Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo

Detalhes bibliográficos
Autor(a) principal: Silva, Samantha Ribeiro Campos da
Data de Publicação: 2019
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)
Texto Completo: http://repositorio.ufes.br/handle/10/13351
Resumo: Crude oil is the term used for a wide variety of oils extracted from sedimentary rocks. Due to the variety and complexity of oil matrices an important oil assay is to quantify the content of saturated, aromatic, resin and asphaltene compounds (SARA). However, proper separation of saturated and aromatic components depends on the internal phase of the chromatographic column and on the method used for its quantification. Here works were described: aiming at the relative quantification of nonpolar components present in the saturated petroleum fraction and the use silica gel modified with boric acid to obtain aromatic fractions enriched with nitrogen aromatic compounds. The results showed that GCxGC-qMS technique was efficient in the relative quantification of n-paraffins from C11 to C35 and of branched paraffins in the saturated petroleum fraction. In addition, it allowed the determination of bicyclic, tricyclic, tetracyclic and pentacyclic compounds. In general, the classes of monocyclic and iso-paraffin compounds were the most abundant in the undegraded petroleum saturated fraction. Relative quantification of normal and branched paraffins allowed an understanding of the pour point values of light oils (API gravity greater than 30). The modification of the silica gel (column) with boric acid in the separation of the aromatic components of petroleum was selective to obtain fractions enriched with nitrogen aromatic compounds. However, the nitrogenous components identified in the aromatics fraction are characteristic of resins. Combining the FT-ICR MS (ESI (±) and APPI (±) sources using the Intensity vs DBE graphs) and GCxGC-qMS techniques allowed to ratify the good selectivity of the modified silica gel for the elution of aromatic nitrogen compounds. In the FT-ICR MS analyzes it was possible to visualize intense signals in all ionization sources for the nitrogen classes. The other visualized classes, such as hydrocarbons and oxygenated, were shown as low intensity peaks, corroborating the efficiency of separation of the modified column for nitrogen compounds. The concentration of nitrogenous compounds in crude oils is generally less than 2 wt%, however, they are detrimental to the refining processes and knowledge of the nitrogenous species present in crude oil is desirable. Thus, the methodology using the silica gel modified with boric acid column aimed to supply this important refining demand.
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spelling Castro, Eustaquio Vinicius Ribeiro dehttps://orcid.org/0000-0002-7888-8076http://lattes.cnpq.br/1055263403980509Silva, Samantha Ribeiro Campos dahttps://orcid.org/http://lattes.cnpq.br/8592661743827044Cunha Neto, Alvarohttps://orcid.org/0000-0002-1814-6214http://lattes.cnpq.br/7448379486432052Franca, Hildegardo Seiberthttps://orcid.org/0000-0001-6129-8793http://lattes.cnpq.br/1284874997224988Lacerda Junior, Valdemar https://orcid.org/0000000282575443http://lattes.cnpq.br/9819471276433138Santos, Roberto Pereira2024-05-29T22:11:00Z2024-05-29T22:11:00Z2019-09-19Crude oil is the term used for a wide variety of oils extracted from sedimentary rocks. Due to the variety and complexity of oil matrices an important oil assay is to quantify the content of saturated, aromatic, resin and asphaltene compounds (SARA). However, proper separation of saturated and aromatic components depends on the internal phase of the chromatographic column and on the method used for its quantification. Here works were described: aiming at the relative quantification of nonpolar components present in the saturated petroleum fraction and the use silica gel modified with boric acid to obtain aromatic fractions enriched with nitrogen aromatic compounds. The results showed that GCxGC-qMS technique was efficient in the relative quantification of n-paraffins from C11 to C35 and of branched paraffins in the saturated petroleum fraction. In addition, it allowed the determination of bicyclic, tricyclic, tetracyclic and pentacyclic compounds. In general, the classes of monocyclic and iso-paraffin compounds were the most abundant in the undegraded petroleum saturated fraction. Relative quantification of normal and branched paraffins allowed an understanding of the pour point values of light oils (API gravity greater than 30). The modification of the silica gel (column) with boric acid in the separation of the aromatic components of petroleum was selective to obtain fractions enriched with nitrogen aromatic compounds. However, the nitrogenous components identified in the aromatics fraction are characteristic of resins. Combining the FT-ICR MS (ESI (±) and APPI (±) sources using the Intensity vs DBE graphs) and GCxGC-qMS techniques allowed to ratify the good selectivity of the modified silica gel for the elution of