Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/14679 |
Resumo: | The burning of fuels in the industry or in vehicle engines is a direct agent in the generation of the atmospheric pollution through the emission of contaminating gases such as NOx and SOx. To minimize this impact, environmental regulations have become increasingly stricter. Thus, the production of clean fuels became of fundamental importance, which has been deeply addressed by the environmental catalysis. Among the most used processes, the hydrodesulfurization (HDS) of hydrocarbons stands out a method in which the sulfur of compounds such as thiophenes, benzothiophenes, dibenzothiophenes, is reduced to H2S. The most used catalysts to this process have as active phase molybdenum (Mo) or tungsten (W) sulfides, promoted by cobalt (Co) or nickel (Ni). The commercial used support is γ-alumina, synthesized by sol-gel, which has a uniform particle size and high specific area. However, with the aim to increase the activity and stability of these catalysts, additives can be added, being niobium one of them, which has shown promising results. In this work, catalysts based on Ni and Mo sulfides were prepared, adding Nb as additive. The precursors were supported via impregnation on γ-alumina prepared by the sol-gel method or via one-pot during the synthesis of that support, with or without the presence of the surfactant CTAB. The metals were incorporated with nominal contents of 4 wt.% of NiO, 18 wt.% of MoO3 and 0.7 wt.% of Nb2O5. The catalysts in their oxide form were characterized by energy dispersive X-ray spectrometry (EDX), X-ray diffraction (including low angle diffraction), nitrogen physisorption, visible ultraviolet diffuse reflectance spectroscopy (DRS-UVvis) and evaluated at 300ºC in the HDS of thiophene, used as a model molecule. γ-Alumina showed high surface area and pore volume, and that synthesized in the presence of CTAB resulted in a more homogeneous mesopores distribution. XRD data showed an efficient dispersion of the active species on the support, which was confirmed by DRS-UVvis. The HDS of thiophene on the studied catalysts confirmed the promoting effect of Ni on the Mo activity and a promising impact of Nb as an additive, which increased the activity of the NiMo catalyst. |
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Valdés-de-Freitas, Carlos EduardoUrquieta-González, Ernesto Antoniohttp://lattes.cnpq.br/2389975677904655http://lattes.cnpq.br/04690345317885701057c6b5-0d20-4074-9c14-af9276037c3e2021-07-28T18:19:02Z2021-07-28T18:19:02Z2021-04-30VALDÉS-DE-FREITAS, Carlos Eduardo. Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno. 2021. Dissertação (Mestrado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/14679.https://repositorio.ufscar.br/handle/ufscar/14679The burning of fuels in the industry or in vehicle engines is a direct agent in the generation of the atmospheric pollution through the emission of contaminating gases such as NOx and SOx. To minimize this impact, environmental regulations have become increasingly stricter. Thus, the production of clean fuels became of fundamental importance, which has been deeply addressed by the environmental catalysis. Among the most used processes, the hydrodesulfurization (HDS) of hydrocarbons stands out a method in which the sulfur of compounds such as thiophenes, benzothiophenes, dibenzothiophenes, is reduced to H2S. The most used catalysts to this process have as active phase molybdenum (Mo) or tungsten (W) sulfides, promoted by cobalt (Co) or nickel (Ni). The commercial used support is γ-alumina, synthesized by sol-gel, which has a uniform particle size and high specific area. However, with the aim to increase the activity and stability of these catalysts, additives can be added, being niobium one of them, which has shown promising results. In this work, catalysts based on Ni and Mo sulfides were prepared, adding Nb as additive. The precursors were supported via impregnation on γ-alumina prepared by the sol-gel method or via one-pot during the synthesis of that support, with or without the presence of the surfactant CTAB. The metals were incorporated with nominal contents of 4 wt.% of NiO, 18 wt.% of MoO3 and 0.7 wt.% of Nb2O5. The catalysts in their oxide form were characterized by energy dispersive X-ray spectrometry (EDX), X-ray diffraction (including low angle diffraction), nitrogen physisorption, visible ultraviolet diffuse reflectance spectroscopy (DRS-UVvis) and evaluated at 300ºC in the HDS of thiophene, used as a model molecule. γ-Alumina showed high surface area and pore volume, and that synthesized in the presence of CTAB resulted in a more homogeneous mesopores distribution. XRD data showed an efficient dispersion of the active species on the support, which was confirmed by DRS-UVvis. The HDS of thiophene on the studied catalysts confirmed the promoting effect of Ni on the Mo activity and a promising impact of Nb as an additive, which increased the activity of the NiMo catalyst.A queima de combustíveis na indústria ou em motores de veículos é um