Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol
Autor(a) principal: | |
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Data de Publicação: | 2017 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) |
Texto Completo: | http://repositorio.uem.br:8080/jspui/handle/1/3653 |
Resumo: | Socioeconomic and political problems caused by the environmental impacts of polluting and non-renewable energy sources have aroused an increasing interest for renewable and nonpolluting energy sources. Among the candidates for supplying this need is hydrogen. For hydrogen to fulfill the requirements for a renewable and clean combustible, its production line itself must have these characteristics. Ethanol reforming is an alternative hydrogen production process that meets these requirements. Nevertheless, despite the great number of investigations about this technology, ethanol reforming is a highly complex process and several points still need to be clarified. In this context, this work provides important information for a better comprehension of ethanol reforming. Inert and oxidative atmosphere tests were conducted with different catalytic supports with the aim of understanding the contribution of each of them to the process. Three CeO2 supports were tested one, of which was from commercial source and two others were calcined at different temperatures, namely, 550 and 800 oC. Moreover, Nb2O5 supports were tested in three different ways, namely, in pure form, impregnated with Na2O, and impregnated with CeO2. The CeO2 support calcined at 800 oC presented the smaller deactivation among the six tested supports, and it also presented the smaller flow rate of undesirable products, like ethene, acetone and CO. As for the Nb2O5 support impregnated with Na2O, considerable modifications in its characteristics were observed relative to the pure support. This doping propitiated less undesirable products, like ethene, and diminished coke formation. The study of the supports allowed us to suggest that ethene production and its polymerization are intimately connected to the concentration of hydroxyl groups on the surface, which were quantified by DTP -CO2 analyses. Moreover, the study conducted with the supports suggests that the oxidation reactions are catalyzed, that is, they are dependent on the catalyst employed. In addition to the support study, a statistical investigation was conducted to evaluate the contribution of the factors: active phase (Ni, Cu), O2/C2H5OH ratio, and temperature. It was observed that Ni and Cu favor the reactional route of ethanol reforming, decreasing the flow rate of parallel reaction products. Temperature increase acted in the same direction, favoring the ethanol reforming route - specifically, the methane reforming. The presence of oxygen influenced significantly some parallel reactions, like ethanol oxidation, ethene formation, and increasing of the CH4 flow rate. Finally, the information obtained in this work propitiated the production of a map of possible reaction routes for the studied system that can be helpful for further developments in this technology. In other words, the employed statistical method was innovative and brought significant contributions for the understanding of ethanol reforming. |
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Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanolInfluence of parameters in the reaction mechanisms of steam reforming and oxidative reforming of ethanolReação catalíticaEtanolReação de reformaHidrogênioProduçãoBrasil.EngenhariasEngenharia QuímicaSocioeconomic and political problems caused by the environmental impacts of polluting and non-renewable energy sources have aroused an increasing interest for renewable and nonpolluting energy sources. Among the candidates for supplying this need is hydrogen. For hydrogen to fulfill the requirements for a renewable and clean combustible, its production line itself must have these characteristics. Ethanol reforming is an alternative hydrogen production process that meets these requirements. Nevertheless, despite the great number of investigations about this technology, ethanol reforming is a highly complex process and several points still need to be clarified. In this context, this work provides important information for a better comprehension of ethanol reforming. Inert and oxidative atmosphere tests were conducted with different catalytic supports with the aim of understanding the contribution of each of them to the process. Three CeO2 supports were tested one, of which was from commercial source and two others were calcined at different temperatures, namely, 550 and 800 oC. Moreover, Nb2O5 supports were tested in three different ways, namely, in pure form, impregnated with Na2O, and impregnated with CeO2. The CeO2 support calcined at 800 oC presented the smaller deactivation among the six tested supports, and it also presented the smaller flow rate of undesirable products, like ethene, acetone and CO. As for the Nb2O5 support impregnated with Na2O, considerable modifications in its characteristics were observed relative to the pure support. This doping propitiated less undesirable products, like ethene, and diminished coke formation. The study of the supports allowed us to suggest that ethene production and its polymerization are intimately connected to the concentration of hydroxyl groups on the