2D and 3D nanopore characterization of gas shale in Longmaxi formation based on FIB-SEM

Studying complex pore structures is the key to understanding the mechanism of shale gas accumulation. FIB-SEM (focused ion beam-scanning electron microscope) is the mainstream and effective instrument for imaging nanopores in gas shales. Based on this technology, 2D and 3D characteristics of shale samples from Lower Silurian Longmaxi formation in southern Sichuan Basin were investigated. 2D experimental results show that the pores in shale are nanometer-sized, and the structure of those nanopores can be classified into three types: organic pores, inorganic pores and micro fractures. Among the three types, organic pores are dominantly developed in the OM (organic matter) with three patterns such as continuous distributed OM, OM between clay minerals and OM between pyrite particles, and the size of organic pores range from 5 nm to 200 nm.Inveresly, inorganic pores and micro fractures are less developed in the Longmaxi shales. 3D digital rocks were reconstructed and segmented by 600 continuous images by FIB cutting and SEM imaging simultaneously. The pore size distribution and porosity can be calculated by this 3D digital core, showing that its average value is 32 nm and porosity is 3.62%.The 3D digital porosity is higher than its helium porosity, which can be regarded as one important parameter for evaluation of shale gas reserves. The 2D and 3D characterized results suggest that the nanometer-sized pores in organic matter take up the fundamental storage space for the Longmaxi shale. These characteristics have contributed to the preservation of shale gas in this complex tectonic area.     

Characteristics and controlling factors of reservoir space of mudstone and shale in Es3x in the Zhanhua Sag

Zhanhua Sag is a widely accepted target zone with huge exploration and development potential for shale oil and shale gas resources. Many detailed studies have been undertaken around the geochemistry of the lower section of the third member of the Shahejie Formation (Es3x), while few studies have focused on the reservoir. In this study, based on the mineralogical features and geochemical characteristics, and by using statistical methods, the characteristics and controlling factors of reservoir space of mudstone and shale in Es3x in the Zhanhua Sag are explored through field-emission scanning electron microscopy (FE-SEM), high pressure mercury injection capillary pressure (MICP), and nuclear magnetic resonance (NMR) techniques. Three major findings were obtained. ① There are micropores and microfractures in the reservoir space, which include intergranular pores, clay intercrystal pores, pyrite intercrystal pores, dissolved pores, structural microfractures, and bedding microfractures. ② According to the features of pore size distribution (PSD), the pore distribution can be divided into the following three categories: 0–50 nm, 50 nm–2 μm, and >2 μm; the average volumes of these components are 0.01079 mL g⁻¹, 0.00361 mL g⁻¹, and 0.00355 mL g⁻¹, respectively, thus showing that the pores whose radii are distributed at 0–50 nm form the most important reservoir space (though those with the 50 nm–2 μm and >2 μm radii are also important and cannot be ignored). ③ There are different controlling factors when it comes to different scale pores. Based on statistics and FE-SEM results, the dissolved pores in calcite were determined to be the controlling factor for the 0–50 nm portion, the intercrystalline pores in clay and pyrite, and intergranular pores between authigenic minerals (calcite, dolomite, and pyrite) and clastic minerals (calcite and dolomite) were determined to be the controlling factors for the 50 nm–2 μm portion, and the structural microfractures and bedding microfractures were determined to be the main factors for the >2 μm portion. Furthermore, it is the brittle minerals content and bedded structure that control the microfractures. This study thus clarifies the types and characteristics of reservoir space and identifies pore structure controlling factors of mudstone and shale in Es3x in the Zhanhua Sag; this information has important significance for future reservoir evaluations.     

Mineral types and organic matters of the Ordovician-Silurian Wufeng and Longmaxi Shale in the Sichuan Basin,China: Implications for pore systems,diagenetic pathways,and reservoir quality in fine-grained sedimentary rocks

