Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono

Detalhes bibliográficos
Autor(a) principal: Caetano, Gabriela Costa
Data de Publicação: 2021
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Repositório Institucional da UFG
dARK ID: ark:/38995/00130000060bj
Texto Completo: http://repositorio.bc.ufg.br/tede/handle/tede/11515
Resumo: Petroporphyrins are aromatic and nitrogenous macrocycles, of organic origin, which occur naturally in oil and also in sedimentary rocks. In addition to being important biomarker parameters, they have several applications, such as in catalysis and photodynamic therapy. However, they cause damage to the catalytic stages in oil refining. Therefore, due to the importance of removing these compounds from their original fraction, adsorption has been proposed as an alternative process to the commonly used extractive and chromatographic methods. Considering the adsorption and desorption processes of nickel octaethylporphyrin (Ni-OEP), the selection of adsorbents (activated carbon, graphite and partially oxidized graphite) and the optimization of the process operating conditions (solvent, temperature and solid/liquid ratio) were performed. In response, the variables for evaluating the adsorption, adsorption capacity (qe), and desorption, desorption percentage (%desorption) processes were maximized through qualitative and quantitative experimental designs. The kinetics, equilibrium and adsorption thermodynamics studies were carried out; and the adsorbent regeneration cycles were evaluated. As validation of the optimized conditions, qe and %desorption were obtained close to 7.12 mg.g-1 and 37.68%, respectively. As for the adsorption kinetics, the model that best fitted the experimental data was the Elovich equation, in which the equilibrium was reached between 540 and 600 min, with qe = 6.83 mg.g-1; while the equilibrium data were better adjusted by the Freundlich model. The obtained thermodynamic parameters suggest that, under the considered conditions, the adsorption process is spontaneous (ΔG0ads < 0) and exothermic (ΔH0ads < 0). An extraction process was also carried out on the bituminous shales, taken from the Irati Formation, and the presence of nickel octaethylporphyrin was found in the extract. The adsorption and desorption processes of Ni-OEP in the real system had behavior similar to those developed in the model system, with approximately 50% efficiency in petroporphyrin separation. The results obtained allowed to infer that the adsorptive mechanism can be based on the formation of acid-base and π-π interactions between the Ni-OEP molecules and the heterogeneous surface of the coconut shell activated charcoal (CAD), with characteristics of chemical and physical adsorption, respectively.
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spelling Ostroski, Indianara Conceiçãohttp://lattes.cnpq.br/9689394915288313Andrade, Laiane Alves deBarros, Maria Angélica Simões Dornellas deOstroski, Indianara Conceiçãohttp://lattes.cnpq.br/4933223135302093Caetano, Gabriela Costa2021-07-23T12:05:32Z2021-07-23T12:05:32Z2021-06-10CAETANO, G. C. Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono. 2021. 159 f. Dissertação (Mestrado em Engenharia Química) - Universidade Federal de Goiás, Goiânia, 2021.http://repositorio.bc.ufg.br/tede/handle/tede/11515ark:/38995/00130000060bjPetroporphyrins are aromatic and nitrogenous macrocycles, of organic origin, which occur naturally in oil and also in sedimentary rocks. In addition to being important biomarker parameters, they have several applications, such as in catalysis and photodynamic therapy. However, they cause damage to the catalytic stages in oil refining. Therefore, due to the importance of removing these compounds from their original fraction, adsorption has been proposed as an alternative process to the commonly used extractive and chromatographic methods. Considering the adsorption and desorption processes of nickel octaethylporphyrin (Ni-OEP), the selection of adsorbents (activated carbon, graphite and partially oxidized graphite) and the optimization of the process operating conditions (solvent, temperature and