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Estudo de propriedades reológicas de suspensões de hidratos

Detalhes bibliográficos
Ano de defesa: 2023
Autor(a) principal: Mühlstedt, Guilherme
Orientador(a): Não Informado pela instituição
Banca de defesa: Não Informado pela instituição
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Tecnológica Federal do Paraná
Curitiba
Brasil
Programa de Pós-Graduação em Engenharia Mecânica e de Materiais
UTFPR
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.utfpr.edu.br/jspui/handle/1/37376
Resumo: Hydrates are crystalline structures that resemble ice, formed through the occlusion of small molecules, such as light hydrocarbons, within cage-like structures composed of water molecules, usually under thermodynamic conditions of high pressure and low temperature. The formation of gas hydrates leading to plugging is regarded as the main issue by the oil and gas industry. While thermodynamic inhibitors have been employed throughout the 20th century to prevent the occurrence of these structures, high costs and environmental regulations have prompted a change in approach. Managing risks associated with the presence of hydrates in transportation lines has undergone a paradigm shift in the 21st century. Keeping the hydrates in suspension is an option, but it only feasible if there is no crystals agglomeration or wall deposition. The aim of this thesis is to analyze the rheological characteristics of hydrate suspensions during crystal formation and transportation. To accomplish this, the Haake MARS III rotational rheometer was utilized. For experimental purpose, tetrahydrofuran (THF) was chosen as the hydrate formation agent. Due to its unique ability to form sII hydrate structures, which are similar to those that occur in the majority of natural gas systems, at atmospheric pressure and temperatures above the water freezing point, THF is frequently used by research groups as a model. Four fluids were used as the basis for the suspension: (i) water; (ii) THF; (iii) brine; and (iv) water-based drilling fluid. Shear influence during hydrate formation and its impact on microstructure degradation were investigated in all cases. A more comprehensive analysis was performed for the drilling fluid samples, which included assessment of yield stress and system brittleness in the solid-like regime. In THF-water systems, samples containing water in excess exhibited a shorter induction time. The application of shear rates at 100 s-1 and 300 s-1 did not result in any significant differences in the induction time of the first three samples. However, a shorter induction time, a faster transition to the steady-state, and a higher rate of particle growth and agglomeration were the results of the increased shear rate in drilling fluid samples. The experimental findings indicate that the THF hydrate suspension in drilling fluid is an elasto-viscoplastic material that exhibits time-dependent behavior, in which the microstructure is irreversibly affected by shear. The elastic moduli and yield stress of samples formed at rest (without shear) were one order of magnitude higher than those obtained under shear. Interestingly, it was revealed that hydrates formed under static conditions have lower resistance to deformation compared to those formed under shear. Finally, visual observations indicated that the presence of limestone particles in the drilling fluid composition had a direct influence on the size of hydrate crystals, as their growth and agglomeration were restricted due to particle interactions between barite and hydrate.
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spelling Estudo de propriedades reológicas de suspensões de hidratosStudy of the rheological properties of hydrate suspensionsHidratosTetrahidrofuranoReologiaSuspensões (Química)Inibidores químicosEscoamento multifásicoPoços de petróleo - PerfuraçãoIndústria petrolíferaHydratesTetrahydrofuranRheologySuspensions (Chemistry)Chemical inhibitorsMultiphase flowOil well drillingPetroleum, Industry and tradeCNPQ::ENGENHARIAS::ENGENHARIA MECANICA::ENGENHARIA TERMICAEngenharia MecânicaHydrates are crystalline structures that resemble ice, formed through the occlusion of small molecules, such as light hydrocarbons, within cage-like structures composed of water molecules, usually under thermodynamic conditions of high pressure and low temperature. The formation of gas hydrates leading to plugging is regarded as the main issue by the oil and gas industry. While thermodynamic inhibitors have been employed throughout the 20th century to prevent the occurrence of these structures, high costs and environmental regulations have prompted a change in approach. Managing risks associated with the presence of hydrates in transportation lines has undergone a paradigm shift in the 21st century. Keeping the hydrates in suspension is an option, but it only feasible if there is no crystals