A Proposed Thermodynamic Model for Gas Hydrate Equilibrium in Electrolyte Solutions

In this work, the thermodynamic stability of gas hydrates is investigated in the presence of electrolyte solutions. The proposed model is based on the Van der Waals-Platteeuw model for gas hydrate equilibrium, and the Pitzer and Mayorga model is employed to calculate the water activity in the electrolyte solutions. Available values for the Pitzer model parameters are usually adjusted using experimental data at 25 degrees C, which is usually higher than the gas hydrate formation temperature. In order to eliminate this problem, those adjustable parameters are re-optimized using experimental data from the literature at the lowest temperature. In the case of mixed electrolyte solutions and without using any adjustable parameters, a mixing rule is proposed to estimate the water activity. The new mixing rule is based on the ionic strength of the mixture and estimates the mixture water activity by using properties of the single electrolytes that constitute the mixture. The results show the proposed model can calculate hydrate equilibrium conditions with good accuracy, especially at low concentrations, which is the case for most industrial applications.