Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio
| Ano de defesa: | 2016 |
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| Autor(a) principal: | |
| Orientador(a): | |
| Banca de defesa: | |
| Tipo de documento: | Dissertação |
| Tipo de acesso: | Acesso aberto |
| Idioma: | por |
| Instituição de defesa: |
Universidade Estadual Paulista (Unesp)
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| Programa de Pós-Graduação: |
Não Informado pela instituição
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| Departamento: |
Não Informado pela instituição
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| País: |
Não Informado pela instituição
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| Palavras-chave em Português: | |
| Palavras-chave em Inglês: | |
| Link de acesso: | http://hdl.handle.net/11449/143500 |
Resumo: | Glycerol is the major by-product of biodiesel production. This organic compound has received much attention in recent years due to its growing supply, which has easily surpassed the demand. Therefore, there is a relevant necessity to find a destination for this product. Dehydration reaction is one of the most interesting and challenging routes, which produces acrolein in the presence of an acid catalyst. In order to have a catalytic dehydration of glycerol with high conversion and acrolein selectivity, it’s important to develop an efficient acid catalyst. This outlook will be achieved from the coherent combination of several physicochemical characteristics of the catalyst, such as suitable acid strength and porosity. With respect to acidity control, the isomorphous substitution of heteroatoms in zeolite framework may reduce the Brønsted acidity, resulting in decreased coke formation during the catalytic reaction. With respect to porosity, it’s possible to obtain hierarchically structured zeolites, which play an important role in molecular diffusion. In this way, the study of the synthesis of MWW and FER lamellar zeolites, incorporated with gallium and boron atoms is proposed. Lamellar zeolites are very interesting materials because they can be exfoliated, enhancing accessibility to active sites. The MWW and FER zeolites were synthesized with boron, aluminum and gallium atoms. The XRD patterns of the samples show that different heteroatoms induce the formation of different crystalline phases for MWW structure. These phases were qualified and quantified. Additionally, the SEM images were obtained for the different crystal phases. On the other hand, X-ray diffraction patterns of FER structure show no formation of contaminant crystalline phases. The materials were also characterized by Infrared Spectroscopy and Thermal Analysis. The first one provided important structural informations especially for the materials incorporated with B, providing evidence of the non-incorporation of this heteroatom in the structure of the material synthesized with HMI. In addition, the thermal analysis of the materials provided relevant informations about structural nature of the catalysts, confirming the lamellar nature of the MWW and ferrierite materials. Finally, the characterization by Temperature-Programmed Desorption of Ammonia for FER zeolites structure was performed. From this, it was possible to confirm a lower acidity for B-FER zeolite. On the other hand, the low concentration of acid sites for Al-FER zeolite suggests that the heteroatom was slightly incorporated in the structure. Additionally, the greatest acid strength for Al-MCM-22 zeolite in comparison to Ga-MCM-22 was verified. |
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Catuzo, Gabriel Liscia [UNESP]Universidade Estadual Paulista (Unesp)Frem, Regina Célia GalvãoCardoso, DilsonMartins, Leandro [UNESP]2016-08-31T15:00:25Z2016-08-31T15:00:25Z2016-08-04http://hdl.handle.net/11449/14350000087209733004030072P833004030072P857826965656023400000-0003-2229-5316Glycerol is the major by-product of biodiesel production. This organic compound has received much attention in recent years due to its growing supply, which has easily surpassed the demand. Therefore, there is a relevant necessity to find a destination for this product. Dehydration reaction is one of the most interesting and challenging routes, which produces acrolein in the presence of an acid catalyst. In order to have a catalytic dehydration of glycerol with high conversion and acrolein selectivity, it’s important to develop an efficient acid catalyst. This outlook will be achieved from the coherent combination of several physicochemical characteristics of the catalyst, such as suitable acid strength and porosity. With respect to acidity control, the isomorphous substitution of heteroatoms in zeolite framework may reduce the Brønsted acidity, resulting in decreased coke formation during the catalytic reaction. With respect