Mineral types (detrital and authigenic) and organic-matter components of the Ordovician-Silurian Wufeng and Longmaxi Shale (siliceous, silty, argillaceous, and calcareous/dolomitic shales) in the Sichuan Basin, China are used as a case study to understand the control of grain assemblages and organic matter on pores systems, diagenetic pathway, and reservoir quality in fine-grained sedimentary rocks. This study has been achieved using a combination of petrographic, geochemical, and mercury intrusion methods. The results reveal that siliceous shale comprises an abundant amount of diagenetic quartz (40–60% by volume), and authigenic microcrystalline quartz aggregates inhibit compaction and preserve internal primary pores as rigid framework for oil filling during oil window. Although silty shale contains a large number of detrital silt-size grains (30–50% by volume), which is beneficial to preserve interparticle pores, the volumetric contribution of interparticle pores (mainly macropores) is small. Argillaceous shale with abundant extrabasinal clay minerals (>50% by volume) undergoes mechanical and chemical compactions during burial, leading to a near-absence of primary interparticle pores, while pores preserved between clay platelets are dominant with more than 10 nm in pore size. Pore-filling calcite and dolomite precipitated during early diagenesis inhibit later compaction in calcareous/dolomitic shale, but the cementation significantly reduces the primary interparticle pores. Pore-throat size distributions of dolomitic shale show a similar trend with silty shale. Besides argillaceous shale, all of the other lithofacies are dominated by OM pores, which contribute more micropores and mesopores and is positively related to TOC and quartz contents. The relationship between pore-throat size and pore volume shows that most pore volumes are provided by pore throats with diameters <50 nm, with a proportion in the order of siliceous (80.3%) > calcareous/dolomitic (78.4%) > silty (74.9%) > argillaceous (61.3%) shales. In addition, development degree and pore size of OM pores in different diagenetic pathway with the same OM type and maturity show an obvious difference. Therefore, we suggest that the development of OM pores should take OM occurrence into account, which is related to physical interaction between OM and inorganic minerals during burial diagenesis. Migrated OM in siliceous shale with its large connected networks is beneficial for forming more and larger pores during gas window. The result of the present work implies that the study of mineral types (detrital and authigenic) and organic matter-pores are better understanding the reservoir quality in fine-grained sedimentary rocks.     

Evolution of porosity and pore types in organic-rich,calcareous, Lower Toarcian Posidonia Shale

Low and high resolution petrographic studies have been combined with mineralogical, TOC, RockEval and porosity data to investigate controls on the evolution of porosity in stratigraphically equivalent immature, oil-window and gas-window samples from the Lower Toarcian Posidonia Shale formation. A series of 26 samples from three boreholes (Wickensen, Harderode and Haddessen) in the Hils syncline was investigated. The main primary components of the shales are microfossiferous calcite (30–50%), clay minerals (20–30%) and Type II organic matter (TOC = 7–15%, HI = 630–720 mg/gC in immature samples). Characteristic sub-centimetric light and dark lamination reflects rapid changes in the relative supply of these components. Total porosities decrease from 10 to 14% at Ro = 0.5% to 3–5% at Ro = 0.9% and then increase to 9–12% at Ro = 1.45%. These maturity-related porosity changes can be explained by (a) the primary composition of the shales, (b) carbonate diagenesis, (c) compaction and (d) the maturation, micro-migration, local trapping and gasification of heterogeneous organic phases. Calcite undergoes dissolution and reprecipitation reactions throughout the maturation sequence. Pores quantifiable in SEM (>ca. 50 nm) account for 14–25% of total porosity. At Ro = 0.5%, SEM-visible macropores¹ are associated mainly with biogenic calcite. At this maturity, clays and organic matter are not visibly porous but nevertheless hold most of the shale porosity. Porosity loss into the oil window reflects (a) compaction, (b) carbonate cementation and (c) perhaps the swelling of kerogen by retained oil. In addition, porosity is occluded by a range of bituminous phases, especially in microfossil macropores and microfractures. In the gas window, mineral-hosted porosity is still the primary form of macroporosity, most commonly observed at the organic-inorganic interface. Increasing porosity into the gas window also coincides with the formation of isolated, spongy and complex meso- and macropores within organic particles, related to thermal cracking and gas generation. This intraorganic porosity is highly heterogeneous: point-counted macroporosity of individual organic particles ranges from 0 to 40%, with 65% of organic particles containing no macropores. We suggest that this reflects the physicochemical heterogeneity of the organic phases plus the variable mechanical protection afforded by the mineral matrix to allow macroporosity to be retained. The development of organic macroporosity cannot alone account for the porosity increase observed from oil to gas window; major contributions also come from the increased volume of organic micro- and meso-porosity, and perhaps by kerogen shrinkage.     

