Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol
Autor(a) principal: | |
---|---|
Data de Publicação: | 2021 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/15490 |
Resumo: | Biodiesel production by transesterification reaction generates large amounts of glycerol as a by-product. The development of chemical routes to use glycerol as raw material for products with high added value is essential to foment the biodiesel industry. Therefore, acetol emerge as an interesting product derived from glycerol that can be an intermediary for other chemical products, such as propylene glycol, pyruvic acid, and propionic acid, among others. In this work, the study of the heterogeneous catalytic conversion of glycerol to acetol and other products of interest was evaluated. For that, copper and zirconium catalysts were synthesized with different compositions by co-precipitation method, which evaluated the influence of precipitating agents: triethylamine (Et3N), sodium hydroxide (NaOH), and sodium carbonate (Na2CO3). The materials were characterized by X-ray diffraction, temperature-programmed reduction, N2 physisorption, selective Cu oxidation by N2O, NH3 temperature-programmed desorption, and in situ infrared analysis with pyridine. Characterizations results showed that, in addition to the mass composition, the precipitating agent used affected the physicochemical properties of the catalysts and, consequently, their catalytic performance. Reactions tests were carried out in a batch reactor and after previous evaluation, the reaction parameters were fixed at T = 180 °C, stirring at 800 rpm, V = 30 mL (80% aqueous glycerol(m/m)), during 1 h, with an initial pressure of 1 atm (N2) and 300 mg of catalyst. The catalysts showed activity for the dehydration reaction of glycerol to acetol and subsequent in situ hydrogenation to propylene glycol without adding H2 to the reaction medium. It was observed a correlation between the concentration of acidic sites and the selectivity in the conversion of glycerol to acetol, propylene glycol, and other products. Furthermore, the strength distribution of acidic sites, particle size, and textural properties, such as porosity can regulate the selectivity of the reaction. Finally, the reuse tests showed moderate loss of catalyst activity, although the used catalysts did not go through a reactivation step between each reaction. |
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Corrêa, João Vítor SoaresSantos, João Batista Oliveira doshttp://lattes.cnpq.br/0285313473901330Chimentão, Ricardo Joséhttp://lattes.cnpq.br/3079491942548735http://lattes.cnpq.br/85781968899284352022-01-19T18:00:54Z2022-01-19T18:00:54Z2021-07-23CORRÊA, João Vítor Soares. Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15490.https://repositorio.ufscar.br/handle/ufscar/15490Biodiesel production by transesterification reaction generates large amounts of glycerol as a by-product. The development of chemical routes to use glycerol as raw material for products with high added value is essential to foment the biodiesel industry. Therefore, acetol emerge as an interesting product derived from glycerol that can be an intermediary for other chemical products, such as propylene glycol, pyruvic acid, and propionic acid, among others. In this work, the study of the heterogeneous catalytic conversion of glycerol to acetol and other products of interest was evaluated. For that, copper and zirconium catalysts were synthesized with different compositions by co-precipitation method, which evaluated the influence of precipitating agents: triethylamine (Et3N), sodium hydroxide (NaOH), and sodium carbonate (Na2CO3). The materials were characterized by X-ray diffraction, temperature-programmed reduction, N2 physisorption, selective Cu oxidation by N2O, NH3 temperature-programmed desorption, and in situ infrared analysis with pyridine. Characterizations results showed that, in addition to the mass composition, the precipitating agent used affected the physicochemical properties of the catalysts and, consequently, their catalytic performance. Reactions tests were carried out in a batch reactor and after previous evaluation, the reaction parameters were fixed at T = 180 °C, stirring at 800 rpm, V = 30 mL (80% aqueous glycerol(m/m)), during 1 h, with an initial pressure of 1 atm (N2) and 300 mg of catalyst. The catalysts showed activity for the dehydration reaction of glycerol to acetol and subsequent in situ hydrogenation to propylene glycol without adding H2 to the reaction medium. It was observed a correlation between the concentration of acidic sites and the selectivity in the conversion of glycerol to acetol, propylene glycol, and other products. Furthermore, the strength distribution of acidic sites, particle size, and textural properties, such as porosity can regulate the selectivity of the reaction. Finally, the reuse tests showed moderate loss of catalyst activity, although the used catalysts did not go through a reactivation step between each reaction.A produção de biodiesel via