Upper Ordovician-Lower Silurian Wufeng-Longmaxi Formation is the most developed strata of shale gas in southern China.Due to the complex sedimentary environment adjacent to the Kangdian Uplift,the favorable area for o...Upper Ordovician-Lower Silurian Wufeng-Longmaxi Formation is the most developed strata of shale gas in southern China.Due to the complex sedimentary environment adjacent to the Kangdian Uplift,the favorable area for organic-rich shale development is still undetermined.The authors,therefore,focus on the mechanism of accumulation of organic matter and the characterization of the sedimentary environment of the Wufeng-Longmaxi Shales to have a more complete understanding and new discovering of organic matter enrichment and favorable area in the marginal region around Sichuan Basin.Multiple methods were applied in this study,including thin section identification,scanning electron microscopy(SEM)observations and X-ray diffraction(XRD),and elemental analysis on outcrop samples.Five lithofacies have been defined according to the mineralogical and petrological analyses,including mudstone,bioclastic limestone,silty shale,dolomitic shale,and carbonaceous siliceous shale.The paleo-environments have been reconstructed and the organic enrichment mechanism has been identified as a reduced environment and high productivity.The Wufeng period is generally a suboxic environment and the early Longmaxi period is a reducing environment based on geochemical characterization.High dolomite content in the study area is accompanied by high TOC,which may potentially indicate the restricted anoxic environment formed by biological flourishing in shallower water.And for the area close to the Kangdian Uplift,the shale gas generation capability is comparatively favorable.The geochemical parameters implied that new favorable areas for shale gas exploration could be targeted,and more shale gas resources in the mountain-basin transitional zone might be identified in the future.展开更多
Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential en...Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential energy and mineral resources for the development of human society.They also record the evolution process of the earth and improve the understanding of the earth.This review focuses on the diagenesis and formation mechanisms of black shales sedimentation,composition,evolution,and reconstruction,which have had a significant impact on the formation and enrichment of shale oil and gas.In terms of sedimentary environment,black shales can be classified into three types:Marine,terrestrial,and marine-terrestrial transitional facies.The formation processes include mechanisms such as eolian input,hypopycnal flow,gravity-driven and offshore bottom currents.From a geological perspective,the formation of black shales is often closely related to global or regional major geological events.The enrichment of organic matter is generally the result of the interaction and coupling of several factors such as primary productivity,water redox condition,and sedimentation rate.In terms of evolution,black shales have undergone diagenetic evolution of inorganic minerals,thermal evolution of organic matter and hydrocarbon generation,interactions between organic matter and inorganic minerals,and pore evolution.In terms of reconstruction,the effects of fold deformation,uplift and erosion,and fracturing have changed the stress state of black shale reservoirs,thereby having a significant impact on the pore structure.Fluid activity promotes the formation of veins,and have changed the material composition,stress structure,and reservoir properties of black shales.Regarding resource effects,the deposition of black shales is fundamental for shale oil and gas resources,the evolution of black shales promotes the shale oil and gas formation and storage,and the reconstruction of black shales would have caused the heterogeneous distribution of oil and gas in shales.Exploring the formation mechanisms and interactions of black shales at different scales is a key to in-depth research on shale formation and evolution,as well as the key to revealing the mechanism controlling shale oil and gas accumulation.The present records can reveal how these processes worked in geological history,and improve our understanding of the coupling mechanisms among regional geological events,black shales evolution,and shale oil and gas formation and enrichment.展开更多
