nm) in the samples synthesized by sol-gel method. All samples with 1:9 dilution (catalyst/ inert SiC) were active, stable and resistant to deactivation by coke deposition after 24 h of DRM and BR reactions, but with molar ratio H2/CO < 1. The La0,90Ce0,10NiO3 catalyst synthesized by sol-gel method, with 1:1 dilution (catalyst/ inert SiC) showed the greatest resistance to the carbon formation (1,06 mg Carbon / gcat h). The catalysts synthesized by the combustion method, when 1:9 diluted, showed TOFCH4 values between 13 - 16 in the DRM and between 15 - 19 in BR, with molar ratio H2/CO next 1. The catalysts synthesized by combustion method, with 1:1 dilution (catalyst/inert SiC) were more active (TOFCH4 8 13 h-1) in BR reaction than the catalysts synthesized by sol-gel method (TOFCH4 3 4 h-1). The lower values for the stoichiometric H2/CO <1 indicate favoring the reverse reaction of water-gas shift in catalytic tests, supported by the fact that higher CO2 conversion in all reactions usin catalysts with 1:9 dilution. There was a molar ratio H2/CO increase in the RB, especially when used as the catalyst with 1:1 dilution (catalyst/inert SiC), indicating that reverse water-gas shift reaction is less favored when feed CH4: CO2 = 2 and using a larger amount of catalyst.
id UFU_dc6d0447d5bd1ccc9de50d4f065f9757
oai_identifier_str oai:repositorio.ufu.br:123456789/15208
network_acronym_str UFU
network_name_str Repositório Institucional da UFU
repository_id_str
spelling Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cérioPerovskitaNíquelLantânioCérioCaracterização de catalisadoresReforma do metanoReforma de biogásHidrogênioCatalisadoresPerovskiteNickelLanthanumCeriumCatalysts characterizationMethane reformingBiogas reformingCNPQ::ENGENHARIAS::ENGENHARIA QUIMICAIn the present study, the behavior of La1-xCexNiO3 (x = 0; 0.05 and 0.10) perovskite-type oxides catalysts was investigated, acting as catalysts, in reactions of dry reforming of methane (DRM) and biogas reforming (BR). The catalysts were synthesized by sol-gel method (or citrate) and by combustion with urea. Later, they were structurally evaluated and studied on the catalytic performance. The synthesized perovskite-type oxides were characterized by X-ray diffraction, nitrogen adsorption temperature programmed reduction and thermal gravimetric analysis. The catalysts showed low values of specific area (< 10 m2 g-1). The LaNiO3 phase present in all the calcined samples was converted into La2O3, Ni0 and La(OH)3 after reduction, keeping the phase CeO2 in the doped samples with cerium. It was observed more evident La(OH)3 phase in the samples synthesized by combustion method. The average crystallite sizes, on the main stage LaNiO3, remained between 13 to 17 nm. La0,90Ce0,10NiO3 synthesized by combustion had the lowest average crystallite size whereas La0, 95Ce0,05NiO3 and La0,90Ce0,10NiO3 synthesized by sol-gel method has the highest value. The sol-gel method produced NiO grains (20-25 nm) smaller than those produced by the combustion method (31 - 38 nm). But for all samples is observed a decrease in average Ni0 grain sizes after reduction. In the samples synthesized by combustion method the mean Ni0 crystallite size were similar (20, 19 and 21 nm), whereas the values increased with Ce addition (13 21 nm) in the samples synthesized by sol-gel method. All samples with 1:9 dilution (catalyst/ inert SiC) were active, stable and resistant to deactivation by coke deposition after 24 h of DRM and BR reactions, but with molar ratio H2/CO < 1. The La0,90Ce0,10NiO3 catalyst synthesized by sol-gel method, with 1:1 dilution (catalyst/ inert SiC) showed the greatest resistance to the carbon formation (1,06 mg Carbon / gcat h). The catalysts synthesized by the combustion method, when 1:9 diluted, showed TOFCH4 values between 13 - 16 in the DRM and between 15 - 19 in BR, with molar ratio H2/CO