Evolution of Pore Spaces in Marine Organic-Rich Shale: Insights from Multi-Scale Analysis of a Permian-Pennsylvanian Sample

The quantitative evolution pattern of pore space and genetic pore types along the maturation process in organic-rich shale reservoirs is unclear, which affects the assessment of shale storage capacity and petroleum production. A black shale outcrop sample from Kansas that is of Permian-Pennsylvanian age was collected and subjected to thermal simulation experiments at 10 different maturity stages to understand the pore sizes and pore types. Scanning electron microscopy (SEM) and image processing were used to characterize the full-scale pore-size distribution and volume evolution of this shale sample by combining low-temperature gas (CO2 and N-2) physisorption and mercury intrusion porosimetry (MIP) in order to discuss the effects of hydrocarbon generation and diagenesis (HG&D) on pore development at different pore sizes. The study showed that the original shale sample is dominated by slit-like pores, with mainly organic matter (OM) pores distributed in 0-100 nm, intraparticle pores (Intra-P) of clays distributed in 30-100 nm, and interparticle pores (Inter-P) distributed in 100-1000 nm. With the increase in maturity or Ro, the OM pores increased gradually, and the OM pore-size distribution diverged to the two poles. In the oil generation stage, the OM pores were distributed in the range of 30-100 nm, while in the gas generation stage, the OM-hosted pores were mainly distributed in the range of 10-20 nm and 100-500 nm. Further into the over-maturity stage, the OM pores were mainly distributed in the range of 0-10 nm and >100 nm. The pore volume distribution across the whole pore sizes showed that the pore volume of low-maturity shale samples was mainly provided by 100-1000 nm (macropores), and the pore volumes of 0-2 nm, 30-100 nm and 1000+ nm pores gradually increase with increasing thermal maturity, with the final pore-size distribution having four peaks at 0-2, 30-100, 500-1000 nm, and 10-100 mu m. Hydrocarbon generation mainly affects the pore volume in the 0-2 nm and 100-1000 nm intervals, with a positive correlation. The 2-30 nm and 30-100 nm pores were likely controlled by diagenesis, such as mineral transformation, illitization, and cementation during the maturation process.