The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts.
Autor(a) principal: | |
---|---|
Data de Publicação: | 2022 |
Tipo de documento: | Tese |
Idioma: | eng |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da USP |
Texto Completo: | https://www.teses.usp.br/teses/disponiveis/3/3137/tde-29042022-074945/ |
Resumo: | Worldwide there is an increasing demand for primary energy sources (PES). The current scenario suggests a low-rate shift of PES using clean fossil fuels, in particular natural gas (NG) and renewable energy sources, which also impacts the chemical industry. In this context, the gas-to-liquids (GTL) process may play a strategic role on this transition. The CO hydrogenation reaction, which is the core of this technology, leads to the production of many products, such as paraffins and olefins, from syngas (H2+CO). The Fischer-Tropsch Synthesis (FTS) is limited by many critical factors, so efficiency improvements through catalyst design and lifetime is mandatory to provide higher competitiveness to the technology. In this study, the performance of cobalt-based catalyst for the CO hydrogenation reaction was evaluated, using -alumina and SBA-15 supports, aiming at understanding the operating condition effects. The evaluated supports and catalysts were synthesized and characterized for textural, morphological and structural properties assessment. The effects of temperature and space velocity over the 15% Co/SBA-15 and 15% Co/-Al 2O3 catalysts were evaluated in terms of activity, selectivity to lower olefins (C2=-C4=) and C5+ selectivity. The catalyst deactivation with time-on-stream (TOS) was also evaluated in terms of carbon formation by TGA/DTA and Raman spectroscopy techniques. Overall, results show that both catalysts produced paraffins as main product and presented a higher activity at lower space velocity and higher temperature and higher selectivity to higher hydrocarbons (HC) and lower olefins at lower space velocity and lower temperature. From the tested catalysts, the 15% Co/SBA-15 presented higher activity and selectivity to lower HC up to the gasoline range, with a slightly higher selectivity to lower olefins, whereas the 15% Co/-Al2O3 produced higher HC according to the C5+ selectivity. Two deactivation stages with similar carbon depositions were detected for both catalysts. Differences in yield loss with TOS can be explained by the carbon migration phenomenon. |
id |
USP_16328e0520dd8cf0aa3ac96a63b6a7e6 |
---|---|
oai_identifier_str |
oai:teses.usp.br:tde-29042022-074945 |
network_acronym_str |
USP |
network_name_str |
Biblioteca Digital de Teses e Dissertações da USP |
repository_id_str |
2721 |
spelling |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts.Hidrogenação de CO em catalisadores de Co/SBA-15 e Co/Al2O3.CatalisadoresCobalt-based catalystsCobaltoCombustíveis líquidosFischer-Tropsch synthesisLight olefinsLiquid fuelsOlefinas levesOxide supportsSíntese de Fischer-TropschSuportes óxidosWorldwide there is an increasing demand for primary energy sources (PES). The current scenario suggests a low-rate shift of PES using clean fossil fuels, in particular natural gas (NG) and renewable energy sources, which also impacts the chemical industry. In this context, the gas-to-liquids (GTL) process may play a strategic role on this transition. The CO hydrogenation reaction, which is the core of this technology, leads to the production of many products, such as paraffins and olefins, from syngas (H2+CO). The Fischer-Tropsch Synthesis (FTS) is limited by many critical factors, so efficiency improvements through catalyst design and lifetime is mandatory to provide higher competitiveness to the technology. In this study, the performance of cobalt-based catalyst for the CO hydrogenation reaction was evaluated, using -alumina and SBA-15 supports, aiming at understanding the operating condition effects. The evaluated supports and catalysts were synthesized and characterized for textural, morphological and structural properties assessment. The effects of temperature and space velocity over the 15% Co/SBA-15 and 15% Co/-Al 2O3 catalysts were evaluated in terms of activity, selectivity to lower olefins (C2=-C4=) and C5+ selectivity. The catalyst deactivation with time-on-stream (TOS) was also evaluated in terms of carbon formation by TGA/DTA and Raman spectroscopy