next 1. The catalysts synthesized by combustion method, with 1:1 dilution (catalyst/inert SiC) were more active (TOFCH4 8 13 h-1) in BR reaction than the catalysts synthesized by sol-gel method (TOFCH4 3 4 h-1). The lower values for the stoichiometric H2/CO <1 indicate favoring the reverse reaction of water-gas shift in catalytic tests, supported by the fact that higher CO2 conversion in all reactions usin catalysts with 1:9 dilution. There was a molar ratio H2/CO increase in the RB, especially when used as the catalyst with 1:1 dilution (catalyst/inert SiC), indicating that reverse water-gas shift reaction is less favored when feed CH4: CO2 = 2 and using a larger amount of catalyst.Mestre em Engenharia QuímicaNo presente trabalho, foi avaliado o comportamento de óxidos do tipo perovskitas La1-xCexNiO3 (x = 0; 0,05 e 0,10), atuando como catalisadores, frente às reações de reforma seca do metano (RSM) e reforma de biogás (RB). Os catalisadores foram sintetizados pelo método sol-gel (ou citrato) e pelo método de combustão com uréia. Posteriormente, foram avaliados estruturalmente e quanto ao seu desempenho catalítico. Os precursores catalíticos foram caracterizados por difração de raios X, medidas de área específica BET, redução a temperatura programada e análise termogravimétrica. Todos os catalisadores apresentaram baixos valores de área específica (< 10 m2 g-1). A fase principal LaNiO3, presente em todas as amostras calcinadas, foi convertida em La2O3, Ni0 e La(OH)3 após redução, sendo observada a fase CeO2 nas amostras dopadas com cério. A presença da fase La(OH)3 foi mais evidente nas amostras sintetizadas pelo método de combustão. Os tamanhos médios de cristalito, referentes à fase principal LaNiO3, se mantiveram entre 13 17 nm. A amostra La0,90Ce0,10NiO3 sintetizada pelo método de combustão apresentou o menor tamanho médio de cristalito enquanto que as amostras La0,95Ce0,05NiO3 e La0,90Ce0,10NiO3 sintetizadas pelo método sol-gel tem o maior valor. O método sol-gel produziu tamanhos médios de cristalito do NiO (20 25 nm) menores do que os produzidos pelo método de combustão (31 38 nm). Porém, para todas as amostras, é observada uma diminuição nos tamanhos médios de cristalito de Ni0 após a redução/passivação. Nas amostras sintetizadas pelo método de combustão os tamanhos médios de cristalito do Ni0 foram semelhantes (20, 19 e 21 nm), enquanto que nas amostras sintetizadas por sol-gel os valores cresceram com a adição de Ce (13 21 nm). Todas as amostras com diluição de 1:9 (catalisador/inerte SiC) foram ativas, estáveis e resistentes à desativação pela deposição de coque após as 24 h das reações RSM e RB, porém com razão molar H2/CO < 1. O catalisador La0,90Ce0,10NiO3 sintetizado pelo método sol-gel, com diluição 1:1 (catalisador/inerte SiC) apresentou a maior resistência à formação de carbono (1,06 mg Carbono / gcat h). Os catalisadores sintetizados pelo método de combustão, quando diluídos 1:9 (catalisador/inerte SiC), apresentaram valores de TOFCH4 entre 13 16 h-1 na RSM e entre 15 - 19 h-1 na RB com razões molares H2/CO próximas de 1. Os catalisadores sintetizados pelo método de combustão com diluição de 1:1 (catalisador/inerte SiC) se mostraram mais ativos (TOFCH4 8 13 h-1) na RB do que os catalisadores sintetizados pelo método sol-gel (TOFCH4 3 4 h-1). Os valores menores que o estequiométrico para H2/CO < 1 indicam o favorecimento da reação reversa de deslocamento gás-água nos testes catalíticos, fato suportado pela maior conversão de CO2 em todas as reações utilizando catalisadores com diluição 1:9. Na condição de RB houve um aumento da razão molar H2/CO, especialmente quando forma utilizados os catalisadores com diluição 1:1 (catalisador/inerte SiC), indicando que reação reversa de deslocamento gás-água é menos favorecida quando a razão de alimentação é de CH4:CO2 = 2 e utilizando uma maior quantidade de