Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia
Autor(a) principal: | |
---|---|
Data de Publicação: | 2009 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/3876 |
Resumo: | The selective catalytic reduction of NOx with ammonia is the best technology available today to carry out the abatement of nitrogen oxide emissions in industrial gas effluents. Currently, vanadia-titania catalysts promoted with WO3 or MoO3 are the most active catalysts for the mentioned reaction. They show a very good catalytic stability for a long time. However, vanadia is also active in the oxidation of SO2 (a compound commonly found in industrial effluents) to SO3 this reaction is highly undesirable since SO3 reacts with water present at effluent gas and ammonia, producing sulfuric acid and ammonium sulfates, NH4HSO4 and (NH4)2SO4. The ammonium sulfates can deposit and accumulate themselves on the catalyst surface besides causing pressure drop problems or equipment corrosion. Apart from this, vanadia-titania catalysts are partially sulfated in SO2 presence, they have specific surface area relatively low (in the order of 40 m2/g) and they can show difficulties when they are discarded because vanadia (as well as WO3 and MoO3) is poisonous to the soil and water. Thus, the optimization or search for new catalytic systems for the selective reduction of NOx with ammonia acquires a significative importance. For this reason, the present work was set in the context of technological route of the selective catalytic reduction of NOx with ammonia and it has the objective of investigate the performance of some catalysts and/or supports (zeolites, mesoporous molecular sieves and transition metal oxides) in the reaction in focus. The studied catalysts were prepared through incipient wet impregnation method or by ionic exchange between a support and a VOSO4 solution. Afterwards, the solids were analyzed by a number of characterization techniques and they were tested in the selective catalytic reduction of NOx with ammonia in the presence of oxygen, in a temperature range of 200°C to 500°C. The materials that have shown the best performances in this first test were subjected to stability tests with water and SO2. The results demonstrated that the Si/Al ratio and the molecular sieve structure, as well as the original cation nature to be exchanged, had influence on the catalyst behavior in the face of the reaction in focus. Finally, accordingly to the test battery accomplished in this investigation, one can say that zeolite H-ZSM-5 exchanged with VO2+ ion was the best catalyst to the selective catalytic reduction of NOx with ammonia, in the temperature range of 350°C to 500°C. It was better, in the test conditions, than the V2O5-WO3/TiO2 (similar to a commercial type). |
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Lima Neto, Antonio VieiraUrquieta-González, Ernesto Antoniohttp://lattes.cnpq.br/2389975677904655http://lattes.cnpq.br/848821544415260819f8b5b8-002e-4adc-946a-65e537c714262016-06-02T19:55:25Z2009-11-232016-06-02T19:55:25Z2009-08-03LIMA NETO, Antonio Vieira. Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia. 2009. 160 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2009.https://repositorio.ufscar.br/handle/ufscar/3876The selective catalytic reduction of NOx with ammonia is the best technology available today to carry out the abatement of nitrogen oxide emissions in industrial gas effluents. Currently, vanadia-titania catalysts promoted with WO3 or MoO3 are the most active catalysts for the mentioned reaction. They show a very good catalytic stability for a long time. However, vanadia is also active in the oxidation of SO2 (a compound commonly found in industrial effluents) to SO3 this reaction is highly undesirable since SO3 reacts with water present at effluent gas and ammonia, producing sulfuric acid and ammonium sulfates, NH4HSO4 and (NH4)2SO4. The ammonium sulfates can deposit and accumulate themselves on the catalyst surface besides causing pressure drop problems or equipment corrosion. Apart from this, vanadia-titania catalysts are partially sulfated in SO2 presence, they have specific surface area relatively low (in the order of 40 m2/g) and they can show difficulties when they are discarded because vanadia (as well as WO3 and MoO3) is poisonous to the soil and water. Thus, the optimization or search for new catalytic systems for the selective reduction of NOx with ammonia acquires a significative importance. For this reason, the present work was set in the context of technological route of the selective catalytic reduction of NOx with ammonia and it has the objective of investigate the performance of some catalysts and/or supports (zeolites, mesoporous molecular sieves and transition metal oxides) in the reaction in focus. The studied catalysts were prepared through incipient wet