to porosity, it’s possible to obtain hierarchically structured zeolites, which play an important role in molecular diffusion. In this way, the study of the synthesis of MWW and FER lamellar zeolites, incorporated with gallium and boron atoms is proposed. Lamellar zeolites are very interesting materials because they can be exfoliated, enhancing accessibility to active sites. The MWW and FER zeolites were synthesized with boron, aluminum and gallium atoms. The XRD patterns of the samples show that different heteroatoms induce the formation of different crystalline phases for MWW structure. These phases were qualified and quantified. Additionally, the SEM images were obtained for the different crystal phases. On the other hand, X-ray diffraction patterns of FER structure show no formation of contaminant crystalline phases. The materials were also characterized by Infrared Spectroscopy and Thermal Analysis. The first one provided important structural informations especially for the materials incorporated with B, providing evidence of the non-incorporation of this heteroatom in the structure of the material synthesized with HMI. In addition, the thermal analysis of the materials provided relevant informations about structural nature of the catalysts, confirming the lamellar nature of the MWW and ferrierite materials. Finally, the characterization by Temperature-Programmed Desorption of Ammonia for FER zeolites structure was performed. From this, it was possible to confirm a lower acidity for B-FER zeolite. On the other hand, the low concentration of acid sites for Al-FER zeolite suggests that the heteroatom was slightly incorporated in the structure. Additionally, the greatest acid strength for Al-MCM-22 zeolite in comparison to Ga-MCM-22 was verified.O glicerol, coproduto da reação de transesterificação da síntese do biodiesel, tem recebido muita atenção nos últimos anos devido a sua ascendente oferta, que tem facilmente superado a sua demanda. Surge, portanto, a necessidade de se encontrar uma destinação adequada a este produto como forma de melhor aproveitamento e também para agregar valor à cadeia produtiva do biodiesel. A desidratação é uma das rotas mais interessantes e desafiadoras, a qual produz acroleína na presença de um catalisador ácido. Para que a reação catalítica de desidratação do glicerol ocorra com alta conversão e seletividade à acroleína, há a necessidade de desenvolvimento de um catalisador ácido eficiente. Isto ocorrerá a partir da combinação de várias características físico-químicas adequadas do catalisador, tais como a força ácida e a porosidade. Com relação ao controle da acidez, há a possibilidade de substituição isomórfica de heteroátomos que diminuem a acidez de Brønsted, o que poderia resultar na diminuição da formação de coque durante a reação e, consequentemente, em um melhor desempenho catalítico. Com relação à porosidade, há a possibilidade de se obter uma zeólita hierarquicamente estruturada, característica importante para solução das limitações difusionais do glicerol que apresenta diâmetro cinético da mesma ordem de grandeza dos poros das zeólitas. Desta forma, é proposto o estudo da síntese das zeólitas lamelares MWW e FER, incorporadas com átomos de gálio e boro. As zeólitas lamelares são interessantes, pois elas podem ser esfoliadas e aumentar significativamente a acessibilidade aos sítios ativos por conta do contato do reagente com a superfície das lâminas. As sínteses das zeólitas MWW e FER foram realizadas na presença de B, Al e Ga como heteroátomos. Por meio da técnica de difratometria de raios X, constatou-se que os heteroátomos induzem a formação de diferentes fases, no caso da zeólita de estrutura MWW. Essas fases foram identificadas como pertencentes as estruturas MFI, Kenyaite e α-quartzo e, posteriormente, quantificadas. Adicionalmente, as imagens dos cristais das diferentes fases foram obtidas por microscopia de varredura eletrônica. Já no caso da zeólitas de topologia FER, esta foi a única estrutura formada, não havendo contaminação por outras fases cristalinas. Todos os materiais também foram caracterizados por espectroscopia na região do infravermelho e por análise térmica. A primeira forneceu informações estruturais importantes dos materiais estudados, sobretudo para aqueles cristalizadas com boro, fornecendo uma evidência da não incorporação deste átomo na estrutura dos materiais sintetizados com HMI. Além disso, a análise térmica das amostras deu informações relevantes acerca da natureza estrutural dos catalisadores, confirmando a natureza lamelar dos materiais MWW, Kenyaite e ferrierita. Por fim, a caracterização por dessorção a temperatura programada de amônia para alguns dos materiais de estrutura FER, Kenyaite e MWW foi realizada. A partir desta, pôde-se confirmar uma menor acidez para a zeólita B-FER; por outro lado, a baixa concentração de sítios ácidos para zeólita Al-FER sugere que este heteroátomo foi pouco incorporado na estrutura. Adicionalmente, a não acidez para a estrutura Kenyaite foi verificada e a maior força dos sítios ácidos para a zeólita Al-MCM-22 em relação a Ga-MCM-22 foi comprovada. Os materiais zeolíticos preparados apresentam, portanto, uma característica lamelar importante e com força de sitio ativo adequada para a aplicação postulada, ou seja, a desidratação do glicerol a acroleína.