Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation
We use the molecular theory of liquids to review the Perturbed Chain-Statistical Association Fluid Theory Equation of State (PC-SAFT EoS) and formulate new dispersive and repulsive terms for this model. As a well-known fact in the literature, the original PC-SAFT normally predicts accelerated asphal...
- Autores:
-
Cañas Marín, Wilson Antonio
- Tipo de recurso:
- Doctoral thesis
- Fecha de publicación:
- 2021
- Institución:
- Universidad Nacional de Colombia
- Repositorio:
- Universidad Nacional de Colombia
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.unal.edu.co:unal/79496
- Palabra clave:
- 660 - Ingeniería química
330 - Economía::333 - Economía de la tierra y de la energía
Teoría molecular
Ecuaciones integrales
Perturbación (Dinámica cuántica)
PC-SAFT
Thermodynamic perturbation theory
Integral equation theory
Effective diameter
Asphaltene onset pressure
Soft repulsion
Teoría de perturbaciones termodinámicas
Teoría de ecuaciones integrales
Potencial intermolecular
Diámetro efectivo
Presión de inicio de asfaltenos
- Rights
- openAccess
- License
- Atribución-NoComercial-SinDerivadas 4.0 Internacional
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| dc.title.eng.fl_str_mv |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation |
| dc.title.translated.spa.fl_str_mv |
Desarrollo de una ecuación de estado fundamentada en teoría de perturbación termodinámica (TPT) para mezclas propensas a la precipitación de asfaltenos |
| title |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation |
| spellingShingle |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation 660 - Ingeniería química 330 - Economía::333 - Economía de la tierra y de la energía Teoría molecular Ecuaciones integrales Perturbación (Dinámica cuántica) PC-SAFT Thermodynamic perturbation theory Integral equation theory Effective diameter Asphaltene onset pressure Soft repulsion Teoría de perturbaciones termodinámicas Teoría de ecuaciones integrales Potencial intermolecular Diámetro efectivo Presión de inicio de asfaltenos |
| title_short |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation |
| title_full |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation |
| title_fullStr |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation |
| title_full_unstemmed |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation |
| title_sort |
Development of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitation |
| dc.creator.fl_str_mv |
Cañas Marín, Wilson Antonio |
| dc.contributor.advisor.none.fl_str_mv |
Gonzalez, Doris Hoyos Madrigal, Bibian Alonso |
| dc.contributor.author.none.fl_str_mv |
Cañas Marín, Wilson Antonio |
| dc.contributor.researchgroup.spa.fl_str_mv |
Termodinámica Aplicada y Energías Alternativas |
| dc.subject.ddc.spa.fl_str_mv |
660 - Ingeniería química 330 - Economía::333 - Economía de la tierra y de la energía |
| topic |
660 - Ingeniería química 330 - Economía::333 - Economía de la tierra y de la energía Teoría molecular Ecuaciones integrales Perturbación (Dinámica cuántica) PC-SAFT Thermodynamic perturbation theory Integral equation theory Effective diameter Asphaltene onset pressure Soft repulsion Teoría de perturbaciones termodinámicas Teoría de ecuaciones integrales Potencial intermolecular Diámetro efectivo Presión de inicio de asfaltenos |
| dc.subject.lemb.none.fl_str_mv |
Teoría molecular Ecuaciones integrales Perturbación (Dinámica cuántica) |
| dc.subject.proposal.eng.fl_str_mv |
PC-SAFT Thermodynamic perturbation theory Integral equation theory Effective diameter Asphaltene onset pressure Soft repulsion |
| dc.subject.proposal.spa.fl_str_mv |
Teoría de perturbaciones termodinámicas Teoría de ecuaciones integrales Potencial intermolecular Diámetro efectivo Presión de inicio de asfaltenos |
| description |