solid/liquid ratio) were performed. In response, the variables for evaluating the adsorption, adsorption capacity (qe), and desorption, desorption percentage (%desorption) processes were maximized through qualitative and quantitative experimental designs. The kinetics, equilibrium and adsorption thermodynamics studies were carried out; and the adsorbent regeneration cycles were evaluated. As validation of the optimized conditions, qe and %desorption were obtained close to 7.12 mg.g-1 and 37.68%, respectively. As for the adsorption kinetics, the model that best fitted the experimental data was the Elovich equation, in which the equilibrium was reached between 540 and 600 min, with qe = 6.83 mg.g-1; while the equilibrium data were better adjusted by the Freundlich model. The obtained thermodynamic parameters suggest that, under the considered conditions, the adsorption process is spontaneous (ΔG0ads < 0) and exothermic (ΔH0ads < 0). An extraction process was also carried out on the bituminous shales, taken from the Irati Formation, and the presence of nickel octaethylporphyrin was found in the extract. The adsorption and desorption processes of Ni-OEP in the real system had behavior similar to those developed in the model system, with approximately 50% efficiency in petroporphyrin separation. The results obtained allowed to infer that the adsorptive mechanism can be based on the formation of acid-base and π-π interactions between the Ni-OEP molecules and the heterogeneous surface of the coconut shell activated charcoal (CAD), with characteristics of chemical and physical adsorption, respectively.Petroporfirinas são macrociclos aromáticos e nitrogenados, de origem orgânica, que ocorrem naturalmente no petróleo e também em rochas sedimentares. Além de constituirem importantes parâmetros biomarcadores, possuem diversas aplicações, como na catálise e terapia fotodinâmica. No entanto, causam prejuízos às etapas catalíticas no refino do petróleo. Logo, devido a importância de remoção desses compostos a partir da sua fração original, a adsorção foi proposta como processo alternativo aos métodos extrativos e cromatográficos comumente empregados. Considerando os processos de adsorção e dessorção da octaetilporfirina de níquel (Ni-OEP), foram feitas a seleção dos adsorventes (carvão ativado, grafite e grafite parcialmente oxidado) e a otimização das condições operacionais de processo (solvente, temperatura e razão sólido/líquido). Como resposta buscou-se maximizar as variáveis de avaliação dos processos adsortivo, capacidade de adsorção (qe), e dessortivo, porcentagem de dessorção (%dessorção), por meio de planejamentos experimentais qualitativo e quantitativos. Os estudos de cinética, equilíbrio e termodinâmica de adsorção foram realizados; e os ciclos de regeneração do adsorvente avaliados. Como validação das condições otimizadas, foram obtidos qe e %dessorção próximos de 7,12 mg.g-1 e 37,68%, respectivamente. Quanto à cinética de adsorção, o modelo que melhor se ajustou aos dados experimentais foi a equação de Elovich, em que o equilíbrio foi atingido entre 540 e 600 min, com qe = 6,83 mg.g-1; enquanto os dados de equilíbrio foram melhor ajustados pelo modelo de Freundlich. Os parâmetros termodinâmicos obtidos sugerem que, nas condições consideradas, o processo de adsorção é espontâneo (ΔG0ads < 0) e exotérmico (ΔH0ads < 0). Também foi realizado um processo de extração nos folhelhos betuminosos, retirados da Formação Irati, e constatou-se a presença da octaetilporfirina de níquel no extrato. Os processos de adsorção e dessorção da Ni-OEP no sistema real tiveram comportamento semelhante aos desenvolvidos no sistema modelo, com aproximadamente 50% de eficiência na separação da petroporfirina. Os resultados obtidos permitiram inferir que o mecanismo adsortivo pode ser baseado na formação de interações do tipo ácido-base e π-π entre as moléculas de Ni-OEP e a superfície heterogênea do carvão ativado de casca de dendê (CAD), com características de adsorção química e física, respectivamente.Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2021-07-22T11:12:01Z No. of bitstreams: 2 Dissertação - Gabriela Costa Caetano - 2021.pdf: 3900028 bytes, checksum: 511c6d6074303b2e1230c8e21fb717d0 (MD5) license_rdf: 805 bytes, checksum: 4460e5956bc1d1639be9ae6146a50347 (MD5)Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2021-07-23T12:05:32Z (GMT) No. of bitstreams: 2 Dissertação - Gabriela Costa Caetano - 2021.pdf: 3900028 bytes, checksum: 511c6d6074303b2e1230c8e21fb717d0 (MD5) license_rdf: 805 bytes, checksum: 4460e5956bc1d1639be9ae6146a50347 (MD5)Made available in DSpace on 2021-07-23T12:05:32Z (GMT). No. of bitstreams: 2 Dissertação - Gabriela Costa Caetano - 2021.pdf: 3900028 bytes, checksum: 511c6d6074303b2e1230c8e21fb717d0 (MD5) license_rdf: 805 bytes, checksum: 4460e5956bc1d1639be9ae6146a50347 (MD5) Previous issue date: 2021-06-10Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade Federal de GoiásPrograma de Pós-graduação em Engenharia Química (IQ)UFGBrasilInstituto de Química - IQ (RG)Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessPetroporfirinasBiomarcadoresProcessos de separaçãoOtimizaçãoBiomarkersSeparation processesOptimizationPetroporphyrinsENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICAOtimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbonoOptimization of adsorption and desorption processes of nickel octaethylporphyrin on carbon-based adsorbentsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesis50500500500500294621reponame:Repositório Institucional da UFGinstname:Universidade Federal de Goiás (UFG)instacron:UFGLICENSElicense.txtlicense.txttext/plain; charset=utf-81748http://repositorio.bc.ufg.br/tede/bitstreams/4d1bb715-c6d1-4c77-95bf-91fa0a93808d/download8a4605be74aa9ea9d79846c1fba20a33MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.bc.ufg.br/tede/bitstreams/81d23a75-d347-4e1a-8d86-5d6b2a14001b/download4460e5956bc1d1639be9ae6146a50347MD52ORIGINALDissertação - Gabriela Costa Caetano - 2021.pdfDissertação - Gabriela Costa Caetano - 2021.pdfapplication/pdf3900028http://repositorio.bc.ufg.br/tede/bitstreams/c9076e94-bb29-4149-b506-e36645abe86a/download511c6d6074303b2e1230c8e21fb717d0MD53tede/115152021-07-23 09:05:32.931http://creativecommons.org/licenses/by-nc-nd/4.0/Attribution-NonCommercial-NoDerivatives 4.0 Internationalopen.accessoai:repositorio.bc.ufg.br:tede/11515http://repositorio.bc.ufg.br/tedeRepositório InstitucionalPUBhttp://repositorio.bc.ufg.br/oai/requesttasesdissertacoes.bc@ufg.bropendoar:2021-07-23T12:05:32Repositório Institucional da UFG - Universidade Federal de Goiás (UFG)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
dc.title.pt_BR.fl_str_mv Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
dc.title.alternative.eng.fl_str_mv Optimization of adsorption and desorption processes of nickel octaethylporphyrin on carbon-based adsorbents
title Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
spellingShingle Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
Caetano, Gabriela Costa
Petroporfirinas
Biomarcadores
Processos de separação
Otimização
Biomarkers
Separation processes
Optimization
Petroporphyrins
ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA
title_short Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
title_full Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
title_fullStr Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
title_full_unstemmed Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
title_sort Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono
author Caetano, Gabriela Costa
author_facet Caetano, Gabriela Costa
author_role author
dc.contributor.advisor1.fl_str_mv Ostroski, Indianara Conceição
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/9689394915288313
dc.contributor.referee1.fl_str_mv Andrade, Laiane Alves de
dc.contributor.referee2.fl_str_mv Barros, Maria Angélica Simões Dornellas de
dc.contributor.referee3.fl_str_mv Ostroski, Indianara Conceição
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/4933223135302093
dc.contributor.author.fl_str_mv Caetano, Gabriela Costa
contributor_str_mv Ostroski, Indianara Conceição
Andrade, Laiane Alves de
Barros, Maria Angélica Simões Dornellas de
Ostroski, Indianara Conceição
dc.subject.por.fl_str_mv Petroporfirinas
Biomarcadores