reação de transesterificação gera enormes quantidades de glicerol como coproduto. O desenvolvimento de rotas químicas para utilização do glicerol como matéria-prima de produtos com alto valor agregado é fundamental para impulsionar a indústria do biodiesel. Nesse sentido, o acetol surge como um produto derivado do glicerol que pode ser intermediário para outros produtos químicos, como: propilenoglicol, ácido pirúvico e ácido propiônico, entre outros. Dessa forma, esse trabalho dedica-se ao estudo da conversão catalítica heterogênea de glicerol ao acetol e outros produtos de interesse. Para isso, catalisadores de cobre e zircônio foram sintetizados com diferentes composições mássicas pelo método de coprecipitação, onde avaliou-se a influência dos agentes precipitantes: trietilamina (Et3N), hidróxido de sódio (NaOH) e carbonato de sódio (Na2CO3). Os materiais foram caracterizados por difração de raios X, redução a temperatura programada, fisissorção de N2, oxidação seletiva de Cu por N2O, dessorção a temperatura programada de NH3 e análise de infravermelho in situ com piridina. As caracterizações dos materiais mostraram que além da composição mássica, o agente precipitante utilizado afetou as propriedades físico-químicas dos catalisadores e por consequência seu desempenho catalítico. Os ensaios para avaliação catalítica foram realizados em reator batelada e após avaliação prévia, os parâmetros de reação foram fixados em: T = 180 °C, agitação de 800 rpm, V = 30 mL (80% de glicerol aquoso em massa), por 1 h e pressão inicial de 1 atm (N2) com 300 mg de catalisador. Os catalisadores demonstraram atividade para a reação de desidratação de glicerol ao acetol e posterior hidrogenação in situ ao propilenoglicol sem adição de H2 no meio reacional. Foi observada uma relação entre a concentração de sítios ácidos e a seletividade na conversão de glicerol para acetol, propilenoglicol e outros produtos. Além disso, a distribuição de força dos sítios ácidos, o tamanho de partícula e propriedades texturais como a porosidade podem regular a seletividade da reação. Por fim, os ensaios de reuso demonstraram perda moderada de atividade do catalisador, embora este não tenha passado por processo de reativação entre os reusos.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)140180/2018-4porUniversidade 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/openAccessCatálise heterogêneaGlicerolAcetolPropilenoglicolCobreZircônioHeterogeneous catalysisGlycerolPropylene glycolCopperZirconiumENGENHARIAS::ENGENHARIA QUIMICAInfluência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicolInfluence of the precipitating agent on the synthesis of Cu-ZrO2 catalysts applied in the conversion of glycerol to acetol and propylene glycolinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTese João Vítor Corrêa 17012022 versão corrigida.pdfTese João Vítor Corrêa 17012022 versão corrigida.pdfTeseapplication/pdf9223198https://repositorio.ufscar.br/bitstream/ufscar/15490/1/Tese%20Jo%c3%a3o%20V%c3%adtor%20Corr%c3%aaa%2017012022%20vers%c3%a3o%20corrigida.pdfc747ba6f2b5529adfd97a7fa089911f1MD51Autorizacao-Tese-corrigida-Joao-Vitor.pdfAutorizacao-Tese-corrigida-Joao-Vitor.pdfCarta comprovante assinada pelo orientadorapplication/pdf66898https://repositorio.ufscar.br/bitstream/ufscar/15490/2/Autorizacao-Tese-corrigida-Joao-Vitor.pdf5d586b3a7cfba4b3bfbaa780d499659fMD52CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/15490/3/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD53TEXTTese João Vítor Corrêa 17012022 versão corrigida.pdf.txtTese João Vítor Corrêa 17012022 versão corrigida.pdf.txtExtracted texttext/plain228184https://repositorio.ufscar.br/bitstream/ufscar/15490/4/Tese%20Jo%c3%a3o%20V%c3%adtor%20Corr%c3%aaa%2017012022%20vers%c3%a3o%20corrigida.pdf.txte7bce45abbf01c94ad2d9294fc4bfe95MD54Autorizacao-Tese-corrigida-Joao-Vitor.pdf.txtAutorizacao-Tese-corrigida-Joao-Vitor.pdf.txtExtracted texttext/plain996https://repositorio.ufscar.br/bitstream/ufscar/15490/6/Autorizacao-Tese-corrigida-Joao-Vitor.pdf.txt7d3ac11c93d3532139bf1e9ff03305c4MD56THUMBNAILTese João Vítor Corrêa 17012022 versão corrigida.pdf.jpgTese João Vítor Corrêa 17012022 versão corrigida.pdf.jpgIM Thumbnailimage/jpeg6899https://repositorio.ufscar.br/bitstream/ufscar/15490/5/Tese%20Jo%c3%a3o%20V%c3%adtor%20Corr%c3%aaa%2017012022%20vers%c3%a3o%20corrigida.pdf.jpg2e3a03be7721c5f95d07cf0f7d8498c5MD55Autorizacao-Tese-corrigida-Joao-Vitor.pdf.jpgAutorizacao-Tese-corrigida-Joao-Vitor.pdf.jpgIM Thumbnailimage/jpeg6309https://repositorio.ufscar.br/bitstream/ufscar/15490/7/Autorizacao-Tese-corrigida-Joao-Vitor.pdf.jpg919b0318e7b21e4bbf34cfcf80f25a8eMD57ufscar/154902022-01-20 03:35:03.472oai:repositorio.ufscar.br:ufscar/15490Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222022-01-20T03:35:03Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol |
dc.title.alternative.eng.fl_str_mv |
Influence of the precipitating agent on the synthesis of Cu-ZrO2 catalysts applied in the conversion of glycerol to acetol and propylene glycol |
