Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos
| Ano de defesa: | 2017 |
|---|---|
| Autor(a) principal: | |
| Orientador(a): | |
| Banca de defesa: | |
| Tipo de documento: | Tese |
| Tipo de acesso: | Acesso aberto |
| dARK ID: | ark:/26339/001300000hb7k |
| Idioma: | por |
| Instituição de defesa: |
Universidade Federal de Santa Maria
Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
| 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://repositorio.ufsm.br/handle/1/14126 |
Resumo: | Asphalt cement (AC) is a dark-colored binder material, consisting of a mixture of naturally occurring petroleum hydrocarbons or obtained from distillation, which contains small fractions of sulfur, nitrogen, oxygen and metals (Ni, V, Fe) . During the application of AC, the generated emission of the hot mix contains a large number of compounds, some of which being potentially harmful to the health of the professionals involved in these procedures. In addition, the occurrence of trace metals is of great analytical interest as they are corrosive and cause environmental pollution. With the aging process, there are changes in the chemical composition of the AC involving these compounds, resulting from reactions such as oxidation, condensation and dealkylation that lead to changes in the rheological properties of the matrix. In this work, the behavior of AC were studied for PAHs and derivatives (N-PACs and O-PAHs) and metals such as Ni and V against the modifications caused by aging (RTFOT/SUNTEST). First, the samples (virgin and aged) were separated into acidic, basic and neutral fractions of maltenes and asphaltenes. Next, a sample cleaning method was developed for analysis of PAHs and derivatives by LC-ESI-MS/MS. For the Ni and V studies, the total amount of these compounds was investigated by GFAAS and the loss of Ni and V metaloporphyrins (volatile compounds) of the AC using the DEC (extraction and collection device) was shown. The results showed that PAHs are more concentrated in the maltenic fraction and N-PACs and O-PAHs in the asphaltene fraction, both in virgin and aged samples. In addition, PAHs are more concentrated in the neutral fraction, while N-PACs and O-PAHs are more in the acidic and basic acidic and asphaltenes. With the aging process, N- PACs (e.g. nitroanthracene and nitropyrene) and O-PAHs (e.g. phenanthrenecarboxyaldehyde and hydroxypyrene) are the most affected, mainly in the acidic fraction, and can be considered markers of this process. In relation to the Ni and V compounds, both decrease with the aging process, Ni having a loss between 45 and 50% and V between 35 and 40% both in the acid fractions of AC. The results presented here are important in the sense of understanding a little more on the phenomena involved in the aging process of AC and of the contributions that these compounds have in chemical modifications. Based on this fact, possible chemical and physical transformations were proposed based on the study of 6 different asphalt binders and the predicted reactions in the literature for AC (oxidation, condensation and volatilization). A total of 7 PAHs were indicated as the most reactive in the binders and 4 porphyrins of Ni and V were studied as models of organic compounds involved in aging under the action of UV radiation. |
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Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidosDetermination of polycyclic aromatic hydrocarbons, nickel and vanadium in acid, basic and neutral fractions of virgin and aged asphaltsCAPHPAsNíquelVanádioEnvelhecimentoACPAHNickelVanadiumAgingCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAAsphalt cement (AC) is a dark-colored binder material, consisting of a mixture of naturally occurring petroleum hydrocarbons or obtained from distillation, which contains small fractions of sulfur, nitrogen, oxygen and metals (Ni, V, Fe) . During the application of AC, the generated emission of the hot mix contains a large number of compounds, some of which being potentially harmful to the health of the professionals involved in these procedures. In addition, the occurrence of trace metals is of great analytical interest as they are corrosive and cause environmental pollution. With the aging process, there are changes in the chemical composition of the AC involving these compounds, resulting from reactions such as oxidation, condensation and dealkylation that lead to changes in the rheological properties of the matrix. In this work, the behavior of AC were studied for PAHs and derivatives (N-PACs and O-PAHs) and metals such as Ni and V against the modifications caused by aging (RTFOT/SUNTEST). First, the samples (virgin and aged) were separated into acidic, basic and neutral fractions of maltenes and asphaltenes. Next, a sample cleaning method was developed for analysis of PAHs and derivatives by LC-ESI-MS/MS. For the Ni and V studies, the total amount of these compounds was investigated by GFAAS and the loss of Ni and V metaloporphyrins (volatile compounds) of the AC using the DEC (extraction and collection device) was shown. The results showed that PAHs are more concentrated in the maltenic fraction and N-PACs and O-PAHs in