agglomeration or wall deposition. The aim of this thesis is to analyze the rheological characteristics of hydrate suspensions during crystal formation and transportation. To accomplish this, the Haake MARS III rotational rheometer was utilized. For experimental purpose, tetrahydrofuran (THF) was chosen as the hydrate formation agent. Due to its unique ability to form sII hydrate structures, which are similar to those that occur in the majority of natural gas systems, at atmospheric pressure and temperatures above the water freezing point, THF is frequently used by research groups as a model. Four fluids were used as the basis for the suspension: (i) water; (ii) THF; (iii) brine; and (iv) water-based drilling fluid. Shear influence during hydrate formation and its impact on microstructure degradation were investigated in all cases. A more comprehensive analysis was performed for the drilling fluid samples, which included assessment of yield stress and system brittleness in the solid-like regime. In THF-water systems, samples containing water in excess exhibited a shorter induction time. The application of shear rates at 100 s-1 and 300 s-1 did not result in any significant differences in the induction time of the first three samples. However, a shorter induction time, a faster transition to the steady-state, and a higher rate of particle growth and agglomeration were the results of the increased shear rate in drilling fluid samples. The experimental findings indicate that the THF hydrate suspension in drilling fluid is an elasto-viscoplastic material that exhibits time-dependent behavior, in which the microstructure is irreversibly affected by shear. The elastic moduli and yield stress of samples formed at rest (without shear) were one order of magnitude higher than those obtained under shear. Interestingly, it was revealed that hydrates formed under static conditions have lower resistance to deformation compared to those formed under shear. Finally, visual observations indicated that the presence of limestone particles in the drilling fluid composition had a direct influence on the size of hydrate crystals, as their growth and agglomeration were restricted due to particle interactions between barite and hydrate.Petróleo Brasileiro (Petrobrás)Hidratos são estruturas cristalinas semelhantes ao gelo, formadas por oclusão de pequenas moléculas, como hidrocarbonetos leves, em estruturas em forma de gaiola compostas por moléculas de água, geralmente em condições termodinâmicas de alta pressão e baixa temperatura. A formação de plugues de hidratos é reconhecida como o principal risco enfrentado pela indústria de petróleo e gás. Embora inibidores termodinâmicos tenham sido empregados ao longo do século XX para evitar a ocorrência dessas estruturas, elevados custos e novas regulamentações ambientais exigiram mudanças. O gerenciamento de riscos associados à presença de hidratos em linhas de transporte vivencia uma quebra de paradigmas no século XXI. Manter os hidratos em suspensão é uma alternativa viável, desde que não haja aglomeração nem deposição. O objetivo desta tese é analisar as características reológicas de suspensões de hidrato durante a formação e transporte de cristais. Para tal, foi utilizado o reômetro rotacional Haake MARS III. Tetrahidrofurano (THF) foi escolhido como agente de formação de hidratos. Devido à sua capacidade de formar estruturas de hidratos sII, semelhantes às que ocorrem na maioria dos sistemas de gás natural, em pressão atmosférica e a temperaturas acima do ponto de congelamento da água, o THF é frequentemente utilizado por pesquisadores como modelo. Quatro fluidos foram utilizados como base para a suspensão: (i) água; (ii) THF; (iii) salmoura; e (iv) fluido de perfuração base-água. A influência do cisalhamento durante a formação de hidratos e seu impacto na degradação da microestrutura foi investigada para todas as amostras. Uma análise mais abrangente foi realizada para as amostras de fluido de perfuração, que incluiu a avaliação da tensão limite de escoamento e da fragilidade da estrutura em regime transicional. Em sistemas THF-água, amostras contendo água em excesso apresentaram menor tempo de indução. A aplicação de taxas de cisalhamento de 100 s-1e 300 s-1 não apresentaram diferenças significativas sobre o tempo de indução das três primeiras amostras. Entretanto, o aumento da taxa de cisalhamento nas amostras de fluido de perfuração resultou na redução do tempo de indução, no aumento da taxa de crescimento/aglomeração das partículas, além de resultar em uma transição mais rápida para o regime permanente. Os resultados experimentais indicam que a suspensão de hidratos de THF em fluido de perfuração é um material elasto-viscoplástico dependente do tempo, na qual a microestrutura é irreversivelmente afetada pelo cisalhamento. Os módulos elásticos e a tensão limite de escoamento das amostras formadas em repouso foram uma ordem de grandeza