Temperature and pressure conditions of deep shale are beyond experiment range, and the amount of adsorbed gas is difficult to determine. To predict the adsorbed gas content of deep shales under formation conditions, isothermal adsorption experiments and model building were conducted on shale samples from Longmaxi Formation in China. A temperature-dependent adsorption model based on the Langmuir equation is proposed, which can be well-fitted by observed isotherms with a high correlation coefficient. Based on the fitted parameters at 303.15 K, the isothermal adsorption curves at 333.15 K, 363.15 K, and 393.15 K are predicted, showing a good agreement with experimental curves available. Compared with previous prediction methods, the biggest advantage of the proposed method is that it can be carried out only based on one-time isothermal adsorption experiment. Based on the predictions, the downward trend of the excess adsorption curves will slow down under high temperature and pressure conditions, and when the pressure reaches a certain level (> 80 MPa), the temperature has little effect on the excess adsorption capacity. While for absolute adsorption, the gas adsorption reaches saturation much slowly at high temperature, it can also reach saturation under formation pressure. Under the burial depth of marine shale, temperature plays a major role in controlling the adsorbed gas, resulting in the decrease of adsorbed gas content in deep shale, and its ratio will further decrease as the depth increases.

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 nanometersized 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.