Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III)
Autor(a) principal: | |
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Data de Publicação: | 2010 |
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/1/3667 |
Resumo: | In this work it was synthesized six mononucleous Fe(III) pyperazine-derived complexes, both in its free form and as encapsulated form in zeolite Y made by flexible ligand methodology called "ship in a bottle". Also were tested the reproducibility of the methodology synthesizing complexes in triplicate and making a mechanical mixture of the zeolite FeY with ligands. Many physical-chemistry techniques were performed to determine the chemical structure of the complexes formed and to verify the iron atom environment (IRFT, RMN 1H e 13C, DRX, FRX, TGA/DTA, CHN elementary analysis, AAS, BET textural analysis e adsorption/desorption isotherms, DRS-UV, Mössbauer spectrometry). Experimental testes of the reaction of direct partial oxidation of methane to methanol were performed under various conditions of temperature (100-450 °C) and pressure (1-40- 70 bar), by analyzing two different compositions of the reaction mixture (9% methane; 1% oxygen; 90% Helium e 2,5% methane; 7,5% oxygen; 90% Helium), obtaining methanol as primary reaction product and the final products of methane oxidation. Reactions containing a mixture rich in methane, under the conditions investigated, only the FeY zeolite presented favorable performance to product methanol, but other oxygenates were formed with great selectivity beyond the final oxidation products. However, reactions containing a reaction mixture rich in oxygen, under the conditions investigated, were favored the methanol formation as low as the high reaction pressure. The increase pressure in the system favored the conversion increase, as well as the increase selectivity in the methanol formation, and also decreases the energy barrier required for methane conversion. Methanol was obtained from 150 °C temperature at 40 bar pressure system with the use of free catalysts. Computer simulations by the method of the minimization of Gibbs free energy indicated favorable conditions for the methanol formation, taking into account the two reaction mixtures used in the tests, in addition to temperature and pressure. The simulations show that there is room for improving conversion rates and selectivity observed by experimental tests, but to reach this objective, the reactions should be conducted in reaction routes that are far from the thermodynamic equilibrium reaction and, consequently, energy displaced for the Gibbs minimum energy. |
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Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III)CatalizadorFerroMetanoOxidaçãoMetanolBrasil.EngenhariasEngenharia QuímicaIn this work it was synthesized six mononucleous Fe(III) pyperazine-derived complexes, both in its free form and as encapsulated form in zeolite Y made by flexible ligand methodology called "ship in a bottle". Also were tested the reproducibility of the methodology synthesizing complexes in triplicate and making a mechanical mixture of the zeolite FeY with ligands. Many physical-chemistry techniques were performed to determine the chemical structure of the complexes formed and to verify the iron atom environment (IRFT, RMN 1H e 13C, DRX, FRX, TGA/DTA, CHN elementary analysis, AAS, BET textural analysis e adsorption/desorption isotherms, DRS-UV, Mössbauer spectrometry). Experimental testes of the reaction of direct partial oxidation of methane to methanol were performed under various conditions of temperature (100-450 °C) and pressure (1-40- 70 bar), by analyzing two different compositions of the reaction mixture (9% methane; 1% oxygen; 90% Helium e 2,5% methane; 7,5% oxygen; 90% Helium), obtaining methanol as primary reaction product and the final products of methane oxidation. Reactions containing a mixture rich in methane, under the conditions investigated, only the FeY zeolite presented favorable performance to product methanol, but other oxygenates were formed with great selectivity beyond the final oxidation products. However, reactions containing a reaction mixture rich in oxygen, under the conditions investigated, were favored the methanol formation as low as the high reaction pressure. The increase pressure in the system favored the conversion increase, as well as the increase selectivity in the methanol formation, and also decreases