Pore characteristic analysis of a lacustrine shale: A case study in the Ordos Basin,NW China

Organic shales deposited in a continental environment are well developed in the Ordos Basin, NW China, which is rich in hydrocarbons. However, previous research concerning shales has predominantly focused on marine shales and barely on continental shales. In this study, geochemical and mineralogical analyses, high-pressure mercury intrusion and low-pressure adsorption were performed on 18 continental shale samples obtained from a currently active shale gas play, the Chang 7 member of Yanchang Formation in the Ordos Basin. A comparison of all these techniques is provided for characterizing the complex pore structure of continental shales.Geochemical analysis reveals total organic carbon (TOC) values ranging from 0.47% to 11.44%, indicating that there is abundant organic matter (OM) in the study area. Kerogen analysis shows vitrinite reflectance (Ro) of 0.68%–1.02%, indicating that kerogen is at a mature oil generation stage. X-ray diffraction mineralogy (XRD) analysis indicates that the dominant mineral constituents of shale samples are clay minerals (which mainly consist of illite, chlorite, kaolinite, and negligible amounts of montmorillonite), quartz and feldspar, followed by low carbonate content. All-scale pore size analysis indicates that the pore size distribution (PSD) of shale pores is mainly from 0.3 to 60 nm. Note that accuracy of all-scale PSD analysis decreases for pores less than 0.3 nm and more than 10 μm. Experimental analysis indicates that mesopores (2–50 nm) are dominant in continental shales, followed by micropores (<2 nm) and macropores (50 nm–10 μm). Mesopores have the largest contribution to pore volume (PV) and specific surface area (SSA). In addition, plate- and sheet-shaped pores are dominant with poor connectivity, followed by hybrid pores. Results of research on factors controlling pore structure development show that it is principally controlled by clay mineral contents and Ro, and this is different from marine systems. This study has important significance in gaining a comprehensive understanding of continental shale pore structure and the shale gas storage–seepage mechanism.     

Multiple controls on the paleoenvironment of the Early Cambrian marine black shales in the Sichuan Basin,SW China: Geochemical and organic carbon isotopic evidence

In order to understand the paleoenvironment of the Early Cambrian black shale deposition in the western part of the Yangtze Block, geochemical and organic carbon isotopic studies have been performed on two wells that have drilled through the Qiongzhusi Formation in the central and southeastern parts of Sichuan Basin. It shows that the lowest part of the Qiongzhusi Formation has high TOC abundance, while the middle and upper parts display relative low TOC content. Redox-sensitive element (Mo) and trace elemental redox indices (e.g., Ni/Co, V/Cr, U/Th and V/(V + Ni)) suggest that the high-TOC layers were deposited under anoxic conditions, whereas the low-TOC layers under relatively dysoxic/oxic conditions. The relationship of the enrichment factors of Mo and U further shows a transition from suboxic low-TOC layers to euxinic high-TOC layers. On the basis of the Mo-TOC relationship, the Qiongzhusi Formation black shales were deposited in a basin under moderately restricted conditions. Organic carbon isotopes display temporal variations in the Qiongzhusi Formation, with a positive excursion of δ¹³C_org values in the lower part and a continuous positive shift in the middle and upper parts. All these geochemical and isotopic criteria indicate a paleoenvironmental change from bottom anoxic to middle and upper dysoxic/oxic conditions for the Qiongzhusi Formation black shales. The correlation of organic carbon isotopic data for the Lower Cambrian black shales in different regions of the Yangtze Block shows consistent positive excursion of δ¹³C_org values in the lower part for each section. This excursion can be ascribed to the widespread Early Cambrian transgression in the Yangtze Block, under which black shales were deposited.     

Properties and shale oil potential of saline lacustrine shales in the Qianjiang Depression,Jianghan Basin,China

The geochemical and petrographic characteristics of saline lacustrine shales from the Qianjiang Formation, Jianghan Basin were investigated by organic geochemical analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and low pressure nitrogen adsorption analysis. The results indicate that: the saline lacustrine shales of Eq3 member with high oil content are characterized by type I and type II oil-prone kerogen, variable TOC contents (1.0–10.0 wt%) and an early-maturity stage (R_o ranges between 0.41 and 0.76%). The mineral compositions of Eq3 saline shale show strong heterogeneity: brittle intervals with high contents of quartz and carbonate are frequently alternated with ductile intervals with high glauberite and clay contents. This combination might be beneficial for oil accumulation, but may cause significant challenges for the hydraulic stimulation strategy and long-term production of shale oil. The interparticle pores and intraparticle pores dominate the pore system of Eq3 shale, and organic matter hosted pores are absent. Widely distributed fractures, especially tectonic fractures, might play a key role in hydrocarbon migration and accumulation. The pore network is contributed to by both large size inorganic pores and abundant micro-factures, leading to a relatively high porosity (2.8–30.6%) and permeability (0.045–6.27 md) within the saline shale reservoir, which could enhance the flow ability and storage capacity of oil. The oil content (S₁ × 100/TOC, mg HC/g TOC and S₁, mg HC/g rock) and brittleness data demonstrate that the Eq3^3x section has both great potential for being a producible oil resource and hydraulic fracturing. Considering the hydrocarbon generation efficiency and properties of oil, the mature shale of Eq3 in the subsidence center of the Qianjiang Depression would be the most favorable zone for shale oil exploitation.     