Processos de separação
topic Petroporfirinas
Biomarcadores
Processos de separação
Otimização
Biomarkers
Separation processes
Optimization
Petroporphyrins
ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA
dc.subject.eng.fl_str_mv Otimização
Biomarkers
Separation processes
Optimization
Petroporphyrins
dc.subject.cnpq.fl_str_mv ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA
description Petroporphyrins are aromatic and nitrogenous macrocycles, of organic origin, which occur naturally in oil and also in sedimentary rocks. In addition to being important biomarker parameters, they have several applications, such as in catalysis and photodynamic therapy. However, they cause damage to the catalytic stages in oil refining. Therefore, due to the importance of removing these compounds from their original fraction, adsorption has been proposed as an alternative process to the commonly used extractive and chromatographic methods. Considering the adsorption and desorption processes of nickel octaethylporphyrin (Ni-OEP), the selection of adsorbents (activated carbon, graphite and partially oxidized graphite) and the optimization of the process operating conditions (solvent, temperature and solid/liquid ratio) were performed. In response, the variables for evaluating the adsorption, adsorption capacity (qe), and desorption, desorption percentage (%desorption) processes were maximized through qualitative and quantitative experimental designs. The kinetics, equilibrium and adsorption thermodynamics studies were carried out; and the adsorbent regeneration cycles were evaluated. As validation of the optimized conditions, qe and %desorption were obtained close to 7.12 mg.g-1 and 37.68%, respectively. As for the adsorption kinetics, the model that best fitted the experimental data was the Elovich equation, in which the equilibrium was reached between 540 and 600 min, with qe = 6.83 mg.g-1; while the equilibrium data were better adjusted by the Freundlich model. The obtained thermodynamic parameters suggest that, under the considered conditions, the adsorption process is spontaneous (ΔG0ads < 0) and exothermic (ΔH0ads < 0). An extraction process was also carried out on the bituminous shales, taken from the Irati Formation, and the presence of nickel octaethylporphyrin was found in the extract. The adsorption and desorption processes of Ni-OEP in the real system had behavior similar to those developed in the model system, with approximately 50% efficiency in petroporphyrin separation. The results obtained allowed to infer that the adsorptive mechanism can be based on the formation of acid-base and π-π interactions between the Ni-OEP molecules and the heterogeneous surface of the coconut shell activated charcoal (CAD), with characteristics of chemical and physical adsorption, respectively.
publishDate 2021
dc.date.accessioned.fl_str_mv 2021-07-23T12:05:32Z
dc.date.available.fl_str_mv 2021-07-23T12:05:32Z
dc.date.issued.fl_str_mv 2021-06-10
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/masterThesis
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dc.identifier.citation.fl_str_mv CAETANO, G. C. Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono. 2021. 159 f. Dissertação (Mestrado em Engenharia Química) - Universidade Federal de Goiás, Goiânia, 2021.
dc.identifier.uri.fl_str_mv http://repositorio.bc.ufg.br/tede/handle/tede/11515
dc.identifier.dark.fl_str_mv ark:/38995/00130000060bj
identifier_str_mv CAETANO, G. C. Otimização dos processos de adsorção e dessorção da octaetilporfirina de níquel em adsorventes à base de carbono. 2021. 159 f. Dissertação (Mestrado em Engenharia Química) - Universidade Federal de Goiás, Goiânia, 2021.
ark:/38995/00130000060bj
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dc.publisher.none.fl_str_mv Universidade Federal de Goiás
dc.publisher.program.fl_str_mv Programa de Pós-graduação em Engenharia Química (IQ)
dc.publisher.initials.fl_str_mv UFG
dc.publisher.country.fl_str_mv Brasil
dc.publisher.department.fl_str_mv Instituto de Química - IQ (RG)
publisher.none.fl_str_mv Universidade Federal de Goiás
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