maiores aos valores obtidos sob cisalhamento. Curiosamente, resultados mostraram que hidratos formados em condições estáticas têm menor resistência à deformação comparados aos formados sob cisalhamento. Por fim, observações visuais revelaram que as partículas de calcário presentes no fluido de perfuração exercem impacto direto no tamanho das estruturas dos hidratos, restringido o crescimento e aglomeração devido as interações entre partículas.Universidade Tecnológica Federal do ParanáCuritibaBrasilPrograma de Pós-Graduação em Engenharia Mecânica e de MateriaisUTFPRNegrão, Cezar Otaviano Ribeirohttps://orcid.org/0000-0001-7090-2729http://lattes.cnpq.br/4344790398205987Andrade, Diogo Elias da Vinhahttps://orcid.org/0000-0002-1191-9931http://lattes.cnpq.br/5726562903368886Franco, Admilson Teixeirahttps://orcid.org/0000-0002-7977-6404http://lattes.cnpq.br/3561428456009236Thompson, Roney Leonhttp://orcid.org/0000-0002-3642-0766http://lattes.cnpq.br/4870003562574001Andrade, Diogo Elias da Vinhahttps://orcid.org/0000-0002-1191-9931http://lattes.cnpq.br/5726562903368886Oliveira, Flávio Henrique Marchesini dehttps://orcid.org/0000-0002-7494-2506http://lattes.cnpq.br/2318507129457109Naccache, Monica Feijohttps://orcid.org/0000-0002-5867-5436http://lattes.cnpq.br/0010848295031388Mühlstedt, Guilherme2025-07-08T19:03:36Z2025-07-08T19:03:36Z2023-06-14info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfMÜHLSTEDT, Guilherme. Estudo de propriedades reológicas de suspensões de hidratos. 2025. Tese (Doutorado em Engenharia Mecânica e de Materiais) - Universidade Tecnológica Federal do Paraná, Curitiba, 2023.http://repositorio.utfpr.edu.br/jspui/handle/1/37376porhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UTFPR (da Universidade Tecnológica Federal do Paraná (RIUT))instname:Universidade Tecnológica Federal do Paraná (UTFPR)instacron:UTFPR2025-07-09T06:13:15Zoai:repositorio.utfpr.edu.br:1/37376Repositório InstitucionalPUBhttp://repositorio.utfpr.edu.br:8080/oai/requestriut@utfpr.edu.br || sibi@utfpr.edu.bropendoar:2025-07-09T06:13:15Repositório Institucional da UTFPR (da Universidade Tecnológica Federal do Paraná (RIUT)) - Universidade Tecnológica Federal do Paraná (UTFPR)false
dc.title.none.fl_str_mv Estudo de propriedades reológicas de suspensões de hidratos
Study of the rheological properties of hydrate suspensions
title Estudo de propriedades reológicas de suspensões de hidratos
spellingShingle Estudo de propriedades reológicas de suspensões de hidratos
Mühlstedt, Guilherme
Hidratos
Tetrahidrofurano
Reologia
Suspensões (Química)
Inibidores químicos
Escoamento multifásico
Poços de petróleo - Perfuração
Indústria petrolífera
Hydrates
Tetrahydrofuran
Rheology
Suspensions (Chemistry)
Chemical inhibitors
Multiphase flow
Oil well drilling
Petroleum, Industry and trade
CNPQ::ENGENHARIAS::ENGENHARIA MECANICA::ENGENHARIA TERMICA
Engenharia Mecânica
title_short Estudo de propriedades reológicas de suspensões de hidratos
title_full Estudo de propriedades reológicas de suspensões de hidratos
title_fullStr Estudo de propriedades reológicas de suspensões de hidratos
title_full_unstemmed Estudo de propriedades reológicas de suspensões de hidratos
title_sort Estudo de propriedades reológicas de suspensões de hidratos
author Mühlstedt, Guilherme
author_facet Mühlstedt, Guilherme
author_role author
dc.contributor.none.fl_str_mv Negrão, Cezar Otaviano Ribeiro
https://orcid.org/0000-0001-7090-2729
http://lattes.cnpq.br/4344790398205987
Andrade, Diogo Elias da Vinha
https://orcid.org/0000-0002-1191-9931
http://lattes.cnpq.br/5726562903368886
Franco, Admilson Teixeira
https://orcid.org/0000-0002-7977-6404
http://lattes.cnpq.br/3561428456009236
Thompson, Roney Leon
http://orcid.org/0000-0002-3642-0766
http://lattes.cnpq.br/4870003562574001
Andrade, Diogo Elias da Vinha
https://orcid.org/0000-0002-1191-9931
http://lattes.cnpq.br/5726562903368886
Oliveira, Flávio Henrique Marchesini de
https://orcid.org/0000-0002-7494-2506
http://lattes.cnpq.br/2318507129457109
Naccache, Monica Feijo
https://orcid.org/0000-0002-5867-5436
http://lattes.cnpq.br/0010848295031388
dc.contributor.author.fl_str_mv Mühlstedt, Guilherme
dc.subject.por.fl_str_mv Hidratos
Tetrahidrofurano
Reologia
Suspensões (Química)
Inibidores químicos
Escoamento multifásico
Poços de petróleo - Perfuração
Indústria petrolífera
Hydrates
Tetrahydrofuran
Rheology
Suspensions (Chemistry)
Chemical inhibitors
Multiphase flow
Oil well drilling
Petroleum, Industry and trade
CNPQ::ENGENHARIAS::ENGENHARIA MECANICA::ENGENHARIA TERMICA
Engenharia Mecânica
topic Hidratos
Tetrahidrofurano
Reologia
Suspensões (Química)
Inibidores químicos
Escoamento multifásico
Poços de petróleo - Perfuração
Indústria petrolífera
Hydrates
Tetrahydrofuran
Rheology
Suspensions (Chemistry)
Chemical inhibitors
Multiphase flow
Oil well drilling
Petroleum, Industry and trade
CNPQ::ENGENHARIAS::ENGENHARIA MECANICA::ENGENHARIA TERMICA
Engenharia Mecânica