impregnation method or by ionic exchange between a support and a VOSO4 solution. Afterwards, the solids were analyzed by a number of characterization techniques and they were tested in the selective catalytic reduction of NOx with ammonia in the presence of oxygen, in a temperature range of 200°C to 500°C. The materials that have shown the best performances in this first test were subjected to stability tests with water and SO2. The results demonstrated that the Si/Al ratio and the molecular sieve structure, as well as the original cation nature to be exchanged, had influence on the catalyst behavior in the face of the reaction in focus. Finally, accordingly to the test battery accomplished in this investigation, one can say that zeolite H-ZSM-5 exchanged with VO2+ ion was the best catalyst to the selective catalytic reduction of NOx with ammonia, in the temperature range of 350°C to 500°C. It was better, in the test conditions, than the V2O5-WO3/TiO2 (similar to a commercial type).A redução catalítica seletiva de NOx com amônia é a melhor tecnologia disponível nos dias de hoje para fazer o abatimento de emissões de óxidos de nitrogênio dos efluentes gasosos produzidos por fontes estacionárias (indústrias e plantas de geração de energia). Atualmente, os catalisadores de vanádia-titânia promovidos com WO3 ou MoO3 são os mais ativos para aquela reação, exibindo uma estabilidade catalítica muito boa ao longo do tempo. Contudo, a vanádia é ativa, também, na oxidação de SO2 (um composto encontrado comumente em efluentes gasosos industriais) a SO3 reação altamente indesejada porque o SO3 reage com a água presente no gás efluente e com a amônia, produzindo ácido sulfúrico e os sulfatos de amônio, NH4HSO4 e (NH4)2SO4. Os sulfatos de amônio podem depositar-se e acumular-se sobre o catalisador ou causar problemas de perda de carga ou de corrosão em equipamentos. Além disso, catalisadores de vanádia-titânia são parcialmente sulfatados em presença de SO2, possuem uma área superficial específica relativamente baixa (da ordem de 40 m2/g) e podem representar dificuldades para serem descartados, uma vez que a vanádia pode ser venenosa ao solo ou à água (o mesmo pode ser dito em relação aos óxidos WO3 e MoO3). Assim sendo, a questão da otimização ou busca de novos sistemas catalíticos para a redução seletiva de NOx com amônia adquire importância considerável. Por essa razão, o presente trabalho foi situado dentro do contexto da rota tecnológica da redução catalítica seletiva de NOx com NH3, tendo como objetivo principal a investigação do desempenho de certo número de catalisadores e/ou suportes abrangendo materiais de diferentes naturezas (zeólitas, peneiras moleculares mesoporosas e óxidos de metais de transição) frente à reação em foco. Os catalisadores estudados foram preparados através do método da impregnação a umidade incipiente ou por meio de trocas iônicas entre um suporte e uma solução de sulfato de vanadila (VOSO4). Em seguida, os sólidos tiveram a sua composição, textura e estrutura caracterizadas por um conjunto de técnicas e foram avaliados na redução catalítica seletiva de NOx com NH3 em presença de oxigênio, no intervalo de temperaturas de 200°C a 500°C. Os materiais que se destacaram nessa primeira avaliação foram, posteriormente, submetidos a teste de estabilidade com água e teste de estabilidade com SO2. Os resultados obtidos neste trabalho demonstraram que a razão Si/Al e a estrutura da peneira molecular utilizada nas trocas iônicas, assim como a natureza do cátion original a ser trocado, exercem influência no comportamento do catalisador na reação em foco. Finalmente, os testes realizados nesta investigação apontaram a zeólita H-ZSM-5 trocada com o íon VO2+ como o melhor catalisador para a redução catalítica seletiva do NOx com amônia, na faixa 350°C 500°C. Ela superou, nas condições dos testes, o V2O5-WO3/TiO2 (semelhante a um tipo comercial).application/pdfporUniversidade Federal de São CarlosPrograma de Pós-Graduação em Engenharia Química - PPGEQUFSCarBRCatáliseRedução de NOAmôniaZeólitaVanadilaPeneiras molecularesENGENHARIAS::ENGENHARIA QUIMICACatalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amôniainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis-1-10fecd90c-2648-4551-9f5a-7b6c106679b1info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINAL2605.pdfapplication/pdf2742879https://repositorio.ufscar.br/bitstream/ufscar/3876/1/2605.pdfd9cd64d43e54800c1766d6c2f4940a33MD51THUMBNAIL2605.pdf.jpg2605.pdf.jpgIM Thumbnailimage/jpeg6236https://repositorio.ufscar.br/bitstream/ufscar/3876/2/2605.pdf.jpg86b558335dc7e01f08b2891540767777MD52ufscar/38762023-09-18 18:31:19.856oai:repositorio.ufscar.br:ufscar/3876Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:19Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia |
title |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia |
spellingShingle |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia Lima Neto, Antonio Vieira Catálise Redução de NO Amônia Zeólita Vanadila Peneiras moleculares ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia |
title_full |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia |
title_fullStr |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia |
title_full_unstemmed |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia |
title_sort |
Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia |
author |
Lima Neto, Antonio Vieira |
author_facet |
Lima Neto, Antonio Vieira |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8488215444152608 |
dc.contributor.author.fl_str_mv |
Lima Neto, Antonio Vieira |
dc.contributor.advisor1.fl_str_mv |
Urquieta-González, Ernesto Antonio |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/2389975677904655 |
dc.contributor.authorID.fl_str_mv |
19f8b5b8-002e-4adc-946a-65e537c71426 |
contributor_str_mv |
Urquieta-González, Ernesto Antonio |
dc.subject.por.fl_str_mv |
Catálise Redução de NO Amônia Zeólita Vanadila Peneiras moleculares |
topic |
Catálise Redução de NO Amônia Zeólita Vanadila Peneiras moleculares ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA |
description |
The selective catalytic reduction of NOx with ammonia is the best technology available today to carry out the abatement of nitrogen oxide emissions in industrial gas effluents. Currently, vanadia-titania catalysts promoted with WO3 or MoO3 are the most active catalysts for the mentioned reaction. They show a very good catalytic stability for a long time. However, vanadia is also active in the oxidation of SO2 (a compound commonly found in industrial effluents) to SO3 this reaction is highly undesirable since SO3 reacts with water present at effluent gas and ammonia, producing sulfuric acid and ammonium sulfates, NH4HSO4 and (NH4)2SO4. The ammonium sulfates can deposit and accumulate themselves on the catalyst surface besides causing pressure drop problems or equipment corrosion. Apart from this, vanadia-titania catalysts are partially sulfated in SO2 presence, they have specific surface area relatively low (in the order of 40 m2/g) and they can show difficulties when they are discarded because vanadia (as well as WO3 and MoO3) is poisonous to the soil and water. Thus, the optimization or search for new catalytic systems for the selective reduction of NOx with ammonia acquires a significative importance. For this reason, the present work was set in the context of technological route of the selective catalytic reduction of NOx with ammonia and it has the objective of investigate the performance of some catalysts and/or supports (zeolites, mesoporous molecular sieves and transition metal oxides) in the reaction in focus. The studied catalysts were prepared through incipient wet impregnation method or by ionic exchange between a support and a VOSO4 solution. Afterwards, the solids were analyzed by a number of characterization techniques and they were tested in the selective catalytic reduction of NOx with ammonia in the presence of oxygen, in a temperature range of 200°C to 500°C. The materials that have shown the best performances in this first test were subjected to stability tests with water and SO2. The results demonstrated that the Si/Al ratio and the molecular sieve structure, as well as the original cation nature to be exchanged, had influence on the catalyst behavior in the face of the reaction in focus. Finally, accordingly to the test battery accomplished in this investigation, one can say that zeolite H-ZSM-5 exchanged with VO2+ ion was the best catalyst to the selective catalytic reduction of NOx with ammonia, in the temperature range of 350°C to 500°C. It was better, in the test conditions, than the V2O5-WO3/TiO2 (similar to a commercial type). |
publishDate |
2009 |
dc.date.available.fl_str_mv |
2009-11-23 2016-06-02T19:55:25Z |
dc.date.issued.fl_str_mv |
2009-08-03 |
dc.date.accessioned.fl_str_mv |
2016-06-02T19:55:25Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
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info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
LIMA NETO, Antonio Vieira. Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia. 2009. 160 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2009. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/3876 |
identifier_str_mv |
LIMA NETO, Antonio Vieira. Catalisadores contendo espécies V2O5 ou VO2+ : atividade e seletividade na redução de NO com amônia. 2009. 160 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2009. |
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https://repositorio.ufscar.br/handle/ufscar/3876 |
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Universidade Federal de São Carlos |
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