Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Tipo de documento: | Tese |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/13216 |
Resumo: | Methane (CH4) is a stable molecule abundantly found on our planet with reserves even greater than crude oil. Due to its high availability and environmental impacts caused by its emission into the atmosphere, the development of processes for its conversion into high value-added products is highly desired. Direct conversion of CH4 to methanol is advantageous as this process converts CH4 at low temperatures (<300 ° C) through the step-wise methane to methanol direct conversion (MMet). Intense scientific studies have been conducted on this reaction and all of them converged to the use of metal ionexchanged zeolites, especially copper. Although CH4 is easily activated on these materials, controlling methane total oxidation to COx is still a challenge and a limiting for methanol yield. In addition, only a fraction of Cu species actually participates in the reaction, which means that methanol yield is also limited to this factor. Since different Cu structures can be formed in zeolites by copper exchanged method, such as [Cu3 (μ-O)3]2+, [Cu2 (μ-O) 2]2+, [Cu2 (μ-O)]2+, and CuO, there are still fundamental questions to be answered for a better understanding of this reaction, such as the effect of zeolite structure on the formation of Cu species and how to maximize its participation in the reaction. We herein carried out a careful study of different copper-exchanged zeolite materials varying several synthesis/reaction parameters and related the activity to the structure of the Cu species. Our results suggested that high Cu content and low Si/Al ratio were unfavorable and the counter ion affects the performance of mazzite zeolite on MMet reaction. With this study, we hope to contribute with important aspects that might help in a future process scale-up. |
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Mizuno, Stefanie Caroline MayumiBueno, José Maria Corrêahttp://lattes.cnpq.br/0157452280626031http://lattes.cnpq.br/0805524022565035603e670a-6409-4498-ad2a-73ca6411109c2020-09-04T21:22:05Z2020-09-04T21:22:05Z2020-03-06MIZUNO, Stefanie Caroline Mayumi. Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre. 2020. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2020. Disponível em: https://repositorio.ufscar.br/handle/ufscar/13216.https://repositorio.ufscar.br/handle/ufscar/13216Methane (CH4) is a stable molecule abundantly found on our planet with reserves even greater than crude oil. Due to its high availability and environmental impacts caused by its emission into the atmosphere, the development of processes for its conversion into high value-added products is highly desired. Direct conversion of CH4 to methanol is advantageous as this process converts CH4 at low temperatures (<300 ° C) through the step-wise methane to methanol direct conversion (MMet). Intense scientific studies have been conducted on this reaction and all of them converged to the use of metal ionexchanged zeolites, especially copper. Although CH4 is easily activated on these materials, controlling methane total oxidation to COx is still a challenge and a limiting for methanol yield. In addition, only a fraction of Cu species actually participates in the reaction, which means that methanol yield is also limited to this factor. Since different Cu structures can be formed in zeolites by copper exchanged method, such as [Cu3 (μ-O)3]2+, [Cu2 (μ-O) 2]2+, [Cu2 (μ-O)]2+, and CuO, there are still fundamental questions to be answered for a better understanding of this reaction, such as the effect of zeolite structure on the formation of Cu species and how to maximize its participation in the reaction. We herein carried out a careful study of different copper-exchanged zeolite materials varying several synthesis/reaction parameters and related the activity to the structure of the Cu species. Our results suggested that high Cu content and low Si/Al ratio were unfavorable and the counter ion affects the performance of mazzite zeolite on MMet reaction. With this study, we hope to contribute with important aspects that might help in a future process scale-up.O metano (CH4) é uma molécula estável abundantemente encontrada no nosso planeta possuindo reservas ainda