Experimental study and thermodynamic modeling of CO2+CH4 gas mixture hydrate phase equilibria for gas separation efficiency

Gas separation is a critical application of gas hydrates, and accurately predicting separation performance is crucial. In this study, we used thermodynamic calculations to predict the equilibrium phase of gas hydrates for various mole fractions of CO₂ + CH₄ gas mixtures. We also determined the mole fraction of each gas component trapped within the hydrate clathrate. To predict the equilibrium points, we used the Soave–Redlich–Kwong（(SRK) equation of state for the gas phase, the nonrandom two-liquid (NRTL)model for the liquid phase, and the Chen–Guo model for the hydrate phase. We modified the hydrate fugacity formula and introduced a new function to improve the accuracy of the Chen–Guo model. By incorporating experimental equilibrium results from our study and another study, we developed a correlation based on gas mixture composition and temperature, resulting in highly accurate predictions. The use of this new correlation for hydrate fugacity calculation significantly improved precision, as evidenced by an average absolute deviation percent of calculated pressures (AADP) of 1.34% for pure CO₂ and 1.25% for CH₄. When considering the 27 data points of different CO₂ + CH₄ mixtures, the AADP% was 1.98%.To implement the model to predict equilibrium phases, we used the Chen–Guo framework to determine the mole fraction of each gas component in the hydrate mixture. Interestingly, we discovered a linear correlation between the CO₂ mole fraction in the hydrate and equilibrium pressure, with a slope of approximately 0.001 and a y-intercept of less than one, for all gas compositions. Therefore, we can conclude that low thermodynamic conditions (temperature and pressure) result in a high CO₂ mole fraction in the hydrate phase and great separation efficiency.