the asphaltene fraction, both in virgin and aged samples. In addition, PAHs are more concentrated in the neutral fraction, while N-PACs and O-PAHs are more in the acidic and basic acidic and asphaltenes. With the aging process, N- PACs (e.g. nitroanthracene and nitropyrene) and O-PAHs (e.g. phenanthrenecarboxyaldehyde and hydroxypyrene) are the most affected, mainly in the acidic fraction, and can be considered markers of this process. In relation to the Ni and V compounds, both decrease with the aging process, Ni having a loss between 45 and 50% and V between 35 and 40% both in the acid fractions of AC. The results presented here are important in the sense of understanding a little more on the phenomena involved in the aging process of AC and of the contributions that these compounds have in chemical modifications. Based on this fact, possible chemical and physical transformations were proposed based on the study of 6 different asphalt binders and the predicted reactions in the literature for AC (oxidation, condensation and volatilization). A total of 7 PAHs were indicated as the most reactive in the binders and 4 porphyrins of Ni and V were studied as models of organic compounds involved in aging under the action of UV radiation.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqCimento Asfáltico de petróleo (CAP) é um material aglutinante de cor escura, constituído de uma mistura de hidrocarbonetos derivados do petróleo de forma natural ou destilação, além de conter pequenas frações de enxofre, nitrogênio, oxigênio e metais (Ni, V, Fe). Durante a aplicação do CAP a emissão gerada da mistura aplicada a quente contém um grande número de compostos, sendo alguns potencialmente nocivos à saúde dos profissionais ligados nestes procedimentos. Além disso, a ocorrência de metais traços é de grande interesse analítico, uma vez que são corrosivos e causam poluição ambiental. Com o processo de envelhecimento, ocorrem mudanças na composição química do CAP envolvendo estes compostos, decorrentes de reações como oxidação, condensação e desalquilação que levam a alterações nas propriedades reológicas do mesmo. Neste trabalho, foi estudado o comportamento do CAP frente a essas modificações sofridas durante o envelhecimento (RTFOT/SUNTEST) para HPAs e derivados (NHPAs e OHPAs) e metais como Ni e V. Para isso, primeiramente as amostras (virgens e envelhecidas) foram separadas em frações ácidas, básicas e neutras de maltenos e asfaltenos. Em seguida, foi desenvolvido um método de limpeza da amostra para análise de HPAs e derivados por LC-ESI-MS/MS. Para o estudo de Ni e V, foi investigado a quantidade total destes compostos nas frações por GFAAS e mostrado a perda de metaloporfirinas (compostos voláteis) de Ni e V do CAP utilizando o DEC (Dispositivo de extração e coleta). Os resultados mostraram que os HPAs estão mais concentrados na fração maltênica e NHPAs e OHPAs na fração asfaltênica, tanto nas amostras virgens como nas envelhecidas. Além disso, HPAs estão mais concentrados na fração neutra, enquanto NHPAs e OHPAs estão em maior quantidade nas fações ácidas e básicas de maltenos e asfaltenos. Com o processo de envelhecimento, os NHPAs (nitroantraceno e nitropireno) e os OHPAs (fenantrenocarboxialdeído e hidroxipireno) são os que mais se alteram, principalmente na fração ácida, podendo ser considerados marcadores nesse processo. Em relação aos compostos de Ni e V, ambos diminuem com o processo de envelhecimento, tendo Ni uma perda entre 45 e 50% e V entre 35 e 40%, sendo mais significativa na fração ácida. Os resultados aqui mostrados são importantes no sentido de compreender um pouco mais dos fenômenos envolvidos no processo de envelhecimento do CAP e das contribuições que estes compostos têm nas modificações químicas. Baseado nisso, possíveis transformações químicas e físicas foram propostas com base no estudo de 6 diferentes ligantes asfálticos e nas reações previstas na literatura para CAP (oxidação, condensação e volatilização). Um total de 7 HPAs foram indicados como os mais reativos nos ligantes e 4 porfirinas de Ni e V foram estudadas como modelos de compostos orgânicos envolvidos no envelhecimento sob ação da radiação UV.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasNascimento, Paulo Cícero dohttp://lattes.cnpq.br/7151513617218161Carvalho, Leandro Machado dehttp://lattes.cnpq.br/6652387343920028Mortari, Sergio Robertohttp://lattes.cnpq.br/7784609477475171Specht, Luciano Pivotohttp://lattes.cnpq.br/8038412953408618Claussen, Luís Evandro2018-08-29T20:45:20Z2018-08-29T20:45:20Z2017-08-15info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/14126ark:/26339/001300000hb7kporAttribution-NonCommercial-NoDerivatives 4.0 Internationalinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2018-08-29T20:45:20Zoai:repositorio.ufsm.br:1/14126Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/PUBhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.com||manancial@ufsm.bropendoar:2018-08-29T20:45:20Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
| dc.title.none.fl_str_mv |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos Determination of polycyclic aromatic hydrocarbons, nickel and vanadium in acid, basic and neutral fractions of virgin and aged asphalts |