Effects of composition and pore structure on the reservoir gas capacity of Carboniferous shale from Qaidam Basin,China

Shale adsorption and breakthrough pressure are important indicators of shale gas development and key factors in evaluating the reservoir capacities of shales. In this study, geochemical tests, pore-structure tests, methane adsorption tests, and breakthrough-pressure tests were conducted on shales from the Carboniferous Hurleg Formation in eastern Qaidam Basin. The effects of the shale compositions and pore structures on the adsorption and breakthrough pressures were studied, and the reservoir capacities of the shales were evaluated by analyzing the shale adsorptions and sealing effects. The results indicate that the organic carbon content was only one of factors in affecting the adsorption capacity of the shale samples while the effect of the clay minerals was limited. Based on the positive correlation between the adsorption capacity and specific surface area of the shale, the specific surface area of the micropores can be used as an indicator to determine the adsorption capacity of shale. The micro-fracturing of brittle minerals, such as quartz, create a primary path for shale gas breakthrough, whereas the expansion of clay minerals with water greatly increases the breakthrough pressure in the shale samples. Methane adsorption tests showed that maximum methane adsorption for shale samples Z045 and S039 WAS 0.107 and 0.09655 mmol/g, respectively. The breakthrough pressure was 39.36 MPa for sample S039, maintained for 13 days throughout the experiment; however, no breakthrough was observed in sample Z045 when subjected to an injected pressure of 40 MPa for 26 days. This indicates that sample Z045, corresponding to a depth of 846.24 m, exhibited higher adsorption capacity and a better reservoir-sealing effect than sample S039 (498.4 m depth). This study provides useful information for future studies of Qaidam Basin shale gas exploration and development and for evaluation of shale quality.     

Novel 3D centimetre-to nano-scale quantification of an organic-rich mudstone: The Carboniferous Bowland Shale,Northern England

X-ray computed tomography and serial block face scanning electron microscopy imaging techniques were used to produce 3D images with a resolution spanning three orders of magnitude from ∼7.7 μm to 7 nm for one typical Bowland Shale sample from Northern England, identified as the largest potential shale gas reservoir in the UK. These images were used to quantitatively assess the size, geometry and connectivity of pores and organic matter. The data revealed four types of porosity: intra-organic pores, organic interface pores, intra- and inter-mineral pores. Pore sizes are bimodal, with peaks at 0.2 μm and 0.04 μm corresponding to pores located at organic–mineral interfaces and within organic matter, respectively. These pore-size distributions were validated by nitrogen adsorption data. The multi-scale imaging of the four pore types shows that there is no connected visible porosity at these scales with equivalent diameter of 20 nm or larger in this sample. However, organic matter and clay minerals are connected and so the meso porosity (<20 nm) within these phases provides possible diffusion transport pathways for gas. This work confirms multi-scale 3D imaging as a powerful quantification method for shale reservoir characterisation allowing the representative volumes of pores, organic and mineral phases to be defined to model shale systems. The absence of connected porosity at scales greater than 20 nm indicates the likely importance of the organic matter network, and associated smaller-scale pores, in controlling hydrocarbon transport. . The application of these techniques to shale gas plays more widely should lead to a greater understanding of properties in the low permeability systems.     

Pore structure of the graptolite-derived OM in the Longmaxi Shale,southeastern Upper Yangtze Region,China

