Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações
Autor(a) principal: | |
---|---|
Data de Publicação: | 2022 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional Manancial UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/25890 |
Resumo: | The asphalt binder is composed mostly of aromatic hydrocarbons. However, the presence of sulfur in the matrices warrant special attention, since it stands out for being the major heteroatom. Sulfur compounds are known for their influence as a precursor of the asphalt matrix aging process. An undesirable process that affects pavement durability, making it became less resistant, with holes and cracks that lead to pavement deterioration. In addition, the presence of sulfur compounds in fumes emitted through the matrix heating have relation to health problems that can affect workers of the area. Therefore, this work aims to develop and validate a high-performance liquid chromatography method with pulsed amperometric detection (HPLC-PAD) and an ultra-high performance liquid chromatography with atmospheric pressure photoionization and detection by tandem mass spectrometry (UHPLC-APPI-MS/MS), which allows the speciation of sulfur compounds in the asphalt matrices, the fumes and the particulate matter emitted during the samples heating. With these in mind, three methodologies of sample preparation were evaluated. In order to verify the presence of the organosulfur compounds in the crude sample a procedure of solid phase extraction using ion exchange cartridges was used. And to evaluate sulfur compounds emitted in the volatiles an extractor and collector device (DEC) was used. While the particulate matter emissions were extracted using ultrasound. In addition, the determination of total sulfur in the asphalt matrix and its fractions, was made through dispersive energy X-ray fluorescence (FRX-ED). To study the samples and their fractions before and after forced aging methods, so that the impact of this process on the chemistry of the asphalt cements were evaluated. In an attempt to probe the transformations that occur with the sulfur during the process, and the migrations of it between the fractions. In addition, the chemical changes caused by aging were also surrounded by the alterations in the molecular fluorescence spectra of the samples. |
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2022-08-15T13:16:39Z2022-08-15T13:16:39Z2022-07-22http://repositorio.ufsm.br/handle/1/25890The asphalt binder is composed mostly of aromatic hydrocarbons. However, the presence of sulfur in the matrices warrant special attention, since it stands out for being the major heteroatom. Sulfur compounds are known for their influence as a precursor of the asphalt matrix aging process. An undesirable process that affects pavement durability, making it became less resistant, with holes and cracks that lead to pavement deterioration. In addition, the presence of sulfur compounds in fumes emitted through the matrix heating have relation to health problems that can affect workers of the area. Therefore, this work aims to develop and validate a high-performance liquid chromatography method with pulsed amperometric detection (HPLC-PAD) and an ultra-high performance liquid chromatography with atmospheric pressure photoionization and detection by tandem mass spectrometry (UHPLC-APPI-MS/MS), which allows the speciation of sulfur compounds in the asphalt matrices, the fumes and the particulate matter emitted during the samples heating. With these in mind, three methodologies of sample preparation were evaluated. In order to verify the presence of the organosulfur compounds in the crude sample a procedure of solid phase extraction using ion exchange cartridges was used. And to evaluate sulfur compounds emitted in the volatiles an extractor and collector device (DEC) was used. While the particulate matter emissions were extracted using ultrasound. In addition, the determination of total sulfur in the asphalt matrix and its fractions, was made through dispersive energy X-ray fluorescence (FRX-ED). To study the samples and their fractions before and after forced aging methods, so that the impact of this process on the chemistry of the asphalt cements were evaluated. In an attempt to probe the transformations that occur with the sulfur during the process, and the migrations of it between the fractions. In addition, the chemical changes caused by aging were also surrounded by the alterations in the molecular fluorescence spectra of the samples.O asfalto é constituído em sua maioria de hidrocarbonetos aromáticos, entretanto a presença de enxofre nas matrizes merece atenção especial, visto que esse se destaca por ser o heteroátomo majoritário. Os compostos de enxofre são conhecidos pela sua influência como precursores do processo de envelhecimento da matriz asfáltica. Um processo indesejável que fragiliza a matriz e degrada suas propriedades, sendo prejudicial para o desempenho dos pavimentos. Além disso, os compostos de enxofre presentes nos voláteis emitidos pela matriz já foram relacionados com possíveis problemas de saúde que podem afetar trabalhadores que atuam na área. Sendo assim, entender o papel do enxofre, bem como a especiação dos compostos presentes no asfalto, tem relevância comprovada. Dessa forma, este trabalho tem como objetivo desenvolver e validar um método de cromatografia líquida de alta eficiência com detecção pulso amperométrica (HPLC-PAD) e um método de cromatografia de ultra alta eficiência com fotoionização a pressão atmosférica e detecção por massas (UHPLC-APPI-MS/MS), que permitem a especiação de compostos de enxofre nas matrizes asfálticas, nos voláteis e nos particulados emitidos durante o aquecimento das amostras. Para isso, foram avaliadas três metodologias de preparo de amostras. A primeira consiste em um procedimento de extração em fase sólida utilizando cartuchos de troca iônica, a fim de verificar a presença dos compostos organossulfurados fixos nas amostras brutas. Já a segunda metodologia consiste na utilização de um dispositivo de extração e coleta (DEC) para avaliar os compostos sulfurados emitidos na forma de voláteis. Enquanto as amostras de emissões de material particulado foram extraídas com uso do ultrassom. Além disso, também foi utilizada a fluorescência de raios X com energia dispersiva (FRX-ED) para a determinação de enxofre total. Foram analisadas as amostras brutas e suas frações, virgens e após a realização do método de envelhecimento forçado para avaliar a influência desse processo na química dos ligantes. Na tentativa de sondar as transformações que ocorrem com o enxofre durante o processo, e as migrações desse entre as frações. Além disso, as alterações químicas provocadas pelo envelhecimento também foram cercadas através da alteração dos espectros de fluorescência molecular das amostras.