Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma
Autor(a) principal: | |
---|---|
Data de Publicação: | 2021 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/18065 |
Resumo: | This thesis evaluated the application of Ni-, Fe- and Ni-Fe/MgAl2O4 catalysts in Ethanol Steam Reforming (ESR), Ethanol Steam Reforming with hydrogen gas (ESRH), Methane Dry Reforming (RSM), Methane Steam Reforming (RVM) and Methane Bi-Reforming (BRM) reactions evaluating the influence of reaction medium composition and Ni:Fe ratio on the catalytic behavior. Two series of NiFe/MgAl2O4 catalysts were prepared, the first keeping the Ni content at 8 wt.% and varying the Fe content, and the second keeping the total metallic content fixed at 15 wt.%. The properties of the catalysts were investigated by X-ray diffraction, N2 physisorption and temperature-programmed reduction. The characterizations showed the formation of high purity support with high surface area. Although the iron catalyst had low activity in methane reforms, the Ni and NiFe catalysts were active in these reactions. The addition of iron increased the conversion of methane on RVM, indicating the iron-promoter character on this reaction. Ethanol catalytic tests were carried out under ESR conditions (H2O/C2H6O ratio equal to 3) and in ESRH (ESR strongly reduced by the addition of H2) between 250 and 650 °C. In situ XRD and in situ XANES analyzes were performed during the reduction in H2 and in the ESR and ESRH reactions to evaluate the catalyst dynamics under these conditions. The addition of iron reduced methane production and carbon deposition, increasing stability in ESR. The bimetallic catalysts formed the NiFe2O4 phase which, when reduced, formed the NiFe alloy. When the catalysts were placed in contact with the ESR reagents, partial oxidation of nickel and iron particles occurred at low temperatures, reducing the catalytic activity. As the temperature increased, nickel particles reduced and activity increased. Iron particles were more susceptible to oxidation, migrating to the surface in the form of oxides and partially segregating from the alloy. This small oxidation favored the catalytic stability by reducing the carbon production compared to the catalyst that contained only nickel. The intensity of this process depends on the composition of the reactants and catalysts. In ESRH, the oxidation process of the particles was milder, stabilizing the catalyst structure and increasing the activity at low temperatures. In this way, it was possible to evaluate that the composition of the reaction medium and the metallic charge influenced the catalytic performance. |
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Lara, Thais Paula NogueiraBueno, José Maria Corrêahttp://lattes.cnpq.br/0157452280626031http://lattes.cnpq.br/9889214612048325https://orcid.org/0000-0002-4229-111222f1b10b-9811-41cd-ad03-5d413c90a6992023-05-24T14:17:03Z2023-05-24T14:17:03Z2021-12-20LARA, Thais Paula Nogueira. Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/18065.https://repositorio.ufscar.br/handle/ufscar/18065This thesis evaluated the application of Ni-, Fe- and Ni-Fe/MgAl2O4 catalysts in Ethanol Steam Reforming (ESR), Ethanol Steam Reforming with hydrogen gas (ESRH), Methane Dry Reforming (RSM), Methane Steam Reforming (RVM) and Methane Bi-Reforming (BRM) reactions evaluating the influence of reaction medium composition and Ni:Fe ratio on the catalytic behavior. Two series of NiFe/MgAl2O4 catalysts were prepared, the first keeping the Ni content at 8 wt.% and varying the Fe content, and the second keeping the total metallic content fixed at 15 wt.%. The properties of the catalysts were investigated by X-ray diffraction, N2 physisorption and temperature-programmed reduction. The characterizations showed the formation of high purity support with high surface area. Although the iron catalyst had low activity in methane reforms, the Ni and NiFe catalysts were active in these reactions. The addition of iron increased the conversion of methane on RVM, indicating the iron-promoter character on this reaction. Ethanol catalytic tests were carried out under ESR conditions (H2O/C2H6O ratio equal to 3) and in ESRH (ESR strongly reduced by the addition of H2) between 250 and 650 °C. In situ XRD and in situ XANES analyzes were performed during the reduction in H2 and in the ESR and ESRH reactions to evaluate the catalyst dynamics under these conditions. The addition of iron reduced methane production and carbon deposition, increasing stability in ESR. The bimetallic catalysts formed the NiFe2O4 phase which, when reduced, formed the NiFe alloy. When the catalysts were placed in contact with the ESR reagents, partial oxidation of nickel and iron particles occurred at low temperatures, reducing the catalytic activity. As the temperature increased, nickel particles reduced and activity increased. Iron particles were more susceptible to oxidation, migrating to the surface in the form of oxides and partially segregating from the alloy. This small oxidation favored the catalytic stability by reducing the carbon production compared to the catalyst that contained only nickel. The intensity