China is home to shales of three facies:Marine shale,continental shale,and marine-continental transitional shale.Different types of shale gas are associated with significantly different formation conditions and major ...China is home to shales of three facies:Marine shale,continental shale,and marine-continental transitional shale.Different types of shale gas are associated with significantly different formation conditions and major controlling factors.This study compared the geological characteristics of various shales and analyzed the influences of different parameters on the formation and accumulation of shale gas.In general,shales in China’s several regions exhibit high total organic carbon(TOC)contents,which lays a sound material basis for shale gas generation.Marine strata generally show high degrees of thermal evolution.In contrast,continental shales manifest low degrees of thermal evolution,necessitating focusing on areas with relatively high degrees of thermal evolution in the process of shale gas surveys for these shales.The shales of the Wufeng and Silurian formations constitute the most favorable shale gas reservoirs since they exhibit the highest porosity among the three types of shales.These shales are followed by those in the Niutitang and Longtan formations.In contrast,the shales of the Doushantuo,Yanchang,and Qingshankou formations manifest low porosities.Furthermore,the shales of the Wufeng and Longmaxi formations exhibit high brittle mineral contents.Despite a low siliceous mineral content,the shales of the Doushantuo Formation feature a high carbonate mineral content,which can increase the shales’brittleness to some extent.For marine-continental transitional shales,where thin interbeds of tight sandstone with unequal thicknesses are generally found,it is recommended that fracturing combined with drainage of multiple sets of lithologic strata should be employed to enhance their shale gas production.展开更多
The occurrence characteristics of shale oil are of great significance to the movability of shale oil.In this study,the occurrence characteristics of oil in the shale matrix at Funing Formation shale in Subei Basin wer...The occurrence characteristics of shale oil are of great significance to the movability of shale oil.In this study,the occurrence characteristics of oil in the shale matrix at Funing Formation shale in Subei Basin were quantitatively evaluated by organic geochemistry and microscopic pore structure characterization experiments.The Multiple Isothermal Stages Pyrolysis(MIS)experiment results show that the content of total oil,adsorbed oil,and free oil in the shales are 3.15-11.25 mg/g,1.41-4.95 mg/g,and 1.74-6.51 mg/g,respectively.among which the silicon-rich shale has the best oil-bearing.The relative content of free oil shows an increasing trend in pores with pore diameters greater than 3 nm.When the relative content of free oil reaches 100%,the pore size of silicon-rich shale is about 200 nm,while that of calcium-rich shale,clay-rich shale,and siliceous mixed shale is about 10 nm.The occurrence law of adsorbed oil is opposite to that of free oil,which indicates that shale oil will occur in the pores and fractures in a free state in a more extensive pore size range(>200 nm).This study also enables us to further understand the occurrence characteristics of shale oil under the interaction of occurrence state and occurrence space.展开更多
Deep shale reservoirs(3500–4500 m)exhibit significantly different stress states than moderately deep shale reservoirs(2000–3500 m).As a result,the brittleness response mechanisms of deep shales are also different.It...Deep shale reservoirs(3500–4500 m)exhibit significantly different stress states than moderately deep shale reservoirs(2000–3500 m).As a result,the brittleness response mechanisms of deep shales are also different.It is urgent to investigate methods to evaluate the brittleness of deep shales to meet the increasingly urgent needs of deep shale gas development.In this paper,the quotient of Young’s modulus divided by Poisson’s ratio based on triaxial compression tests under in situ stress conditions is taken as SSBV(Static Standard Brittleness Value).A new and pragmatic technique is developed to determine the static brittleness index that considers elastic parameters,the mineral content,and the in situ stress conditions(BIEMS).The coefficient of determination between BIEMS and SSBV reaches 0.555 for experimental data and 0.805 for field data.This coefficient is higher than that of other brittleness indices when compared to SSBV.BIEMS can offer detailed insights into shale brittleness under various conditions,including different mineral compositions,depths,and stress states.This technique can provide a solid data-based foundation for the selection of‘sweet spots’for single-well engineering and the comparison of the brittleness of shale gas production layers in different areas.展开更多
Thin section and argon-ion polishing scanning electron microscope observations were used to analyze the sedimentary and diagenetic environments and main diagenesis of the Permian Fengcheng Formation shales in differen...Thin section and argon-ion polishing scanning electron microscope observations were used to analyze the sedimentary and diagenetic environments and main diagenesis of the Permian Fengcheng Formation shales in different depositional zones of Mahu Sag in the Junggar Basin,and to reconstruct their differential diagenetic evolutional processes.The diagenetic environment of shales in the lake-central zone kept alkaline,which mainly underwent the early stage(Ro<0.5%)dominated by the authigenesis of Na-carbonates and K-feldspar and the late stage(Ro>0.5%)dominated by the replacement of Na-carbonates by reedmergnerite.The shales from the marginal zone underwent a transition from weak alkaline to acidic diagenetic environments,with the early stage dominated by the authigenesis