Pore changes of slickwater-containing shale under supercritical CO2 treatment

Abstract

Application of liquid CO2-slickwater hybrid fracturing technology can significantly improve the energy-enhancing efficiency and fracturing fluid flowback efficiency of shale reservoirs. However, supercritical CO2 (ScCO2) fluid and slickwater are inevitably retained in reservoirs after fracturing, resulting in limited understanding of the changes of shale pore structure, further impacting the evaluation of the gas adsorption and transportation behaviors as well as CO2 sequestration capacity in shale reservoirs. Therefore, the influences of the ScCO2-slickwater coupling effect on shale pore structure was analyzed by using X-ray diffraction, low-pressure nitrogen gas adsorption (N2GA), mercury intrusion porosimetry (MIP), field emission-scanning electron microscopy (FE-SEM), and fractal analysis. After ScCO2-slickwater treatment, the calcite and albite contents decreased, while the quartz and clay minerals contents increased in shale. The increase in number of micropores and mesopores and the reduction in number of macropores were observed by a combination of N2GA and MIP, which led to the total specific surface area (TSSA) and total pore volume (TPV) of the shale enlarged, while the average pore size reduced. Meanwhile, the fractal dimensions calculated by N2GA (D1, D2) and MIP (D3) were raised, indicating that pore surface roughness and structural complexity were strengthened. D1, D2 and D3 can roughly reflect fractal characteristic of micropores (<3.5 nm), mesopores (3.5–50 nm) and macropores (>50 nm), respectively. Thus, D1 and D2/D3 can be used to evaluate the gas adsorption and flow behaviors of shale, respectively. By analyzing the control experimental results of ScCO2-water and He-slickwater treatment and the FE-SEM images, shale pore changes after ScCO2-slickwater treatment can be explained by CO2 extraction and dissolution, secondary mineral precipitation and polyacrylamide adsorption. After treatment, the increase of micropores and mesopores as well as TSSA and TPV makes the gas-adsorption capacity of shale improved, showing that the coupling effect of ScCO2-slickwater can not only improve shale gas productivity, but also benefit geological storage of CO2.