Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos

Detalhes bibliográficos
Ano de defesa: 2021
Autor(a) principal: Marques, João Paulo Cordeiro
Orientador(a): Ricardo, Nágila Maria Pontes Silva
Banca de defesa: Não Informado pela instituição
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Não Informado pela instituição
Programa de Pós-Graduação: Não Informado pela instituição
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Palavras-chave em Português:
Link de acesso: http://www.repositorio.ufc.br/handle/riufc/60070
Resumo: In this work, synthesis and characterization of biolubricant esters, the production and characterization of biolubricant blends and the catalytic study of polystyrene sulfonated (PSSA) and polystyrene sulfonated supported on silica matrix (SiO2-PSSA) were performed. In the first part of the work, it was evaluated the influence of linear and branched side chains on the biolubricants physicochemical properties. Four biolubricants (ISO 32) were synthesized from oleic acid. These syntheses occur from the route of esterification, with 1-octanol and 2-ethylhexanol, epoxidation and oxirane rings opening, with 1-octanol and 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties were measured and the reactions were monitored by 1H NMR. The biolubricant with branched side chains showed best cold property (PP = -6 °C) and the one with linear side chains showed better oxidative stability (EO = 3.19 h). In the second part of the work, it was evaluated the influence of the unsaturated fatty acids concentration of the raw material on the biolubricants physicochemical properties. Three biolubricants (ISO 32) were synthesized from soybean oil derivatives. These syntheses occur from the route of esterification/transesterification with 2-ethylhexanol, epoxidation and oxirane rings opening with 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties were measured and the reactions were monitored by 1H NMR. The biolubricant synthesized from the raw material with the highest concentration of unsaturated fatty acids showed best cold behavior (PP = -12 °C) and the one synthesized from soybean biodiesel showed the best application properties (PP = -6 °C, EO = 2.33 h and IA = 0.19 mg KOH/g). The thermogravimetric analysis of the samples showed that the concentration of unsaturated does not influence the thermal behavior and that the evaluated products suffer two thermal events: volatilization and combustion. In the third part of the work, it was evaluated the use of di-2-ethylhexyl sebacate as a bioadditive. The bioproduct was synthesized from the esterification reaction of sebacic acid with 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties of the blends were measured and the reaction was monitored by 1H NMR. The bioproduct was able to produce biolubricant blends with three viscosity degrees (ISO 15, ISO 22 and ISO 32) and improve the physicochemical properties of a synthesized biolubricant, mainly the pour point, which reached -24 °C in an isovolumetric blend. In the fourth part of the work, two catalysts in the study of the oxirane rings opening reaction, PSSA and SiO2-PSSA were tested. The reactions were monitored by 1H NMR. A first test showed that PSSA had better catalytic properties (100% conversion) than SiO2-PSSA (9% conversion). Subsequently, it was performed a more robust catalytic study with the PSSA, where it was possible to evaluate that: the higher the catalyst percentage, the higher the conversion (10% catalyst; 100% conversion); the ideal reaction temperature is 50 °C (lowest temperature; 100% conversion); after 1 h, the conversion stabilizes; and until the third reaction cycle, with the catalyst recovered, there was not reduction in catalytic efficiency.