techniques. Overall, results show that both catalysts produced paraffins as main product and presented a higher activity at lower space velocity and higher temperature and higher selectivity to higher hydrocarbons (HC) and lower olefins at lower space velocity and lower temperature. From the tested catalysts, the 15% Co/SBA-15 presented higher activity and selectivity to lower HC up to the gasoline range, with a slightly higher selectivity to lower olefins, whereas the 15% Co/-Al2O3 produced higher HC according to the C5+ selectivity. Two deactivation stages with similar carbon depositions were detected for both catalysts. Differences in yield loss with TOS can be explained by the carbon migration phenomenon.Em todo o mundo, há demanda crescente por fontes de energia primária (FEP). O cenário atual sugere lenta transição de FEPs para combustíveis fósseis limpos, particularmente para gás natural (GN) e fontes de energia renováveis, com impactos também na indústria química. Nesse contexto, o processo gas-to-liquids (GTL) pode ter um papel estratégico nessa transição. A reação de hidrogenação do CO, o núcleo dessa tecnologia, leva à produção de produtos diversos, como parafinas e olefinas, a partir do gás de síntese (H 2+CO). A síntese de Fischer- Tropsch (SFT) é limitada por muitos fatores críticos e melhorias de eficiência por meio do design e da vida útil do catalisador são mandatórias para fornecer maior competitividade à tecnologia. Neste estudo foi avaliado o desempenho de catalisadores à base de cobalto para a reação de hidrogenação do CO utilizando suportes de -alumina e SBA-15 visando compreender os efeitos de condições operacionais sobre o desempenho dos catalisadores. Os suportes e catalisadores avaliados foram sintetizados e caracterizados para avaliação de propriedades texturais, morfológicas e estruturais. Os efeitos da temperatura e velocidade espacial sobre a atividade e seletividade para olefinas leves (C2=-C4=) e hidrocarbonetos pesados (C5+) dos catalisadores 15% Co/SBA-15 e 15% Co/-Al2O3 foram avaliados. A desativação do catalisador com o tempo em fluxo (TEF) também foi avaliada em termos de formação de carbono por técnicas de espectroscopia TGA/DTA e Raman. De maneira geral, os resultados mostram que ambos os catalisadores produzem parafinas como produto principal e apresentaram maior atividade em velocidade espacial mais baixa e temperatura mais alta e maior seletividade para hidrocarbonetos (HC) pesados e olefinas leves em velocidade espacial mais baixa e temperatura mais baixa. Dentre os catalisadores, o 15% Co/SBA-15 apresentou maior atividade e seletividade para HC leves até a faixa da gasolina, com seletividade para olefinas leves ligeiramente mais alta, enquanto o 15% Co/-Al 2O3 produziu HC mais pesados de acordo com a seletividade para C5+. Dois estágios de desativação com deposição de carbono foram detectados para ambos os catalisadores. Diferenças na perda de rendimento com o TEF pode ser explicada pelo fenômeno de migração de carbono.Biblioteca Digitais de Teses e Dissertações da USPAlves, Rita Maria de BritoSchmal, MartinAbreu, Thiago Ferreira de2022-02-24info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttps://www.teses.usp.br/teses/disponiveis/3/3137/tde-29042022-074945/reponame:Biblioteca Digital de Teses e Dissertações da USPinstname:Universidade de São Paulo (USP)instacron:USPLiberar o conteúdo para acesso público.info:eu-repo/semantics/openAccesseng2022-04-29T12:38:49Zoai:teses.usp.br:tde-29042022-074945Biblioteca Digital de Teses e Dissertaçõeshttp://www.teses.usp.br/PUBhttp://www.teses.usp.br/cgi-bin/mtd2br.plvirginia@if.usp.br|| atendimento@aguia.usp.br||virginia@if.usp.bropendoar:27212022-04-29T12:38:49Biblioteca Digital de Teses e Dissertações da USP - Universidade de São Paulo (USP)false |
dc.title.none.fl_str_mv |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. Hidrogenação de CO em catalisadores de Co/SBA-15 e Co/Al2O3. |
title |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. |
spellingShingle |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. Abreu, Thiago Ferreira de Catalisadores Cobalt-based catalysts Cobalto Combustíveis líquidos Fischer-Tropsch synthesis Light olefins Liquid fuels Olefinas leves Oxide supports Síntese de Fischer-Tropsch Suportes óxidos |
title_short |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. |
