Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona

Detalhes bibliográficos
Autor(a) principal: Lima, Marcelo Souza
Data de Publicação: 2021
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Repositório Institucional da UFSCAR
Texto Completo: https://repositorio.ufscar.br/handle/ufscar/15122
Resumo: The petroleum is used to manufacture plastics, solvents and, mainly, to produce fuels. However, some factors such as fluctuation in the price of the barrel, its non-renewable origin and the release of greenhouse gases make it necessary to diversify this energy matrix. In this way, furfural, derived from a renewable source, can undergo aldol condensation with ketone and form aviation kerosene precursors. This reaction is catalyzed by acid or base, however, studies in the literature show that heterogeneous catalysts do not have stability, with loss of the material's active phase, suffer from deactivation and, mainly, have low product selectivity (1E,4E)-1,5-di (furan-2-yl)penta-1,4-dien-3-one (F₂Ac). Therefore, in this work, catalysts are proposed in order to increase the efficiency of materials in this reaction. Therefore, in Chapter 1, mesoporous materials of the SBA-15 family were synthesized functionalized with: (3-aminopropyl)triethoxysilane (APTES), 3-(2-Imidazolin-1-yl)propyltriethoxysilane (IMPTES), (3-anilinopropyl)trimethoxysilane (PAPTMS) that would give basic properties to materials. Thus, they were characterized by X-Ray diffraction, Infrared spectroscopy, thermal (TGA) and CHN elemental analysis. In addition, catalytic tests were carried out that investigated the best experimental conditions and revealed that the SBA-15-APTES material has the best activity, fully converting furfural and being 47% selective to the product (1E,4E)-1,5-di (furan-2-yl)penta-1,4-dien-3-one (F₂Ac) of greatest interest and 7% to (E)-4-(furan-2-yl)but-3-en-2-one (FAc). In chapter 2, the synthesis of materials with Sn (IV) is proposed, which would give acidic Lewis properties, aiming to stabilize the enolate anion formed from F₂Ac and functionalized with the aforementioned silanizing agents that confer basicity. Then, the catalysts were synthesized by post-functionalization of Sn-SBA-15 precursor materials and characterized by UV-vis spectroscopy, ICP-OES and by the analyzes already mentioned in the previous chapter. In the catalytic tests all materials were active, however, the results revealed that the acidity did not contribute to the desired action.
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spelling Lima, Marcelo SouzaGallo, Jean Marcel Ribeirohttp://lattes.cnpq.br/3485408327490746Marques, Clelia Mara de Paulahttp://lattes.cnpq.br/0451284088402660http://lattes.cnpq.br/13299512784879344d58b1e0-35b8-4e05-a442-100ca67cffcc2021-11-17T13:11:11Z2021-11-17T13:11:11Z2021-10-14LIMA, Marcelo Souza. Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona. 2021. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15122.https://repositorio.ufscar.br/handle/ufscar/15122The petroleum is used to manufacture plastics, solvents and, mainly, to produce fuels. However, some factors such as fluctuation in the price of the barrel, its non-renewable origin and the release of greenhouse gases make it necessary to diversify this energy matrix. In this way, furfural, derived from a renewable source, can undergo aldol condensation with ketone and form aviation kerosene precursors. This reaction is catalyzed by acid or base, however, studies in the literature show that heterogeneous catalysts do not have stability, with loss of the material's active phase, suffer from deactivation and, mainly, have low product selectivity (1E,4E)-1,5-di (furan-2-yl)penta-1,4-dien-3-one (F₂Ac). Therefore, in this work, catalysts are proposed in order to increase the efficiency of materials in this reaction. Therefore, in Chapter 1, mesoporous materials of the SBA-15 family were synthesized functionalized with: (3-aminopropyl)triethoxysilane (APTES), 3-(2-Imidazolin-1-yl)propyltriethoxysilane (IMPTES), (3-anilinopropyl)trimethoxysilane (PAPTMS) that would give basic properties to materials. Thus, they were characterized by X-Ray diffraction, Infrared spectroscopy, thermal (TGA) and CHN elemental analysis. In addition, catalytic tests were carried out that investigated the best experimental conditions and revealed that the SBA-15-APTES material has the best activity, fully converting furfural and being 47% selective to the product (1E,4E)-1,5-di (furan-2-yl)penta-1,4-dien-3-one (F₂Ac) of greatest interest and 7% to (E)-4-(furan-2-yl)but-3-en-2-one (FAc). In chapter 2, the synthesis of materials with Sn (IV) is proposed, which would give acidic Lewis properties, aiming to stabilize the enolate anion formed from F₂Ac and functionalized with the aforementioned silanizing agents that confer basicity. Then, the