Investigation of methane adsorption mechanism on Longmaxi shale by combining the micropore filling and monolayer coverage theories

Understanding the methane adsorption mechanism is critical for studying shale gas storage and transport in shale nanopores. In this work, we conducted low-pressure nitrogen adsorption (LPNA), scanning electron microscopy (SEM), and high-pressure methane adsorption experiments on seven shale samples from the Longmaxi formation in Sichuan basin. LPNA and SEM results show that pores in the shale samples are mainly nanometer-sized and have a broad size distribution. We have also shown that methane should be not only adsorbed in micropores (< 2 nm) but also in mesopores (2-50 nm) by two hypotheses. Therefore, we established a novel DA-LF model by combining the micropore filling and monolayer coverage theories to describe the methane adsorption process in shale. This new model can fit the high-pressure isotherms quite well, and the fitting error of this new model is slightly smaller than the commonly used D-A and L-F models. The absolute adsorption isotherms and the capacities for micropores and mesopores can be calculated using this new model separately, showing that 77% to 97% of methane molecules are adsorbed in micropores. In addition, we conclude that the methane adsorption mechanism in shale is: the majority of methane molecules are filled in micropores, and the remainder are monolayer-adsorbed in mesopores. It is anticipated that our results provide a more accurate explanation of the shale gas adsorption mechanism in shale formations.