共查询到20条相似文献，搜索用时 31 毫秒
1.
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. 相似文献
2.
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. 相似文献
3.
The microstructure of black siliceous shale from the lower Cambrian Niutitang Formation, Sichuan Basin in China was investigated by the combination of field emission scanning electron microscope (FE-SEM) and argon ion beam milling. The nanometer-to micrometer-scale pore systems of shales are an important control on gas storage and fluid migration. In this paper, the organic porosity in shale samples within oil and gas window has been investigated, and the formation mechanism and diagenetic evolution of nanopores have been researched.FE-SEM reveals five pore types that are classified as follows: organic nanopores, pores in clay minerals, nanopores of framework minerals, intragranular pores in microfossils, and microfractures. Numerous organic nanopores are observed in shales in the gas window, whereas microfractures can be seen within the organic matter of shales in the oil window. Microfractures in oil window shales could be attributed to pressure buildup in the organic matter when incompressible liquid hydrocarbon are generated, and the orientation of microfractures is probably parallel to the bedding and strength anisotropy of the formation. Pores in clay minerals are always associated with the framework of clay flakes, and develop around rigid mineral grains because the pressure shadows of mineral grains protect pores from collapse, and the increasing of silt content would lead to an increase in pressure shadows and improve porosity. Nanopores of rock framework are probably related to dissolution by acidic fluids from hydrocarbon generation, and the dissolution-related pores promote permeability of shales. Porosity in the low-TOC, low-thermal-maturity shales contrast greatly with those of high-TOC, high-thermal-maturity shales. While the high-TOC shales contain abundant organic microporosity, the inorganic pores can contribute a lot to the porosity of the low-TOC shales. 相似文献
4.
Shales from the Lower Silurian Longmaxi Formation in the Sichuan Basin are among the most important shale gas reservoirs in China, and have been investigated because of their great shale gas potential. To understand the pore structure and fractal characteristics of the shales, a series of experiments was conducted on core samples from the Lower Silurian Longmaxi Formation in the Sichuan Basin of China, including X-ray diffraction (XRD), total organic carbon (TOC) content and vitrinite reflectance (Ro) analysis, field emission-environmental scanning electron microscope (FE-ESEM) observation, and low-pressure N2 adsorption-desorption experiments. Frenkel-Halsey-Hill (FHH) method was applied to calculate fractal dimensions. In addition, the pore genesis, the relationships between composition and thermal maturity, the pore structure parameters, and the fractal dimensions are discussed. FE-ESEM observation results show that the Longmaxi Formation shales are dominated by organic-matter (OM) pores along with interparticle (interP) pores, intraparticle (intraP) pores and fracture pores. This study identified the fractal dimensions at relative pressures of 0–0.45 and 0.45–1 as D1 and D2 respectively. D1 ranged from 2.60 to 2.71 and D2 ranged from 2.71 to 2.82. D1 was typically smaller than D2, indicating that the smaller pores in shales were more homogeneous than the larger ones. The formation of these OM pores is owing to kerogen deformation during the thermal maturation, which results in a large number of nanopores. The pore structure of the Longmaxi Formation shales is primarily controlled by TOC content and thermal maturity. TOC content is a controlling factor on the fractal dimensions as it exhibited positive correlations with D1 and D2. Fractal dimensions are useful for the characterization of the pore structures complexity of the Longmaxi Formation shales because D1 and D2 correlate well with pore structure parameters as they both increase with the increase of surface area and the decrease of average pore diameter. 相似文献
5.
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. 相似文献
6.
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. 相似文献
7.
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. 相似文献
8.
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 (Ro 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 Eq33x 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. 相似文献
9.
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. 相似文献
10.
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. 相似文献
11.
Currently, the Upper Ordovician Wufeng (O3w) and Lower Silurian Longmaxi (S1l) Formations in southeast Sichuan Basin have been regarded as one of the most important target plays of shale gas in China. In this work, using a combination of low-pressure gas adsorption (N2 and CO2), mercury injection porosimetry (MIP) and high-pressure CH4 adsorption, we investigate the pore characteristics and methane sorption capacity of the over-mature shales, and discuss the main controlling factors for methane sorption capacity and distribution of methane gas in pore spaces.Low pressure CO2 gas adsorption shows that micropore volumes are characterized by three volumetric maxima (at about 0.35, 0.5 and 0.85 nm). The reversed S-shaped N2 adsorption isotherms are type Ⅱ with hysteresis being noticeable in all the samples. The shapes of hysteresis loop are similar to the H3 type, indicating the pores are slit- or plate-like. Mesopore size distributions are unimodal and pores with diameters of 2–16 nm account for the majority of mesopore volume, which is generally consistent with MIP results. The methane sorption capacities of O3w-S1l shales are in a range of 1.63–3.66 m3/t at 30 °C and 10 MPa. Methane sorption capacity increase with the TOC content, surface area and micropore volume, suggesting organic matter might provide abundant adsorption site and enhance the strong methane sorption capacity. Samples with higher quartz content and lower clay content have larger sorption capacity. Our data confirmed that the effects of temperature and pressure on methane sorption capacity of shale formation are opposite to some extent, suggesting that, during the burial or uplift stage, the gas sorption capacity of hydrocarbon reservoirs can be expressed as a function of burial depth. Based on the adsorption energy theory, when the pore diameter is larger than 2 nm, much methane molecular will be adsorbed in pores space with distance to pore wall less than 2 nm; while free gas is mainly stored in the pore space with distance to pore wall larger than 2 nm. Distributions of adsorption space decrease with the increasing pore size, while free gas volume increase gradually, assuming the pore are cylindrical or sphere. Particularly, when the pore size is larger than 30 nm, the content of adsorbed gas space volume is very low and its contribution to the all gas content is negligible. 相似文献
12.
