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1.
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
2.
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
3.
This article reviews the abnormal characteristics of shale gases (natural gases produced from organic-rich shales) and discusses the cause of the anomalies and mechanisms for gas enrichment and depletion in high-maturity organic-rich shales. The reported shale gas geochemical anomalies include rollover of iso-alkane/normal alkane ratios, rollover of ethane and propane isotopic compositions, abnormally light ethane and propane δ13C values as well as isotope reversals among methane, ethane and propane. These anomalies reflect the complex histories of gas generation and associated isotopic fractionation as well as in-situ “mixing and accumulation” of gases generated from different precursors at different thermal maturities. A model was proposed to explain the observed geochemical anomalies. Gas generation from kerogen cracking at relatively low thermal maturity accounted for the increase of iso-alkane/normal alkane ratios and ethane and propane δ13C values (normal trend). Simultaneous cracking of kerogen, retained oil and wet gas and associated isotopic fractionation at higher maturity caused decreasing iso-alkane/normal alkane ratios, lighter ethane and propane δ13C and corresponding conversion of carbon isotopic distribution patterns from normal through partial reversal to complete reversal. Relatively low oil expulsion efficiency at peak oil generation, low expulsion efficiency at peak gas generation and little gas loss during post-generation evolution are necessary for organic-rich shales to display the observed geochemical anomalies. High organic matter richness, high thermal maturity (high degrees of kerogen-gas and oil-gas conversions) and late-stage (the stage of peak gas generation and post-generation evolution) closed system accounted for gas enrichment in shales. Loss of free gases during post-generation evolution may result in gas depletion or even undersaturation (total gas content lower than the gas sorption capacity) in high-maturity organic-rich shales. 相似文献
4.
Gas-in-place (GIP) is one of the primary controlling factors in shale gas production, but studies examining GIP have been lacking for the Lower Silurian Longmaxi shale in South China. In the present study, a suite of Longmaxi shale samples was collected from an exploratory well in Southeast Chongqing, South China, and the adsorption parameters were fitted using a supercritical Dubinin-Radushkevich (SDR) model based on the high-pressure methane adsorption experiment data for the samples. The results show that the adsorbed phase density and the adsorbed gas capacity of the samples have a positive correlation with the content of total organic carbon (TOC) but a negative correlation with temperature. Combined with the geological characteristics of the Longmaxi shale in Southeast Chongqing, GIP models were constructed under three different fluid pressure conditions. The absolute adsorbed amount of the samples increases and later decreases with increasing depth with a maximum corresponding to depths between 800 and 1200 m. The fluid pressure coefficient has no obvious effect on the absolute adsorbed amount when burial depth is over 2000 m but controls the free gas content. Overpressure primarily increases the free gas content and thus increases the total gas content. The free gas content of the Longmaxi shale in the Pengshui Block is reduced to 47%–58% of that in the Fuling Block, which is the main reason for its low gas production. Further exploration of the Longmaxi Formation should be expanded to deeper burial shales in the eastern area of Southeast Chongqing. 相似文献
5.
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. 相似文献
6.
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. 相似文献
7.
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
8.
《Marine and Petroleum Geology》2012,32(1):125-136
As a result of a long-lasting and complex geological history, organic-matter-rich fine-grained rocks (black shales) with widely varying ages can be found on Ukrainian territory. Several of them are proven hydrocarbon source rocks and may hold a significant shale gas potential.Thick Silurian black shales accumulated along the western margin of the East European Craton in a foreland-type basin. By analogy with coeval organic-matter-rich rocks in Poland, high TOC contents and gas window maturity can be expected. However, to date information on organic richness is largely missing and maturity patterns remain to be refined.Visean black shales with TOC contents as high as 8% and a Type III-II kerogen accumulated along the axis of the Dniepr-Donets rift basin (DDB). They are the likely source for conventional oil and gas. Oil-prone Serpukhovian black shales accumulated in the shallow northwestern part of the DDB. Similar black shales probably may be present in the Lviv-Volyn Basin (western Ukraine).Middle Jurassic black shales up to 500 m thick occur beneath the Carpathian Foredeep. They are the likely source for some heavy oil deposits. TOC contents up to 12% (Type II) have been recorded, but additional investigations are needed to study the vertical and lateral variability of organic matter richness and maturity.Lower Cretaceous black shales with a Type III(-II) kerogen (TOC > 2%) are widespread at the base of the Carpathian flysch nappes, but Oligocene black shales (Menilite Fm.) rich in organic matter (4–8% TOC) and containing a Type II kerogen are the main source rock for oil in the Carpathians. Their thermal maturity increases from the external to the internal nappes.Oligocene black shales are also present in Crimea (Maykop Fm.). These rocks typically contain high TOC contents, but data from Ukraine are missing. 相似文献
9.