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spelling Marques, João Paulo CordeiroRicardo, Nágila Maria Pontes Silva2021-08-20T14:09:07Z2021-08-20T14:09:07Z2021MARQUES, João Paulo Cordeiro. Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos. 2020. 153 f. Tese (Doutorado em Química) - Universidade Federal do Ceará, Fortaleza, 2021.http://www.repositorio.ufc.br/handle/riufc/60070In this work, synthesis and characterization of biolubricant esters, the production and characterization of biolubricant blends and the catalytic study of polystyrene sulfonated (PSSA) and polystyrene sulfonated supported on silica matrix (SiO2-PSSA) were performed. In the first part of the work, it was evaluated the influence of linear and branched side chains on the biolubricants physicochemical properties. Four biolubricants (ISO 32) were synthesized from oleic acid. These syntheses occur from the route of esterification, with 1-octanol and 2-ethylhexanol, epoxidation and oxirane rings opening, with 1-octanol and 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties were measured and the reactions were monitored by 1H NMR. The biolubricant with branched side chains showed best cold property (PP = -6 °C) and the one with linear side chains showed better oxidative stability (EO = 3.19 h). In the second part of the work, it was evaluated the influence of the unsaturated fatty acids concentration of the raw material on the biolubricants physicochemical properties. Three biolubricants (ISO 32) were synthesized from soybean oil derivatives. These syntheses occur from the route of esterification/transesterification with 2-ethylhexanol, epoxidation and oxirane rings opening with 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties were measured and the reactions were monitored by 1H NMR. The biolubricant synthesized from the raw material with the highest concentration of unsaturated fatty acids showed best cold behavior (PP = -12 °C) and the one synthesized from soybean biodiesel showed the best application properties (PP = -6 °C, EO = 2.33 h and IA = 0.19 mg KOH/g). The thermogravimetric analysis of the samples showed that the concentration of unsaturated does not influence the thermal behavior and that the evaluated products suffer two thermal events: volatilization and combustion. In the third part of the work, it was evaluated the use of di-2-ethylhexyl sebacate as a bioadditive. The bioproduct was synthesized from the esterification reaction of sebacic acid with 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties of the blends were measured and the reaction was monitored by 1H NMR. The bioproduct was able to produce biolubricant blends with three viscosity degrees (ISO 15, ISO 22 and ISO 32) and improve the physicochemical properties of a synthesized biolubricant, mainly the pour point, which reached -24 °C in an isovolumetric blend. In the fourth part of the work, two catalysts in the study of the oxirane rings opening reaction, PSSA and SiO2-PSSA were tested. The reactions were monitored by 1H NMR. A first test showed that PSSA had better catalytic properties (100% conversion) than SiO2-PSSA (9% conversion). Subsequently, it was performed a more robust catalytic study with the PSSA, where it was possible to evaluate that: the higher the catalyst percentage, the higher the conversion (10% catalyst; 100% conversion); the ideal reaction temperature is 50 °C (lowest temperature; 100% conversion); after 1 h, the conversion stabilizes; and until the third reaction cycle, with the catalyst recovered, there was not reduction in catalytic efficiency.Neste trabalho foi realizada a síntese e caracterização de ésteres biolubrificantes, a produção e caracterização de blendas biolubrificantes e o estudo catalítico do poliestireno sulfonado (PSSA) e do poliestireno sulfonado suportado em matriz de sílica (SiO2-PSSA). Na primeira parte do trabalho foi avaliada a influência das cadeias laterais lineares e ramificadas nas propriedades físico-químicas de biolubrificantes. Foram sintetizados quatro biolubrificantes (ISO 32) a partir do ácido oleico. Estas sínteses ocorreram a partir da rota de esterificação, com 1-octanol e 2-etilhexanol, epoxidação e abertura dos anéis oxiranos, com 1-octanol e 2-etilhexanol, utilizando Amberlyst 15 como catalisador. As propriedades físico-químicas foram medidas e as reações foram acompanhadas por RMN 1H. O biolubrificante com cadeias laterais ramificadas apresentou melhor propriedade