surface, which were quantified by DTP -CO2 analyses. Moreover, the study conducted with the supports suggests that the oxidation reactions are catalyzed, that is, they are dependent on the catalyst employed. In addition to the support study, a statistical investigation was conducted to evaluate the contribution of the factors: active phase (Ni, Cu), O2/C2H5OH ratio, and temperature. It was observed that Ni and Cu favor the reactional route of ethanol reforming, decreasing the flow rate of parallel reaction products. Temperature increase acted in the same direction, favoring the ethanol reforming route - specifically, the methane reforming. The presence of oxygen influenced significantly some parallel reactions, like ethanol oxidation, ethene formation, and increasing of the CH4 flow rate. Finally, the information obtained in this work propitiated the production of a map of possible reaction routes for the studied system that can be helpful for further developments in this technology. In other words, the employed statistical method was innovative and brought significant contributions for the understanding of ethanol reforming.Os problemas políticos e socioeconômicos causados pelos impactos ambientais decorrentes de fontes de energia poluidoras e não renováveis suscitaram maior interesse por fontes de energia renováveis e não poluentes. Um combustível que pode ajudar a suprir essa necessidade é o hidrogênio. Para que o hidrogênio seja realmente um combustível renovável e limpo, a sua linha de produção precisa possuir essas características também. A reforma do etanol é um processo alternativo de produção de hidrogênio que atende essas exigências. A reforma do etanol é uma reação de alta complexidade e por isso, apesar de já haver diversas pesquisas sobre essa tecnologia, muitos fatores ainda precisam ser esclarecidos. Nesse contexto, esse trabalho visa fornecer informações importantes para a melhor compreensão da reforma do etanol. Para tanto, foram realizados testes de reforma com vapor d'água e reforma oxidativa do etanol com diferentes suportes catalíticos com o intuito de compreender a contribuição de cada um deles no desenvolvimento dessa tecnologia. Foram testados três suportes de CeO2, sendo um na forma comercial e outros dois calcinados a diferentes temperaturas: 550 ºC e 800 °C. Além desses, foram testados os suportes de Nb2O5: puro, impregnado com Na2O e impregnado com CeO2. O suporte CeO2 calcinado a 800 °C apresentou menor desativação dentre os seis suportes testados, além de também ser o que apresentou menor produção de produtos indesejáveis, como eteno, acetona e CO. O suporte de Nb2O5 impregnado com Na2O apresentou modificações consideráveis nas suas características, quando comparado ao Nb2O5 puro. Essa dopagem propiciou menor formação de produtos indesejáveis, como eteno e também diminuiu a formação de coque. O estudo dos suportes propiciou a sugestão de que a produção de eteno e a polimerização do mesmo estão intimamente ligadas à concentração de grupos hidroxilas na superfície, quantificada pela análise de DTP-CO2. Além disso, o estudo realizado com os suportes sugere que as reações de oxidação são catalisadas, isto é, dependem do catalisador empregado. Além do estudo realizado com os suportes, foi realizado um estudo estatístico para avaliar a contribuição da fase ativa (Ni e/ou Cu), da razão O2/C2H5OH e da temperatura. Observou-se que o Ni e o Cu favorecem a rota reacional da reforma do etanol, diminuindo a produção de produtos de reações paralelas. O aumento da temperatura atuou no mesmo sentido, favorecendo a rota de reforma do etanol, especificamente, a reforma do metano proveniente de etapas anteriores. A presença do oxigênio influenciou significativamente algumas reações paralelas, como a oxidação parcial do etanol, a formação de eteno e o aumento da vazão de CH4. Por fim, os resultados obtidos neste trabalho propiciaram a produção de um esquema de rotas reacionais que podem ser favorecidas, dependendo do sistema reacional testado. Ou seja, o método empregado do estudo estatístico foi inovador e trouxe contribuições significativas para a compreensão da reforma do etanol.1 CD-ROM (xxiii, 178 f.)Universidade Estadual de MaringáBrasilDepartamento de Engenharia QuímicaPrograma de Pós-Graduação em Engenharia QuímicaUEMMaringá, PRCentro de TecnologiaNádia Regina Camargo Fernandes-MachadoMarcos de SouzaMara Heloisa Neves Olsen ScalianteFabio Souza TonioloChristian Gonçalves AlonsoDancini-Pontes, Isabela2018-04-17T17:39:53Z2018-04-17T17:39:53Z2017info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesishttp://repositorio.uem.br:8080/jspui/handle/1/3653porinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Estadual de Maringá (RI-UEM)instname:Universidade Estadual de Maringá (UEM)instacron:UEM2018-10-15T18:07:30Zoai:localhost:1/3653Repositório InstitucionalPUBhttp://repositorio.uem.br:8080/oai/requestopendoar:2024-04-23T14:56:48.057036Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) - Universidade Estadual de Maringá (UEM)false |
dc.title.none.fl_str_mv |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol Influence of parameters in the reaction mechanisms of steam reforming and oxidative reforming of ethanol |
title |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol |
spellingShingle |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol Dancini-Pontes, Isabela Reação catalítica Etanol Reação de reforma Hidrogênio Produção Brasil. Engenharias Engenharia Química |
