Development of an Electrolyte CPA Equation of state for Applications in the Petroleum and Chemical Industries

This thesis extends the Cubic Plus Association (CPA) equation of state (EoS) to handle mixtures containing ions from fully dissociated salts. The CPA EoS has during the past 18 years been applied to thermodynamic modeling of a wide range of industrially important chemicals, mainly in relation to the oil- and gas sector. One of the strengths of the CPA EoS is that it reduces to the Soave Redlich Kwong (SRK) cubic EoS in the absence of associating compounds and is therefore compatible with existing tools for oil characterization. In a similar fasion, the electrolyte CPA (e-CPA) EoS reduces to the CPA EoS in the absence of electrolytes, making it possible to extend the applicability of the CPA EoS while retaining backwards compatibility and resuing the parameters for non-electrolyte systems . There are many challenges related to thermodynamic modeling of mixtures containing electrolytes, and many different approaches to the development of an electrolyte EoS have been suggested by scientists in the field. However, most of these approaches are focusing on aqueous solutions and cannot easily be extended to handle mixed solvents. Furthermore, the approaches suggested in current literature have rarely been applied to all types of thermodynamic equilibrium calculations relevant to electrolyte solutions. This project has aimed to determine the best recipe to deliver a complete thermodynamic model capable of handling electrolytes in mixed solvents and at a wide range of temperature and pressure. Different terms describing the electrostatic interactions have been compared and it was concluded that the differences between the Debye-Hückel and the "mean spherical approximation" models are negligible. A term accounting for the Gibbs energy of hydration (such as the Born term) must be included in order to provide sufficient driving forces for electrolytes towards the most polar phase. The static permittivity of the mixture was found to be the most important property; yet it was shown that the empirical models suggested by literature could lead to unphysical behavior of the equation of state. A new theoretical model was developed to extend the framework for modeling of the static permittivity to hydrogen-bonding compounds and salts. The model relates the geometrical configuration of hydrogen-bonding dipolar molecules to the Kirkwood g-factor using the Wertheim association model that is included with modern EoS such as CPA or SAFT (Statistical Associating Fluid Theory). This new model was shown to give excellent predictions of the static permittivity of mixtures over wide ranges of temperature, pressure, and composition and thereby generalizes the handling of electrolytes in mixed solvents in an electrolyte EoS. The CPA EoS was extended with a Debye-Hückel and a Born term to account for the electrostatics along with the new model for the static permittivity. This new e-CPA EoS was parameterized against osmotic coefficient, density, and mean ionic activity coefficient data of pure salts and validated against salt mixture data. The model was then applied to predict: • the solubility of light gases, hydrocarbons, and aromatics in aqueous mixtures and mixed solvents • solid-liquid equilibrium in aqueous salt mixtures and mixed solvents • gas hydrate formation pressures of methane with salts in water+methanol • liquid-liquid and liquid-liquid-liquid equilibrium with water-propan-1-ol-NaCl-octane solutions It was demonstrated that the model has a good potential for applications in relation to e.g. flow assurance during the production of natural gas. The parameterization of electrolyte EoS is of high importance and more work is needed in order to obtain good ion-specific parameters that include interaction parameters with gases and relevant chemicals.