description Hydrates are crystalline structures that resemble ice, formed through the occlusion of small molecules, such as light hydrocarbons, within cage-like structures composed of water molecules, usually under thermodynamic conditions of high pressure and low temperature. The formation of gas hydrates leading to plugging is regarded as the main issue by the oil and gas industry. While thermodynamic inhibitors have been employed throughout the 20th century to prevent the occurrence of these structures, high costs and environmental regulations have prompted a change in approach. Managing risks associated with the presence of hydrates in transportation lines has undergone a paradigm shift in the 21st century. Keeping the hydrates in suspension is an option, but it only feasible if there is no crystals agglomeration or wall deposition. The aim of this thesis is to analyze the rheological characteristics of hydrate suspensions during crystal formation and transportation. To accomplish this, the Haake MARS III rotational rheometer was utilized. For experimental purpose, tetrahydrofuran (THF) was chosen as the hydrate formation agent. Due to its unique ability to form sII hydrate structures, which are similar to those that occur in the majority of natural gas systems, at atmospheric pressure and temperatures above the water freezing point, THF is frequently used by research groups as a model. Four fluids were used as the basis for the suspension: (i) water; (ii) THF; (iii) brine; and (iv) water-based drilling fluid. Shear influence during hydrate formation and its impact on microstructure degradation were investigated in all cases. A more comprehensive analysis was performed for the drilling fluid samples, which included assessment of yield stress and system brittleness in the solid-like regime. In THF-water systems, samples containing water in excess exhibited a shorter induction time. The application of shear rates at 100 s-1 and 300 s-1 did not result in any significant differences in the induction time of the first three samples. However, a shorter induction time, a faster transition to the steady-state, and a higher rate of particle growth and agglomeration were the results of the increased shear rate in drilling fluid samples. The experimental findings indicate that the THF hydrate suspension in drilling fluid is an elasto-viscoplastic material that exhibits time-dependent behavior, in which the microstructure is irreversibly affected by shear. The elastic moduli and yield stress of samples formed at rest (without shear) were one order of magnitude higher than those obtained under shear. Interestingly, it was revealed that hydrates formed under static conditions have lower resistance to deformation compared to those formed under shear. Finally, visual observations indicated that the presence of limestone particles in the drilling fluid composition had a direct influence on the size of hydrate crystals, as their growth and agglomeration were restricted due to particle interactions between barite and hydrate.
publishDate 2023
dc.date.none.fl_str_mv 2023-06-14
2025-07-08T19:03:36Z
2025-07-08T19:03:36Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/doctoralThesis
format doctoralThesis
status_str publishedVersion
dc.identifier.uri.fl_str_mv MÜHLSTEDT, Guilherme. Estudo de propriedades reológicas de suspensões de hidratos. 2025. Tese (Doutorado em Engenharia Mecânica e de Materiais) - Universidade Tecnológica Federal do Paraná, Curitiba, 2023.
http://repositorio.utfpr.edu.br/jspui/handle/1/37376
identifier_str_mv MÜHLSTEDT, Guilherme. Estudo de propriedades reológicas de suspensões de hidratos. 2025. Tese (Doutorado em Engenharia Mecânica e de Materiais) - Universidade Tecnológica Federal do Paraná, Curitiba, 2023.
url http://repositorio.utfpr.edu.br/jspui/handle/1/37376
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universidade Tecnológica Federal do Paraná
Curitiba
Brasil
Programa de Pós-Graduação em Engenharia Mecânica e de Materiais
UTFPR
publisher.none.fl_str_mv Universidade Tecnológica Federal do Paraná
Curitiba
Brasil
Programa de Pós-Graduação em Engenharia Mecânica e de Materiais
UTFPR
dc.source.none.fl_str_mv reponame:Repositório Institucional da UTFPR (da Universidade Tecnológica Federal do Paraná (RIUT))
instname:Universidade Tecnológica Federal do Paraná (UTFPR)
instacron:UTFPR
instname_str Universidade Tecnológica Federal do Paraná (UTFPR)
instacron_str UTFPR
institution UTFPR
reponame_str Repositório Institucional da UTFPR (da Universidade Tecnológica Federal do Paraná (RIUT))
collection Repositório Institucional da UTFPR (da Universidade Tecnológica Federal do Paraná (RIUT))
repository.name.fl_str_mv Repositório Institucional da UTFPR (da Universidade Tecnológica Federal do Paraná (RIUT)) - Universidade Tecnológica Federal do Paraná (UTFPR)
repository.mail.fl_str_mv riut@utfpr.edu.br || sibi@utfpr.edu.br
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