of Mg-bearing clay and silica and the late stage dominated by the dissolution of feldspar and carbonate minerals.The shales from the transitional zone also underwent a transition from an early alkaline diagenetic environment,evidenced by the formation of dolomite and zeolite,to a late acidic diagenetic environment,represented by the reedmergnerite replacement and silicification of feldspar and carbonate minerals.The differences in formation of authigenic minerals during early diagenetic stage determine the fracability of shales.The differences in dissolution of minerals during late diagenetic stage control the content of free shale oil.Dolomitic shale in the transitional zone and siltstone in the marginal zone have relatively high content of free shale oil and strong fracability,and are favorable“sweet spots”for shale oil exploitation and development.展开更多
This study conducted a comparative analysis of extractable hopanoid hydrocarbons and those released via stepwise pyrolysis of typical Eocene immature oil shales in China,namely the Huadian,Maoming,and Fushun shales.Bo...This study conducted a comparative analysis of extractable hopanoid hydrocarbons and those released via stepwise pyrolysis of typical Eocene immature oil shales in China,namely the Huadian,Maoming,and Fushun shales.Both the Huadian and Maoming shales exhibit immature indicators in extractable and kerogen-bound hopanoids(notably,high abundance of C_(29)to C_(32)17β,21β-hopanes and unsaturated hopenes).In contrast,the Fushun oil shale's hopanoids from extracts and pyrolyzates suggest a higher maturity level.The absence of neohopenes in the pyrolyzates of the shales underpins that the kerogenbound hopanoid skeletons resist rearrangement.However,the Huadian oil shale's asymmetric distribution of C_(29)and C_(30)hopenes and neohopenes hints at the presence of an additional source.Novel unsaturated hopenes,such as hop-20(21)-enes,identified in pyrolyzates of the three kerogens at various pyrolysis temperatures,reveal the occurrence of double bonds in kerogen-bound hopanoid skeletons without methyl rearrangements.The absence of hop-20-(21)-ene in extracts suggests that it might act as an intermediate of these novel hopenes during the epimerization of hopanoid skeletons within kerogen.The extractable and pyrolytic hopanoids'stereochemical alignment indicates that epimerization may occur in both ring systems and alkyl side chains of kerogen-bound hopanoid skeletons.Sequential stepwise pyrolysis proves to be a quick screening method for geological hopanoids without causing any significant alteration to the original skeletons even when cracking multiple covalent bonds is necessary.展开更多
Methane adsorption is a critical assessment of the gas storage capacity(GSC)of shales with geological conditions.Although the related research of marine shales has been well-illustrated,the methane adsorption of marin...Methane adsorption is a critical assessment of the gas storage capacity(GSC)of shales with geological conditions.Although the related research of marine shales has been well-illustrated,the methane adsorption of marine-continental transitional(MCT)shales is still ambiguous.In this study,a method of combining experimental data with analytical models was used to investigate the methane adsorption characteristics and GSC of MCT shales collected from the Qinshui Basin,China.The Ono-Kondo model was used to fit the adsorption data to obtain the adsorption parameters.Subsequently,the geological model of GSC based on pore evolution was constructed using a representative shale sample with a total organic carbon(TOC)content of 1.71%,and the effects of reservoir pressure coefficient and water saturation on GSC were explored.In experimental results,compared to the composition of the MCT shale,the pore structure dominates the methane adsorption,and meanwhile,the maturity mainly governs the pore structure.Besides,maturity in the middle-eastern region of the Qinshui Basin shows a strong positive correlation with burial depth.The two parameters,micropore pore volume and non-micropore surface area,induce a good fit for the adsorption capacity data of the shale.In simulation results,the depth,pressure coefficient,and water saturation of the shale all affect the GSC.It demonstrates a promising shale gas potential of the MCT shale in a deeper block,especially with low water saturation.Specifically,the economic feasibility of shale gas could be a major consideration for the shale with a depth of<800 m and/or water saturation>60%in the Yushe-Wuxiang area.This study provides a valuable reference for the reservoir evaluation and favorable block search of MCT shale gas.展开更多