maiores do que as de petróleo bruto. Devido à sua alta disponibilidade e impactos ambientais causados pela sua emissão exacerbada na atmosfera, o desenvolvimento de processos para sua conversão em produtos de alto valor agregado está em ascenção. A conversão direta de CH4 a metanol mostra-se vantajosa já que este processo converte CH4 a baixas temperaturas (<300oC) através da reação ‘step-wise’ de oxidação parcial direta do metano (OPDM). Intenso estudo científico tem sido realizado sobre esta reação e todos eles convergem para a utilização de materiais baseados em metais trocados ionicamente com zeólitas, especialmente cobre. Apesar de o CH4 ser facilmente ativado sobre esses materiais, controlar a oxidação total dos intermediários de reação a COx ainda é um desafio e um limitante para o rendimento de metanol. Além disso, sabe-se que apenas uma fração do Cu participa efetivamente da reação o que faz com que o rendimento de metanol também seja limitado a mais este fator. Diferentes estruturas de Cu podem ser formadas em zeólitas pelo método de troca iônica, tais como: ([Cu3(μ-O)3]2+, ([Cu2(μ-O)2]2+, ([Cu2(μ- O)]2+, e CuO, além disso, ainda existem questões fundamentais a serem respondidas para maior entendimento desta reação como, por exemplo, o efeito da estrutura zeolítica na formação das espécies de Cu e como maximizar a sua partipação na reação. Neste trabalho, realizamos um estudo criterioso de diferentes materiais zeolíticos trocados ionicamente com cobre variando diversos parâmetros de síntese e reação, relacionando a atividade com a estrutura do sítio ativo. Nossos resultados sugerem que altas cargas de Cu e baixa razão Si/Al são desfavoráveis e o contra-íon afeta a performance da zeólita mazzita em reação. Com esses resultados, buscamos contribuir em aspectos importantes para uma possível implementação deste processo em escala industrial.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)CAPES: Código de Financiamento 001engUniversidade 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/openAccessOxidação parcialMetanoMetanolCobreZeólitaPartial oxidationMethaneMethanolCopperZeoliteENGENHARIAS::ENGENHARIA QUIMICACompreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobreUnderstanding trends in step-wise methane to methanol conversion using Cu-exchanged zeolitesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis6006003b275236-acc5-4218-a33b-8f802e7f5a18reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALtesefinal_StefanieMizuno.pdftesefinal_StefanieMizuno.pdfTese de doutoradoapplication/pdf4707832https://repositorio.ufscar.br/bitstream/ufscar/13216/1/tesefinal_StefanieMizuno.pdfbeaae4c137954e4becaf704381d67b86MD51carta comprovante_ZM.pdfcarta comprovante_ZM.pdfapplication/pdf296524https://repositorio.ufscar.br/bitstream/ufscar/13216/3/carta%20comprovante_ZM.pdf5895cbbb1a21eabe8f5b725d30bff6f1MD53CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/13216/4/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD54TEXTtesefinal_StefanieMizuno.pdf.txttesefinal_StefanieMizuno.pdf.txtExtracted texttext/plain176176https://repositorio.ufscar.br/bitstream/ufscar/13216/5/tesefinal_StefanieMizuno.pdf.txtba5e9649fbaede5335bedaf7e88fede8MD55carta comprovante_ZM.pdf.txtcarta comprovante_ZM.pdf.txtExtracted texttext/plain1325https://repositorio.ufscar.br/bitstream/ufscar/13216/7/carta%20comprovante_ZM.pdf.txtbdb8f9cf4c5b4c8403fc659b4987dafaMD57THUMBNAILtesefinal_StefanieMizuno.pdf.jpgtesefinal_StefanieMizuno.pdf.jpgIM Thumbnailimage/jpeg10153https://repositorio.ufscar.br/bitstream/ufscar/13216/6/tesefinal_StefanieMizuno.pdf.jpge4eb28f8e3ae1c9594525e72a7e1e76cMD56carta comprovante_ZM.pdf.jpgcarta comprovante_ZM.pdf.jpgIM Thumbnailimage/jpeg13660https://repositorio.ufscar.br/bitstream/ufscar/13216/8/carta%20comprovante_ZM.pdf.jpg5dc2d06db1ae56a7bc559b0564fb3123MD58ufscar/132162023-09-18 18:32:00.208oai:repositorio.ufscar.br:ufscar/13216Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre |
dc.title.alternative.eng.fl_str_mv |
Understanding trends in step-wise methane to methanol conversion using Cu-exchanged zeolites |
title |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre |
spellingShingle |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre Mizuno, Stefanie Caroline Mayumi Oxidação parcial Metano Metanol Cobre Zeólita Partial oxidation Methane Methanol Copper Zeolite ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre |
title_full |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre |
title_fullStr |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre |
title_full_unstemmed |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre |
title_sort |
Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre |
author |
Mizuno, Stefanie Caroline Mayumi |
author_facet |
Mizuno, Stefanie Caroline Mayumi |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/0805524022565035 |
dc.contributor.author.fl_str_mv |
Mizuno, Stefanie Caroline Mayumi |
dc.contributor.advisor1.fl_str_mv |
Bueno, José Maria Corrêa |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/0157452280626031 |
dc.contributor.authorID.fl_str_mv |
603e670a-6409-4498-ad2a-73ca6411109c |
contributor_str_mv |
Bueno, José Maria Corrêa |
dc.subject.por.fl_str_mv |
Oxidação parcial Metano Metanol Cobre Zeólita |
topic |
Oxidação parcial Metano Metanol Cobre Zeólita Partial oxidation Methane Methanol Copper Zeolite ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Partial oxidation Methane Methanol Copper Zeolite |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA |
description |
Methane (CH4) is a stable molecule abundantly found on our planet with reserves even greater than crude oil. Due to its high availability and environmental impacts caused by its emission into the atmosphere, the development of processes for its conversion into high value-added products is highly desired. Direct conversion of CH4 to methanol is advantageous as this process converts CH4 at low temperatures (<300 ° C) through the step-wise methane to methanol direct conversion (MMet). Intense scientific studies have been conducted on this reaction and all of them converged to the use of metal ionexchanged zeolites, especially copper. Although CH4 is easily activated on these materials, controlling methane total oxidation to COx is still a challenge and a limiting for methanol yield. In addition, only a fraction of Cu species actually participates in the reaction, which means that methanol yield is also limited to this factor. Since different Cu structures can be formed in zeolites by copper exchanged method, such as [Cu3 (μ-O)3]2+, [Cu2 (μ-O) 2]2+, [Cu2 (μ-O)]2+, and CuO, there are still fundamental questions to be answered for a better understanding of this reaction, such as the effect of zeolite structure on the formation of Cu species and how to maximize its participation in the reaction. We herein carried out a careful study of different copper-exchanged zeolite materials varying several synthesis/reaction parameters and related the activity to the structure of the Cu species. Our results suggested that high Cu content and low Si/Al ratio were unfavorable and the counter ion affects the performance of mazzite zeolite on MMet reaction. With this study, we hope to contribute with important aspects that might help in a future process scale-up. |
publishDate |
2020 |
dc.date.accessioned.fl_str_mv |
2020-09-04T21:22:05Z |
dc.date.available.fl_str_mv |
2020-09-04T21:22:05Z |
dc.date.issued.fl_str_mv |
2020-03-06 |
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.citation.fl_str_mv |
MIZUNO, Stefanie Caroline Mayumi. Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre. 2020. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2020. Disponível em: https://repositorio.ufscar.br/handle/ufscar/13216. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/13216 |
identifier_str_mv |
MIZUNO, Stefanie Caroline Mayumi. Compreendendo a reação ‘step-wise’ de conversão de metano a metanol usando zeólitas trocadas ionicamente com cobre. 2020. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2020. Disponível em: https://repositorio.ufscar.br/handle/ufscar/13216. |
url |
https://repositorio.ufscar.br/handle/ufscar/13216 |
dc.language.iso.fl_str_mv |
eng |
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eng |
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600 600 |
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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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Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Engenharia Química - PPGEQ |
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