title |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol |
spellingShingle |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol Corrêa, João Vítor Soares Catálise heterogênea Glicerol Acetol Propilenoglicol Cobre Zircônio Heterogeneous catalysis Glycerol Propylene glycol Copper Zirconium ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol |
title_full |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol |
title_fullStr |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol |
title_full_unstemmed |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol |
title_sort |
Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol |
author |
Corrêa, João Vítor Soares |
author_facet |
Corrêa, João Vítor Soares |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8578196889928435 |
dc.contributor.author.fl_str_mv |
Corrêa, João Vítor Soares |
dc.contributor.advisor1.fl_str_mv |
Santos, João Batista Oliveira dos |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/0285313473901330 |
dc.contributor.advisor-co1.fl_str_mv |
Chimentão, Ricardo José |
dc.contributor.advisor-co1Lattes.fl_str_mv |
http://lattes.cnpq.br/3079491942548735 |
contributor_str_mv |
Santos, João Batista Oliveira dos Chimentão, Ricardo José |
dc.subject.por.fl_str_mv |
Catálise heterogênea Glicerol Acetol Propilenoglicol Cobre Zircônio |
topic |
Catálise heterogênea Glicerol Acetol Propilenoglicol Cobre Zircônio Heterogeneous catalysis Glycerol Propylene glycol Copper Zirconium ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Heterogeneous catalysis Glycerol Propylene glycol Copper Zirconium |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA |
description |
Biodiesel production by transesterification reaction generates large amounts of glycerol as a by-product. The development of chemical routes to use glycerol as raw material for products with high added value is essential to foment the biodiesel industry. Therefore, acetol emerge as an interesting product derived from glycerol that can be an intermediary for other chemical products, such as propylene glycol, pyruvic acid, and propionic acid, among others. In this work, the study of the heterogeneous catalytic conversion of glycerol to acetol and other products of interest was evaluated. For that, copper and zirconium catalysts were synthesized with different compositions by co-precipitation method, which evaluated the influence of precipitating agents: triethylamine (Et3N), sodium hydroxide (NaOH), and sodium carbonate (Na2CO3). The materials were characterized by X-ray diffraction, temperature-programmed reduction, N2 physisorption, selective Cu oxidation by N2O, NH3 temperature-programmed desorption, and in situ infrared analysis with pyridine. Characterizations results showed that, in addition to the mass composition, the precipitating agent used affected the physicochemical properties of the catalysts and, consequently, their catalytic performance. Reactions tests were carried out in a batch reactor and after previous evaluation, the reaction parameters were fixed at T = 180 °C, stirring at 800 rpm, V = 30 mL (80% aqueous glycerol(m/m)), during 1 h, with an initial pressure of 1 atm (N2) and 300 mg of catalyst. The catalysts showed activity for the dehydration reaction of glycerol to acetol and subsequent in situ hydrogenation to propylene glycol without adding H2 to the reaction medium. It was observed a correlation between the concentration of acidic sites and the selectivity in the conversion of glycerol to acetol, propylene glycol, and other products. Furthermore, the strength distribution of acidic sites, particle size, and textural properties, such as porosity can regulate the selectivity of the reaction. Finally, the reuse tests showed moderate loss of catalyst activity, although the used catalysts did not go through a reactivation step between each reaction. |
publishDate |
2021 |
dc.date.issued.fl_str_mv |
2021-07-23 |
dc.date.accessioned.fl_str_mv |
2022-01-19T18:00:54Z |
dc.date.available.fl_str_mv |
2022-01-19T18:00:54Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
CORRÊA, João Vítor Soares. Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15490. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/15490 |
identifier_str_mv |
CORRÊA, João Vítor Soares. Influência do agente precipitante na síntese de catalisadores Cu-ZrO2 aplicados na conversão de glicerol a acetol e propilenoglicol. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15490. |
url |
https://repositorio.ufscar.br/handle/ufscar/15490 |
dc.language.iso.fl_str_mv |
por |
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por |
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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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openAccess |
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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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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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