Shale oil resources are abundant, but reservoirs exhibit strong heterogeneity with extremely low porosity and permeability, and their development is challenging. Carbon dioxide (CO₂) injection technology is crucial for efficient shale oil development. When CO₂ is dissolved in reservoir formation water, it undergoes a series of physical and chemical reactions with various rock minerals present in the reservoir. These reactions not only modify the reservoir environment but also lead to precipitation that impacts the development of the oil reservoir. In this paper, the effects of water–rock interaction on core porosity and permeability during CO₂ displacement are investigated by combining static and dynamic tests. The results reveal that the injection of CO₂ into the core leads to reactions between CO₂ and rock minerals upon dissolution in formation water. These reactions result in the formation of new minerals and the obstruction of clastic particles, thereby reducing core permeability. However, the generation of fine fractures through carbonic acid corrosion yields an increase in core permeability. The CO₂–water–rock reaction is significantly influenced by the PV number, pressure, and temperature. As the injected PV number increases, the degree of pore throat plugging gradually increases. As the pressure increases, the volume of larger pore spaces gradually decreases, resulting in an increase in the degree of pore blockage. However, when the pressure exceeds 20 MPa, the degree of carbonic acid dissolution will be enhanced, resulting in the formation of small cracks and an increase in the volume of small pores. As the temperature reaches the critical point, the degree of blockage of macropores gradually increases, and the blockage of small pores also occurs, which eventually leads to a decrease in core porosity.

Unlike conventional reservoirs, shale is particularly complex in its mineral composition. As typical components in shale reservoirs, clay and organic matter have different pore structures and strong interactions with fluids, resulting in complex fluid occurrence-states in shale. For example, there are both free water and adsorbed water in clay, and both free oil and ad/absorbed oil in organic matter. Key properties such as fluid content, organic/inorganic porosity, and permeability in clay-rich shale have been poorly characterized in previous studies. In this paper, we used a vacuum-imbibition experimental method combined with nuclear magnetic resonance technique and mathematical modeling to characterize the fluid content, organic/inorganic porosity, saturation, and permeability of clay-rich shale. We conducted vacuum-imbibition experiments on both shale samples and pure clay samples to distinguish the adsorbed oil and water in clay and organic matter. The effects of clay content and total organic matter content (TOC) on porosity and adsorbed-fluid content are then discussed. Our results show that, for the tested samples, organic porosity accounts for 26–76% of total porosity. The oil content in organic matter ranges from 29% to 69% of the total oil content, and 2% to 58% of the organic oil content is ad/absorbed in kerogen. The inorganic porosity has a weak positive correlation with clay content, and organic porosity increases with rising levels of organic matter content. The organic permeability is 1–3 orders of magnitude lower than the inorganic permeability.