Effect of water on methane adsorption on the kaolinite (0 0 1) surface based on molecular simulations

Abstract

CH4 adsorption isotherms of kaolinite with moisture contents ranging from 0 to 5 wt% water, the effects of water on maximum adsorption capacity, kaolinite swelling, and radial distribution function were modelled by the implementing combined Monte Carlo (MC) and molecular dynamics (MD) simulations at 293.15 K (20 °C) and a pressure range of 1–20 MPa. The simulation results showed that the absolute adsorption of CH4 on both dry and moist kaolinite followed a Langmuir isotherm within the simulated pressure range, and both the adsorption capacity and the rate of CH4 adsorption decreased with the water content increases. The adsorption isosteric heats of CH4 on kaolinite decreased linearly with increasing water content, indicating that at higher water contents, the interaction energy between the CH4 and kaolinite was weaker. The interaction between kaolinite and water dominates and was the main contributing factor to kaolinite clay swelling. Water molecules were preferentially adsorbed onto oxygen and hydrogen atoms in kaolinite, while methane showed a tendency to be adsorbed only onto oxygen. The simulation results of our study provide the quantitative analysis of effect of water on CH4 adsorption capacity, adsorption rate, and interaction energy from a microscopic perspective. We hope that our study will contribute to the development of strategies for the further exploration of coal bed methane and shale gas.