Aiming at exploring the dynamic changes in wettability within a nanoscale slit of coal during hot flue gas injection, a competitive wetting model of coal–water–multicomponent gas that considers real gas occurrence pressures was established in this study. Additionally, various methods that influence the wettability within the slit at different hot flue gas injection pressures were investigated, and the mechanism of wettability changes within the slit was elucidated based on the analyses on interaction energy, radial distribution function curve, molecular migration characteristics at the slit outlet, density distribution, and contact angle. The research findings are as follows. The intensities of the interaction energy between high-temperature and low-temperature water molecules differ markedly after the completion of hot flue gas injection at different pressures. Both the radial distribution function and the interaction energy indicate that the two types of water molecules fuse the most thoroughly at 20 MPa. At low pressures, the number of water molecules in the observation area changes slightly. The high-yielding period of the two types of water molecules at 20 MPa is 1.5 ns longer than that at 25 MPa, and the numbers of the two types of water molecules are less different at the same time at 20 MPa except for the case at 3 ns. After the injection, the densities of the preexisting water molecules and CO2 and the contact angle of the hot flue gas bubble demonstrate that the wettability transition within the slit is more complete at relatively high pressures (20 and 25 MPa) from two perspectives. At 20 MPa, the “re-absorption” is milder, and the bubble is milder and forms a smaller contact angle on the coal substrate. Based on the above research findings, it is concluded that raising the injection pressure of hot flue gas is conducive to the transition from water wetting to gas wetting and the elimination of the water lock effect. This research provides support for selecting the optimal hot flue gas injection pressure at the molecular level.
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