Hydrate growth model in the presence of thermodynamic inhibitors or promoters

Detalhes bibliográficos
Autor(a) principal: Young, Ingrid Azevedo de Oliveira
Data de Publicação: 2020
Tipo de documento: Tese
Idioma: eng
Título da fonte: Repositório Institucional da UFRJ
Texto Completo: http://hdl.handle.net/11422/21721
Resumo: There are scenarios in which hydrate formation is desired, such as in its technological application for gas storage or in natural reserves with potential sources of energy. There are other scenarios in which these solids formation is undesirable, as hydrate precipitation in pipelines causing flow assurance problems in the oil and gas industry. In both cases, an understanding of the thermodynamics and dynamics of the hydrate formation in the presence of chemical additives is essential. In this work, it is proposed to improve the calculation of hydrate equilibrium in the presence of a thermodynamic inhibitor, ethanol (EtOH), or a thermodynamic promoter, tetrahydrofuran (THF). The knowledge about hydrate equilibria is used to develop a kinetic model of growth capable of accounting the effects of additives, based on the non-equilibrium thermodynamics theory, and using chemical affinity as a driving force. As a result, adequate modeling of the double CH4/THF hydrate was obtained with a maximum deviation of 0.27% in the equilibrium temperature. Besides, 15 wt% of EtOH in the liquid phase was defined as the limited for its application only as an inhibitor by combining experimental results with equilibrium calculations. The effects of coupling diffusion and reaction on the CH4 hydrate growth in freshwater were mainly dependent on pressure. The kinetic model of CH4-hydrate growth in the presence of EtOH, including the effects of non-ideality, can describe the behavior of EtOH as a thermodynamic inhibitor and as a potential kinetic inhibitor, observed in the literature.
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spelling Hydrate growth model in the presence of thermodynamic inhibitors or promotersHidratoCrescimentoInibidores termodinâmicosPromotores termodinâmicosEngenharia QuímicaThere are scenarios in which hydrate formation is desired, such as in its technological application for gas storage or in natural reserves with potential sources of energy. There are other scenarios in which these solids formation is undesirable, as hydrate precipitation in pipelines causing flow assurance problems in the oil and gas industry. In both cases, an understanding of the thermodynamics and dynamics of the hydrate formation in the presence of chemical additives is essential. In this work, it is proposed to improve the calculation of hydrate equilibrium in the presence of a thermodynamic inhibitor, ethanol (EtOH), or a thermodynamic promoter, tetrahydrofuran (THF). The knowledge about hydrate equilibria is used to develop a kinetic model of growth capable of accounting the effects of additives, based on the non-equilibrium thermodynamics theory, and using chemical affinity as a driving force. As a result, adequate modeling of the double CH4/THF hydrate was obtained with a maximum deviation of 0.27% in the equilibrium temperature. Besides, 15 wt% of EtOH in the liquid phase was defined as the limited for its application only as an inhibitor by combining experimental results with equilibrium calculations. The effects of coupling diffusion and reaction on the CH4 hydrate growth in freshwater were mainly dependent on pressure. The kinetic model of CH4-hydrate growth in the presence of EtOH, including the effects of non-ideality, can describe the behavior of EtOH as a thermodynamic inhibitor and as a potential kinetic inhibitor, observed in the literature.Existem cenários em que a formação de hidrato é desejada, como na sua aplicação tecnológica para armazenamento de gás ou em reservas naturais com potencial energético. Existem outros cenários em que a formação desses sólidos é indesejada, como na formação de hidratos em tubulações, dificultando a garantia de escoamento na indústria de petróleo e gás. Em ambos os casos, a compreensão da termodinâmica e da dinâmica de formação desses sólidos na presença de aditivos químicos é essencial. Neste trabalho propõe-se aperfeiçoar o cálculo de equilíbrio de hidratos na presença de um inibidor termodinâmico, etanol (EtOH), ou de um promotor termodinâmico, tetrahidrofurano (THF). O conhecimento sobre o equilíbrio é usado para desenvolver um modelo de crescimento capaz de contabilizar os efeitos desses aditivos, baseado na teoria da termodinâmica de não-equilíbrio e usando a afinidade química como força motriz. Como resultado, obteve-se adequada modelagem do hidrato duplo de CH4 com THF com desvio máximo de 0.27% na temperatura de equilíbrio. Além disso, 15% em peso de EtOH na fase líquida foi definido como o limite para sua aplicação apenas como um inibidor, combinando resultados experimentais com cálculos de equilíbrio de fases. Os efeitos de acoplamento entre difusão e reação no crescimento de hidrato de CH4 em água pura se mostraram dependentes principalmente da pressão. O crescimento de hidrato de CH4 na presença de EtOH, incluindo os efeitos de não-idealidade, permitiram descrever o comportamento duplo desse álcool, normalmente observado na literatura, como