GCMC-MD prediction of adsorption and diffusion behavior of shale gas in nanopores

• GCMC and MD are used to study adsorption and diffusion characteristics of CH 4 . • The adsorption amount of CH 4 increases with pressure and pore size. • The increased CO 2 content and temperature result in a decrease in CH 4 adsorption. • The diffusion coefficient is proportional to the pore size and temperature. In natural gas exploitation, CO 2 has become an effective development method with its advantages of adsorption replacement from CH 4 , through continuous convection displacement and gas reservoir energy supplement for CH 4 . However, one limitation is how to explain the behavior of adsorption replacement based on microscopic mechanisms. In this work, grand canonical Monte Carlo incorporating with molecular dynamics (GCMC-MD) method are used to numerically simulate the adsorption and diffusion characteristics of CH 4 in quartz pores with various sizes (1, 1.5 and 2 nm), temperature, pressure and CO 2 content. Simulation results indicate that the adsorption amount of CH 4 decreases as CO 2 content and temperature rise, while it increases with increments in pressure and pore size. Meanwhile the CH 4 density peak occurs only on the pore wall for 1 nm pore with a thickness in 3.8 Å, while its secondary peak appears in the pore center as the pore size and pressure increase. The diffusion coefficient is proportional to the pore size and temperature, but goes down sharply with increasing pressure. Compared to CO 2 diffusion properties, CH 4 diffusion is more likely. According to the selectivity parameter S CH4 / CO2 , CH 4 shows the characteristics of being easily displaced under low pressure and small pores. The energy of CH 4 adsorption sites is always higher than that of CO 2 , and the energy of adsorption sites is higher with large pore sizes. The adsorption behaviors of CH 4 and CO 2 are regards as physical adsorption according to their maximum adsorption heat less than 42 kJ/mol. In addition, the increments in pressure and CO 2 content can promote the average isosteric heat of adsorption. This study expands the understanding of the adsorption and diffusion behavior of shale gas in nanopores and also provides theoretical and technical support for the development of shale gas.