Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol
Autor(a) principal: | |
---|---|
Data de Publicação: | 2015 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/8274 |
Resumo: | The replacement of chemical products by renewable raw materials is an important factor for the emission control of CO2. Consequently, there is a great commercial interest in the conversion of ethanol into 1,3-butadiene. The 1,3-butadiene compound is used in the production of a variety of synthetic rubbers and one important example is butadiene-styrene rubber (SBR), which is used in the production of car tires. This work studied the modification of the acid-base properties of MgO/SiO2 bifunctional catalysts and the understanding of different methodologies used in the preparation of these materials for the conversion reaction of ethanol into 1,3-butadiene. MgO/SiO2 catalysts of varying amounts of magnesia/silica were prepared by four different methods: i) precipitation followed by the mixing of the oxides in a ball mill, ii) precipitation of MgO followed by its mixing with aerosil silica in a ball mill, iii) precipitation of MgO followed by the mechanical mixing of the oxides and iv) sol-gel. The catalysts were characterized by X-ray diffraction, CO2 Temperature Programmed Desorption, Scanning Electron Microscopy and Specific Surface Area. Catalytic tests showed that the highest selectivities for 1,3 -butadiene were observed for the (MgO/SiO2) coprecipitation method and oxides mixed in a ball mill. The TPD-CO2 results demonstrate the formation of basic sites with the addition of SiO2 to MgO and the density of basic sites presents a great variation in the ratio MgO: SiO2. The catalyst MgO/SiO2 (5:1) was the most active and selective for 1,3-butadiene. The addition of CaO or SrO these catalysts have not resulted in increased selectivity for the formation of butadiene, but observed an increase in the acid properties, possibly due to non-inclusion of these oxides in MgO lattice and later the formation of basic sites of the type MgO-Mg-O-Si. |
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Laier, Letícia OliveiraMarques, Clélia Mara de Paulahttp://lattes.cnpq.br/0451284088402660http://lattes.cnpq.br/808107313702893485a0fe90-9735-42ab-bd51-50c35dba61742016-11-08T18:38:21Z2016-11-08T18:38:21Z2015-05-22LAIER, Letícia Oliveira. Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol. 2015. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8274.https://repositorio.ufscar.br/handle/ufscar/8274The replacement of chemical products by renewable raw materials is an important factor for the emission control of CO2. Consequently, there is a great commercial interest in the conversion of ethanol into 1,3-butadiene. The 1,3-butadiene compound is used in the production of a variety of synthetic rubbers and one important example is butadiene-styrene rubber (SBR), which is used in the production of car tires. This work studied the modification of the acid-base properties of MgO/SiO2 bifunctional catalysts and the understanding of different methodologies used in the preparation of these materials for the conversion reaction of ethanol into 1,3-butadiene. MgO/SiO2 catalysts of varying amounts of magnesia/silica were prepared by four different methods: i) precipitation followed by the mixing of the oxides in a ball mill, ii) precipitation of MgO followed by its mixing with aerosil silica in a ball mill, iii) precipitation of MgO followed by the mechanical mixing of the oxides and iv) sol-gel. The catalysts were characterized by X-ray diffraction, CO2 Temperature Programmed Desorption, Scanning Electron