Ever since a breakthrough of marine shales in China, lacustrine shales have been attracting by the policy makers and scientists. Organic-rich shales of the Middle Jurassic strata are widely distributed in the Yuqia Coalfield of northern Qaidam Basin. In this paper, a total of 42 shale samples with a burial depth ranging from 475.5 m to 658.5 m were collected from the Shimengou Formation in the YQ-1 shale gas borehole of the study area, including 16 samples from the Lower Member and 26 samples from the Upper Member. Geochemistry, reservoir characteristics and hydrocarbon generation potential of the lacustrine shales in YQ-1 well were preliminarily investigated using the experiments of vitrinite reflectance measurement, maceral identification, mineralogical composition, carbon stable isotope, low-temperature nitrogen adsorption, methane isothermal adsorption and rock eval pyrolysis. The results show that the Shimengou shales have rich organic carbon (averaged 3.83%), which belong to a low thermal maturity stage with a mean vitrinite reflectance (Ro) of 0.49% and an average pyrolytic temperature of the generated maximum remaining hydrocarbon (Tmax) of 432.8 °C. Relative to marine shales, the lacustrine shales show low brittleness index (averaged 34.9) but high clay contents (averaged 55.1%), high total porosities (averaged 13.71%) and great Langmuir volumes (averaged 4.73 cm−3 g). Unlike the marine and marine-transitional shales, the quartz contents and brittleness index (BI) values of the lacustrine shales first decrease then increase with the rising TOC contents. The kerogens from the Upper Member shales are dominant by the oil-prone types, whereas the kerogens from the Lower Member shales by the gas-prone types. The sedimentary environment of the shales influences the TOC contents, thus has a close connection with the hydrocarbon potential, mineralogical composition, kerogen types and pore structure. Additionally, in terms of the hydrocarbon generation potential, the Upper Member shales are regarded as very good and excellent rocks whereas the Lower Member shales mainly as poor and fair rocks. In overall, the shales in the top of the Upper Member can be explored for shale oil due to the higher free hydrocarbon amount (S1), whereas the shales in the Lower Member and the Upper Member, with the depths greater than 1000 m, can be suggested to explore shale gas. 相似文献
10.
In this study, 32 experimental measurements on the isothermal adsorption of methane for 18 shale samples from China's three largest continental oil basins—Songliao, Bohai Bay, and Ordos basins—were used to construct comprehensive polynomial simulation and prediction models for Langmuir volume and Langmuir pressure. The models were based on shale properties (total organic carbon (TOC) content, amount of residual hydrocarbon S1, and mineral composition of rocks) and adsorption condition (temperature) using a weighted sum of multiple variables. The influences of various factors were quantitatively characterized, and the prediction accuracy was verified. Langmuir volume is mainly affected by temperature, shale TOC content, amount of residual hydrocarbon, and clay mineral content; Langmuir pressure is mainly affected by clay, carbonate, feldspar and illite content (because shale pore size can be affected by shale mineral composition). Based on the resource potential and the producibility of shale gas, the area suitable for shale gas exploration and development should have high abundance of organic matter (TOC and residual hydrocarbon S1), low clay mineral content and feldspar content, high conversion rate of montmorillonite to illite (strong diagenesis), and high carbonate content. The comprehensive polynomial prediction model can effectively simulate and predict Langmuir volume and Langmuir pressure, thereby reducing the amount of work necessary for evaluation of shale gas resource potential and economic feasibility. 相似文献
11.
The Songliao Basin is a large-scale petroliferous basin in China. With a gradual decline in conventional oil production, the exploration and development of replacement resources in the basin is becoming increasingly important. Previous studies have shown that the Cretaceous Qingshankou Formation (K2qn) has favorable geological conditions for the formation of shale oil. Thus, shale oil in the Qingshankou Formation represents a promising and practical replacement resource for conventional oil. In this study, geological field surveys, core observation, sample tests, and the analysis of well logs were applied to study the geochemical and reservoir characteristics of shales, identify shale oil beds, build shale oil enrichment models, and classify favorable exploration areas of shale oil from the Cretaceous Qingshankou Formation. The organic matter content is high in shales from the first member of the Cretaceous Qingshankou Formation (K2qn1), with average total organic carbon (TOC) content exceeding 2%. The organic matter is mainly derived from lower aquatic organisms in a reducing brackish to fresh water environment, resulting in mostly type I kerogen. The vitrinite reflectance (Ro) and the temperature at which the maximum is release of hydrocarbons from cracking of kerogen occurred during pyrolysis (Tmax) respectively range from 0.5% to 1.1% and from 430 °C to 450 °C, indicating that the K2qn1 shales are in the low-mature to mature stage (Ro ranges from 0.5% to 1.2%) and currently generating a large amount of oil. The favorable depth for oil generation and expulsion is 1800–2200 m and 1900–2500 m, respectively as determined by basin modeling. The reserving space of the K2qn1 shale oil includes micropores and mircofractures. The micropore reservoirs are developed in shales interbedded with siltstones exhibiting high gamma ray (GR), high resistivity (Rt), low density (DEN), and slightly abnormal spontaneous potential (SP) in the well-logging curves. The microfracture reservoirs are mainly thick shales with high Rt, high AC (acoustic transit time), high GR, low DEN, and abnormal SP. Based on the shale distribution, geochemical characteristics, reservoir types, fracture development, and the process of shale oil generation and enrichment, the southern Taikang and northern Da'an are classified as two favorable shale oil exploration areas in the Songliao Basin. 相似文献
12.