catalysts were synthesized by post-functionalization of Sn-SBA-15 precursor materials and characterized by UV-vis spectroscopy, ICP-OES and by the analyzes already mentioned in the previous chapter. In the catalytic tests all materials were active, however, the results revealed that the acidity did not contribute to the desired action.O petróleo é utilizado para a fabricação de plásticos, solventes e, principalmente, para a produção de combustíveis. Contudo, alguns fatores como flutuação do preço do barril, sua origem não renovável e a liberação de gases do efeito estufa fazem com que seja necessário a diversificação dessa matriz energética. Nesse caminho, o furfural, derivado de uma fonte renovável, pode sofrer condensação aldólica com a cetona e formar precursores de querosene de aviação. Essa reação é catalisada por ácido ou base, contudo, os trabalhos da literatura mostram que os catalisadores heterogêneos não possuem estabilidade, com perda de fase ativa do material, sofrem de desativação e, principalmente, apresentam baixa seletividade ao produto (1E,4E)-1,5-di(furan-2-il)penta-1,4-dien-3-ona (F₂Ac). Portanto, neste trabalho é proposto catalisadores no sentido de aumentar a eficiência de materiais nessa reação. Para tanto, no Capítulo 1 foram sintetizados materiais mesoporosos da família SBA-15 funcionalizados com: (3-aminopropil)trietóxisilano (APTES), 3-(2-Imidazolin-1-il)propiltrietóxisilano (IMPTES), (3-anilinopropil)trimetóxisilano (PAPTMS) que dariam propriedades básicas aos materiais. Assim, foram caracterizados por difração de Raios-X, espectroscopia no Infravermelho, análises térmicas (TGA) e elementar CHN. Além disso, foram realizados ensaios catalíticos que investigaram as melhores condições experimentais e revelaram que o material SBA-15-APTES apresenta a melhor atividade, convertendo totalmente o furfural e sendo 47% seletivo ao produto (1E,4E)-1,5-di(furan-2-il)penta-1,4-dien-3-ona (F₂Ac) de maior interesse e 7% ao (E)-4-(furan-2-il)but-3-en-2-ona (FAc). Já no capítulo 2 é proposto a síntese de materiais com Sn (IV), que dariam propriedades ácidas de Lewis, visando estabilizar o ânion enolato formado do F₂Ac e funcionalizados com os agentes silanizantes citados que conferem basicidade. Logo, os catalisadores foram sintetizados pela pós funcionalização de materiais Sn-SBA-15 precursores e caracterizados por espectroscopia UV-vis, ICP-OES e pelas análises já mencionadas do capítulo anterior. Nos ensaios catalíticos todos os materiais foram ativos, contudo, os resultados revelaram que a acidez não contribuiu para a ação desejada.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)132101/2019-0porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessAgentes silanizantesCondensação aldólicaMateriais mesoporososAldol condensationMesoporous materialsSilanizing agentsCIENCIAS EXATAS E DA TERRA::QUIMICACIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICASíntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetonaSynthesis of the SBA-15 functionalized with aminosilanes and its application in the aldol condensation between furfural and acetoneinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesis60060055f26ad6-4e1e-4727-9713-0fe8011516bfreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALDissertação.pdfDissertação.pdfapplication/pdf2181839https://repositorio.ufscar.br/bitstream/ufscar/15122/3/Disserta%c3%a7%c3%a3o.pdfe7729443c4e6563c0a251f4646246c09MD53Carta homologação.pdfCarta homologação.pdfapplication/pdf237880https://repositorio.ufscar.br/bitstream/ufscar/15122/4/Carta%20homologa%c3%a7%c3%a3o.pdf01e9a0c23e00b3b4b5908ed7a7a04942MD54CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/15122/5/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD55TEXTDissertação.pdf.txtDissertação.pdf.txtExtracted texttext/plain139418https://repositorio.ufscar.br/bitstream/ufscar/15122/6/Disserta%c3%a7%c3%a3o.pdf.txt10dd3cf430399e7818d93b69f4f49d91MD56Carta homologação.pdf.txtCarta homologação.pdf.txtExtracted texttext/plain1463https://repositorio.ufscar.br/bitstream/ufscar/15122/8/Carta%20homologa%c3%a7%c3%a3o.pdf.txt9220e98f713a4f362f5379280264836eMD58THUMBNAILDissertação.pdf.jpgDissertação.pdf.jpgIM Thumbnailimage/jpeg9793https://repositorio.ufscar.br/bitstream/ufscar/15122/7/Disserta%c3%a7%c3%a3o.pdf.jpg88da781600fa04eee58965b32bca490aMD57Carta homologação.pdf.jpgCarta homologação.pdf.jpgIM Thumbnailimage/jpeg12039https://repositorio.ufscar.br/bitstream/ufscar/15122/9/Carta%20homologa%c3%a7%c3%a3o.pdf.jpgc7321a12b2ee1d1eb45a82d73c446b91MD59ufscar/151222023-09-18 18:32:20.251oai:repositorio.ufscar.br:ufscar/15122Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32:20Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false
dc.title.por.fl_str_mv Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