Microscopy and Specific Surface Area. Catalytic tests showed that the highest selectivities for 1,3 -butadiene were observed for the (MgO/SiO2) coprecipitation method and oxides mixed in a ball mill. The TPD-CO2 results demonstrate the formation of basic sites with the addition of SiO2 to MgO and the density of basic sites presents a great variation in the ratio MgO: SiO2. The catalyst MgO/SiO2 (5:1) was the most active and selective for 1,3-butadiene. The addition of CaO or SrO these catalysts have not resulted in increased selectivity for the formation of butadiene, but observed an increase in the acid properties, possibly due to non-inclusion of these oxides in MgO lattice and later the formation of basic sites of the type MgO-Mg-O-Si.A substituição de petroquímicos por produtos químicos obtidos a partir de matérias primas renováveis será um fator importante para o controle de emissão de CO2. Consequentemente, existe um grande interesse comercial na conversão do etanol em 1,3-butadieno também crescerá. O 1,3- butadieno é utilizado na produção de uma grande variedade de borrachas sintéticas. Um importante exemplo é a borracha de estireno-butadeino (SBR) usada na produção de pneus de automóveis. Neste trabalho foi estudada a modificação das propriedades ácido-base dos catalisadores bifuncionais de MgO/SiO2 e a compreensão de diferentes metodologias empregadas na preparação destes catalisadores aplicados na reação de conversão de etanol em 1,3- butadieno. Foram preparados catalisadores MgO/SiO2 com várias razões de magnésia/sílica preparados por quatro métodos de preparação diferentes, sendo estes: i) precipitação com mistura dos óxidos em um moinho de bolas; ii) precipitação do MgO misturado com sílica aerosil em um moinho de bolas; iii) precipitação com mistura mecânica dos óxidos e iv) sol-gel. Os catalisadores foram caracterizados por Difração de Raios X, Dessorção de CO2 à Temperatura Programada, Microscopia Eletrônica de Varredura e Área Superficial Específica. Os testes catalíticos mostraram que as maiores seletividades para o 1,3-butadieno foram observadas para os óxidos (MgO/SiO2) obtidos através do método de coprecipitação e misturados em moinho de bolas. Os resultados de TPD-CO2 demostram a formação de sítios básicos com adição de SiO2 ao MgO e a densidade de sítios básicos apresentam um ótimo, com variação da razão MgO:SiO2. O catalisador MgO/SiO2 (5:1) foi o mais ativo e seletivo para butadieno. A adição de CaO ou SrO nestes catalisadores não resultaram em um aumento de seletividade para a formação de butadieno, mas observa-se um aumento na propriedades ácidas, possivelmente devido a não inclusão destes óxidos no reticulado de MgO e posteriormente a formação de sítios básicos do tipo MgO-Mg-O-Si.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarOxidos metálicosOxido alcalino-terrososÓxido de magnésioSílicaOUTROSCatalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanolinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisOnline600600a20981f8-5050-4af2-b325-04e85155cc87info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALDissLOL.pdfDissLOL.pdfapplication/pdf2360469https://repositorio.ufscar.br/bitstream/ufscar/8274/1/DissLOL.pdfb98326ae018890796891604df0a3c7ebMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstream/ufscar/8274/2/license.txtae0398b6f8b235e40ad82cba6c50031dMD52TEXTDissLOL.pdf.txtDissLOL.pdf.txtExtracted texttext/plain125563https://repositorio.ufscar.br/bitstream/ufscar/8274/3/DissLOL.pdf.txtb473d0e5c1771c455c203da6d80faf59MD53THUMBNAILDissLOL.pdf.jpgDissLOL.pdf.jpgIM