catalisador.Universidade Federal de UberlândiaBRPrograma de Pós-graduação em Engenharia QuímicaEngenhariasUFUNoronha, Fabio Bellothttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782218A6Hori, Carla Eponinahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784205E1Dantas, Sandra Cristinahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4737572Y0Watanabe, érika Ohtahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762096Z9Lima, Sania Maria dehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4707955P5Xavier, Thiago Padovani2016-06-22T18:41:48Z2013-08-122016-06-22T18:41:48Z2011-08-22info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfapplication/pdfXAVIER, Thiago Padovani. Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério. 2011. 89 f. Dissertação (Mestrado em Engenharias) - Universidade Federal de Uberlândia, Uberlândia, 2011. DOI https://doi.org/10.14393/ufu.di.2011.79https://repositorio.ufu.br/handle/123456789/15208https://doi.org/10.14393/ufu.di.2011.79porinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFUinstname:Universidade Federal de Uberlândia (UFU)instacron:UFU2022-12-27T14:50:46Zoai:repositorio.ufu.br:123456789/15208Repositório InstitucionalONGhttp://repositorio.ufu.br/oai/requestdiinf@dirbi.ufu.bropendoar:2022-12-27T14:50:46Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)false
dc.title.none.fl_str_mv Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
title Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
spellingShingle Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
Xavier, Thiago Padovani
Perovskita
Níquel
Lantânio
Cério
Caracterização de catalisadores
Reforma do metano
Reforma de biogás
Hidrogênio
Catalisadores
Perovskite
Nickel
Lanthanum
Cerium
Catalysts characterization
Methane reforming
Biogas reforming
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
title_short Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
title_full Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
title_fullStr Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
title_full_unstemmed Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
title_sort Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério
author Xavier, Thiago Padovani
author_facet Xavier, Thiago Padovani
author_role author
dc.contributor.none.fl_str_mv Noronha, Fabio Bellot
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782218A6
Hori, Carla Eponina
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784205E1
Dantas, Sandra Cristina
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4737572Y0
Watanabe, érika Ohta
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762096Z9
Lima, Sania Maria de
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4707955P5
dc.contributor.author.fl_str_mv Xavier, Thiago Padovani
dc.subject.por.fl_str_mv Perovskita
Níquel
Lantânio
Cério
Caracterização de catalisadores
Reforma do metano
Reforma de biogás
Hidrogênio
Catalisadores
Perovskite
Nickel
Lanthanum
Cerium
Catalysts characterization
Methane reforming
Biogas reforming
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
topic Perovskita
Níquel
Lantânio
Cério
Caracterização de catalisadores
Reforma do metano
Reforma de biogás
Hidrogênio
Catalisadores
Perovskite
Nickel
Lanthanum
Cerium
Catalysts characterization
Methane reforming
Biogas reforming
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