title_full |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. |
title_fullStr |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. |
title_full_unstemmed |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. |
title_sort |
The CO hydrogenation on Co/SBA-15 and Co/Al2O3 catalysts. |
author |
Abreu, Thiago Ferreira de |
author_facet |
Abreu, Thiago Ferreira de |
author_role |
author |
dc.contributor.none.fl_str_mv |
Alves, Rita Maria de Brito Schmal, Martin |
dc.contributor.author.fl_str_mv |
Abreu, Thiago Ferreira de |
dc.subject.por.fl_str_mv |
Catalisadores Cobalt-based catalysts Cobalto Combustíveis líquidos Fischer-Tropsch synthesis Light olefins Liquid fuels Olefinas leves Oxide supports Síntese de Fischer-Tropsch Suportes óxidos |
topic |
Catalisadores Cobalt-based catalysts Cobalto Combustíveis líquidos Fischer-Tropsch synthesis Light olefins Liquid fuels Olefinas leves Oxide supports Síntese de Fischer-Tropsch Suportes óxidos |
description |
Worldwide there is an increasing demand for primary energy sources (PES). The current scenario suggests a low-rate shift of PES using clean fossil fuels, in particular natural gas (NG) and renewable energy sources, which also impacts the chemical industry. In this context, the gas-to-liquids (GTL) process may play a strategic role on this transition. The CO hydrogenation reaction, which is the core of this technology, leads to the production of many products, such as paraffins and olefins, from syngas (H2+CO). The Fischer-Tropsch Synthesis (FTS) is limited by many critical factors, so efficiency improvements through catalyst design and lifetime is mandatory to provide higher competitiveness to the technology. In this study, the performance of cobalt-based catalyst for the CO hydrogenation reaction was evaluated, using -alumina and SBA-15 supports, aiming at understanding the operating condition effects. The evaluated supports and catalysts were synthesized and characterized for textural, morphological and structural properties assessment. The effects of temperature and space velocity over the 15% Co/SBA-15 and 15% Co/-Al 2O3 catalysts were evaluated in terms of activity, selectivity to lower olefins (C2=-C4=) and C5+ selectivity. The catalyst deactivation with time-on-stream (TOS) was also evaluated in terms of carbon formation by TGA/DTA and Raman spectroscopy techniques. Overall, results show that both catalysts produced paraffins as main product and presented a higher activity at lower space velocity and higher temperature and higher selectivity to higher hydrocarbons (HC) and lower olefins at lower space velocity and lower temperature. From the tested catalysts, the 15% Co/SBA-15 presented higher activity and selectivity to lower HC up to the gasoline range, with a slightly higher selectivity to lower olefins, whereas the 15% Co/-Al2O3 produced higher HC according to the C5+ selectivity. Two deactivation stages with similar carbon depositions were detected for both catalysts. Differences in yield loss with TOS can be explained by the carbon migration phenomenon. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-02-24 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
https://www.teses.usp.br/teses/disponiveis/3/3137/tde-29042022-074945/ |
url |
https://www.teses.usp.br/teses/disponiveis/3/3137/tde-29042022-074945/ |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
|
dc.rights.driver.fl_str_mv |
Liberar o conteúdo para acesso público. info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Liberar o conteúdo para acesso público. |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.coverage.none.fl_str_mv |
|
dc.publisher.none.fl_str_mv |
Biblioteca Digitais de Teses e Dissertações da USP |
publisher.none.fl_str_mv |
Biblioteca Digitais de Teses e Dissertações da USP |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações da USP instname:Universidade de São Paulo (USP) instacron:USP |
instname_str |
Universidade de São Paulo (USP) |
instacron_str |
USP |
institution |
USP |
reponame_str |
Biblioteca Digital de Teses e Dissertações da USP |
collection |
Biblioteca Digital de Teses e Dissertações da USP |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações da USP - Universidade de São Paulo (USP) |
repository.mail.fl_str_mv |
virginia@if.usp.br|| atendimento@aguia.usp.br||virginia@if.usp.br |
_version_ |
1815257463612506112 |