In-situ upgrading by heating is feasible for low-maturity shale oil,where the pore space dynamically evolves.We characterize this response for a heated substrate concurrently imaged by SEM.We systematically follow the...In-situ upgrading by heating is feasible for low-maturity shale oil,where the pore space dynamically evolves.We characterize this response for a heated substrate concurrently imaged by SEM.We systematically follow the evolution of pore quantity,size(length,width and cross-sectional area),orientation,shape(aspect ratio,roundness and solidity)and their anisotropy—interpreted by machine learning.Results indicate that heating generates new pores in both organic matter and inorganic minerals.However,the newly formed pores are smaller than the original pores and thus reduce average lengths and widths of the bedding-parallel pore system.Conversely,the average pore lengths and widths are increased in the bedding-perpendicular direction.Besides,heating increases the cross-sectional area of pores in low-maturity oil shales,where this growth tendency fluctuates at<300℃ but becomes steady at>300℃.In addition,the orientation and shape of the newly-formed heating-induced pores follow the habit of the original pores and follow the initial probability distributions of pore orientation and shape.Herein,limited anisotropy is detected in pore direction and shape,indicating similar modes of evolution both bedding-parallel and bedding-normal.We propose a straightforward but robust model to describe evolution of pore system in low-maturity oil shales during heating.展开更多
Through microscopic analyses(e.g.,organic macerals,thin section observation,scanning electron microscope(SEM)imaging of fresh bedding planes via argon ion milling,and energy spectrum tests)combined with Rock-Eval anal...Through microscopic analyses(e.g.,organic macerals,thin section observation,scanning electron microscope(SEM)imaging of fresh bedding planes via argon ion milling,and energy spectrum tests)combined with Rock-Eval analyses,this study systematically investigated the organic matter and pyrites in the continental shales in the 3^(rd)submember of the Chang 7 Member(Chang 7^(3)submember)in the Yanchang Formation,Ordos Basin and determined their types and the formation and evolutionary characteristics.The results are as follows.The organic matter of the continental shales in the Chang 7^(3)submember is dominated by amorphous bituminites and migrabitumens,which have come into being since the early diagenetic stage and middle diagenetic stage A,respectively.The formation and transformation of organic matter is a prerequisite for the formation of pyrites.The Ordos Basin was a continental freshwater lacustrine basin and lacked sulphates in waters during the deposition of the Chang 7 Member.Therefore,the syndiagenetic stage did not witness the formation of large quantities of pyrites.Since the basin entered early diagenetic stage A,large quantities of sulfur ions were released as the primary organic matter got converted into bituminites and,accordingly,pyrites started to form.However,this stage featured poorer fluid and spatial conditions compared with the syndepositional stage due to withdraw of water,the partial formation of bituminites,and a certain degree of compaction.As a result,large quantities of pyrrhotite failed to transition into typical spherical framboidal pyrites but grew into euhedral monocrystal aggregates.In addition,pyrites are still visible in the migrabitumens in both microfractures and inorganic pores of mudstones and shales,indicating that the pyrite formation period can extend until the middle diagenetic stage A.展开更多
The Saghro massif constitutes a vast metallogenic province with numerous deposits and shows of base metals (lead, zinc, copper) and precious metals (gold and silver), besides various useful substances (talc, pyrophyll...The Saghro massif constitutes a vast metallogenic province with numerous deposits and shows of base metals (lead, zinc, copper) and precious metals (gold and silver), besides various useful substances (talc, pyrophyllite, barite, fluorite). Silver/lead occurrences are concentrated along the Cryogenian Imiter series and moderately at Boumalne and Sidi Flah. Copper occupies the plutonic intrusions and intrusive rocks of the East-Central Saghro while barite deposits are widespread throughout the Cambrian cover of the East Saghro in contact with the Ediacaran basement. To justify this distribution, the new contributions of the cartography and the organic geochemistry of the black shales of Jbel Saghro have clearly shown the particularity of the Imiter black shales in terms of the richness in organic matter (TOC = 0.18%), the blackish color and the friability. The Boumalne and Sidi Flah groups present some similarities with the Imiter group, such as the sub-equatorial structuring, the friable pelites and the richness in organic matter (Boumalne TOC = 0.11% and SidiFlah TOC = 0.16%), which is a quite good show that requires to reinforce the exploration works. For Western Saghro in the Iknioun and Qalaa’t M’Gouna groups, the variations in the thickness of the volcanic cover show an irregular paleotopography with hard, greenish, organic-poor pelitic sediments (TOC = 0.01 to 0.04%). We can conclude that the formation of Imiter-type silver concentrations requires the combination of the sedimentological, the volcanic and structural factors. For Imiter-type silver these factors are: a fine pelitic and argillic casing deposited in a confined environment, a basic volcanism source of metals and other intermediate to acid generated by the hydrothermalism and heat, a convenable paleotopography and a network of fracturations to trap the mineralizations.展开更多
Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sa...Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sag,Songliao Basin is a classic lacustrine pure shale reservoir that contains abundant shale oil resources.The predicted geological reserves of the shale are 1.268×10^(9) t.In this study,field emission scanning electron microscope(FE-SEM),the modular automated processing system(MAPS),pyrolysisgas chromatography(Py-GC),low-pressure nitrogen gas adsorption(LPNA),Soxhlet extraction,pyrolysis,and 2-D nuclear magnetic resonance(NMR)were integrated to describe the shale oil components,microscopic occurrence,mobility,and the effective pore size distribution.Meanwhile,the related controlling factors are discussed.The shale oil in the Qingshankou Fm exists dominantly in the matrix pores of the clay minerals,with small amounts distributed in the intergranular pores of terrigenous clastic grains,intercrystalline pores of pyrite,intragranular pores of ostracod shells,and micro-fractures.Shale oil is distributed in the pore spaces of variable sizes in different lithofacies.The clay mineral-laminated shales are characterized by the broadest range of pore size and largest volume of pore spaces with shale oil distribution,while the ostracod-laminated shales have limited pore spaces retaining oil.Furthermore,the proposed integrated analysis evaluates the shale oil molecules existing in two states:movable,and adsorbed oil,respectively.The result illustrates that movable oil takes up 30.6%e79.4%of the total residual oil.TOC,mineral composition,and pore structures of the shale joint together to control the states and mobility of the shale oil.TOC values are positively correlated with the quantities of shale oil regardless of the state of oil.The mineral components significantly impact the state of shale oil.Noticeable differences in the states of oil were observed following the changing types of minerals,possibly due to their difference in adsorption capacity and wettability.Clay minerals attract more adsorbed oil than movable oil.Felsic minerals generally decrease the occurrence of total and adsorbed oil.Carbonate plays a positive role in hydrocarbon retention of all the shale oil states.As for the pore structure,the average pore size exerts a critical impact on the total,movable,and adsorbed oil content.The total pore volume and specific surface area of shales play a principal role in controlling the total yields and amounts of adsorbed oil.This research improves the understanding of the occurrence characteristics and enrichment mechanisms of shale oil in terrestrial pure shales and provides a reference for locating favorable shale oil exploration areas.展开更多
With increase in shale gas exploration, inorganic and organic geochemical investigations of shale have become extremely important. Here, we explore the six argillaceous (shale) intervals (Arangi, Koldaha, Rampur, Bija...With increase in shale gas exploration, inorganic and organic geochemical investigations of shale have become extremely important. Here, we explore the six argillaceous (shale) intervals (Arangi, Koldaha, Rampur, Bijaygarh, Rewa and Sirbu shale) from Son valley sector, Vindhyan Basin with an aim to understand provenance conditions, palaeoclimate, tectonic setting and hydrocarbon generation potential. Whole rock geochemistry indicates Vindhyan sediments derived from felsic source(s) except for Sirbu shale that indicates additional influx of mafic rocks with differentiated felsic source. A comparative study of Vindhyan shale rare earth elements (REEs) points to Mahakoshals and Chhotanagpur gneissic complex (CGC) as probable sediment provenance for Vindhyan sediments. CIA analysis, after necessary corrections for K-metasomatism, suggests evolution in weathering and palaeoclimate indicating a transformation from moderate weathering conditions with warm and humid climate during lower Vindhyan deposition to intense weathering conditions with hot and humid climate during upper Vindhyan deposition. Trace (La/Y vs. Sc/Cr) and REE analysis indicates passive margin setting for Vindhyan sediments whereas a wide range spanning passive to active continental margin setting is also inferred using (Th-Sc-Zr/10) and (Th–La-Sc) ternary diagrams. However, these tectonic discriminant diagrams lack in explaining rift- or sag-related origin of any intracratonic basin such as the Vindhyan Basin. The total organic carbon (TOC) content in Vindhyan shales ranges from 0.29% to 8.44%. The thermally liberated hydrocarbon (S1) values range from 0.01 to 0.18 mg HC/g rock (milligram hydrocarbon per gram of rock sample), whereas hydrocarbon from cracking of the kerogen (S2) shows values ranging from 0.04 to 0.47 mg HC/g rock. Based on modified Van Krevelen correlation (HI vs. Tmax) diagram, organic matter from Arangi and Bijaygarh shales is characterized as thermally mature, Type III kerogen of gas prone character indicating good to very good gas generation potential.展开更多