description In the present study, the behavior of La1-xCexNiO3 (x = 0; 0.05 and 0.10) perovskite-type oxides catalysts was investigated, acting as catalysts, in reactions of dry reforming of methane (DRM) and biogas reforming (BR). The catalysts were synthesized by sol-gel method (or citrate) and by combustion with urea. Later, they were structurally evaluated and studied on the catalytic performance. The synthesized perovskite-type oxides were characterized by X-ray diffraction, nitrogen adsorption temperature programmed reduction and thermal gravimetric analysis. The catalysts showed low values of specific area (< 10 m2 g-1). The LaNiO3 phase present in all the calcined samples was converted into La2O3, Ni0 and La(OH)3 after reduction, keeping the phase CeO2 in the doped samples with cerium. It was observed more evident La(OH)3 phase in the samples synthesized by combustion method. The average crystallite sizes, on the main stage LaNiO3, remained between 13 to 17 nm. La0,90Ce0,10NiO3 synthesized by combustion had the lowest average crystallite size whereas La0, 95Ce0,05NiO3 and La0,90Ce0,10NiO3 synthesized by sol-gel method has the highest value. The sol-gel method produced NiO grains (20-25 nm) smaller than those produced by the combustion method (31 - 38 nm). But for all samples is observed a decrease in average Ni0 grain sizes after reduction. In the samples synthesized by combustion method the mean Ni0 crystallite size were similar (20, 19 and 21 nm), whereas the values increased with Ce addition (13 21 nm) in the samples synthesized by sol-gel method. All samples with 1:9 dilution (catalyst/ inert SiC) were active, stable and resistant to deactivation by coke deposition after 24 h of DRM and BR reactions, but with molar ratio H2/CO < 1. The La0,90Ce0,10NiO3 catalyst synthesized by sol-gel method, with 1:1 dilution (catalyst/ inert SiC) showed the greatest resistance to the carbon formation (1,06 mg Carbon / gcat h). The catalysts synthesized by the combustion method, when 1:9 diluted, showed TOFCH4 values between 13 - 16 in the DRM and between 15 - 19 in BR, with molar ratio H2/CO next 1. The catalysts synthesized by combustion method, with 1:1 dilution (catalyst/inert SiC) were more active (TOFCH4 8 13 h-1) in BR reaction than the catalysts synthesized by sol-gel method (TOFCH4 3 4 h-1). The lower values for the stoichiometric H2/CO <1 indicate favoring the reverse reaction of water-gas shift in catalytic tests, supported by the fact that higher CO2 conversion in all reactions usin catalysts with 1:9 dilution. There was a molar ratio H2/CO increase in the RB, especially when used as the catalyst with 1:1 dilution (catalyst/inert SiC), indicating that reverse water-gas shift reaction is less favored when feed CH4: CO2 = 2 and using a larger amount of catalyst.
publishDate 2011
dc.date.none.fl_str_mv 2011-08-22
2013-08-12
2016-06-22T18:41:48Z
2016-06-22T18:41:48Z
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 XAVIER, Thiago Padovani. Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério. 2011. 89 f. Dissertação (Mestrado em Engenharias) - Universidade Federal de Uberlândia, Uberlândia, 2011. DOI https://doi.org/10.14393/ufu.di.2011.79
https://repositorio.ufu.br/handle/123456789/15208
https://doi.org/10.14393/ufu.di.2011.79
identifier_str_mv XAVIER, Thiago Padovani. Reforma de biogás para produção de hidrogênio usando catalisadores tipo perovskitas a base de lantânio e níquel, dopados com cério. 2011. 89 f. Dissertação (Mestrado em Engenharias) - Universidade Federal de Uberlândia, Uberlândia, 2011. DOI https://doi.org/10.14393/ufu.di.2011.79
url https://repositorio.ufu.br/handle/123456789/15208
https://doi.org/10.14393/ufu.di.2011.79
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Uberlândia
BR
Programa de Pós-graduação em Engenharia Química
Engenharias
UFU
publisher.none.fl_str_mv Universidade Federal de Uberlândia
BR
Programa de Pós-graduação em Engenharia Química
Engenharias
UFU
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFU
instname:Universidade Federal de Uberlândia (UFU)
instacron:UFU
instname_str Universidade Federal de Uberlândia (UFU)
instacron_str UFU
institution UFU
reponame_str Repositório Institucional da UFU
collection Repositório Institucional da UFU
repository.name.fl_str_mv Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)
repository.mail.fl_str_mv diinf@dirbi.ufu.br
_version_ 1813711378638176256