aromatic nitrogen compounds. In the FT-ICR MS analyzes it was possible to visualize intense signals in all ionization sources for the nitrogen classes. The other visualized classes, such as hydrocarbons and oxygenated, were shown as low intensity peaks, corroborating the efficiency of separation of the modified column for nitrogen compounds. The concentration of nitrogenous compounds in crude oils is generally less than 2 wt%, however, they are detrimental to the refining processes and knowledge of the nitrogenous species present in crude oil is desirable. Thus, the methodology using the silica gel modified with boric acid column aimed to supply this important refining demand.Petróleo é o termo utilizado para uma grande variedade de óleos extraídos de rochas sedimentares. Devido a variedade e complexidade das matrizes oleosas, um importante ensaio sobre o petróleo consiste em quantificar o teor de compostos saturados, aromáticos, resinas e asfaltenos (SARA). No entanto, uma apropriada separação dos componentes saturados e aromáticos depende da fase estacionária da coluna cromatográfica e do método utilizado para sua quantificação. Aqui são descritos trabalhos: visando a quantificação relativa de componentes apolares presentes na fração saturada de petróleo e a utilização de sílica gel modificada com ácido bórico para obtenção de frações aromáticas enriquecidas com compostos aromáticos nitrogenados. Os resultados mostraram que a técnica CGxCG-EMq foi eficiente na quantificação relativa de n-parafinas de C11 a C35 e parafinas ramificadas na fração saturada de petróleo. Ademais, permitiu a determinação de compostos bicíclicos, tricíclicos, tetracíclicos e pentacíclicos. Em geral, as classes de compostos monocíclicos e iso-parafinas foram as mais abundantes na fração saturada de petróleo não degradados. A quantificação relativa das parafinas normais e ramificadas permitiu uma compreensão dos valores de ponto de fluidez de petróleos leves (gravidade API maior que 30). A modificação da sílica gel (coluna) com ácido bórico na separação dos componentes aromáticos do petróleo foi seletiva para a obtenção de frações enriquecidas com compostos aromáticos nitrogenados. Entretanto, os componentes nitrogenados identificados na fração de aromáticos são característicos de resinas. Combinando as técnicas FT-ICR MS (fontes ESI (±) e APPI (±) através da utilização de gráficos DBE pela Intensidade) e CGxCG-EMq permitiu ratificar a boa seletividade da sílica gel modificada para a eluição de compostos nitrogenados aromáticos. Nas análises FT-ICR MS foi possível visualizar sinais intensos em todas as fontes de ionização para as classes nitrogenadas. As demais classes visualizadas, como hidrocarbonetos e oxigenadas, se mostraram como picos de baixa intensidade, corroborando a eficácia de separação da coluna modificada para os compostos nitrogenados. A concentração de compostos nitrogenados em petróleos crus geralmente é menor que 2 wt%, no entanto, eles são prejudiciais aos processos de refino sendo desejável o conhecimento das espécies nitrogenadas presentes no petróleo cru. Assim, a metodologia utilizando a coluna com sílica gel modificada com ácido bórico visou suprir esta importante demanda do refino.Fundação Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Texthttp://repositorio.ufes.br/handle/10/13351porUniversidade Federal do Espírito SantoDoutorado em QuímicaPrograma de Pós-Graduação em QuímicaUFESBRCentro de Ciências Exatassubject.br-rjbnQuímicaPetróleoSARASaturadosAromáticosCGxCG-EMqFT-ICR MSOilSaturatedAromaticsAplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleoApplication of comprehensive two-dimensional gas chromatography in the characterization of petroleum compound classesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)instname:Universidade Federal do Espírito Santo (UFES)instacron:UFESORIGINALSamanthaRibeiroCamposdaSilva-2019-tese.pdfapplication/pdf4895295http://repositorio.ufes.br/bitstreams/d9c0f19d-614b-40f1-8dc0-e18bd43c02fb/download64f5d7259db938c219802b797bbebbfaMD5110/133512024-08-14 14:59:55.159oai:repositorio.ufes.br:10/13351http://repositorio.ufes.brRepositório InstitucionalPUBhttp://repositorio.ufes.br/oai/requestopendoar:21082024-10-15T17:59:45.873507Repositório Institucional da Universidade Federal do Espírito Santo (riUfes) - Universidade Federal do Espírito Santo (UFES)false
dc.title.none.fl_str_mv Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
dc.title.alternative.none.fl_str_mv Application of comprehensive two-dimensional gas chromatography in the characterization of petroleum compound classes
title Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
spellingShingle Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
Silva, Samantha Ribeiro Campos da
Química
Petróleo
SARA
Saturados
Aromáticos
CGxCG-EMq
FT-ICR MS
Oil
Saturated
Aromatics
subject.br-rjbn
title_short Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
title_full Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
title_fullStr Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
