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Nanoscale pore structure characteristics and their main controlling factors are key elements affecting the gas storage capacity, permeability, and the accumulation mechanism of shale. A multidisciplinary analytical program was applied to quantify the pore structure of all sizes of Xiamaling shale from Zhangjiakou, Hebei. The result implies that Mercury injection porosimetry (MIP) and low-pressure N2 curves of the samples can be divided into three and four types, respectively, reflecting different connectivity performances. The maximum CO2 adsorbing capacity increases with increasing total organic carbon (TOC) content, pore volume (PV), and surface area (SA) of the micropores are distributed in a three-peak type. The full-scale pore structure distribution characteristics reveal the coexistence of multiple peaks with multiple dominant scales and bi-peak forms with mesopores and micropores. The porosity positively correlates with the TOC and quartz content, but negatively correlates with clay mineral content. Organic matter (OM) is the main contributor to micropore and mesopore development. Smectite and illite/smectite (I/S) assist the development of the PV and SA of pores with different size. Illite promotes the development of the nanoscale PV, but is detrimental to the development of the SA. Thermal maturity controls the evolution of pores with different size, and the evolution model for the TOC-normalized PVs of different diameter scales is established. Residual hydrocarbon is mainly accumulated in micropores sized 0.3 to 1.0 nm and mesopores sized 40 nm, 2 nm and less than 10 nm. Since the samples were extracted, the pore space occupied by residual hydrocarbon was released, resulting in a remarkable increase in PV and SA.

Coalbed methane primarily exists as adsorbed gas within the microscopic pores and fractures of coal. However, the complex pore structure of deep coal seams and its quantitative relationship with methane adsorption capacity remain unclear. This study investigated nine samples from a coal seam in the Ningwu Basin, representing different burial depths, including five middle-shallow and four deep burials. This was accomplished through a series of experiments, including high-pressure mercury injection (HPMI), low-temperature nitrogen adsorption (LTGA–N2), low-pressure carbon dioxide adsorption (LPGA–CO2), and high-pressure (30 MPa) methane isothermal adsorption (HPGA–CH4). The study revealed the characteristics of the pore structure in deep coal seams and their differences compared to those in middle-shallow coal seams. Moreover, it clarified the mechanism by which the pore structure influences CH4 adsorption capacity. Given the differences in methane adsorption mechanisms at various pore scales, a novel method for quantitatively assessing the methane adsorption capacity using pore structure parameters is proposed. The results showed that the micropore pore volume and specific surface area of the deep coal seam were significantly higher than those of the middle-shallow coal seams. In contrast, the development of mesopores and macropores was relatively limited. The CH4 adsorption capacity of a coal seam was calculated using pore structure parameters across multiple scales, considering the coexistence of two-dimensional “filling adsorption” and three-dimensional “monolayer adsorption” mechanisms. The calculated capacity VL’ closely matched the measured value of VL, with error of less than 10%. The degree of micropore development is the main factor influencing the accuracy of this method. Therefore, using pore structure parameters at different scales to calculate methane adsorption capacity is effective and feasible for deep coal seams with extensive micropore development. This study established a connection between microscopic pore structure and macroscopic methane adsorption capacity, offering a novel method to determine the methane adsorption capacity of deep coal seams.

The nano-scale pore systems in shale reservoirs control shale gas transportation and aggregation, which is of great significance for the resource evaluation of shale oil and gas and the selection of a “sweet spot”. Taking twelve marine shale samples from the Wufeng–Longmaxi Formation in the Zigong area, southwest Sichuan Basin, as the research target, we carried out a series of experiments, including total organic carbon (TOC) analysis, X-ray diffraction (XRD), gas adsorption (CO2 + N2), and mercury intrusion porosimetry (MIP), to study the full-scale pore structure characterization and controlling factors of pore volume and specific surface area. The results presented the following findings. (1) Marine shale samples from the target area are rich in organic matter, with an average TOC value of 3.86%; additionally, the mineral composition was dominated by quartz and clay minerals, with average contents of 44.1% and 31.4%, respectively. (2) The full-scale pore size distribution curves of pore volume developed multimodally, with the main peaks at 0.5 nm–2 nm, 3 nm–6 nm, and 700 nm–2.2 um; moreover, the full-scale pore size distribution curves of a specific surface area developed unimodally, with the main peak ranging from 0.5 nm to 1.2 nm. (3) Pore volume was mainly contributed by mesopores and macropores, with an average contribution of 46.66% and 42.42%, respectively, while the contribution of micropores was only 10.91%. The specific surface area was mainly contributed by micropores and mesopores, with an average contribution of 64.63% and 29.22%, respectively, whereas the contribution of micropores was only 6.15%. (4) The TOC content mainly controlled the pore volume and specific surface area of micropores and mesopores, while the clay and feldspar content generally controlled the pore volume and specific surface area of macropores. Additionally, the quartz content had an inhibitory effect on the development of all pore types. These results will help researchers understand the laws of gas accumulation and migration.