of this process depends on the composition of the reactants and catalysts. In ESRH, the oxidation process of the particles was milder, stabilizing the catalyst structure and increasing the activity at low temperatures. In this way, it was possible to evaluate that the composition of the reaction medium and the metallic charge influenced the catalytic performance.Esta tese avaliou a aplicação de catalisadores Ni-, Fe- e Ni-Fe/MgAl2O4 nas reações de Reforma à Vapor do Etanol (ESR), Reforma a Vapor do Etanol com Gás Hidrogênio (ESRH), Reforma Seca do Metano (RSM), Reforma a Vapor do Metano (RVM) e Bireforma do Metano (BRM) avaliando a influência da composição do meio reacional e da proporção Ni:Fe no comportamento catalítico. Foram preparadas duas séries de catalisadores NiFe/MgAl2O4, a primeira com a carga de Ni mantida em 8 wt.% e variando-se a carga de Fe, e a segunda mantendo-se a carga metálica total fixada em 15 wt.%. As propriedades dos catalisadores foram investigadas por difração de Raios X, fisissorção de N2 e redução programada à temperatura. As caracterizações mostraram a formação de suporte de alta pureza e elevada área superficial. Embora o catalisador de ferro tenha apresentado baixa atividade nas reformas do metano, os catalisadores de Ni e NiFe se mostraram ativos nestas reações. A adição de ferro aumentou a conversão de metano na RVM, indicando o caráter promotor do ferro nessa reação. Os testes catalíticos de etanol foram realizados nas condições de ESR (relação H2O/C2H6O igual a 3) e em ESRH (ESR fortemente redutor pela adição de H2) entre 250 e 650 °C. As análises de DRX in situ e XANES in situ foram realizadas durante a redução em H2 e nas reações ESR e ESRH para avaliar a dinâmica dos catalisadores nestas condições. A adição de ferro reduziu a produção de metano e a deposição de carbono, aumentado a estabilidade em ESR. Nos catalisadores bimetálicos ocorreu a formação da fase NiFe2O4 que ao ser reduzida formou a liga NiFe. Quando os catalisadores foram colocados em contato com os reagentes de ESR ocorreu a oxidação parcial das partículas de níquel e de ferro em baixas temperaturas, reduzindo a atividade catalítica. Com o aumento de temperatura as partículas de níquel se reduziam e a atividade aumentava. As partículas de ferro foram mais suscetíveis a oxidação, migrando para a superfície na forma de óxidos e segregando parcialmente da liga. Essa pequena oxidação favoreceu a estabilidade catalítica ao reduzir a produção de carbono em relação ao catalisador que continha apenas níquel. A intensidade desse processo dependeu da composição dos reagentes e dos catalisadores. Em ESRH o processo de oxidação das partículas foi mais brando, estabilizando a estrutura do catalisador e aumentando a atividade em baixas temperaturas. Desta forma foi possível avaliar que a composição do meio reacional e a carga metálica influenciaram no desempenho catalítico.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Processo nº 2018/01258-5, Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – 88882.332805/2019-01Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Código de Financiamento 001porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Engenharia Química - PPGEQUFSCarAttribution-NonCommercial 3.0 Brazilhttp://creativecommons.org/licenses/by-nc/3.0/br/info:eu-repo/semantics/openAccessCatalisador bimetálicoProdução de H2Gás de sínteseLiga metálicaBimetallic catalystH2 productionSyngasAlloyENGENHARIAS::ENGENHARIA QUIMICAInfluência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reformaInfluence of the composition of the reaction mixture on the performance of NiFe/MgAl2O4 catalysts in reforming reactionsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis6006003b275236-acc5-4218-a33b-8f802e7f5a18reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARCC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8919https://repositorio.ufscar.br/bitstream/ufscar/18065/2/license_rdf7554719e5627c8f97902419c869e4761MD52ORIGINALTese Thais Lara final.pdfTese Thais Lara final.pdfArtigo principalapplication/pdf7505898https://repositorio.ufscar.br/bitstream/ufscar/18065/1/Tese%20Thais%20Lara%20final.pdf280f3ebcc9b0bacffcd1fb3f58d4b034MD51TEXTTese Thais Lara final.pdf.txtTese Thais Lara final.pdf.txtExtracted texttext/plain185290https://repositorio.ufscar.br/bitstream/ufscar/18065/3/Tese%20Thais%20Lara%20final.pdf.txta6c4cc5bcdde63d56975970ebd5fca3aMD53THUMBNAILTese Thais Lara final.pdf.jpgTese Thais Lara final.pdf.jpgIM Thumbnailimage/jpeg6002https://repositorio.ufscar.br/bitstream/ufscar/18065/4/Tese%20Thais%20Lara%20final.pdf.jpg02b3b969f7e1fd2d22ea9088ba875e3eMD54ufscar/180652023-09-18 18:32:37.279oai:repositorio.ufscar.br:ufscar/18065Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32:37Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma |
dc.title.alternative.eng.fl_str_mv |
Influence of the composition of the reaction mixture on the performance of NiFe/MgAl2O4 catalysts in reforming reactions |
title |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma |
spellingShingle |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma Lara, Thais Paula Nogueira Catalisador bimetálico Produção de H2 Gás de síntese Liga metálica Bimetallic catalyst H2 production Syngas Alloy ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma |
title_full |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma |
title_fullStr |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma |
title_full_unstemmed |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma |
title_sort |
Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma |
author |
Lara, Thais Paula Nogueira |
author_facet |
Lara, Thais Paula Nogueira |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/9889214612048325 |
dc.contributor.advisor1orcid.por.fl_str_mv |
https://orcid.org/0000-0002-4229-1112 |
dc.contributor.author.fl_str_mv |
Lara, Thais Paula Nogueira |
dc.contributor.advisor1.fl_str_mv |
Bueno, José Maria Corrêa |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/0157452280626031 |
dc.contributor.authorID.fl_str_mv |
22f1b10b-9811-41cd-ad03-5d413c90a699 |
contributor_str_mv |
Bueno, José Maria Corrêa |
dc.subject.por.fl_str_mv |
Catalisador bimetálico Produção de H2 Gás de síntese Liga metálica |
topic |
Catalisador bimetálico Produção de H2 Gás de síntese Liga metálica Bimetallic catalyst H2 production Syngas Alloy ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Bimetallic catalyst H2 production Syngas Alloy |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA |
description |
This thesis evaluated the application of Ni-, Fe- and Ni-Fe/MgAl2O4 catalysts in Ethanol Steam Reforming (ESR), Ethanol Steam Reforming with hydrogen gas (ESRH), Methane Dry Reforming (RSM), Methane Steam Reforming (RVM) and Methane Bi-Reforming (BRM) reactions evaluating the influence of reaction medium composition and Ni:Fe ratio on the catalytic behavior. Two series of NiFe/MgAl2O4 catalysts were prepared, the first keeping the Ni content at 8 wt.% and varying the Fe content, and the second keeping the total metallic content fixed at 15 wt.%. The properties of the catalysts were investigated by X-ray diffraction, N2 physisorption and temperature-programmed reduction. The characterizations showed the formation of high purity support with high surface area. Although the iron catalyst had low activity in methane reforms, the Ni and NiFe catalysts were active in these reactions. The addition of iron increased the conversion of methane on RVM, indicating the iron-promoter character on this reaction. Ethanol catalytic tests were carried out under ESR conditions (H2O/C2H6O ratio equal to 3) and in ESRH (ESR strongly reduced by the addition of H2) between 250 and 650 °C. In situ XRD and in situ XANES analyzes were performed during the reduction in H2 and in the ESR and ESRH reactions to evaluate the catalyst dynamics under these conditions. The addition of iron reduced methane production and carbon deposition, increasing stability in ESR. The bimetallic catalysts formed the NiFe2O4 phase which, when reduced, formed the NiFe alloy. When the catalysts were placed in contact with the ESR reagents, partial oxidation of nickel and iron particles occurred at low temperatures, reducing the catalytic activity. As the temperature increased, nickel particles reduced and activity increased. Iron particles were more susceptible to oxidation, migrating to the surface in the form of oxides and partially segregating from the alloy. This small oxidation favored the catalytic stability by reducing the carbon production compared to the catalyst that contained only nickel. The intensity of this process depends on the composition of the reactants and catalysts. In ESRH, the oxidation process of the particles was milder, stabilizing the catalyst structure and increasing the activity at low temperatures. In this way, it was possible to evaluate that the composition of the reaction medium and the metallic charge influenced the catalytic performance. |
publishDate |
2021 |
dc.date.issued.fl_str_mv |
2021-12-20 |
dc.date.accessioned.fl_str_mv |
2023-05-24T14:17:03Z |
dc.date.available.fl_str_mv |
2023-05-24T14:17:03Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
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dc.identifier.citation.fl_str_mv |
LARA, Thais Paula Nogueira. Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/18065. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/18065 |
identifier_str_mv |
LARA, Thais Paula Nogueira. Influência da composição da mistura reacional no desempenho de catalisadores NiFe/MgAl2O4 em reações de reforma. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/18065. |
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https://repositorio.ufscar.br/handle/ufscar/18065 |
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Attribution-NonCommercial 3.0 Brazil http://creativecommons.org/licenses/by-nc/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial 3.0 Brazil http://creativecommons.org/licenses/by-nc/3.0/br/ |
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openAccess |
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Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Engenharia Química - PPGEQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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