inibidor termodinâmico e como potencial inibidor cinético.Universidade Federal do Rio de JaneiroBrasilInstituto Alberto Luiz Coimbra de Pós-Graduação e Pesquisa de EngenhariaPrograma de Pós-Graduação em Engenharia QuímicaUFRJTavares, Frederico Wanderleyhttp://lattes.cnpq.br/9319321507255273Barreto Júnior, Amaro GomesFerreira, Gabriel Gonçalves da SilvaPessôa Filho, Pedro de AlcântaraCouto, PauloSum, Amadeu Kun WanYoung, Ingrid Azevedo de Oliveira2023-09-28T15:28:44Z2023-12-21T03:02:04Z2020-10info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesishttp://hdl.handle.net/11422/21721enginfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFRJinstname:Universidade Federal do Rio de Janeiro (UFRJ)instacron:UFRJ2023-12-21T03:02:04Zoai:pantheon.ufrj.br:11422/21721Repositório InstitucionalPUBhttp://www.pantheon.ufrj.br/oai/requestpantheon@sibi.ufrj.bropendoar:2023-12-21T03:02:04Repositório Institucional da UFRJ - Universidade Federal do Rio de Janeiro (UFRJ)false
dc.title.none.fl_str_mv Hydrate growth model in the presence of thermodynamic inhibitors or promoters
title Hydrate growth model in the presence of thermodynamic inhibitors or promoters
spellingShingle Hydrate growth model in the presence of thermodynamic inhibitors or promoters
Young, Ingrid Azevedo de Oliveira
Hidrato
Crescimento
Inibidores termodinâmicos
Promotores termodinâmicos
Engenharia Química
title_short Hydrate growth model in the presence of thermodynamic inhibitors or promoters
title_full Hydrate growth model in the presence of thermodynamic inhibitors or promoters
title_fullStr Hydrate growth model in the presence of thermodynamic inhibitors or promoters
title_full_unstemmed Hydrate growth model in the presence of thermodynamic inhibitors or promoters
title_sort Hydrate growth model in the presence of thermodynamic inhibitors or promoters
author Young, Ingrid Azevedo de Oliveira
author_facet Young, Ingrid Azevedo de Oliveira
author_role author
dc.contributor.none.fl_str_mv Tavares, Frederico Wanderley
http://lattes.cnpq.br/9319321507255273
Barreto Júnior, Amaro Gomes
Ferreira, Gabriel Gonçalves da Silva
Pessôa Filho, Pedro de Alcântara
Couto, Paulo
Sum, Amadeu Kun Wan
dc.contributor.author.fl_str_mv Young, Ingrid Azevedo de Oliveira
dc.subject.por.fl_str_mv Hidrato
Crescimento
Inibidores termodinâmicos
Promotores termodinâmicos
Engenharia Química
topic Hidrato
Crescimento
Inibidores termodinâmicos
Promotores termodinâmicos
Engenharia Química
description There are scenarios in which hydrate formation is desired, such as in its technological application for gas storage or in natural reserves with potential sources of energy. There are other scenarios in which these solids formation is undesirable, as hydrate precipitation in pipelines causing flow assurance problems in the oil and gas industry. In both cases, an understanding of the thermodynamics and dynamics of the hydrate formation in the presence of chemical additives is essential. In this work, it is proposed to improve the calculation of hydrate equilibrium in the presence of a thermodynamic inhibitor, ethanol (EtOH), or a thermodynamic promoter, tetrahydrofuran (THF). The knowledge about hydrate equilibria is used to develop a kinetic model of growth capable of accounting the effects of additives, based on the non-equilibrium thermodynamics theory, and using chemical affinity as a driving force. As a result, adequate modeling of the double CH4/THF hydrate was obtained with a maximum deviation of 0.27% in the equilibrium temperature. Besides, 15 wt% of EtOH in the liquid phase was defined as the limited for its application only as an inhibitor by combining experimental results with equilibrium calculations. The effects of coupling diffusion and reaction on the CH4 hydrate growth in freshwater were mainly dependent on pressure. The kinetic model of CH4-hydrate growth in the presence of EtOH, including the effects of non-ideality, can describe the behavior of EtOH as a thermodynamic inhibitor and as a potential kinetic inhibitor, observed in the literature.
publishDate 2020
dc.date.none.fl_str_mv 2020-10
2023-09-28T15:28:44Z
2023-12-21T03:02:04Z
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 http://hdl.handle.net/11422/21721
url http://hdl.handle.net/11422/21721
dc.language.iso.fl_str_mv eng
language eng
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Universidade Federal do Rio de Janeiro
Brasil
Instituto Alberto Luiz Coimbra de Pós-Graduação e Pesquisa de Engenharia
Programa de Pós-Graduação em Engenharia Química
UFRJ
publisher.none.fl_str_mv Universidade Federal do Rio de Janeiro
Brasil
Instituto Alberto Luiz Coimbra de Pós-Graduação e Pesquisa de Engenharia
Programa de Pós-Graduação em Engenharia Química
UFRJ
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFRJ
instname:Universidade Federal do Rio de Janeiro (UFRJ)
instacron:UFRJ
instname_str Universidade Federal do Rio de Janeiro (UFRJ)
instacron_str UFRJ
institution UFRJ
reponame_str Repositório Institucional da UFRJ
collection Repositório Institucional da UFRJ
repository.name.fl_str_mv Repositório Institucional da UFRJ - Universidade Federal do Rio de Janeiro (UFRJ)
repository.mail.fl_str_mv pantheon@sibi.ufrj.br
_version_ 1815456052254081024

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