The Lower Silurian Longmaxi Shale in the southeastern Upper Yangtze Region, which has been the main target for shale gas exploration and production in China, is black marine organic-rich shale and rich in graptolites. Graptolites, usually only periderms preserved in shales, are important organic component of the Longmaxi Shale. However, the pore structure of graptolite periderms and its contribution to gas storage has not yet been studied before. A combination of optical microscopy for identification and “mark” of graptolite and scanning electron microscope (SEM) for pore observations were conducted for the Longamxi Shale samples. Results show that pores are anisotropic developed in the Longmaxi graptolite periderms and greatly associated with their fine structure. Micrometer-sized fractures and spindle-shaped pores between cortical fibrils in the cortical bandage are greatly developed at section parallel to the bedding, while they are rare at section perpendicular to the bedding. Besides, numerous sapropel detritus rich in nanometer-sized pores are discretely distributed in the shale. Though graptolite periderms are low porosity from SEM image analysis, microfractures and elongated pores along the graptolite periderm wall may still make the graptolite an interconnected system. Together with the discrete porous sapropel detritus in shale, these graptolite-derived Organic Matter (OM) may form an interconnected organic pore system in the shale. The difference of pore development observed in graptolite periderms and sapropel detritus also give us new insight for the organic pore heterogeneity study. The OM composition, their fine structure and orientation in the rock may be important factors controlling OM pore development. The combination of identifying OM type under optical microscopy and pores observation under SEM for may be an effective method to study the OM pore development especially in shale that contain more OM.     

Qualitative and quantitative characterization of a transitional shale reservoir: A case study from the Upper Carboniferous Taiyuan shale in the eastern uplift of Liaohe Depression,China

The paper takes the Upper Carboniferous Taiyuan shale in eastern uplift of Liaohe depression as an example to qualitatively and quantitatively characterize the transitional (coal-associated coastal swamp) shale reservoir. Focused Ion Beam Scanning Electron Microscope (FIB-SEM), nano-CT, helium pycnometry, high-pressure mercury intrusion and low-pressure gas (N₂ & CO₂) adsorption for eight shale samples were taken to investigate the pore structures. Four types of pores, i.e., organic matter (OM) pores, interparticle (InterP) pores, intraparticle (IntraP) pores and micro-fractures are identified in the shale reservoir. Among them, intraP pores and micro-fractures are the major pore types. Slit-shaped pores are the major shape in the pore system, and the connectivity of the pore-throat system is interpreted to be moderate, which is subordinate to marine shale. The porosity from three dimension (3D) reconstruction of SEM images is lower than the porosity of helium pycnometry, while the porosity trend of the above two methods is the same. Combination of mercury intrusion and gas absorption reveals that nanometer-scale pores provide the main storage space, accounting for 87.16% of the pore volume and 99.85% of the surface area. Micropores contribute 34.74% of the total pore volume and 74.92% of the total pore surface area; and mesopores account for 48.27% of the total pore volume and 24.93% of the total pore surface area; and macropores contribute 16.99% of the total pore volume and 0.15% of the total pore surface area. Pores with a diameter of less than 10 nm contribute the most to the pore volume and the surface area, accounting for 70.29% and 97.70%, respectively. Based on single factor analysis, clay minerals are positively related to the volume and surface area of micropores, mesopores and macropores, which finally control the free gas in pores and adsorbed gas content on surface area. Unlike marine shale, TOC contributes little to the development of micropores. Brittle minerals inhibit pore development of Taiyuan shale, which proves the influence of clay minerals in the pore system.     

Pore characterization of organic-rich Lower Cambrian shales in Qiannan Depression of Guizhou Province,Southwestern China

Nine organic-rich shale samples of Lower Cambrian black shales were collected from a recently drilled well in the Qiannan Depression, Guizhou Province where they are widely distributed with shallower burial depth than in Sichuan Basin, and their geochemistry and pore characterization were investigated. The results show that the Lower Cambrian shales in Qiannan Depression are organic rich with TOC content ranging from 2.81% to 12.9%, thermally overmature with equivalent vitrinite reflectance values in the range of 2.92–3.25%, and clay contents are high and range from 32.4% to 53.2%. The samples have a total helium porosity ranging from 2.46% to 4.13% and total surface area in the range of 9.08–37.19 m²/g. The estimated porosity in organic matters (defined as the ratio of organic pores to the volume of total organic matters) based on the plot of TOC vs helium porosity is about 10% for the Lower Cambrian shales in Qiannan Depression and is far lower than that of the Lower Silurian shales (36%) in and around Sichan Basin. This indicates that either the organic pores in the Lower Cambrian shale samples have been more severely compacted than or they did not develop organic pores as abundantly as the Lower Silurian shales. Our studies also reveal that the micropore volumes determined by Dubinin–Radushkevich (DR) equation is usually overestimated and this overestimation is closely related to the non-micropore surface area of shales (i.e. the surface area of meso- and macro-pores). However, the modified BET equation can remove this overestimation and be conveniently used to evaluate the micropore volumes/surface area and the non-micropore surface areas of micropore-rich shales.     

