Molecular Dynamics Simulation of the Three-Phase Equilibrium Line of CO2 Hydrate with OPC Water Model

The three-phase coexistence line of the CO2 hydrate was determined using molecular dynamics (MD) simulations. By using the classical and modified Lorentz-Berthelot (LB) parameters, the simulations were carried out at 10 different pressures from 3 to 500 MPa. For the OPC water model, simulations with the classic and the modified LB parameters both showed negative deviations from the experimental values. For the TIP4P/Ice water model, good agreement with experimental equilibrium data can be achieved when the LB parameter is adjusted based on the solubility of CO2 in water. Our results also show that the influence of the water model on the equilibrium prediction is much larger than the CO2 model. Current simulations indicated that the H2O-H2O and H2O-CO2 cross-interactions' parameters might contribute equally to the accurate prediction of T3. According to our simulations, the prediction of T3 values showed relatively higher accuracy while using the combination of TIP4P/Ice water and EPM2 CO2 with modified LB parameter. Furthermore, varied χ values are recommended for accurate T3 estimation over a wide pressure range. The knowledge obtained in this study will be helpful for further accurate MD simulation of the process of CO2/CH4 replacement.