title_full_unstemmed Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
title_sort Aplicação da cromatografia gasosa bidimensional abrangente na caracterização de classes de compostos do petróleo
author Silva, Samantha Ribeiro Campos da
author_facet Silva, Samantha Ribeiro Campos da
author_role author
dc.contributor.authorID.none.fl_str_mv https://orcid.org/
dc.contributor.authorLattes.none.fl_str_mv http://lattes.cnpq.br/8592661743827044
dc.contributor.advisor1.fl_str_mv Castro, Eustaquio Vinicius Ribeiro de
dc.contributor.advisor1ID.fl_str_mv https://orcid.org/0000-0002-7888-8076
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/1055263403980509
dc.contributor.author.fl_str_mv Silva, Samantha Ribeiro Campos da
dc.contributor.referee1.fl_str_mv Cunha Neto, Alvaro
dc.contributor.referee1ID.fl_str_mv https://orcid.org/0000-0002-1814-6214
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/7448379486432052
dc.contributor.referee2.fl_str_mv Franca, Hildegardo Seibert
dc.contributor.referee2ID.fl_str_mv https://orcid.org/0000-0001-6129-8793
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/1284874997224988
dc.contributor.referee3.fl_str_mv Lacerda Junior, Valdemar
dc.contributor.referee3ID.fl_str_mv https://orcid.org/0000000282575443
dc.contributor.referee3Lattes.fl_str_mv http://lattes.cnpq.br/9819471276433138
dc.contributor.referee4.fl_str_mv Santos, Roberto Pereira
contributor_str_mv Castro, Eustaquio Vinicius Ribeiro de
Cunha Neto, Alvaro
Franca, Hildegardo Seibert
Lacerda Junior, Valdemar
Santos, Roberto Pereira
dc.subject.cnpq.fl_str_mv Química
topic Química
Petróleo
SARA
Saturados
Aromáticos
CGxCG-EMq
FT-ICR MS
Oil
Saturated
Aromatics
subject.br-rjbn
dc.subject.por.fl_str_mv Petróleo
SARA
Saturados
Aromáticos
CGxCG-EMq
FT-ICR MS
Oil
Saturated
Aromatics
dc.subject.br-rjbn.none.fl_str_mv subject.br-rjbn
description Crude oil is the term used for a wide variety of oils extracted from sedimentary rocks. Due to the variety and complexity of oil matrices an important oil assay is to quantify the content of saturated, aromatic, resin and asphaltene compounds (SARA). However, proper separation of saturated and aromatic components depends on the internal phase of the chromatographic column and on the method used for its quantification. Here works were described: aiming at the relative quantification of nonpolar components present in the saturated petroleum fraction and the use silica gel modified with boric acid to obtain aromatic fractions enriched with nitrogen aromatic compounds. The results showed that GCxGC-qMS technique was efficient in the relative quantification of n-paraffins from C11 to C35 and of branched paraffins in the saturated petroleum fraction. In addition, it allowed the determination of bicyclic, tricyclic, tetracyclic and pentacyclic compounds. In general, the classes of monocyclic and iso-paraffin compounds were the most abundant in the undegraded petroleum saturated fraction. Relative quantification of normal and branched paraffins allowed an understanding of the pour point values of light oils (API gravity greater than 30). The modification of the silica gel (column) with boric acid in the separation of the aromatic components of petroleum was selective to obtain fractions enriched with nitrogen aromatic compounds. However, the nitrogenous components identified in the aromatics fraction are characteristic of resins. Combining the FT-ICR MS (ESI (±) and APPI (±) sources using the Intensity vs DBE graphs) and GCxGC-qMS techniques allowed to ratify the good selectivity of the modified silica gel for the elution of aromatic nitrogen compounds. In the FT-ICR MS analyzes it was possible to visualize intense signals in all ionization sources for the nitrogen classes. The other visualized classes, such as hydrocarbons and oxygenated, were shown as low intensity peaks, corroborating the efficiency of separation of the modified column for nitrogen compounds. The concentration of nitrogenous compounds in crude oils is generally less than 2 wt%, however, they are detrimental to the refining processes and knowledge of the nitrogenous species present in crude oil is desirable. Thus, the methodology using the silica gel modified with boric acid column aimed to supply this important refining demand.
publishDate 2019
dc.date.issued.fl_str_mv 2019-09-19
dc.date.accessioned.fl_str_mv 2024-05-29T22:11:00Z
dc.date.available.fl_str_mv 2024-05-29T22:11:00Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.uri.fl_str_mv http://repositorio.ufes.br/handle/10/13351
url http://repositorio.ufes.br/handle/10/13351
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dc.format.none.fl_str_mv Text
dc.publisher.none.fl_str_mv Universidade Federal do Espírito Santo
Doutorado em Química
dc.publisher.program.fl_str_mv Programa de Pós-Graduação em Química
dc.publisher.initials.fl_str_mv UFES
dc.publisher.country.fl_str_mv BR
dc.publisher.department.fl_str_mv Centro de Ciências Exatas
publisher.none.fl_str_mv Universidade Federal do Espírito Santo
Doutorado em Química
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