Competitive adsorption of CH4/CO2 in shale nanopores during static and displacement process

During the development of shale gas, various issues such as low individual well production, rapid decline, limited reservoir control, and low recovery rates have arisen. Enhancing shale gas reservoir recovery rates has consistently been a focal point and challenge within the industry. Therefore, this paper employs molecular dynamic (MD) simulation methods to study the adsorption and diffusion characteristics of CH₄/CO₂ at different temperatures and mixing ratios. It compares the effects of temperature and CH₄/CO₂ molar ratio changes on the selectivity coefficient, adsorption capacity, and diffusion coefficient of CH₄/CO₂. The paper also plots the displacement interface and the function of CH₄/CO₂ injection/residual amounts over time. Furthermore, it analyzes the adsorption capacity of molecules on the graphene surface, the migration capacity of molecules in the slit, and the displacement process of CH₄ by CO₂ on the nanoscale, revealing the microscopic mechanism of CH₄/CO₂ competitive adsorption and displacement. The research results indicate that the influence of temperature on the selectivity coefficient is not significant, with an average decrease of 3% for every 20 K rise in temperature. Pressure has a more pronounced effect on the selectivity coefficient, with values around 1.4 at low pressures and around 1.2 at high pressures. Elevating the mole fraction of CO₂ in the binary gas mixture results in an increase in the total adsorption amount and an accelerated variation of adsorption amount with pressure. As the CH₄ mole fraction rises, the diffusion coefficient of CH₄ increases, while the diffusion coefficient of CO₂ diminishes with an increasing CO₂ mole fraction. Under identical conditions, CO₂ exhibits a stronger adsorption capacity over CH₄ in shale organic nanopores, resulting in a concave moon-shaped displacement interface in the model. The larger the pre-adsorption pressure of CO₂, the more intense the movement of CO₂ along the graphene surface, and the faster the diffusion speed of CO₂ along the wall. In a displacement pore (the pore space used to provide the displacement location or site) with a diameter of 3 nm, at smaller pressure differentials (≤10 MPa), the residual amount of CH₄ remains relatively stable without substantial alteration. However, at a pressure differential of 20 MPa, the residual amount of CH₄ decreases rapidly, and the displacement efficiency significantly improves.