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)porUniversidade Estadual Paulista (Unesp)Zeólitas lamelaresSubstituição IsomórficaZeólita MWWZeólita FERDesidratação do glicerolLamellar zeolitesIsomorphous SubstitutionMWW zeoliteFER zeoliteGlycerol dehydrationEstudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálioStudy of the synthesis of lamellar zeolites containing aluminum, gallium and boron atomsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPQuímica - IQARQuímica dos materiaisCatáliseUniversidade Estadual Paulista (UNESP), Instituto de Química, Araraquara24 meses após a data da defesa57826965656023400000-0003-2229-5316Publicationbc74a1ce-4c4c-4dad-8378-83962d76c4fdvirtual::39878-1bc74a1ce-4c4c-4dad-8378-83962d76c4fdvirtual::39878-161afcbc3-9ae1-47a5-b858-c45020d514d5virtual::35617-161afcbc3-9ae1-47a5-b858-c45020d514d5virtual::35617-1ORIGINALcatuzo_gl_me_araiq_par.pdfcatuzo_gl_me_araiq_par.pdfapplication/pdf715521https://repositorio.unesp.br/bitstreams/f4fe2362-b009-4a34-952a-8a26f46081bc/download549c2ce8dfa3a4736d6c37217b9d1144MD53trueAnonymousREADcatuzo_gl_me_araiq_int.pdfcatuzo_gl_me_araiq_int.pdfapplication/pdf3684835https://repositorio.unesp.br/bitstreams/ce228645-1770-4b4c-b789-42423877ef9e/downloade4fa8b291de30643608cd74de38f9e51MD54falseAnonymousREADLICENSElicense.txtWritten by org.dspace.content.LicenseUtilstext/plain; charset=utf-83056https://repositorio.unesp.br/bitstreams/3f746a37-6923-48c7-b15d-65e570ba583e/download83a7b606b886e866cd78d574f9621332MD52falseAnonymousREADTEXTcatuzo_gl_me_araiq_par.pdf.txtWritten by FormatFilter org.dspace.app.mediafilter.TikaTextExtractionFilter on 2023-11-01T06:15:40Z (GMT).Extracted texttext/plain57949https://repositorio.unesp.br/bitstreams/f0725fb5-4968-409d-a719-329583c2f218/downloadb44da896b5fc3913386f715a9bee8401MD59falseAnonymousREADcatuzo_gl_me_araiq_int.pdf.txtWritten by FormatFilter org.dspace.app.mediafilter.TikaTextExtractionFilter on 2023-11-01T06:15:40Z (GMT).Extracted texttext/plain103347https://repositorio.unesp.br/bitstreams/abd95681-1d1d-4ae1-b62e-633137cc27ff/downloadb72ec8bf5a96ccfac63f54e89447c8afMD510falseAnonymousREADTHUMBNAILcatuzo_gl_me_araiq_par.pdf.jpgWritten by FormatFilter org.dspace.app.mediafilter.ImageMagickPdfThumbnailFilter on 2016-11-16T22:09:38Z (GMT).IM Thumbnailimage/jpeg3791https://repositorio.unesp.br/bitstreams/13edd960-78de-4600-92ff-604c30100f6a/download6f4781da1b07a5558ef3759d8458b1f5MD57falseAnonymousREADcatuzo_gl_me_araiq_int.pdf.jpgWritten by FormatFilter org.dspace.app.mediafilter.ImageMagickPdfThumbnailFilter on 2016-11-16T22:09:38Z (GMT).IM Thumbnailimage/jpeg4017https://repositorio.unesp.br/bitstreams/b424935a-22f7-4198-ac2c-8dcfbd89fe5d/download52a359e67a9d45a1a42bb14258b63561MD58falseAnonymousREAD11449/1435002026-03-11T17:10:33.236279Zopen.accessoai:repositorio.unesp.br:11449/143500https://repositorio.unesp.brRepositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestrepositoriounesp@unesp.bropendoar:29462026-03-11T17:10:33Repositório Institucional da UNESP - 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| dc.title.pt.fl_str_mv |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio |
| dc.title.alternative.en.fl_str_mv |
Study of the synthesis of lamellar zeolites containing aluminum, gallium and boron atoms |
| title |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio |
| spellingShingle |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio Catuzo, Gabriel Liscia [UNESP] Zeólitas lamelares Substituição Isomórfica Zeólita MWW Zeólita FER Desidratação do glicerol Lamellar zeolites Isomorphous Substitution MWW zeolite FER zeolite Glycerol dehydration |
| title_short |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio |
| title_full |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio |
| title_fullStr |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio |
| title_full_unstemmed |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio |
| title_sort |
Estudo da síntese de zeólitas lamelares contendo átomos de alumínio, boro e gálio |
| author |
Catuzo, Gabriel Liscia [UNESP] |
| author_facet |
Catuzo, Gabriel Liscia [UNESP] |
| author_role |
author |
| dc.contributor.institution.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) |
| dc.contributor.committeeMember.none.fl_str_mv |
Frem, Regina Célia Galvão Cardoso, Dilson |