We use the molecular theory of liquids to review the Perturbed Chain-Statistical Association Fluid Theory Equation of State (PC-SAFT EoS) and formulate new dispersive and repulsive terms for this model. As a well-known fact in the literature, the original PC-SAFT normally predicts accelerated asphaltene onset pressures (AOPs) in petroleum reservoir fluids and cloud points (CPs) in polymeric systems at low temperatures. This phenomenon was studied in this thesis. Thermodynamic perturbation theories (TPTs) and integral equation theory (IET) are central. By combining these theories, we formulate several effective diameter expressions dependent upon temperature and density to replace the original effective diameter of PC-SAFT, which depends on temperature only. Barker and Henderson´s second-order dispersion term based upon a concept of correlated shells of fluids was introduced into PC-SAFT and its effect was studied, especially at low temperatures. Both the new effective diameters formulated, and the modified second-order dispersion term produce less accelerated AOPs and CPs curves at low temperatures. The original universal constants (called here as GSUCs) in the attractive part PC-SAFT were also analyzed in this work. The main conclusion is that GSUCs should not be used at all, and the set of these constants presented by Liang and Kontogeorgies (LKUCs) are preferred instead. In fact, LKUCs not only correct the defect of PC-SAFT of predicting multiple density roots at low temperatures but also reduces the tendency of PC-SAFT of predicting accelerated AOP and CP curves at low temperatures. The PC-SAFT predictions of HAOP loci at very high pressures were also studied. New phase diagrams at low temperatures are presented in this work. HAOPs are displaced at very low temperatures when the modified second-order dispersion term is used or when the LKUCs are combined with the temperature- and density-dependent effective diameters presented in this thesis. Unfortunately, these HAOPs are not possible of being experimentally tested. Nonetheless, the high densities at which these HAOPs are predicted by the original PC-SAFT represent non-isotropic conditions. Under those conditions, the TPTs for fluids lose validity. The combination of the LKUCs and the temperature-and density-dependent effective diameters presented in this thesis substantially increases the isotropic range, allowing a most robust use of the TPTs, and then of PC-SAFT. The failure of the original PC-SAFT to predict coherent Amagat curves is also amply studied. As a result, the failure was found to be directly related to the soft-core repulsion included in PC-SAFT by the effective diameter. Intermolecular potentials as the square well square shoulder (SWSS) are not “soft” enough to correctly predict these curves. Then, we demonstrate in this dissertation that intermolecular potentials soft enough, like Lennard-Jones one, need to be introduced. |
| publishDate |
2021 |
| dc.date.accessioned.none.fl_str_mv |
2021-05-11T13:56:41Z |
| dc.date.available.none.fl_str_mv |
2021-05-11T13:56:41Z |
| dc.date.issued.none.fl_str_mv |
2021-01-05 |
| dc.type.spa.fl_str_mv |
Trabajo de grado - Doctorado |
| dc.type.driver.spa.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
| dc.type.version.spa.fl_str_mv |
info:eu-repo/semantics/acceptedVersion |
| dc.type.coar.spa.fl_str_mv |
http://purl.org/coar/resource_type/c_db06 |
| dc.type.content.spa.fl_str_mv |
Text |
| format |
http://purl.org/coar/resource_type/c_db06 |
| status_str |
acceptedVersion |
| dc.identifier.uri.none.fl_str_mv |
https://repositorio.unal.edu.co/handle/unal/79496 |
| dc.identifier.instname.spa.fl_str_mv |
Universidad Nacional de Colombia |
| dc.identifier.reponame.spa.fl_str_mv |
Repositorio Universidad Nacional de Colombia |
| dc.identifier.repourl.spa.fl_str_mv |
https://repositorio.unal.edu.co/ |
| url |
https://repositorio.unal.edu.co/handle/unal/79496 https://repositorio.unal.edu.co/ |
| identifier_str_mv |
Universidad Nacional de Colombia Repositorio Universidad Nacional de Colombia |
| dc.language.iso.spa.fl_str_mv |
eng |
| language |
eng |
| dc.relation.references.spa.fl_str_mv |
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Pietrobon, H. Zeng, Experimental study to understand formation damage due to asphaltene deposition in a deepwater field, SPWLA Formation Testing SIG, 2020 Weminar series. [240] K.J. Leontaritis, G.A. Mansoori, T-S, Jiang, Asphaltene Deposition in Oil Recovery: A Survey of Field Experiences and Field Approaches, Proceeding of International Conference on Advanced Technologies (ICAT), IL, USA, 1986. [241] H. Belhaj, H.A. Khalifeh, N. Al-Huraibi, Asphaltene Stability in Crude Oil during Production Process, J. Pet. Environ. Biotechnol., 4(3) (2013) 1-5. [242] F. Gonzalez, Private Communication, 2021. |
