Experimental measurement and thermodynamic modelling of clathrate hydrate equilibria and salt solubility in aqueous ethylene glycol and electrolyte solutions

We present the extension of a recently developed method for modelling saline water to the thermodynamic prediction of phase behaviour for mixed salt-organic clathrate hydrate inhibitor aqueous solutions. Novel freezing point, boiling point and salt solubility data have been generated for NaCl-ethylene glycol (EG) and KCl-EG aqueous solutions. These data have been used in the optimisation of binary interaction parameters between salts and ethylene glycol. The extended thermodynamic model is capable of predicting complex vapour-liquid-solid (VLSE) equilibria for aqueous electrolytes and/or organic inhibitor solutions over a wide range of pressures, temperatures and inhibitor concentrations. Reliable hydrate dissociation data for two mixed salt-organic inhibitor quaternary systems (CH₄-H₂O-NaCl-EG and CH₄-H₂O-KCl-EG) have been measured at pressures up to 50 MPa. These data are used to validate the predictive capabilities of the model for hydrate equilibria. Good agreement between experimental data and predictions is observed, demonstrating the reliability of the developed model. © 2004 Elsevier B.V. All rights reserved.