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessAsfalto de petróleoEnxofreEnvelhecimentoDetecção pulso amperométricaFluorescência molecularFluorescência de raios-XAsphalt cementSulfurAging processPulsed amperometric detectionX ray fluorescenceMolecular fluorescenceCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAEspeciação de enxofre orgânico em cimento asfáltico de petróleo e suas fraçõesOrganig sulfur speciation in petroleum asphalt cement and their fractionsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisCarvalho, Leandro Machado dehttp://lattes.cnpq.br/6652387343920028Nascimento, Paulo Cícero doDognini, JocineiSpecht, Luciano PivotoCravo, Margareth Carvalho CoutinhoBranco, Verônica Teixeira Franco Castelohttp://lattes.cnpq.br/4892773806882378Schmidt, Patrícia1006000000006006006006006006006006009da44f2c-6556-4846-9d66-386f290b802f5dd8bd5a-f13d-4be5-8f6a-b863f0395f180c505080-8545-4cd2-96b0-d80067446fc2c6793899-104b-4abc-88ae-245b4ea9d899b1fcffea-b4b7-4214-83f0-f277f9a851a77c87b59d-ecb8-4beb-9ca1-d57a14aa4c2d2dbd7752-76a5-4876-b6cf-5f9cfac69dbareponame:Repositório Institucional Manancial UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMLICENSElicense.txtlicense.txttext/plain; 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dc.title.por.fl_str_mv |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações |
dc.title.alternative.eng.fl_str_mv |
Organig sulfur speciation in petroleum asphalt cement and their fractions |
title |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações |
spellingShingle |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações Schmidt, Patrícia Asfalto de petróleo Enxofre Envelhecimento Detecção pulso amperométrica Fluorescência molecular Fluorescência de raios-X Asphalt cement Sulfur Aging process Pulsed amperometric detection X ray fluorescence Molecular fluorescence CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações |
title_full |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações |
title_fullStr |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações |
title_full_unstemmed |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações |
title_sort |
Especiação de enxofre orgânico em cimento asfáltico de petróleo e suas frações |
author |
Schmidt, Patrícia |
author_facet |
Schmidt, Patrícia |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Carvalho, Leandro Machado de |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/6652387343920028 |
dc.contributor.advisor-co1.fl_str_mv |
Nascimento, Paulo Cícero do |
dc.contributor.referee1.fl_str_mv |
Dognini, Jocinei |
dc.contributor.referee2.fl_str_mv |
Specht, Luciano Pivoto |
dc.contributor.referee3.fl_str_mv |
Cravo, Margareth Carvalho Coutinho |
dc.contributor.referee4.fl_str_mv |
Branco, Verônica Teixeira Franco Castelo |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/4892773806882378 |
dc.contributor.author.fl_str_mv |
Schmidt, Patrícia |
contributor_str_mv |
Carvalho, Leandro Machado de Nascimento, Paulo Cícero do Dognini, Jocinei Specht, Luciano Pivoto Cravo, Margareth Carvalho Coutinho Branco, Verônica Teixeira Franco Castelo |
dc.subject.por.fl_str_mv |
Asfalto de petróleo Enxofre Envelhecimento Detecção pulso amperométrica Fluorescência molecular Fluorescência de raios-X |
topic |
Asfalto de petróleo Enxofre Envelhecimento Detecção pulso amperométrica Fluorescência molecular Fluorescência de raios-X Asphalt cement Sulfur Aging process Pulsed amperometric detection X ray fluorescence Molecular fluorescence CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Asphalt cement Sulfur Aging process Pulsed amperometric detection X ray fluorescence Molecular fluorescence |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The asphalt binder is composed mostly of aromatic hydrocarbons. However, the presence of sulfur in the matrices warrant special attention, since it stands out for being the major heteroatom. Sulfur compounds are known for their influence as a precursor of the asphalt matrix aging process. An undesirable process that affects pavement durability, making it became less resistant, with holes and cracks that lead to pavement deterioration. In addition, the presence of sulfur compounds in fumes emitted through the matrix heating have relation to health problems that can affect workers of the area. Therefore, this work aims to develop and validate a high-performance liquid chromatography method with pulsed amperometric detection (HPLC-PAD) and an ultra-high performance liquid chromatography with atmospheric pressure photoionization and detection by tandem mass spectrometry (UHPLC-APPI-MS/MS), which allows the speciation of sulfur compounds in the asphalt matrices, the fumes and the particulate matter emitted during the samples heating. With these in mind, three methodologies of sample preparation were evaluated. In order to verify the presence of the organosulfur compounds in the crude sample a procedure of solid phase extraction using ion exchange cartridges was used. And to evaluate sulfur compounds emitted in the volatiles an extractor and collector device (DEC) was used. While the particulate matter emissions were extracted using ultrasound. In addition, the determination of total sulfur in the asphalt matrix and its fractions, was made through dispersive energy X-ray fluorescence (FRX-ED). To study the samples and their fractions before and after forced aging methods, so that the impact of this process on the chemistry of the asphalt cements were evaluated. In an attempt to probe the transformations that occur with the sulfur during the process, and the migrations of it between the fractions. In addition, the chemical changes caused by aging were also surrounded by the alterations in the molecular fluorescence spectra of the samples. |
publishDate |
2022 |
dc.date.accessioned.fl_str_mv |
2022-08-15T13:16:39Z |
dc.date.available.fl_str_mv |
2022-08-15T13:16:39Z |
dc.date.issued.fl_str_mv |
2022-07-22 |
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 |
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http://repositorio.ufsm.br/handle/1/25890 |
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http://repositorio.ufsm.br/handle/1/25890 |
dc.language.iso.fl_str_mv |
por |
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por |
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100600000000 |
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Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
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