a frio (PP = -6 °C) e o com cadeias laterais lineares apresentou melhor estabilidade oxidativa (EO = 3,19 h). Na segunda parte do trabalho foi avaliada a influência da concentração de ácido graxos insaturados da matéria-prima nas propriedades físico-químicas dos biolubrificantes. Foram sintetizados três biolubrificantes (ISO 32) a partir de derivados do óleo de soja. Estas sínteses ocorreram a partir da rota de esterificação/transesterificação com 2-etilhexanol, epoxidação e abertura dos anéis oxiranos com 2-etilhexanol, utilizando Amberlyst 15 como catalisador. As propriedades físico-químicas foram medidas e as reações foram acompanhadas por RMN 1H. O biolubrificante sintetizado a partir da matéria-prima com maior concentração de ácidos graxos insaturados apresentou melhor comportamento a frio (PP = -12 °C) e o sintetizado a partir do biodiesel de soja apresentou as melhores propriedades de aplicação (PP = -6 °C, EO = 2,33 h e IA = 0,19 mg KOH/g). A análise termogravimétrica das amostras mostrou que a concentração de insaturados não influencia o comportamento térmico e que os produtos avaliados sofrem dois eventos térmicos: volatilização e combustão. Na terceira parte do trabalho foi avaliada a utilização do sebacato de di-2-etilhexila como bioaditivo. O bioproduto foi sintetizado a partir da reação de esterificação do ácido sebácico com 2-etilhexanol, utilizando Amberlyst 15 como catalisador. A reação foi acompanhada por RMN 1H e as propriedades físico-químicas das blendas foram medidas. O bioproduto foi capaz de produzir blendas biolubrificantes com três graus de viscosidade (ISO 15, ISO 22 e ISO 32) e melhorar as propriedades físico-químicas de um biolubrificante sintetizado, principalmente seu ponto de fluidez, que alcançou -24 °C em uma blenda isovolumétrica. Na quarta parte do trabalho foram testados dois catalisadores no estudo da abertura de anéis oxiranos, o PSSA e o SiO2-PSSA. As reações foram acompanhadas por RMN 1H. Um primeiro teste mostrou que o PSSA apresentou melhores propriedades catalíticas (100% de conversão) que o SiO2-PSSA (9% de conversão). Posteriormente, foi realizado um estudo catalítico mais robusto com o PSSA, onde foi possível avaliar que: quanto maior a porcentagem de catalisador, mais alta é a conversão (10% de catalisador; conversão de 100%); a temperatura reacional ideal é 50 °C (menor temperatura; conversão de 100%); a partir de 1 h, a conversão se estabiliza; e até o terceiro ciclo reacional, com o catalisador recuperado, não houve redução na eficiência catalítica.BiolubrificantesÁcido oleicoÓleo de sojaÁcido sebácicoProdução de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicosProduction of high value biolubricating esters using heterogeneous sulfonic catalystinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisporreponame:Repositório Institucional da Universidade Federal do Ceará (UFC)instname:Universidade Federal do Ceará (UFC)instacron:UFCinfo:eu-repo/semantics/openAccessLICENSElicense.txtlicense.txttext/plain; charset=utf-81748http://repositorio.ufc.br/bitstream/riufc/60070/4/license.txt8a4605be74aa9ea9d79846c1fba20a33MD54ORIGINAL2020_tese_jpcmarques.pdf2020_tese_jpcmarques.pdfapplication/pdf4294142http://repositorio.ufc.br/bitstream/riufc/60070/3/2020_tese_jpcmarques.pdfd7476744d25652aca46cf3480524c933MD53riufc/600702021-08-20 11:09:07.29oai:repositorio.ufc.br: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Repositório InstitucionalPUBhttp://www.repositorio.ufc.br/ri-oai/requestbu@ufc.br || repositorio@ufc.bropendoar:2021-08-20T14:09:07Repositório Institucional da Universidade Federal do Ceará (UFC) - Universidade Federal do Ceará (UFC)false
dc.title.pt_BR.fl_str_mv Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
dc.title.en.pt_BR.fl_str_mv Production of high value biolubricating esters using heterogeneous sulfonic catalyst
title Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
spellingShingle Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
Marques, João Paulo Cordeiro
Biolubrificantes
Ácido oleico
Óleo de soja
Ácido sebácico
title_short Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
title_full Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
title_fullStr Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
title_full_unstemmed Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
title_sort Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos
author Marques, João Paulo Cordeiro
author_facet Marques, João Paulo Cordeiro