When trying to improve gas productivity from unconventional sources a first aim is to understand gas storage and gas flow potential through the rock by investigating the microstructure, mineralogy and matrix porosity of unfractured shale. The porosity and mineralogy of the Mulgrave Shale member of the Whitby Mudstone Formation (UK) were characterized using a combination of microscopy, X-ray diffraction and gas adsorption methods on samples collected from outcrops. The Whitby Mudstone is an analogue for the Dutch Posidonia Shale which is a possible unconventional source for gas. The Mulgrave shale member of the Whitby Mudstone Formation can microstructurally be subdivided into a fossil rich (>15%) upper half and a sub-mm mineralogically laminated lower half. All clasts are embedded within a fine-grained matrix (all grains < 2 μm) implying that any possible flow of gas will depend on the porosity and the pore network present within this matrix. The visible SEM porosity (pore diameter > 100 nm) is in the order of 0.5–2.5% and shows a non-connected pore network in 2D. Gas adsorption (N2, Ar, He) porosity (pore diameters down to 2 nm) has been measured to be 0.3–7%. Overall more than 40% of the visible porosity is present within the matrix. Comparing the Whitby Mudstone Formation to other (producing) gas shales shows that the rock plots in the low porosity and high clay mineral content range, which could imply that Whitby Mudstone shales could be less favourable to mechanical fracturing than other gas shales. Estimated permeability indicates values in the micro-to nano-darcy range. 相似文献
13.
As shale oil occurs primarily in micro–nano pores and fractures, research about the effect of pore structure on shale oil accumulation has great significance for shale oil exploration and development. The effect of pore structure on shale oil accumulation in the lower third member of the Shahejie formation (Es3l), Zhanhua Sag, eastern China was investigated using gas adsorption, soxhlet extraction, nuclear magnetic resonance (NMR) analysis, and field emission scanning electron microscope (FE-SEM) observation. The results indicated that the samples contained a larger amount of ink-bottle-shaped and slit-shaped pores after extraction than before extraction. The pore volume and specific surface area of the samples were approximately 2.5 times larger after extraction than before extraction. Residual hydrocarbon occurred primarily in the free-state form in pores with diameters of 10–1000 nm, which can provide sufficient pore volume for free hydrocarbon accumulation. Therefore, pores with diameters of 10–1000 nm were regarded as “oil-enriched pores”, which are effective pores for shale oil exploration, whereas pores with diameters smaller than 10 nm were regarded as “oil-ineffective pores”. Samples with only well-developed small pores with diameters smaller than 1000 nm showed high oil saturation, whereas samples with both small pores and also relatively large pores and micro-fractures presented low oil saturation. As the minimum pore size allowing fluid expulsion is 1000 nm, pores with diameters greater than 1000 nm were considered as “oil-percolated pores”. Large pores and micro-fractures are generally interconnected and may even form a complex fracture mesh, which greatly improves the permeability of shale reservoirs and is beneficial to fluid discharge. 相似文献
14.
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 (ra) 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. 相似文献
15.