title_short |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol |
title_full |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol |
title_fullStr |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol |
title_full_unstemmed |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol |
title_sort |
Influência de parâmetros no mecanismo das reações de reforma com vapor d'água e reforma oxidativa do etanol |
author |
Dancini-Pontes, Isabela |
author_facet |
Dancini-Pontes, Isabela |
author_role |
author |
dc.contributor.none.fl_str_mv |
Nádia Regina Camargo Fernandes-Machado Marcos de Souza Mara Heloisa Neves Olsen Scaliante Fabio Souza Toniolo Christian Gonçalves Alonso |
dc.contributor.author.fl_str_mv |
Dancini-Pontes, Isabela |
dc.subject.por.fl_str_mv |
Reação catalítica Etanol Reação de reforma Hidrogênio Produção Brasil. Engenharias Engenharia Química |
topic |
Reação catalítica Etanol Reação de reforma Hidrogênio Produção Brasil. Engenharias Engenharia Química |
description |
Socioeconomic and political problems caused by the environmental impacts of polluting and non-renewable energy sources have aroused an increasing interest for renewable and nonpolluting energy sources. Among the candidates for supplying this need is hydrogen. For hydrogen to fulfill the requirements for a renewable and clean combustible, its production line itself must have these characteristics. Ethanol reforming is an alternative hydrogen production process that meets these requirements. Nevertheless, despite the great number of investigations about this technology, ethanol reforming is a highly complex process and several points still need to be clarified. In this context, this work provides important information for a better comprehension of ethanol reforming. Inert and oxidative atmosphere tests were conducted with different catalytic supports with the aim of understanding the contribution of each of them to the process. Three CeO2 supports were tested one, of which was from commercial source and two others were calcined at different temperatures, namely, 550 and 800 oC. Moreover, Nb2O5 supports were tested in three different ways, namely, in pure form, impregnated with Na2O, and impregnated with CeO2. The CeO2 support calcined at 800 oC presented the smaller deactivation among the six tested supports, and it also presented the smaller flow rate of undesirable products, like ethene, acetone and CO. As for the Nb2O5 support impregnated with Na2O, considerable modifications in its characteristics were observed relative to the pure support. This doping propitiated less undesirable products, like ethene, and diminished coke formation. The study of the supports allowed us to suggest that ethene production and its polymerization are intimately connected to the concentration of hydroxyl groups on the surface, which were quantified by DTP -CO2 analyses. Moreover, the study conducted with the supports suggests that the oxidation reactions are catalyzed, that is, they are dependent on the catalyst employed. In addition to the support study, a statistical investigation was conducted to evaluate the contribution of the factors: active phase (Ni, Cu), O2/C2H5OH ratio, and temperature. It was observed that Ni and Cu favor the reactional route of ethanol reforming, decreasing the flow rate of parallel reaction products. Temperature increase acted in the same direction, favoring the ethanol reforming route - specifically, the methane reforming. The presence of oxygen influenced significantly some parallel reactions, like ethanol oxidation, ethene formation, and increasing of the CH4 flow rate. Finally, the information obtained in this work propitiated the production of a map of possible reaction routes for the studied system that can be helpful for further developments in this technology. In other words, the employed statistical method was innovative and brought significant contributions for the understanding of ethanol reforming. |
publishDate |
2017 |
dc.date.none.fl_str_mv |
2017 2018-04-17T17:39:53Z 2018-04-17T17:39:53Z |
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 |
http://repositorio.uem.br:8080/jspui/handle/1/3653 |
url |
http://repositorio.uem.br:8080/jspui/handle/1/3653 |
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.publisher.none.fl_str_mv |
Universidade Estadual de Maringá Brasil Departamento de Engenharia Química Programa de Pós-Graduação em Engenharia Química UEM Maringá, PR Centro de Tecnologia |
publisher.none.fl_str_mv |
Universidade Estadual de Maringá Brasil Departamento de Engenharia Química Programa de Pós-Graduação em Engenharia Química UEM Maringá, PR Centro de Tecnologia |
dc.source.none.fl_str_mv |
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Universidade Estadual de Maringá (UEM) |
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UEM |
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UEM |
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Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) |
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Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) |
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Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) - Universidade Estadual de Maringá (UEM) |
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