| dc.contributor.author.fl_str_mv |
Catuzo, Gabriel Liscia [UNESP] |
| dc.contributor.advisor1.fl_str_mv |
Martins, Leandro [UNESP] |
| contributor_str_mv |
Martins, Leandro [UNESP] |
| dc.subject.por.fl_str_mv |
Zeólitas lamelares Substituição Isomórfica Zeólita MWW Zeólita FER Desidratação do glicerol Lamellar zeolites |
| topic |
Zeólitas lamelares Substituição Isomórfica Zeólita MWW Zeólita FER Desidratação do glicerol Lamellar zeolites Isomorphous Substitution MWW zeolite FER zeolite Glycerol dehydration |
| dc.subject.eng.fl_str_mv |
Isomorphous Substitution MWW zeolite FER zeolite Glycerol dehydration |
| description |
Glycerol is the major by-product of biodiesel production. This organic compound has received much attention in recent years due to its growing supply, which has easily surpassed the demand. Therefore, there is a relevant necessity to find a destination for this product. Dehydration reaction is one of the most interesting and challenging routes, which produces acrolein in the presence of an acid catalyst. In order to have a catalytic dehydration of glycerol with high conversion and acrolein selectivity, it’s important to develop an efficient acid catalyst. This outlook will be achieved from the coherent combination of several physicochemical characteristics of the catalyst, such as suitable acid strength and porosity. With respect to acidity control, the isomorphous substitution of heteroatoms in zeolite framework may reduce the Brønsted acidity, resulting in decreased coke formation during the catalytic reaction. With respect to porosity, it’s possible to obtain hierarchically structured zeolites, which play an important role in molecular diffusion. In this way, the study of the synthesis of MWW and FER lamellar zeolites, incorporated with gallium and boron atoms is proposed. Lamellar zeolites are very interesting materials because they can be exfoliated, enhancing accessibility to active sites. The MWW and FER zeolites were synthesized with boron, aluminum and gallium atoms. The XRD patterns of the samples show that different heteroatoms induce the formation of different crystalline phases for MWW structure. These phases were qualified and quantified. Additionally, the SEM images were obtained for the different crystal phases. On the other hand, X-ray diffraction patterns of FER structure show no formation of contaminant crystalline phases. The materials were also characterized by Infrared Spectroscopy and Thermal Analysis. The first one provided important structural informations especially for the materials incorporated with B, providing evidence of the non-incorporation of this heteroatom in the structure of the material synthesized with HMI. In addition, the thermal analysis of the materials provided relevant informations about structural nature of the catalysts, confirming the lamellar nature of the MWW and ferrierite materials. Finally, the characterization by Temperature-Programmed Desorption of Ammonia for FER zeolites structure was performed. From this, it was possible to confirm a lower acidity for B-FER zeolite. On the other hand, the low concentration of acid sites for Al-FER zeolite suggests that the heteroatom was slightly incorporated in the structure. Additionally, the greatest acid strength for Al-MCM-22 zeolite in comparison to Ga-MCM-22 was verified. |
| publishDate |
2016 |
| dc.date.accessioned.fl_str_mv |
2016-08-31T15:00:25Z |
| dc.date.available.fl_str_mv |
2016-08-31T15:00:25Z |
| dc.date.issued.fl_str_mv |
2016-08-04 |
| dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
| dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
| format |
masterThesis |
| status_str |
publishedVersion |
| dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/11449/143500 |
| dc.identifier.aleph.none.fl_str_mv |
000872097 |
| dc.identifier.capes.none.fl_str_mv |
33004030072P8 33004030072P8 |
| dc.identifier.lattes.none.fl_str_mv |
5782696565602340 |
| dc.identifier.orcid.none.fl_str_mv |
0000-0003-2229-5316 |
| url |
http://hdl.handle.net/11449/143500 |
| identifier_str_mv |
000872097 33004030072P8 5782696565602340 0000-0003-2229-5316 |
| 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 Paulista (Unesp) |
| publisher.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) |
| dc.source.none.fl_str_mv |
reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
| instname_str |
Universidade Estadual Paulista (UNESP) |
| instacron_str |
UNESP |
| institution |
UNESP |
| reponame_str |
Repositório Institucional da UNESP |
| collection |
Repositório Institucional da UNESP |
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Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
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repositoriounesp@unesp.br |
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1878343523497934848 |