The influence of oil-expulsion efficiency on nanopore development in highly mature shale was investigated by using anhydrous pyrolysis (425–600 °C) on solvent-extracted and non-extracted shales at a pressure of 50 MPa. Additional pyrolysis studies were conducted using non-extracted shales at pressures of 25 and 80 MPa to further characterize the impact of pressure on pore evolution at high maturity. The pore structures of the original shale and relevant artificially matured samples after pyrolysis were characterized by using low-pressure nitrogen and carbon-dioxide adsorption techniques, and gas yields during pyrolysis were measured. The results show that oil-expulsion efficiency can strongly influence gas generation and nanopore development in highly mature shales, as bitumen remained in shales with low oil expulsion efficiency significantly promotes gaseous hydrocarbon generation and nanopore (diameter < 10 nm) development. The evolution of micropores and fine mesopores at high maturity can be divided into two main stages: Stage I, corresponding to wet gas generation (EasyRo 1.2%–2.4%), and Stage II, corresponding to dry gas generation (EasyRo 2.4%–4.5%). For shales with low oil expulsion efficiency, nanopore (diameter < 10 nm) evolution increases rapidly in Stage I, whereas slowly in Stage II, and such difference between two stages may be attributed to the changes of the organic matter (OM)’s mechanical properties. Comparatively, for shales with high oil expulsion efficiency, the evolution grows slightly in Stage I, not as rapidly as shales with low efficiency, and decays in Stage II. The different pore evolution behaviors of these two types of shales are attributed to the contribution of bitumen. However, the evolution of medium–coarse mesopores and macropores (diameter >10 nm) remains flat at high maturation. In addition, high pressure can promote the development of micropores and fine mesopores in highly mature shales. 相似文献
16.
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. 相似文献
17.
Two sets of Lower Paleozoic organic-rich shales develop well in the Weiyuan area of the Sichuan Basin: the Lower Cambrian Jiulaodong shale and the Lower Silurian Longmaxi shale. The Weiyuan area underwent a strong subsidence during the Triassic to Early Cretaceous and followed by an extensive uplifting and erosion after the Late Cretaceous. This has brought about great changes to the temperature and pressure conditions of the shales, which is vitally important for the accumulation and preservation of shale gas. Based on the burial and thermal history, averaged TOC and porosity data, geological and geochemical models for the two sets of shales were established. Within each of the shale units, gas generation was modeled and the evolution of the free gas content was calculated using the PVTSim software. Results show that the free gas content in the Lower Cambrian and Lower Silurian shales in the studied area reached the maxima of 1.98–2.93 m3/t and 3.29–4.91 m3/t, respectively (under a pressure coefficient of 1.0–2.0) at their maximum burial. Subsequently, the free gas content continuously decreased as the shale was uplifted. At present, the free gas content in the two sets of shales is 1.52–2.43 m3/t and 1.94–3.42 m3/t, respectively (under a current pressure coefficient of 1.0–2.0). The results are roughly coincident with the gas content data obtained from in situ measurements in the Weiyuan area. We proposed that the Lower Cambrian and Lower Silurian shales have a shale gas potential, even though they have experienced a strong uplifting. 相似文献
18.
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. 相似文献
19.
Shale reservoirs of the Middle and Upper Devonian Horn River Group provide an opportunity to study the influence of rock composition on permeability and pore throat size distribution in high maturity formations. Sedimentological, geochemical and petrophysical analyses reveal relationships between rock composition, pore throat size and matrix permeability.In our sample set, measured matrix permeability ranges between 1.69 and 42.81 nanodarcies and increases with increasing porosity. Total organic carbon (TOC) content positively correlates to permeability and exerts a stronger control on permeability than inorganic composition. A positive correlation between silica content and permeability, and abundant interparticle pores between quartz crystals, suggests that quartz may be another factor enhancing the permeability. Pore throat size distributions are strongly related to TOC content. In organic rich samples, the dominant pore throat size is less than 10 nm, whereas in organic lean samples, pore throat size distribution is dominantly greater than 20 nm. SEM images suggest that in organic rich samples, organic matter pores are the dominant pore type, whereas in quartz rich samples, the dominant type is interparticle pores between quartz grains. In clay rich and carbonate rich samples, the dominant pore type is intraparticle pores, which are fewer and smaller in size.High permeability shales are associated with specific depositional facies. Massive and pyritic mudstones, rich in TOC and quartz, have comparatively high permeability. Laminated mudstone, bioturbated mudstone and carbonate facies, which are relatively enriched in clay or carbonate, have fairly low permeability. 相似文献
20.
Thermal maturity has a significant impact on hydrocarbon generation and the storage capacity within shales, but explicit and quantitative characterization of that impact on continental shales is scarce. To better understand how thermal maturation affects the organic and inorganic changes of the continental shale reservoirs, hydrous pyrolysis was performed to simulate the maturation process. TOC, Rock-Eval and adsorption isotherms tests were used to obtain various geochemical parameters of the shale solid residues. The results indicate that with pyrolysis temperature increasing from ambient temperature to 550 °C, the vitrinite reflectance increases from 0.5% to 2.5% Ro and the TOC (total organic carbon) loss weight reaches 25%. Regarding porosity, the fraction of micro-to meso-pores in the shale increases with an increase in the pyrolysis temperature, whereas the macro-pores do not change significantly. The total amount of gas adsorption does not necessarily increase as the TOC is consumed, but the gas adsorption capacity per unit of TOC increases with increasing thermal maturity. Our finding provides theoretical modelling for identifying shale gas development prospective zones according to thermal maturity mapping and for predicting quantitatively the geochemical and inorganic changes that occur with thermal evolution. 相似文献