the energy barrier required for methane conversion. Methanol was obtained from 150 °C temperature at 40 bar pressure system with the use of free catalysts. Computer simulations by the method of the minimization of Gibbs free energy indicated favorable conditions for the methanol formation, taking into account the two reaction mixtures used in the tests, in addition to temperature and pressure. The simulations show that there is room for improving conversion rates and selectivity observed by experimental tests, but to reach this objective, the reactions should be conducted in reaction routes that are far from the thermodynamic equilibrium reaction and, consequently, energy displaced for the Gibbs minimum energy.Neste trabalho foram sintetizados seis complexos mononucleados de Fe(III) derivados da piperazina tanto na sua forma livre quanto na forma encapsulada em zeólita Y pela metodologia do ligante flexível chamada de "ship in a bottle". Também se testou a reprodutibilidade da metodologia sintetizando os complexos em triplicatas e também fazendo uma mistura mecânica entre zeólita FeY com ligantes. Diversas análises físico-químicas foram realizadas para determinar a estrutura química dos complexos formados e verificar o ambiente do átomo de ferro (IR-FT, RMN 1H e 13C, DRX, FRX, TGA/DTA, análise elementar de CHN, AAS, análise textural BET e isotermas de adsorção/dessorção, DRS-UV, espectrometria Mössbauer). Testes experimentais da reação de oxidação parcial direta de metano a metanol foram realizados em várias condições de temperatura (100-450 °C) e pressão (1-40-70 bar), analisando duas composições diferentes de mistura reacional (9% metano; 1% oxigênio; 90% Helio e 2,5% metano; 7,5% oxigênio; 90% Helio), obtendo-se metanol como produto primário da reação, além dos produtos finais de oxidação de metano. Em reações contendo uma mistura reacional rica em metano, sob as condições investigadas, apenas a zeólita FeY apresentou desempenho favorável à produção de metanol, mas outros produtos oxigenados foram formados com boa seletividade, além dos produtos finais de oxidação. No entanto, em reações contendo uma mistura reacional rica em oxigênio, sob as condições investigadas, houve favorecimento à formação de metanol tanto a baixa quanto a alta pressão. O aumento da pressão do sistema favoreceu o aumento da conversão como também o aumento da seletividade à formação do metanol, além de diminuir a barreira energética necessária para conversão do metano. Foi possível obter metanol a partir de 150 °C de temperatura a 40 bar de pressão do sistema com uso de catalisadores livres. Simulações computacionais pelo método da minimização da energia livre de Gibbs indicaram as condições favoráveis para a formação de metanol, levando em consideração as duas misturas reacionais utilizadas nos testes, além das condições de temperatura e pressão. As simulações mostram que existe espaço para a melhoria dos valores de conversão e seletividade observados pelos testes experimentais, porém para atingir este objetivo, as reações devem ser conduzidas em rotas reacionais que estejam longe do equilíbrio termodinâmico da reação e, conseqüentemente, energeticamente deslocadas do mínimo de Gibbs.xviii, 144 fUniversidade Estadual de MaringáBrasilPrograma de Pós-Graduação em Engenharia QuímicaUEMMaringá, PRDepartamento de Engenharia QuímicaLúcio Cardozo FilhoVictor Luis dos Santos Teixeira da Silva - UFRJChristian Gonçalves Alonso - UEMMara Heloisa Neves Olsen Scaliante - UEMPedro Augusto Arroyo - UEMBerezuk, Márcio Eduardo2018-04-17T17:39:55Z2018-04-17T17:39:55Z2010info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesishttp://repositorio.uem.br:8080/jspui/handle/1/3667porinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Estadual de Maringá (RI-UEM)instname:Universidade Estadual de Maringá (UEM)instacron:UEM2023-12-06T18:11:59Zoai:localhost:1/3667Repositório InstitucionalPUBhttp://repositorio.uem.br:8080/oai/requestopendoar:2024-04-23T14:56:48.961633Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) - Universidade Estadual de Maringá (UEM)false |
dc.title.none.fl_str_mv |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) |
title |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) |
spellingShingle |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) Berezuk, Márcio Eduardo Catalizador Ferro Metano Oxidação Metanol Brasil. Engenharias Engenharia Química |
title_short |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) |