Characterization of shale pore system: A case study of Paleogene Xin'gouzui Formation in the Jianghan basin,China

The pore size classification (micropore <2 nm, mesopore 2–50 nm and macropore >50 nm) of IUPAC (1972) has been commonly used in chemical products and shale gas reservoirs; however, it may be insufficient for shale oil reservoirs. To establish a suitable pore size classification for shale oil reservoirs, the open pore systems of 142 Chinese shales (from Jianghan basin) were studied using mercury intrusion capillary pressure analyses. A quantitative evaluation method for I-micropores (0–25 nm in diameter), II-micropores (25–100 nm), mesopores (100–1000 nm) and macropores (>1000 nm) within shales was established from mercury intrusion curves. This method was verified using fractal geometry theory and argon-ion milling scanning electron microscopy images. Based on the combination of pore size distribution with permeability and average pore radius, six types (I-VI) shale open pore systems were analyzed. Moreover, six types open pore systems were graded as good, medium and poor reservoirs. The controlling factors of pore systems were also investigated according to shale compositions and scanning electron microscopy images. The results show that good reservoirs are composed of shales with type I, II and III pore systems characterized by dominant mesopores (mean 68.12 vol %), a few macropores (mean 7.20 vol %), large porosity (mean 16.83%), an average permeability of 0.823 mD and an average pore radius (r_a) of 88 nm. Type IV pore system shales are medium reservoirs, which have a low oil reservoir potential due to the developed II-micropores (mean 57.67 vol %) and a few of mesopores (mean 20.19 vol %). Poor reservoirs (composed of type V and VI pore systems) are inadequate reservoirs for shale oil due to the high percentage of I-micropores (mean 69.16 vol %), which is unfavorable for the flow of oil in shale. Pore size is controlled by shale compositions (including minerals and organic matter), and arrangement and morphology of mineral particles, resulting in the developments of shale pore systems. High content of siliceous mineral and dolomite with regular morphology are advantage for the development of macro- and mesopores, while high content of clay minerals results in a high content of micropores.     

Heterogeneous nanoporosity of the Silurian Longmaxi Formation shale gas reservoir in the Sichuan Basin using the QEMSCAN,FIB-SEM,and nano-CT methods

Nanoporosity of a shale gas reservoir provides essential information on the gas accumulation space and controls the gas reserves. The characteristics of heterogeneous nanoporosity of four shale samples are analyzed by combining quantitative evaluation of minerals by scanning electronic microscopy (QEMSCAN), focused ion beam-scanning electron microscopy (FIB-SEM), and nano-CT. The representative elementary area (REA) is proposed by QEMSCAN to detect the imaging area that can represent the overall contents of minerals and organic matter. Combined with the statistics of pores in minerals and organic matter by FIB-SEM, the quantitative nanoporosity is obtained. The nano-CT is used to compare the total nanoporosity that was obtained by FIB-SEM. The results show that shale has distinct characteristics in nanoporosities due to the variation in organic matter and mineral content. The major pore sizes of the organic matter and clay minerals are smaller than 400 nanometers (nm), and the pore sizes of feldspar and pyrite are mainly 200–600 nm. The pore sizes for pores developed in quartz and carbonate minerals range from a few nanometers to 1000 nm. Furthermore, pores smaller than 400 nm mainly provide the total nanoporosity. The nanoporosities in the organic matter are approximately 17%–21%. Since the organic matter content (0.54%–6.98%) is low, the organic matter contributes approximately 5%–33% of the total nanoporosity in shale. Conversely, the nanoporosities in quartz and clay are generally lower than 3%. Since the mineral content (93.02%–99.46%) is obviously higher than the organic matter content, the minerals contribute approximately 67%–95% of the total nanoporosity in shale.     

Heterogeneity of intergranular,intraparticle and organic pores in Longmaxi shale in Sichuan Basin,South China: Evidence from SEM digital images and fractal and multifractal geometries

