Water Solubility at Saturation for CO₂–CH₄ Mixtures at 323.2 K and 9.000 MPa

Abstract

The concentration of H 2 O dissolved in CO 2 –CH 4 supercritical fluids is an important parameter that can control shale permeability, affect CH 4 transmissivity, and ultimately impact the efficiency of CO 2 enhanced gas recovery (EGR) operations. Here, we use in situ high-pressure infrared (IR) spectroscopic titrations to quantify the solubility of H 2 O in six CO 2 –CH 4 mixtures, ranging from pure CO 2 to pure CH 4, at shallow shale reservoir conditions of 323.2 K and 9.000 MPa. Measured concentrations of H 2 O at saturation increase with increasing mole percent CO 2, and our results are in agreement with limited data available in the literature. We use these experimental results to benchmark three current thermodynamic multiphase routines: the mixed-solvent electrolyte (MSE), STOMP-COMP, and the Statistical Associating Fluid Theory for variable range Mie potentials (SAFT γ-Mie) equations of state. Of these models, MSE and STOMP-COMP accurately predict maximum H 2 O solubilities of the binary CO 2 –H 2 O and CH 4 –H 2 O systems, and they also reproduce the shape of the water solubility curve as a function of mole percent CO 2 . Hence, these routines should work well to predict H 2 O content in reservoir simulations and help to make informed decisions concerning injection strategies for CO 2 EGR in shale plays at shallow depths.