title_full |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) |
title_fullStr |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) |
title_full_unstemmed |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) |
title_sort |
Oxidação parcial direta de metano a metanol com o uso de complexos piperazínicos de ferro(III) |
author |
Berezuk, Márcio Eduardo |
author_facet |
Berezuk, Márcio Eduardo |
author_role |
author |
dc.contributor.none.fl_str_mv |
Lúcio Cardozo Filho Victor Luis dos Santos Teixeira da Silva - UFRJ Christian Gonçalves Alonso - UEM Mara Heloisa Neves Olsen Scaliante - UEM Pedro Augusto Arroyo - UEM |
dc.contributor.author.fl_str_mv |
Berezuk, Márcio Eduardo |
dc.subject.por.fl_str_mv |
Catalizador Ferro Metano Oxidação Metanol Brasil. Engenharias Engenharia Química |
topic |
Catalizador Ferro Metano Oxidação Metanol Brasil. Engenharias Engenharia Química |
description |
In this work it was synthesized six mononucleous Fe(III) pyperazine-derived complexes, both in its free form and as encapsulated form in zeolite Y made by flexible ligand methodology called "ship in a bottle". Also were tested the reproducibility of the methodology synthesizing complexes in triplicate and making a mechanical mixture of the zeolite FeY with ligands. Many physical-chemistry techniques were performed to determine the chemical structure of the complexes formed and to verify the iron atom environment (IRFT, RMN 1H e 13C, DRX, FRX, TGA/DTA, CHN elementary analysis, AAS, BET textural analysis e adsorption/desorption isotherms, DRS-UV, Mössbauer spectrometry). Experimental testes of the reaction of direct partial oxidation of methane to methanol were performed under various conditions of temperature (100-450 °C) and pressure (1-40- 70 bar), by analyzing two different compositions of the reaction mixture (9% methane; 1% oxygen; 90% Helium e 2,5% methane; 7,5% oxygen; 90% Helium), obtaining methanol as primary reaction product and the final products of methane oxidation. Reactions containing a mixture rich in methane, under the conditions investigated, only the FeY zeolite presented favorable performance to product methanol, but other oxygenates were formed with great selectivity beyond the final oxidation products. However, reactions containing a reaction mixture rich in oxygen, under the conditions investigated, were favored the methanol formation as low as the high reaction pressure. The increase pressure in the system favored the conversion increase, as well as the increase selectivity in the methanol formation, and also decreases the energy barrier required for methane conversion. Methanol was obtained from 150 °C temperature at 40 bar pressure system with the use of free catalysts. Computer simulations by the method of the minimization of Gibbs free energy indicated favorable conditions for the methanol formation, taking into account the two reaction mixtures used in the tests, in addition to temperature and pressure. The simulations show that there is room for improving conversion rates and selectivity observed by experimental tests, but to reach this objective, the reactions should be conducted in reaction routes that are far from the thermodynamic equilibrium reaction and, consequently, energy displaced for the Gibbs minimum energy. |
publishDate |
2010 |
dc.date.none.fl_str_mv |
2010 2018-04-17T17:39:55Z 2018-04-17T17:39:55Z |
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/1/3667 |
url |
http://repositorio.uem.br:8080/jspui/handle/1/3667 |
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 Programa de Pós-Graduação em Engenharia Química UEM Maringá, PR Departamento de Engenharia Química |
publisher.none.fl_str_mv |
Universidade Estadual de Maringá Brasil Programa de Pós-Graduação em Engenharia Química UEM Maringá, PR Departamento de Engenharia Química |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) instname:Universidade Estadual de Maringá (UEM) instacron:UEM |
instname_str |
Universidade Estadual de Maringá (UEM) |
instacron_str |
UEM |
institution |
UEM |
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Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) |
collection |
Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) |
repository.name.fl_str_mv |
Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) - Universidade Estadual de Maringá (UEM) |
repository.mail.fl_str_mv |
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1801841410238840832 |