《Marine and Petroleum Geology》2012,32(1):70-89
Hydrocarbon generation and retention processes occurring within gas shales as a response to increases in thermal maturation are still poorly constrained. While efforts have been directed at unravelling the resource potential, composition and textures of these economically important unconventional systems, their spatial variability in chemistry and structure is still poorly documented at the sub-micrometer scale. Here, we have characterized samples of the Lower Toarcian Posidonia Shale samples from northern Germany at varying stages of thermal maturation using a combination of compositional organic geochemistry and spectromicroscopy techniques, including synchrotron-based scanning transmission X-ray microscopy (STXM). We document geochemical and mineralogical heterogeneities down to the nanometer scale within the investigated samples as a function of their level of thermal maturity. In particular, authigenic albite crystals containing nanometric halite inclusions have been documented within the investigated mature and overmature samples. The presence of such tracers of palaeobrine–carbonate interactions supports a maturation scenario for the Lower Toarcian Posidonia Shale intimately related to ascending brine fluids rather than a maturation scenario solely resulting from high heat flows. In addition, various types of asphaltene- and NSO-rich bitumen have been detected within the same samples, very likely genetically derived from thermally degraded organic precursors. Furthermore, the formation of nanoporous pyrobitumen has been inferred for samples of gas window maturity, likely resulting from the formation of gaseous hydrocarbons. By providing in-situ insights into the fate of bitumen and pyrobitumen as a response to the thermal evolution of the macromolecular structure of kerogen, the results reported here constitute an important step towards better constraining hydrocarbon generation processes during natural shale gas maturation. 相似文献
13.
The Qiongdongnan Basin and Zhujiang River(Pearl River) Mouth Basin, important petroliferous basins in the northern South China Sea, contain abundant oil and gas resource. In this study, on basis of discussing impact of oil-base mud on TOC content and Rock-Eval parameters of cutting shale samples, the authors did comprehensive analysis of source rock quality, thermal evolution and control effect of source rock in gas accumulation of the Qiongdongnan and the Zhujiang River Mouth Basins. The contrast analysis of TOC contents and Rock-Eval parameters before and after extraction for cutting shale samples indicates that except for a weaker impact on Rock-Eval parameter S_2, oil-base mud has certain impact on Rock-Eval S_1, Tmax and TOC contents. When concerning oil-base mud influence on source rock geochemistry parameters, the shales in the Yacheng/Enping,Lingshui/Zhuhai and Sanya/Zhuhai Formations have mainly Type Ⅱ and Ⅲ organic matter with better gas potential and oil potential. The thermal evolution analysis suggests that the depth interval of the oil window is between 3 000 m and 5 000 m. Source rocks in the deepwater area have generated abundant gas mainly due to the late stage of the oil window and the high-supper mature stage. Gas reservoir formation condition analysis made clear that the source rock is the primary factor and fault is a necessary condition for gas accumulation. Spatial coupling of source, fault and reservoir is essential for gas accumulation and the inside of hydrocarbon-generating sag is future potential gas exploration area. 相似文献
14.
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
15.