Previous studies have determined many types of pores in shale, such as organic pores, inorganic pores and microfractures. In this study, pores are classified as intergranular, intraparticle, and organic pores based on the location of their occurrence. The heterogeneities of the three pore types and their effects on the occurrence of shale gas, which is of utmost practical importance for shale gas exploration and development, are discussed. In this study, the three types of pores are quantitatively characterized using fractal and multifractal methods. The mean fractal dimension and mean width of the multifractal spectrum of these pores are found to be different, i.e., 1.5985 and 1.665 for intraparticle pores, 1.5869 and 1.475 for intergranular pores, and 1.6 and 1.3725 for organic pores. Intraparticle pores have the highest heterogeneity, intergranular pores have intermediate heterogeneity, and organic pores have the lowest heterogeneity. SEM images show that organic pores have good connectivity, homogeneous distribution, and small range of aperture change but have the lowest heterogeneity even where pores are abundant; thus, they provide the largest shale gas occurrence space. In contrast, intergranular pores are less abundant, have lower connectivity, and have higher heterogeneity than organic pores, thereby providing a relatively smaller shale gas occurrence space. Finally, intraparticle pores are the least abundant and possess the poorest connectivity, largest range of aperture change, and highest heterogeneity of the three pore types, thereby providing the smallest shale gas occurrence space. We conclude that organic pores are crucial to the occurrence of shale gas and can provide a new index for the evaluation of shale gas exploration and development.     

Petroleum source rock potential of the Silurian Dadaş shales in the Hazro and Korudağ regions of Southeast Anatolia,Turkey

Shales of the Silurian Dadaş Formation exposed in the southeast Anatolia were investigated by organic geochemical methods. The TOC contents range from 0.24 to 1.48 wt% for the Hazro samples and 0.19 to 3.58 wt% for the Korudağ samples. Tmax values between 438 and 440 °C in the Hazro samples indicate thermal maturity; Tmax values ranging from 456 to 541 °C in the Korudağ samples indicate late to over-maturity. Based on the calculated vitrinite reflectance and measured vitrinite equivalent reflectance values, the Korudağ samples have a maximum of 1.91%R_(g-v), in the gas generation window, while a maximum value of 0.79%R_(amor-v) of one sample from the Hazro section is in the oil generation window. Illite crystallinity (IC) values of all samples are consistent with maturity results.Pr/Ph ratios ranging from 1.32 to 2.28 and C₂₉/C₃₀ hopane ratios > 1.0 indicate an anoxic to sub-oxic marine-carbonate depositional environment.The Hazro shales do not have any shale oil or shale gas potential because of their low oil saturation index values and early to moderate thermal maturation. At first glance, the Korudağ shales can be considered a shale gas formation because of their organic richness, thickness and thermal over-maturity. However, the low silica content and brittle index values of these shales are preventing their suitability as shale gas resource systems.     

Nano-scale pore structure and fractal dimension of organic-rich Wufeng-Longmaxi shale from Jiaoshiba area,Sichuan Basin: Investigations using FE-SEM,gas adsorption and helium pycnometry

Much attention have been recently paid to the upper Ordovician Wufeng shale (O₃w) and lower Silurian Longmaxi shale (S₁l) in the Jiaoshiba area of Sichuan Basin, which is now the largest producing shale gas field in China. Field emission scanning electron microscopy (FE-SEM), low pressure gas (N₂ and CO₂) adsorption, helium pycnometry, X-ray diffraction and geochemical analyses were performed to investigate the pore structure and fractal dimension of the pores in O₃w-S₁l shale formation in the Jiaoshiba area. FE-SEM images show that organic matter (OM) pores are dominant in the organic-rich samples and these pores are often irregular, bubble-like, elliptical and faveolate in shape, while in organic-poor samples, limited and isolated interparticle (interP), intraparticle (intraP) and OM pores are observed. Reversed S-shaped isotherms obtained from nitrogen adsorption are type Ⅱ, and hysteresis loops indicate that the shape of micropore in the samples is slit-or plate-like. BET surface areas and total pore volume vary from 12.2 to 27.1 m²/g and from 1.8 × 10⁻² to 2.9 × 10⁻² cm³/g, with an average of 19.5 m²/g and 2.3 × 10⁻² cm³/g, respectively. Adsorption volume from both N₂ and CO₂ adsorption increases with respect to TOC contents. Porosities obtained from helium porosimetry are comparable with these from gas (CO₂ and N₂) adsorption in O₃w-S₁l shale. However, porosity determined by quantitative FE-SEM analysis is much smaller, which is mainly related to limited resolution and the small areas of investigation.Based on the Frenkel-Halsey-Hill (FHH) model of low-pressure N₂ adsorption, fractal dimensions of the pores varied from 2.737 to 2.823. Relationships between pore structure parameters and TOC content, mineral composition and fractal dimension reveal that the fractal dimension is mainly associated with micropores. Samples with higher TOC content, higher quartz content and lower clay content tend to contain more heterogeneous micropores, resulting in higher fractal dimensions and more complicated pore structure in shales. Therefore, fractal dimension is an effective parameter to reflect the complexity of pore structure and the degree of micropore development in O₃w-S₁l shale.     