dc.title.alternative.eng.fl_str_mv Synthesis of the SBA-15 functionalized with aminosilanes and its application in the aldol condensation between furfural and acetone
title Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
spellingShingle Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
Lima, Marcelo Souza
Agentes silanizantes
Condensação aldólica
Materiais mesoporosos
Aldol condensation
Mesoporous materials
Silanizing agents
CIENCIAS EXATAS E DA TERRA::QUIMICA
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA
title_short Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
title_full Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
title_fullStr Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
title_full_unstemmed Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
title_sort Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona
author Lima, Marcelo Souza
author_facet Lima, Marcelo Souza
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/1329951278487934
dc.contributor.author.fl_str_mv Lima, Marcelo Souza
dc.contributor.advisor1.fl_str_mv Gallo, Jean Marcel Ribeiro
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/3485408327490746
dc.contributor.advisor-co1.fl_str_mv Marques, Clelia Mara de Paula
dc.contributor.advisor-co1Lattes.fl_str_mv http://lattes.cnpq.br/0451284088402660
dc.contributor.authorID.fl_str_mv 4d58b1e0-35b8-4e05-a442-100ca67cffcc
contributor_str_mv Gallo, Jean Marcel Ribeiro
Marques, Clelia Mara de Paula
dc.subject.por.fl_str_mv Agentes silanizantes
Condensação aldólica
Materiais mesoporosos
topic Agentes silanizantes
Condensação aldólica
Materiais mesoporosos
Aldol condensation
Mesoporous materials
Silanizing agents
CIENCIAS EXATAS E DA TERRA::QUIMICA
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA
dc.subject.eng.fl_str_mv Aldol condensation
Mesoporous materials
Silanizing agents
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::QUIMICA
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA
description The petroleum is used to manufacture plastics, solvents and, mainly, to produce fuels. However, some factors such as fluctuation in the price of the barrel, its non-renewable origin and the release of greenhouse gases make it necessary to diversify this energy matrix. In this way, furfural, derived from a renewable source, can undergo aldol condensation with ketone and form aviation kerosene precursors. This reaction is catalyzed by acid or base, however, studies in the literature show that heterogeneous catalysts do not have stability, with loss of the material's active phase, suffer from deactivation and, mainly, have low product selectivity (1E,4E)-1,5-di (furan-2-yl)penta-1,4-dien-3-one (F₂Ac). Therefore, in this work, catalysts are proposed in order to increase the efficiency of materials in this reaction. Therefore, in Chapter 1, mesoporous materials of the SBA-15 family were synthesized functionalized with: (3-aminopropyl)triethoxysilane (APTES), 3-(2-Imidazolin-1-yl)propyltriethoxysilane (IMPTES), (3-anilinopropyl)trimethoxysilane (PAPTMS) that would give basic properties to materials. Thus, they were characterized by X-Ray diffraction, Infrared spectroscopy, thermal (TGA) and CHN elemental analysis. In addition, catalytic tests were carried out that investigated the best experimental conditions and revealed that the SBA-15-APTES material has the best activity, fully converting furfural and being 47% selective to the product (1E,4E)-1,5-di (furan-2-yl)penta-1,4-dien-3-one (F₂Ac) of greatest interest and 7% to (E)-4-(furan-2-yl)but-3-en-2-one (FAc). In chapter 2, the synthesis of materials with Sn (IV) is proposed, which would give acidic Lewis properties, aiming to stabilize the enolate anion formed from F₂Ac and functionalized with the aforementioned silanizing agents that confer basicity. Then, the catalysts were synthesized by post-functionalization of Sn-SBA-15 precursor materials and characterized by UV-vis spectroscopy, ICP-OES and by the analyzes already mentioned in the previous chapter. In the catalytic tests all materials were active, however, the results revealed that the acidity did not contribute to the desired action.
publishDate 2021
dc.date.accessioned.fl_str_mv 2021-11-17T13:11:11Z
dc.date.available.fl_str_mv 2021-11-17T13:11:11Z
dc.date.issued.fl_str_mv 2021-10-14
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dc.identifier.citation.fl_str_mv LIMA, Marcelo Souza. Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona. 2021. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15122.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/ufscar/15122
identifier_str_mv LIMA, Marcelo Souza. Síntese da SBA-15 funcionalizada com aminossilanos e sua aplicação na condensação aldólica entre o furfural e a acetona. 2021. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15122.
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