Deposition of organic rich black shales and dark gray limestones in the Berriasian-Turonian interval has been documented in many parts of the world. The Early Cretaceous Garau Formation is well exposed in Lurestan zone in Iran and is composed of organic-rich shales and argillaceous limestones. The present study focuses on organic matter characterization and source rock potential of the Garau Formations in central part of Lurestan zone. A total of 81 core samples from 12 exploratory wells were subjected to detailed geochemical analyses. These samples have been investigated to determine the type and origin of the organic matter as well as their petroleum-generation potential by using Rock-Eval/TOC pyrolysis, GC and GCMS techniques. The results showed that TOC content ranges from 0.5 to 4.95 percent, PI and Tmax values are in the range of 0.2 and 0.6, and 437 and 502 °C. Most organic matter is marine in origin with sub ordinary amounts of terrestrial input suggesting kerogen types II-III and III. Measured vitrinite reflectance (Rrandom%) values varying between 0.78 and 1.21% indicating that the Garau sediments are thermally mature and represent peak to late stage of hydrocarbon generation window. Hydrocarbon potentiality of this formation is assessed fair to very good capable of generating chiefly gas and some oil. Biomarker characteristics are used to provide information about source and maturity of organic matter input and depositional environment. The relevant data include normal alkane and acyclic isoprenoids, distribution of the terpane and sterane aliphatic biomarkers. The Garau Formation is characterized by low Pr/Ph ratio (<1.0), high concentrations of C27 regular steranes and the presence of tricyclic terpanes. These data indicated a carbonate/shale source rock containing a mixture of aquatic (algal and bacterial) organic matter with a minor terrigenous organic matter contribution that was deposited in a marine environment under reducing conditions. The results obtained from biomarker characteristics also suggest that the Garau Formation is thermally mature which is in agreement with the results of Rock-Eval pyrolysis. 相似文献
16.
This study investigates the source rock characteristics of Permian shales from the Jharia sub-basin of Damodar Valley in Eastern India. Borehole shales from the Raniganj, Barren Measure and Barakar Formations were subjected to bulk and quantitative pyrolysis, carbon isotope measurements, mineral identification and organic petrography. The results obtained were used to predict the abundance, source and maturity of kerogen, along with kinetic parameters for its thermal breakdown into simpler hydrocarbons.The shales are characterized by a high TOC (>3.4%), mature to post-mature, heterogeneous Type II–III kerogen. Raniganj and Barren Measure shales are in mature, late oil generation stage (Rr%Raniganj = 0.99–1.22; Rr%Barren Measure = 1.1–1.41). Vitrinite is the dominant maceral in these shales. Barakar shows a post-mature kerogen in gas generation stage (Rr%Barakar = 1.11–2.0) and consist mainly of inertinite and vitrinite. The δ13Corg value of kerogen concentrate from Barren Measure shale indicates a lacustrine/marine origin (−24.6–−30.84‰ vs. VPDB) and that of Raniganj and Barakar (−22.72–−25.03‰ vs. VPDB) show the organic provenance to be continental. The δ13C ratio of thermo-labile hydrocarbons (C1–C3) in Barren Measure suggests a thermogenic source.Discrete bulk kinetic parameters indicate that Raniganj has lower activation energies (ΔE = 42–62 kcal/mol) compared to Barren Measure and Barakar (ΔE = 44–68 kcal/mol). Temperature for onset (10%), middle (50%) and end (90%) of kerogen transformation is least for Raniganj, followed by Barren Measure and Barakar. Mineral content is dominated by quartz (42–63%), siderite (9–15%) and clay (14–29%). Permian shales, in particular the Barren Measure, as inferred from the results of our study, demonstrate excellent properties of a potential shale gas system. 相似文献
17.
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. 相似文献
18.
19.
To study the sedimentary environment of the Lower Cambrian organic-rich shales and isotopic geochemical characteristics of the residual shale gas, 20 black shale samples from the Niutitang Formation were collected from the Youyang section, located in southeastern Chongqing, China. A combination of geochemical, mineralogical, and trace element studies has been performed on the shale samples from the Lower Cambrian Niutitang Formation, and the results were used to determine the paleoceanic sedimentary environment of this organic-rich shale. The relationships between total organic carbon (TOC) and total sulfur (TS) content, carbon isotope value (δ13Corg), trace element enrichment, and mineral composition suggest that the high-TOC Niutitang shale was deposited in an anoxic environment and that the organic matter was well preserved after burial. Stable carbon isotopes and biomarkers both indicate that the organic matter in the Niutitang black shales was mainly derived from both lower aquatic organisms and algaes and belong to type I kerogen. The oil-prone Niutitang black shales have limited residual hydrocarbons, with low values of S2, IH, and bitumen A. The carbon isotopic distribution of the residual gas indicate that the shale gas stored in the Niutitang black shale was mostly generated from the cracking of residual bitumen and wet gas during a stage of significantly high maturity. One of the more significant observations in this work involves the carbon isotope compositions of the residual gas (C1, C2, and C3) released by rock crushing. A conventional δ13C1–δ13C2 trend was observed, and most δ13C2 values of the residual gases are heavier than those of the organic matter (OM) in the corresponding samples, indicating the splitting of ethane bonds and the release of smaller molecules, leading to 13C enrichment in the residual ethane. 相似文献
20.
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