| title |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos |
| spellingShingle |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos Claussen, Luís Evandro CAP HPAs Níquel Vanádio Envelhecimento AC PAH Nickel Vanadium Aging CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
| title_short |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos |
| title_full |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos |
| title_fullStr |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos |
| title_full_unstemmed |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos |
| title_sort |
Determinação de hidrocarbonetos policíclicos aromáticos, níquel e vanádio em frações ácidas, básicas e neutras de asfaltos virgens e envelhecidos |
| author |
Claussen, Luís Evandro |
| author_facet |
Claussen, Luís Evandro |
| author_role |
author |
| dc.contributor.none.fl_str_mv |
Nascimento, Paulo Cícero do http://lattes.cnpq.br/7151513617218161 Carvalho, Leandro Machado de http://lattes.cnpq.br/6652387343920028 Mortari, Sergio Roberto http://lattes.cnpq.br/7784609477475171 Specht, Luciano Pivoto http://lattes.cnpq.br/8038412953408618 |
| dc.contributor.author.fl_str_mv |
Claussen, Luís Evandro |
| dc.subject.por.fl_str_mv |
CAP HPAs Níquel Vanádio Envelhecimento AC PAH Nickel Vanadium Aging CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
| topic |
CAP HPAs Níquel Vanádio Envelhecimento AC PAH Nickel Vanadium Aging CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
| description |
Asphalt cement (AC) is a dark-colored binder material, consisting of a mixture of naturally occurring petroleum hydrocarbons or obtained from distillation, which contains small fractions of sulfur, nitrogen, oxygen and metals (Ni, V, Fe) . During the application of AC, the generated emission of the hot mix contains a large number of compounds, some of which being potentially harmful to the health of the professionals involved in these procedures. In addition, the occurrence of trace metals is of great analytical interest as they are corrosive and cause environmental pollution. With the aging process, there are changes in the chemical composition of the AC involving these compounds, resulting from reactions such as oxidation, condensation and dealkylation that lead to changes in the rheological properties of the matrix. In this work, the behavior of AC were studied for PAHs and derivatives (N-PACs and O-PAHs) and metals such as Ni and V against the modifications caused by aging (RTFOT/SUNTEST). First, the samples (virgin and aged) were separated into acidic, basic and neutral fractions of maltenes and asphaltenes. Next, a sample cleaning method was developed for analysis of PAHs and derivatives by LC-ESI-MS/MS. For the Ni and V studies, the total amount of these compounds was investigated by GFAAS and the loss of Ni and V metaloporphyrins (volatile compounds) of the AC using the DEC (extraction and collection device) was shown. The results showed that PAHs are more concentrated in the maltenic fraction and N-PACs and O-PAHs in the asphaltene fraction, both in virgin and aged samples. In addition, PAHs are more concentrated in the neutral fraction, while N-PACs and O-PAHs are more in the acidic and basic acidic and asphaltenes. With the aging process, N- PACs (e.g. nitroanthracene and nitropyrene) and O-PAHs (e.g. phenanthrenecarboxyaldehyde and hydroxypyrene) are the most affected, mainly in the acidic fraction, and can be considered markers of this process. In relation to the Ni and V compounds, both decrease with the aging process, Ni having a loss between 45 and 50% and V between 35 and 40% both in the acid fractions of AC. The results presented here are important in the sense of understanding a little more on the phenomena involved in the aging process of AC and of the contributions that these compounds have in chemical modifications. Based on this fact, possible chemical and physical transformations were proposed based on the study of 6 different asphalt binders and the predicted reactions in the literature for AC (oxidation, condensation and volatilization). A total of 7 PAHs were indicated as the most reactive in the binders and 4 porphyrins of Ni and V were studied as models of organic compounds involved in aging under the action of UV radiation. |
| publishDate |
2017 |
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2017-08-15 2018-08-29T20:45:20Z 2018-08-29T20:45:20Z |
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info:eu-repo/semantics/publishedVersion |
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info:eu-repo/semantics/doctoralThesis |
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por |
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Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
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Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
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reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
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Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
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