苏北盆地阜二段陆相页岩油气勘探潜力分析

苏北盆地古近系为陆相泥页岩沉积,纵向上主要发育阜二段、阜四段两套富有机质泥页岩,其中阜二段泥页岩厚度大,有机质丰度高、类型以Ⅰ-Ⅱ1型为主,主要处于成熟演化阶段;各类微乳隙、微裂缝发育,形成的网状储集体系为油气的赋存与流动提供了空间,具备形成页岩油气的物质基础和储集条件;无机矿物中脆性矿物含量较高,黏土矿物含量较低,利于页岩油的开采;多口井见到油气显示,部分井试获工业油流,展示苏北盆地页岩油具有较大的勘探潜力.     

Experimental investigations on the geometry and connectivity of pore space in organic-rich Wufeng and Longmaxi shales

The nano-scale pore systems of organic-rich shale reservoirs were investigated from Upper Ordovician Wufeng and Lower Silurian Longmaxi Formations in southeast Sichuan Basin. These two formations are the most important target plays of shale gas development in China. The purpose of this article is to assess the geometry and connectivity of multi-scale pore systems, and to reveal the nature and complexity of pore structure for these over-mature gas shales. To achieve these objective, total organic carbon, mineralogy, image analyses by focused ion beam-SEM, low pressure nitrogen adsorption, mercury injection capillary pressure (MICP) and spontaneous fluid [deionized (DI) water and n-decane] imbibition were performed.Most of the visible pores from SEM work in Wufeng and Longmaxi shales are within nm- and μm-size regimes and belong to organic matter (OM) pores. The shapes of OM pore in Longmaxi samples are elliptical, bubble-like, irregular or rounded. Wufeng pores are mainly irregular, linear and faveolated, even though two shales have small depth difference, as well as similar thermal maturity, kerogen type and TOC content. Nano-scale pores in Longmaxi are mainly associated with narrow platelike or slitlike pores with pore size of 3–50 nm; while inkbottle pores are dominant in Wufeng samples and over 88% of the pore volume is contributed by pores with diameter <20 nm. Overall, porosity, pore volume and surface area values from Wufeng samples are much higher than those in Longmaxi, which is mainly correlated with the different TOC contents and mineral compositions. MICP tests show that a total of 5 inflection points (indicative of different connected pore networks) are identified in all pressure regions for Longmaxi, while only 2 for Wufeng in high pressure region with the associated permeability at nano-darcy range. Imbibition curves of n-decane are divided into three stages: the initial stage (Stage Ⅰ), linear imbibition stage (Stage Ⅱ) and late imbibition stage (Stage Ⅲ), and the slopes of linear imbibition stage are around 0.5, suggesting well-connected pore spaces for n-decane. In contrast, imbibition curves for DI water are divided in two stages with linear slopes of between 0.25 and 0.5, indicating moderately-connected pore networks for the movement of DI water. This is consistent with the mixed-wet nature of these shales, with observed weak wettability for hydrophilic, while complete wetting for hydrophobic fluids.     

Shale gas accumulation potential of the Upper Cretaceous Qingshankou Formation in the southeast Songliao Basin,NE China

The purpose of this paper is to provide both quantitative and qualitative visual analyses of the nanometer-scale pore systems of immature and early shales, as well as to discuss the biogenic shale gas accumulation potential of the Upper Cretaceous section of the Songliao Basin. To achieve these goals, mineralogical compositions were determined using transmitted and reflected light petrography, X-ray diffractometry and scanning electron microscopy (SEM), while the nanostructure morphology and pore size distributions (PSDs) were quantified using field emission scanning electron microscopy (FE-SEM) and low-pressure nitrogen gas adsorption (LP-N₂GA). The results of these analyses indicate that nanometer-scale pores are well developed in the immature and low-maturity shale, and that these shales contain many types of reservoir pores. The mudstone layer of the Qingshankou Formation (K₂qn) contains a high permeability characteristic and good rock fracturing conditions, while it is also thick (>9 m in thickness) and rich in fine organic matter. Overall, analysis of the entire formation using source rock and reservoir evaluations indicate that the first member of the Qingshankou Formation (K₂qn₁) has a greater shale gas accumulation potential than the second and third members of the Qingshankou Formation (K₂qn_2-3).