Estudo de propriedades reológicas de suspensões de hidratos
| Ano de defesa: | 2023 |
|---|---|
| Autor(a) principal: | |
| Orientador(a): | |
| Banca de defesa: | |
| 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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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 |
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info:eu-repo/semantics/publishedVersion |
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info:eu-repo/semantics/doctoralThesis |
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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. |
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por |
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por |
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Universidade Tecnológica Federal do Paraná Curitiba Brasil Programa de Pós-Graduação em Engenharia Mecânica e de Materiais UTFPR |
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Universidade Tecnológica Federal do Paraná Curitiba Brasil Programa de Pós-Graduação em Engenharia Mecânica e de Materiais UTFPR |
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