To elucidate the gas adsorption characteristics of medium-rank coal, this study collected samples from fresh mining faces in the Qinshui Basin. A series of experiments were conducted, including low-temperature carbon dioxide adsorption, low-temperature liquid nitrogen adsorption, mercury intrusion, and methane isothermal adsorption experiments, which clarify the pore structure characteristics of medium-rank coals, reveal the gas adsorption behavior in medium-rank coal, and identify the control mechanism. The results demonstrate that the modified Dubinin–Radushkevich (D-R) isothermal adsorption model accurately describes the gas adsorption in medium-rank coal, with fitting errors remaining below 1%. Comprehensive pore structure analysis reveals that the coal pore volume consists primarily of absorption pores (<2 nm), transitional pores (10–100 nm), and seepage pores (>100 nm), while the specific surface area is predominantly contributed by absorption pores (<2 nm). At low pressures, gas molecules form monolayer adsorption on absorption pore (<2 nm) and adsorption pore (2–10 nm) surfaces. With increasing pressure, multilayer adsorption dominates. As pore filling approaches the maximum capacity, the adsorption rate decreases progressively until reaching an equilibrium, at which point the adsorption capacity attains its saturation limit. The adsorption data of the gas in medium-rank coal can be explained by the improved D-R isothermal adsorption model. The priority of gas filling in pores is different, and the absorption pore is normally better than the adsorption pore. The results provide a new idea and understanding for the further study of the coalbed gas adsorption mechanism.

The complex geological environment in deep layers results in differences in the pore and fracture structures and states of coalbed methane (CBM) occurrences between deep and shallow coal reservoirs. The coexistence of multiphase gases endows deep CBM with both “conventional” and “unconventional” geological attributes. Based on systematically collected coal samples from the Benxi Formation in the Daning–Jixian area of the Ordos Basin, high-pressure mercury intrusion (HPMI), low-temperature N2 adsorption (LTN2A), and low-pressure CO2 adsorption (LPCO2A) experiments were conducted to characterise the pore structures across the full pore size distribution of the Benxi Formation coals. The aim of this research is to gain an in-depth understanding of the pore size distribution of full-size pores and to explore the factors influencing their pore structure and control over the gas content in coal reservoirs. The results indicate that the pore size distribution of the coal samples from the Benxi Formation in the study area is unimodal and that nanopores are present. The pore sizes are relatively small, with an average total pore volume (PV) of 0.073 cm3/g and an average total specific surface area (SSA) of 227.87 m2/g. Among these, micropores account for 92.26% of the total PV and 99.57% of the total SSA, making micropores the primary contributors to the gas storage space in the Benxi Formation coals. Mesopores and macropores contribute relatively little to the PV and SSA, which is unfavourable for CBM permeability. The development of pores in the Benxi Formation coals in the study area is influenced by the coal maturity, vitrinite content, and ash yield. Generally, the PV increases when the coal’s rank increases; an increase in the vitrinite content promotes the development of micropores, whereas a relatively high ash yield leads to decreases in the PV and SSA. The influence of the SSAs of coal pores on the gas content is reflected mainly by its effect on the adsorbed gas content. Since adsorbed gas molecules exist mainly in coal pores in the adsorbed state, the SSAs of coal pores strongly affect the storage capacity of coal for adsorbed gas.

Shale and coal in the transitional marine–continental facies of the Ordos Basin serve as unconventional natural gas reservoirs, with their pore structures controlling gas adsorption characteristics and occurrence states. To quantitatively characterize the pore structure features and differences between these two reservoirs, this study takes the Shanxi Formation shale and coal in the Daning–Jixian area on the eastern margin of the Ordos Basin as examples. Field-emission scanning electron microscopy (FE-SEM), high-pressure mercury intrusion, low-temperature N2 adsorption, and low-pressure CO2 adsorption experiments were employed to analyze and compare the full-scale pore structures of the shale and coal reservoirs. Combined with methane isothermal adsorption experiments, the gas adsorption capacity and its differences in these reservoirs were investigated. The results indicate that the average total organic carbon (TOC) content of shale is 2.66%, with well-developed organic pores, inorganic pores, and microfractures. Organic pores are the most common, typically occurring densely and in clusters. The average TOC content of coal is 74.22%, with organic gas pores being the dominant pore type, significantly larger in diameter than those in transitional marine–continental facies shale and marine shale. In coal, micropores contribute the most to pore volume, while mesopores and macropores contribute less. In shale, mesopores dominate, followed by micropores, with macropores being underdeveloped. Both coal and shale exhibit a high SSA primarily contributed by micropores, with organic matter serving as the material basis for micropore development. The methane adsorption capacity of coal is 8–29 times higher than that of shale. Coal contains abundant organic micropores, providing a large SSA and numerous adsorption sites for methane, facilitating gas adsorption and storage. This study comprehensively reveals the similarities and differences in pore structures between transitional marine–continental facies shale and coal reservoirs in the Ordos Basin at the microscale, providing a scientific basis for the precise evaluation and development of unconventional oil and gas resources.