Thumbnailimage/jpeg8231https://repositorio.ufscar.br/bitstream/ufscar/8274/4/DissLOL.pdf.jpg0fd536613b3b16063824bc2861f28015MD54ufscar/82742023-09-18 18:31:04.657oai:repositorio.ufscar.br:ufscar/8274TElDRU7Dh0EgREUgRElTVFJJQlVJw4fDg08gTsODTy1FWENMVVNJVkEKCkNvbSBhIGFwcmVzZW50YcOnw6NvIGRlc3RhIGxpY2Vuw6dhLCB2b2PDqiAobyBhdXRvciAoZXMpIG91IG8gdGl0dWxhciBkb3MgZGlyZWl0b3MgZGUgYXV0b3IpIGNvbmNlZGUgw6AgVW5pdmVyc2lkYWRlCkZlZGVyYWwgZGUgU8OjbyBDYXJsb3MgbyBkaXJlaXRvIG7Do28tZXhjbHVzaXZvIGRlIHJlcHJvZHV6aXIsICB0cmFkdXppciAoY29uZm9ybWUgZGVmaW5pZG8gYWJhaXhvKSwgZS9vdQpkaXN0cmlidWlyIGEgc3VhIHRlc2Ugb3UgZGlzc2VydGHDp8OjbyAoaW5jbHVpbmRvIG8gcmVzdW1vKSBwb3IgdG9kbyBvIG11bmRvIG5vIGZvcm1hdG8gaW1wcmVzc28gZSBlbGV0csO0bmljbyBlCmVtIHF1YWxxdWVyIG1laW8sIGluY2x1aW5kbyBvcyBmb3JtYXRvcyDDoXVkaW8gb3UgdsOtZGVvLgoKVm9jw6ogY29uY29yZGEgcXVlIGEgVUZTQ2FyIHBvZGUsIHNlbSBhbHRlcmFyIG8gY29udGXDumRvLCB0cmFuc3BvciBhIHN1YSB0ZXNlIG91IGRpc3NlcnRhw6fDo28KcGFyYSBxdWFscXVlciBtZWlvIG91IGZvcm1hdG8gcGFyYSBmaW5zIGRlIHByZXNlcnZhw6fDo28uCgpWb2PDqiB0YW1iw6ltIGNvbmNvcmRhIHF1ZSBhIFVGU0NhciBwb2RlIG1hbnRlciBtYWlzIGRlIHVtYSBjw7NwaWEgYSBzdWEgdGVzZSBvdQpkaXNzZXJ0YcOnw6NvIHBhcmEgZmlucyBkZSBzZWd1cmFuw6dhLCBiYWNrLXVwIGUgcHJlc2VydmHDp8Ojby4KClZvY8OqIGRlY2xhcmEgcXVlIGEgc3VhIHRlc2Ugb3UgZGlzc2VydGHDp8OjbyDDqSBvcmlnaW5hbCBlIHF1ZSB2b2PDqiB0ZW0gbyBwb2RlciBkZSBjb25jZWRlciBvcyBkaXJlaXRvcyBjb250aWRvcwpuZXN0YSBsaWNlbsOnYS4gVm9jw6ogdGFtYsOpbSBkZWNsYXJhIHF1ZSBvIGRlcMOzc2l0byBkYSBzdWEgdGVzZSBvdSBkaXNzZXJ0YcOnw6NvIG7Do28sIHF1ZSBzZWphIGRlIHNldQpjb25oZWNpbWVudG8sIGluZnJpbmdlIGRpcmVpdG9zIGF1dG9yYWlzIGRlIG5pbmd1w6ltLgoKQ2FzbyBhIHN1YSB0ZXNlIG91IGRpc3NlcnRhw6fDo28gY29udGVuaGEgbWF0ZXJpYWwgcXVlIHZvY8OqIG7Do28gcG9zc3VpIGEgdGl0dWxhcmlkYWRlIGRvcyBkaXJlaXRvcyBhdXRvcmFpcywgdm9jw6oKZGVjbGFyYSBxdWUgb2J0ZXZlIGEgcGVybWlzc8OjbyBpcnJlc3RyaXRhIGRvIGRldGVudG9yIGRvcyBkaXJlaXRvcyBhdXRvcmFpcyBwYXJhIGNvbmNlZGVyIMOgIFVGU0NhcgpvcyBkaXJlaXRvcyBhcHJlc2VudGFkb3MgbmVzdGEgbGljZW7Dp2EsIGUgcXVlIGVzc2UgbWF0ZXJpYWwgZGUgcHJvcHJpZWRhZGUgZGUgdGVyY2Vpcm9zIGVzdMOhIGNsYXJhbWVudGUKaWRlbnRpZmljYWRvIGUgcmVjb25oZWNpZG8gbm8gdGV4dG8gb3Ugbm8gY29udGXDumRvIGRhIHRlc2Ugb3UgZGlzc2VydGHDp8OjbyBvcmEgZGVwb3NpdGFkYS4KCkNBU08gQSBURVNFIE9VIERJU1NFUlRBw4fDg08gT1JBIERFUE9TSVRBREEgVEVOSEEgU0lETyBSRVNVTFRBRE8gREUgVU0gUEFUUk9Dw41OSU8gT1UKQVBPSU8gREUgVU1BIEFHw4pOQ0lBIERFIEZPTUVOVE8gT1UgT1VUUk8gT1JHQU5JU01PIFFVRSBOw4NPIFNFSkEgQSBVRlNDYXIsClZPQ8OKIERFQ0xBUkEgUVVFIFJFU1BFSVRPVSBUT0RPUyBFIFFVQUlTUVVFUiBESVJFSVRPUyBERSBSRVZJU8ODTyBDT01PClRBTULDiU0gQVMgREVNQUlTIE9CUklHQcOHw5VFUyBFWElHSURBUyBQT1IgQ09OVFJBVE8gT1UgQUNPUkRPLgoKQSBVRlNDYXIgc2UgY29tcHJvbWV0ZSBhIGlkZW50aWZpY2FyIGNsYXJhbWVudGUgbyBzZXUgbm9tZSAocykgb3UgbyhzKSBub21lKHMpIGRvKHMpCmRldGVudG9yKGVzKSBkb3MgZGlyZWl0b3MgYXV0b3JhaXMgZGEgdGVzZSBvdSBkaXNzZXJ0YcOnw6NvLCBlIG7Do28gZmFyw6EgcXVhbHF1ZXIgYWx0ZXJhw6fDo28sIGFsw6ltIGRhcXVlbGFzCmNvbmNlZGlkYXMgcG9yIGVzdGEgbGljZW7Dp2EuCg==Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:04Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol |
title |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol |
spellingShingle |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol Laier, Letícia Oliveira Oxidos metálicos Oxido alcalino-terrosos Óxido de magnésio Sílica OUTROS |
title_short |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol |
title_full |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol |
title_fullStr |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol |
title_full_unstemmed |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol |
title_sort |
Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol |
author |
Laier, Letícia Oliveira |
author_facet |
Laier, Letícia Oliveira |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8081073137028934 |
dc.contributor.author.fl_str_mv |