The Mesozoic and Cenozoic strata in the Junggar basin developed two sets of shallow to semi-deep lacustrine shale, namely, the Cretaceous Qingshuihe Formation (K_(1q)) and the Paleogene Anjihaihe Formation (E_(2-3a))....The Mesozoic and Cenozoic strata in the Junggar basin developed two sets of shallow to semi-deep lacustrine shale, namely, the Cretaceous Qingshuihe Formation (K_(1q)) and the Paleogene Anjihaihe Formation (E_(2-3a)). Through organic petrology and scanning electron microscope (SEM) observation, it is found that the primary hydrocarbon-generating organic matter (OM) in the two sets of strata is different. The biological precursor of the E_(2-3a) OM is mainly green algae (Pediastrum), while the precursor of K_(1q) kerogen is mainly cyanobacteria (Oscillatoria). Then, the E_(2-3a) green algae-rich shale and K_(1q) cyanobacteria-rich shale were subjected to hydrous pyrolysis and kinetic analysis, respectively. The results show that the evolution modes of hydrocarbon generation of the typical shales are very different. Green algae have the characteristics of a low oil generation threshold, heavy oil quality, and no prominent oil peak, while cyanobacteria have the characteristics of late oil generation, concentrated hydrocarbon generation, and relatively light oil quality. The characteristics of oil generation can also be well reflected in the composition evolution of the crude oil components. The carbon isotope of gas, kerogen, and extracts of the E_(2-3a) green algae-rich shale are significantly heavier than the K_(1q) cyanobacteria-rich shale, which may be related to the living habits of their biological precursors, carbon source usage, photosynthesis efficiency, and carbon fixation efficiency.展开更多
Deep shale gas(3500-4500 m)will be the important succeeding field for the growth of shale gas production in China.Under the condition of high temperature and high pressure in deep shale gas reservoirs,its gas occurren...Deep shale gas(3500-4500 m)will be the important succeeding field for the growth of shale gas production in China.Under the condition of high temperature and high pressure in deep shale gas reservoirs,its gas occurrence characteristics are markedly different from those of medium and shallow layers.To elucidate the gas occurrence characteristics and controlling factors of deep shales in the Wufeng-Longmaxi Formation,methane adsorption,low-temperature N2,and cO2 adsorption experi-ments were conducted.The results show that in deep shales,the mesopores provide approximately 75%of the total specific surface area(SA)and 90%of the total pore volume(PV).Based on two hypotheses and comparing the theoretical and actual adsorption capacity,it is speculated that methane is adsorbed in deep shale in the form of micropore filling,and free gas is mainly stored in the mesopores.Correlation analysis demonstrated that ToC is the key material constraint for the adsorption capacity of deep shale,and micropore SSA is the key spatial constraint.Other minerals and mesopore parameters have limited effect on the amount of adsorbed gas.Moreover,the free gas content ranges from 2.72 m^(3)/t to 6.20 m^(3)/t,with an average value of 4.60 m^(3)/t,and the free gas content ratio is approximately 58%,suggesting that the deep shale gas reservoirs are dominated by free gas.This ratio may also increase to approximately 70%when considering the formation temperature effect on adsorbed gas.Gas density,porosity,and gas saturation are the main controlling factors of free gas content,resulting in significantly larger free gas content in deep shale than in shallower formations.展开更多
The majority of oil and gas resources in the world are related to saline sediments, which mainly occur in sedimentary strata in the form of cap rocks or salt-associated shales. A large number of shale oil resources ha...The majority of oil and gas resources in the world are related to saline sediments, which mainly occur in sedimentary strata in the form of cap rocks or salt-associated shales. A large number of shale oil resources have been discovered in the saline shale sediments of the Cenozoic terrestrial lake basin in China. The hydrocarbon generation ability and the reservoir capacity of shale control the oil and gas generation. The reservoir capacity is mainly characterized by pore type, structure and porosity. Most of China’s shale oil and gas resources belong to salt-bearing formations. The role of gypsum-salt rocks in the formation and evolution of organic matter (OM) in such formations has received extensive attention. However, systematic understanding is lacking. Research on the pore formation and evolution in shale under the action of gypsum-salt rock sediments is especially weak. Taking the shales in the third member of the Shahejie Formation (Es_(3)) of the Bohai Bay Basin as an example, the influence of halite on the formation and evolution process of pores was studied in this paper. The results show that halite and gypsum minerals were associated with OM, which made them more likely to develop OM pores. The samples with a high halite mineral content (HC) are more developed regarding the pore volume and specific surface area than those with a low HC. The formation of thick salt rocks is influenced by factors of deep thermal brine upwelling, sea erosion and arid environments. The frequent alternation between humid and arid environments led to the outbreak and death of organisms and the precipitation of gypsum-salt rock, which formed the simultaneous deposition of OM and halite minerals. Finally, we have established a model of shale pore evolution under the participation of the gypsum-salt rock, and halite minerals contribute to pore development in both Stage II and Stage IV. This study provides strong microscopic evidence for the pore system formation and evolution in salt-bearing reservoirs.展开更多