agente direto na geração da poluição atmosférica através da emissão de gases contaminantes como os NOx e SOx. Para combater esse impacto, regulamentações ambientais têm se tornado cada vez mais rígidas. Nessa direção, é de fundamental importância a produção de combustíveis limpos, a que tem sido muito abordada pela catálise ambiental. Dentre os processos mais utilizados, destaca-se a hidrodessulfurização (HDS) de hidrocarbonetos, método em que o enxofre de compostos sulfurados como tiofenos, benzotiofenos, dibenzotiofenos, é reduzido a H2S. Os catalisadores que se destacam nesse processo, possuem fase ativa composta de sulfetos puros dos metais molibdênio (Mo) ou tungstênio (W), promovidos com cobalto (Co) ou níquel (Ni). O suporte comercial tradicional é a alumina, sintetizada pelo método sol-gel, que apresenta granulometria uniforme e área específica elevada. Contudo, na busca de se aumentar a atividade e estabilidade desses catalisadores, adicionam-se elementos aditivos, sendo o nióbio um dos que têm apresentado resultados promissores. Neste trabalho foram preparados catalisadores à base de sulfetos de Ni e Mo aditivados com Nb, cujos precursores foram suportados via impregnação em γ-alumina preparada pelo método sol-gel ou via síntese one-pot durante a síntese desse suporte, com e sem a presença do surfactante CTAB. Os metais foram incorporados com teores nominais de 4% de NiO,18% de MoO3 e 0,7% de Nb2O5. Os catalisadores na forma de óxidos foram caracterizados por espectrometria de raios X de energia dispersiva (EDX), difração de raios X (incluindo difratometria em baixos ângulos), fisissorção de nitrogênio, espectroscopia por refletância difusa no ultravioleta visível (DRS-UVvis) e avaliados a 300ºC na reação de HDS do tiofeno, usada como molécula modelo. A γ-alumina apresentou alta área superficial e volume de poros, sendo que a sintetizada na presença de CTAB, resultou numa distribuição mais homogênea de mesoporos. Dados de DRX evidenciaram uma dispersão eficiente das espécies ativas nos suportes, a que foi confirmada por DRS-UVvis. A reação de HDS do tiofeno sobre os catalisadores estudados, ratificou o efeito promotor do Ni sobre a atividade do Mo e um impacto promissor do Nb como aditivo, o qual aumentou a atividade catalisador.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CNPq: 132639/2019-0porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Engenharia Química - PPGEQUFSCarAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessHDSTiofenoY-aluminaCTABCatalisadores NiMoNióbioThiopheneCatalystsNiobiumENGENHARIAS::ENGENHARIA QUIMICACatalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofenoNiMo/γ-Al2O3 catalysts with Nb additives - Activity for the hydrodesulfurization of thiopheneCatalisadores NiMo/γ-Al2O3 aditivados com Nb - Actividad para la hidrodesulfuración de tiofenoinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesis6000fecd90c-2648-4551-9f5a-7b6c106679b1reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALDissertação C E Valdes - VERSÃO FINAL.pdfDissertação C E Valdes - VERSÃO FINAL.pdfDissertação versão finalapplication/pdf4100810https://repositorio.ufscar.br/bitstream/ufscar/14679/4/Disserta%c3%a7%c3%a3o%20C%20E%20Valdes%20-%20VERS%c3%83O%20FINAL.pdfa993090d589aa227ce4dabd7e5a6b16bMD54Carta Comprovante - Carlos E Valdés de Freitas - 26-07-21.pdfCarta Comprovante - Carlos E Valdés de Freitas - 26-07-21.pdfCarta Comprovanteapplication/pdf131389https://repositorio.ufscar.br/bitstream/ufscar/14679/2/Carta%20Comprovante%20-%20Carlos%20E%20Vald%c3%a9s%20de%20Freitas%20-%2026-07-21.pdf17cea12dfe625c7b76a2df93c4c77dfcMD52CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/14679/5/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD55TEXTDissertação C E Valdes - VERSÃO FINAL.pdf.txtDissertação C E Valdes - VERSÃO FINAL.pdf.txtExtracted texttext/plain196609https://repositorio.ufscar.br/bitstream/ufscar/14679/6/Disserta%c3%a7%c3%a3o%20C%20E%20Valdes%20-%20VERS%c3%83O%20FINAL.pdf.txtc550cf67c9708fd50798d966f11be783MD56Carta Comprovante - Carlos E Valdés de Freitas - 26-07-21.pdf.txtCarta Comprovante - Carlos E Valdés de Freitas - 26-07-21.pdf.txtExtracted texttext/plain1058https://repositorio.ufscar.br/bitstream/ufscar/14679/8/Carta%20Comprovante%20-%20Carlos%20E%20Vald%c3%a9s%20de%20Freitas%20-%2026-07-21.pdf.txt3ddbea00a2ccf75528145cb21f484e1fMD58THUMBNAILDissertação C E Valdes - VERSÃO FINAL.pdf.jpgDissertação C E Valdes - VERSÃO FINAL.pdf.jpgIM Thumbnailimage/jpeg5146https://repositorio.ufscar.br/bitstream/ufscar/14679/7/Disserta%c3%a7%c3%a3o%20C%20E%20Valdes%20-%20VERS%c3%83O%20FINAL.pdf.jpg3834ebfc20c86a5e4df07fac966de4cfMD57Carta Comprovante - Carlos E Valdés de Freitas - 26-07-21.pdf.jpgCarta Comprovante - Carlos E Valdés de Freitas - 26-07-21.pdf.jpgIM Thumbnailimage/jpeg5906https://repositorio.ufscar.br/bitstream/ufscar/14679/9/Carta%20Comprovante%20-%20Carlos%20E%20Vald%c3%a9s%20de%20Freitas%20-%2026-07-21.pdf.jpg4905dd3be2aed277b3e40330a08f290dMD59ufscar/146792023-09-18 18:32:13.946oai:repositorio.ufscar.br:ufscar/14679Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32:13Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno |
dc.title.alternative.eng.fl_str_mv |
NiMo/γ-Al2O3 catalysts with Nb additives - Activity for the hydrodesulfurization of thiophene |
dc.title.alternative.spa.fl_str_mv |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Actividad para la hidrodesulfuración de tiofeno |
title |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno |
spellingShingle |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno Valdés-de-Freitas, Carlos Eduardo HDS Tiofeno Y-alumina CTAB Catalisadores NiMo Nióbio Thiophene Catalysts Niobium ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno |
title_full |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno |
title_fullStr |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno |
title_full_unstemmed |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno |
title_sort |
Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno |
author |
Valdés-de-Freitas, Carlos Eduardo |
author_facet |
Valdés-de-Freitas, Carlos Eduardo |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/0469034531788570 |
dc.contributor.author.fl_str_mv |
Valdés-de-Freitas, Carlos Eduardo |
dc.contributor.advisor1.fl_str_mv |
Urquieta-González, Ernesto Antonio |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2389975677904655 |
dc.contributor.authorID.fl_str_mv |
1057c6b5-0d20-4074-9c14-af9276037c3e |
contributor_str_mv |
Urquieta-González, Ernesto Antonio |
dc.subject.por.fl_str_mv |
HDS Tiofeno Y-alumina CTAB Catalisadores NiMo Nióbio |
topic |
HDS Tiofeno Y-alumina CTAB Catalisadores NiMo Nióbio Thiophene Catalysts Niobium ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Thiophene Catalysts Niobium |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA |
description |
The burning of fuels in the industry or in vehicle engines is a direct agent in the generation of the atmospheric pollution through the emission of contaminating gases such as NOx and SOx. To minimize this impact, environmental regulations have become increasingly stricter. Thus, the production of clean fuels became of fundamental importance, which has been deeply addressed by the environmental catalysis. Among the most used processes, the hydrodesulfurization (HDS) of hydrocarbons stands out a method in which the sulfur of compounds such as thiophenes, benzothiophenes, dibenzothiophenes, is reduced to H2S. The most used catalysts to this process have as active phase molybdenum (Mo) or tungsten (W) sulfides, promoted by cobalt (Co) or nickel (Ni). The commercial used support is γ-alumina, synthesized by sol-gel, which has a uniform particle size and high specific area. However, with the aim to increase the activity and stability of these catalysts, additives can be added, being niobium one of them, which has shown promising results. In this work, catalysts based on Ni and Mo sulfides were prepared, adding Nb as additive. The precursors were supported via impregnation on γ-alumina prepared by the sol-gel method or via one-pot during the synthesis of that support, with or without the presence of the surfactant CTAB. The metals were incorporated with nominal contents of 4 wt.% of NiO, 18 wt.% of MoO3 and 0.7 wt.% of Nb2O5. The catalysts in their oxide form were characterized by energy dispersive X-ray spectrometry (EDX), X-ray diffraction (including low angle diffraction), nitrogen physisorption, visible ultraviolet diffuse reflectance spectroscopy (DRS-UVvis) and evaluated at 300ºC in the HDS of thiophene, used as a model molecule. γ-Alumina showed high surface area and pore volume, and that synthesized in the presence of CTAB resulted in a more homogeneous mesopores distribution. XRD data showed an efficient dispersion of the active species on the support, which was confirmed by DRS-UVvis. The HDS of thiophene on the studied catalysts confirmed the promoting effect of Ni on the Mo activity and a promising impact of Nb as an additive, which increased the activity of the NiMo catalyst. |
publishDate |
2021 |
dc.date.accessioned.fl_str_mv |
2021-07-28T18:19:02Z |
dc.date.available.fl_str_mv |
2021-07-28T18:19:02Z |
dc.date.issued.fl_str_mv |
2021-04-30 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
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masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
VALDÉS-DE-FREITAS, Carlos Eduardo. Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno. 2021. Dissertação (Mestrado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/14679. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/14679 |
identifier_str_mv |
VALDÉS-DE-FREITAS, Carlos Eduardo. Catalisadores NiMo/γ-Al2O3 aditivados com Nb - Atividade para a hidrodessulfurização de tiofeno. 2021. Dissertação (Mestrado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/14679. |
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https://repositorio.ufscar.br/handle/ufscar/14679 |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/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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