Développement du modèle PPR78 pour décrire, comprendre et prédire les diagrammes de phases hautes et basses pressions des systèmes binaires et des fluides pétroliers

Abstract : A predictive thermodynamic model, based on the group contribution concept, and called PPR78, has been developed in order to be able to predict, with high accuracy, the behaviour of petroleum fluids. PPR78 uses the Peng-Robinson equation of state with Van der Waals mixing rules and a temperature dependent binary interaction parameter kij. This method is the equivalent to the constant packing fraction mixing rules with a Van Laar excess Gibbs energy model (gE). To develop the model, an in-depth study on binary systems fluid phase equilibria, was carried out. It was divided into two parts. Firstly, a phenomenological study made a reappraisal of the Van Konynenburg and Scott classification possible. Secondly, some general rules for the calculation of isothermal, isobaric and global phase equilibrium diagrams were demonstrated. It is important to note that the study of the global thermodynamic stability is essential in the calculations. Once these preliminary steps were realized, the extension of the model to the CO2, N2, H2S and sulfhydryl groups was performed. The fluid phase behaviour of binary systems involving these four groups was accurately calculated by the PPR78 model. Finally, the properties of petroleum fluids were predicted by PPR78 with an accuracy close to the experimental uncertainty
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Romain Privat. Développement du modèle PPR78 pour décrire, comprendre et prédire les diagrammes de phases hautes et basses pressions des systèmes binaires et des fluides pétroliers. Autre. Institut National Polytechnique de Lorraine, 2008. Français. ⟨NNT : 2008INPL090N⟩. ⟨tel-01753008⟩

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