author_role author
dc.contributor.author.fl_str_mv Marques, João Paulo Cordeiro
dc.contributor.advisor1.fl_str_mv Ricardo, Nágila Maria Pontes Silva
contributor_str_mv Ricardo, Nágila Maria Pontes Silva
dc.subject.por.fl_str_mv Biolubrificantes
Ácido oleico
Óleo de soja
Ácido sebácico
topic Biolubrificantes
Ácido oleico
Óleo de soja
Ácido sebácico
description In this work, synthesis and characterization of biolubricant esters, the production and characterization of biolubricant blends and the catalytic study of polystyrene sulfonated (PSSA) and polystyrene sulfonated supported on silica matrix (SiO2-PSSA) were performed. In the first part of the work, it was evaluated the influence of linear and branched side chains on the biolubricants physicochemical properties. Four biolubricants (ISO 32) were synthesized from oleic acid. These syntheses occur from the route of esterification, with 1-octanol and 2-ethylhexanol, epoxidation and oxirane rings opening, with 1-octanol and 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties were measured and the reactions were monitored by 1H NMR. The biolubricant with branched side chains showed best cold property (PP = -6 °C) and the one with linear side chains showed better oxidative stability (EO = 3.19 h). In the second part of the work, it was evaluated the influence of the unsaturated fatty acids concentration of the raw material on the biolubricants physicochemical properties. Three biolubricants (ISO 32) were synthesized from soybean oil derivatives. These syntheses occur from the route of esterification/transesterification with 2-ethylhexanol, epoxidation and oxirane rings opening with 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties were measured and the reactions were monitored by 1H NMR. The biolubricant synthesized from the raw material with the highest concentration of unsaturated fatty acids showed best cold behavior (PP = -12 °C) and the one synthesized from soybean biodiesel showed the best application properties (PP = -6 °C, EO = 2.33 h and IA = 0.19 mg KOH/g). The thermogravimetric analysis of the samples showed that the concentration of unsaturated does not influence the thermal behavior and that the evaluated products suffer two thermal events: volatilization and combustion. In the third part of the work, it was evaluated the use of di-2-ethylhexyl sebacate as a bioadditive. The bioproduct was synthesized from the esterification reaction of sebacic acid with 2-ethylhexanol, using Amberlyst 15 as catalyst. The physicochemical properties of the blends were measured and the reaction was monitored by 1H NMR. The bioproduct was able to produce biolubricant blends with three viscosity degrees (ISO 15, ISO 22 and ISO 32) and improve the physicochemical properties of a synthesized biolubricant, mainly the pour point, which reached -24 °C in an isovolumetric blend. In the fourth part of the work, two catalysts in the study of the oxirane rings opening reaction, PSSA and SiO2-PSSA were tested. The reactions were monitored by 1H NMR. A first test showed that PSSA had better catalytic properties (100% conversion) than SiO2-PSSA (9% conversion). Subsequently, it was performed a more robust catalytic study with the PSSA, where it was possible to evaluate that: the higher the catalyst percentage, the higher the conversion (10% catalyst; 100% conversion); the ideal reaction temperature is 50 °C (lowest temperature; 100% conversion); after 1 h, the conversion stabilizes; and until the third reaction cycle, with the catalyst recovered, there was not reduction in catalytic efficiency.
publishDate 2021
dc.date.accessioned.fl_str_mv 2021-08-20T14:09:07Z
dc.date.available.fl_str_mv 2021-08-20T14:09:07Z
dc.date.issued.fl_str_mv 2021
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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status_str publishedVersion
dc.identifier.citation.fl_str_mv MARQUES, João Paulo Cordeiro. Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos. 2020. 153 f. Tese (Doutorado em Química) - Universidade Federal do Ceará, Fortaleza, 2021.
dc.identifier.uri.fl_str_mv http://www.repositorio.ufc.br/handle/riufc/60070
identifier_str_mv MARQUES, João Paulo Cordeiro. Produção de ésteres biolubrificantes de alto valor agregado utilizando catalisadores heterogêneos sulfônicos. 2020. 153 f. Tese (Doutorado em Química) - Universidade Federal do Ceará, Fortaleza, 2021.
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