Laier, Letícia Oliveira |
dc.contributor.advisor1.fl_str_mv |
Marques, Clélia Mara de Paula |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/0451284088402660 |
dc.contributor.authorID.fl_str_mv |
85a0fe90-9735-42ab-bd51-50c35dba6174 |
contributor_str_mv |
Marques, Clélia Mara de Paula |
dc.subject.por.fl_str_mv |
Oxidos metálicos Oxido alcalino-terrosos Óxido de magnésio Sílica |
topic |
Oxidos metálicos Oxido alcalino-terrosos Óxido de magnésio Sílica OUTROS |
dc.subject.cnpq.fl_str_mv |
OUTROS |
description |
The replacement of chemical products by renewable raw materials is an important factor for the emission control of CO2. Consequently, there is a great commercial interest in the conversion of ethanol into 1,3-butadiene. The 1,3-butadiene compound is used in the production of a variety of synthetic rubbers and one important example is butadiene-styrene rubber (SBR), which is used in the production of car tires. This work studied the modification of the acid-base properties of MgO/SiO2 bifunctional catalysts and the understanding of different methodologies used in the preparation of these materials for the conversion reaction of ethanol into 1,3-butadiene. MgO/SiO2 catalysts of varying amounts of magnesia/silica were prepared by four different methods: i) precipitation followed by the mixing of the oxides in a ball mill, ii) precipitation of MgO followed by its mixing with aerosil silica in a ball mill, iii) precipitation of MgO followed by the mechanical mixing of the oxides and iv) sol-gel. The catalysts were characterized by X-ray diffraction, CO2 Temperature Programmed Desorption, Scanning Electron Microscopy and Specific Surface Area. Catalytic tests showed that the highest selectivities for 1,3 -butadiene were observed for the (MgO/SiO2) coprecipitation method and oxides mixed in a ball mill. The TPD-CO2 results demonstrate the formation of basic sites with the addition of SiO2 to MgO and the density of basic sites presents a great variation in the ratio MgO: SiO2. The catalyst MgO/SiO2 (5:1) was the most active and selective for 1,3-butadiene. The addition of CaO or SrO these catalysts have not resulted in increased selectivity for the formation of butadiene, but observed an increase in the acid properties, possibly due to non-inclusion of these oxides in MgO lattice and later the formation of basic sites of the type MgO-Mg-O-Si. |
publishDate |
2015 |
dc.date.issued.fl_str_mv |
2015-05-22 |
dc.date.accessioned.fl_str_mv |
2016-11-08T18:38:21Z |
dc.date.available.fl_str_mv |
2016-11-08T18:38:21Z |
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.citation.fl_str_mv |
LAIER, Letícia Oliveira. Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol. 2015. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8274. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/8274 |
identifier_str_mv |
LAIER, Letícia Oliveira. Catalisadores de MgO-SiO2 : efeito dos promotores CaO e SrO na conversão de etanol. 2015. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8274. |
url |
https://repositorio.ufscar.br/handle/ufscar/8274 |
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por |
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600 600 |
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a20981f8-5050-4af2-b325-04e85155cc87 |
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info:eu-repo/semantics/openAccess |
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openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química - PPGQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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