Response of pore network fractal dimensions and gas adsorption capacities of shales exposed to supercritical CO2: Implications for CH4 recovery and carbon sequestration

The injection of CO2 into shale reservoirs potentially increases rates and masses of CH4 recovery and simultaneously contributes to the sequestration of CO2. At typical reservoir conditions (T>31.08 degrees C, P>7.38 MPa) the CO2 will be supercritical. We compile, analyze, and supplement experimental data of shales from several basins across China, and use X-ray diffraction, scanning electron microscopy and low-pressure gas adsorption to characterize variations in shale pore structure before and after supercritical CO2 (ScCO2) treatment, and supplement these with CH4/CO2 adsorption experiments to characterize changes in shale adsorption capacity. The results show that clay and carbonate contents significantly decrease, and the relative content of quartz is increased after ScCO2 treatment. Pore structure changes significantly after ScCO2 treatment, with the majority of the shales showing a decrease in total specific surface area and total pore volume and an increase in average pore size - indicating the transformation of some micropores and smaller mesopores into mesopores and macropores. After ScCO2 treatment, the experimentally derived absolute adsorption volumes of both CH4 and CO2 decrease, and the volumes of both CH4 and CO2 fitting a Langmuir isotherm decrease with an increase in treatment pressure and increase with an increase in temperature. The adsorption selectivity factors & alpha; CO2/CH4 all remain greater than 1 with & alpha;CO2/CH4 primarily controlled by the pore structure. The fractal dimension is positively correlated with Langmuir volume and negatively correlated with Langmuir pressure while the fractal dimensions are negatively correlated with & alpha;CO2/CH4. The selectivity factor & alpha;CO2/CH4 decreases rapidly above a fractal dimension threshold (D1>2.65, D2>2.80). This paper further reveals critical interactions between ScCO2 and shale and defines controls on and of pore structure and adsorption capacity to speculate on physical and chemical storage mechanisms of CO2 in shale reservoirs. This provides several theoretical bases for shale gas recovery and the sequestration of CO2.& COPY; 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).