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Medellín - Minas - Doctorado en Ingeniería - Sistemas Energéticos |
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Departamento de Procesos y Energía |
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Atribución-NoComercial-SinDerivadas 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Gonzalez, Dorisad81126967a48926079b9fea870711f0600Hoyos Madrigal, Bibian Alonso70c0183ce5ed55bb4bdd191be920467fCañas Marín, Wilson Antonio547cf3c94274763be57e34d2791ae596Termodinámica Aplicada y Energías Alternativas2021-05-11T13:56:41Z2021-05-11T13:56:41Z2021-01-05https://repositorio.unal.edu.co/handle/unal/79496Universidad Nacional de ColombiaRepositorio Universidad Nacional de Colombiahttps://repositorio.unal.edu.co/We use the molecular theory of liquids to review the Perturbed Chain-Statistical Association Fluid Theory Equation of State (PC-SAFT EoS) and formulate new dispersive and repulsive terms for this model. As a well-known fact in the literature, the original PC-SAFT normally predicts accelerated asphaltene onset pressures (AOPs) in petroleum reservoir fluids and cloud points (CPs) in polymeric systems at low temperatures. This phenomenon was studied in this thesis. Thermodynamic perturbation theories (TPTs) and integral equation theory (IET) are central. By combining these theories, we formulate several effective diameter expressions dependent upon temperature and density to replace the original effective diameter of PC-SAFT, which depends on temperature only. Barker and Henderson´s second-order dispersion term based upon a concept of correlated shells of fluids was introduced into PC-SAFT and its effect was studied, especially at low temperatures. Both the new effective diameters formulated, and the modified second-order dispersion term produce less accelerated AOPs and CPs curves at low temperatures. The original universal constants (called here as GSUCs) in the attractive part PC-SAFT were also analyzed in this work. The main conclusion is that GSUCs should not be used at all, and the set of these constants presented by Liang and Kontogeorgies (LKUCs) are preferred instead. In fact, LKUCs not only correct the defect of PC-SAFT of predicting multiple density roots at low temperatures but also reduces the tendency of PC-SAFT of predicting accelerated AOP and CP curves at low temperatures. The PC-SAFT predictions of HAOP loci at very high pressures were also studied. New phase diagrams at low temperatures are presented in this work. HAOPs are displaced at very low temperatures when the modified second-order dispersion term is used or when the LKUCs are combined with the temperature- and density-dependent effective diameters presented in this thesis. Unfortunately, these HAOPs are not possible of being experimentally tested. Nonetheless, the high densities at which these HAOPs are predicted by the original PC-SAFT represent non-isotropic conditions. Under those conditions, the TPTs for fluids lose validity. The combination of the LKUCs and the temperature-and density-dependent effective diameters presented in this thesis substantially increases the isotropic range, allowing a most robust use of the TPTs, and then of PC-SAFT. The failure of the original PC-SAFT to predict coherent Amagat curves is also amply studied. As a result, the failure was found to be directly related to the soft-core repulsion included in PC-SAFT by the effective diameter. Intermolecular potentials as the square well square shoulder (SWSS) are not “soft” enough to correctly predict these curves. Then, we demonstrate in this dissertation that intermolecular potentials soft enough, like Lennard-Jones one, need to be introduced.En esta tesis usamos la teoría molecular de los líquidos para revisar la Ecuación de Estado de la Teoría de Fluidos de Asociación Estadística de Cadena Perturbada (PC-SAFT EoS) y formulamos nuevos términos dispersivos y repulsivos para este modelo. Como es bien sabido en la literatura, la PC-SAFT original normalmente predice curvas de presión de inicio de precipitación de asfaltenos (AOP) en fluidos de yacimientos de petróleo, así como puntos de nube (CP) en sistemas poliméricos, muy aceleradas a bajas temperaturas. Este fenómeno se estudió en esta tesis con la ayuda de las teorías de perturbación termodinámica (TPT) y la teoría de ecuaciones integrales (IET). Al combinar estas teorías, formulamos varias expresiones de diámetro efectivo que dependen de la temperatura y la densidad, con el objetivo de reemplazar el diámetro efectivo original de PC-SAFT, que sólo es función de la temperatura. Además, se introdujo en PC-SAFT una modificación para el término de dispersión de segundo orden de Barker y Henderson, la cual está basada en un concepto de capas correlacionadas de fluido, estududiándese su efecto especialmente a bajas temperaturas. Los nuevos diámetros efectivos formulados y el término de dispersión de segundo orden modificado producen curvas AOP y CPs menos aceleradas a bajas temperaturas. De igual manera, las constantes universales originales (denominadas aquí como GSUC) en la parte atractiva of PC-SAFT también se analizaron en este trabajo. La conclusión principal es que las GSUCs no deben usarse, y en su lugar es preferible utilizar el conjunto de estas constantes presentado por Liang y Kontogeorgies (LKUC). De hecho, estas últimas no sólo corrigen el defecto de PC-SAFT de predecir múltiples raíces de densidad a temperaturas bajas, sino que reducen la tendencia de PC-SAFT de predecir curvas AOP y CP aceleradas a tales condiciones. También se estudiaron las predicciones de PCSAFT de hiper presiones de inicio de precipitación de asfaltenos (HAOPs), reportándose nuevos diagramas de fase a bajas temperaturas para fluidos de yacimiento propensos a la precipitación de asfaltenos. Las HAOPs se desplazan a temperaturas muy bajas cuando se usa la versión modifcada del término de dispersión de segundo orden de Barker y Henderson o cuando los LKUC se combinan con los diámetros efectivos dependientes de la temperatura y densidad desarrollados en esta tesis. Desafortunadamente, la existencia de estas HAOPs no se puede comprobar experimentalmente. Sin embargo, las altas densidades a las que la PC-SAFT original predice estas HAOPs claramente representan condiciones no isotrópicas. En esas condiciones, las TPTs para fluidos pierden validez. No obstante, el efecto de utilizar la combinación de las LKUC y los diámetros efectivos dependientes de la temperatura y la densidad, presentados en esta tesis, aumenta sustancialmente el rango isotrópico, permitiendo así un uso más sólido de las TPT, y por tanto de PC-SAFT. El fracaso de la PC-SAFT original para predecir curvas Amagat coherentes también se estudió en profundidad en esta tesis. Como resultado, se encontró que la falla de PC-SAFT está directamente relacionada con la repulsión de núcleo blando incluida a través de su diámetro efectivo original. Los potenciales intermoleculares como el pozo cuadrado con hombro cuadrado (SWSS), usado en PC-SAFT, no son lo suficientemente "suaves" para predecir correctamente estas curvas. Luego, es entonces necesario introducir potenciales intermoleculares lo suficientemente suaves, como el Lennard-Jones, tal y como se demuestra en esta disertación.DoctoradoHidrocarburos227 páginasapplication/pdfengUniversidad Nacional de ColombiaMedellín - Minas - Doctorado en Ingeniería - Sistemas EnergéticosDepartamento de Procesos y EnergíaFacultad de MinasMedellínUniversidad Nacional de Colombia - Sede Medellín660 - Ingeniería química330 - Economía::333 - Economía de la tierra y de la energíaTeoría molecularEcuaciones integralesPerturbación (Dinámica cuántica)PC-SAFTThermodynamic perturbation theoryIntegral equation theoryEffective diameterAsphaltene onset pressureSoft repulsionTeoría de perturbaciones termodinámicasTeoría de ecuaciones integralesPotencial intermolecularDiámetro efectivoPresión de inicio de asfaltenosDevelopment of an equation of state based on thermodynamic perturbation theory (TPT) for mixtures prone to asphaltene precipitationDesarrollo de una ecuación de estado fundamentada en teoría de perturbación termodinámica (TPT) para mezclas propensas a la precipitación de asfaltenosTrabajo de grado - Doctoradoinfo:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/acceptedVersionhttp://purl.org/coar/resource_type/c_db06Text[1] J. 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