On the basis of sorting out current understanding of solid bitumen (SB) in shales and taking organic-rich shales in the first member of the Cretaceous Qingshankou Formation in the Songliao Basin as an example, the def...On the basis of sorting out current understanding of solid bitumen (SB) in shales and taking organic-rich shales in the first member of the Cretaceous Qingshankou Formation in the Songliao Basin as an example, the definition, classification, occurrence and evolution path of SB are systemtically studied, and the indicative significance of SB reflectance (Rob) on maturity and its influence on the development of reservoir space are discussed and summarized. The results show that the difference of primary maceral types is primarily responsible for the different evolution paths of SB. Most of the pre-oil bitumen is in-situ SB with only a small amount being of migrated SB, while most of the post-oil bitumen and pyrobitumen are migrated SB. From the immature to early oil maturity stage, bituminite, vitrinite, and inertinite can be distinguished from SB based on their optical characteristics under reflected light, and alginite can be differentiated from SB by their fluorescence characteristics. Under scanning electron microscope, in-situ SB and migrated SB can be effectively identified. Rob increases linearly with increasing vitrinite reflectance (Ro), as a result of a decrease of aliphatic structure and the enhancement of aromatization of SB. Within the oil window three types of secondary pores may develop in SB, including modified mineral pores, devolatilization cracks and bubble holes. At a high maturity stage spongy pores may develop in pyrobitumen. Scanning electron microscopy combined with in-situ SEM-Raman spectroscopy can further reveal the structral information of different types of SB, thus providing crucial data for understanding for understanding OM migration paths, dynamics, and distances at micro-scale.展开更多
The relationship between fracture calcite veins and shale gas enrichment in the deep Ordovician Wufeng Formation-Silurian Longmaxi Formation (Wufeng-Longmaxi) shales in southern Sichuan Basin was investigated through ...The relationship between fracture calcite veins and shale gas enrichment in the deep Ordovician Wufeng Formation-Silurian Longmaxi Formation (Wufeng-Longmaxi) shales in southern Sichuan Basin was investigated through core and thin section observations, cathodoluminescence analysis, isotopic geochemistry analysis, fluid inclusion testing, and basin simulation. Tectonic fracture calcite veins mainly in the undulating part of the structure and non-tectonic fracture calcite veins are mainly formed in the gentle part of the structure. The latter, mainly induced by hydrocarbon generation, occurred at the stage of peak oil and gas generation, while the former turned up with the formation of Luzhou paleouplift during the Indosinian. Under the influence of hydrocarbon generation pressurization process, fractures were opened and closed frequently, and oil and gas episodic activities are recorded by veins. The formation pressure coefficient at the maximum paleodepth exceeds 2.0. The formation uplift stage after the Late Yanshanian is the key period for shale gas migration. Shale gas migrates along the bedding to the high part of the structure. The greater the structural fluctuation is, the more intense the shale gas migration activity is, and the loss is more. The gentler the formation is, the weaker the shale gas migration activity is, and the loss is less. The shale gas enrichment in the core of gentle anticlines and gentle synclines is relatively higher.展开更多
Shale samples from the Ordovician Wulalike Formation at the western margin of the Ordos Basin are studied to define the types, microstructures and connectivity of pores as well as the relationships between the pore st...Shale samples from the Ordovician Wulalike Formation at the western margin of the Ordos Basin are studied to define the types, microstructures and connectivity of pores as well as the relationships between the pore structures and gas content of the samples by using experimental techniques such as high-resolution field emission scanning electron microscopy (FESEM), mercury injection capillary pressure (MICP), low-temperature nitrogen adsorption (LTNA), CO_(2) adsorption, and focused ion beam scanning electron microscopy (FIB-SEM). The results show that the shale has 10 different lithofacies, typical mixed sedimentary characteristics, and poorly developed pores. The reservoir space mainly consists of intercrystalline pores, dissolution pores, intergranular pores, and micro-fissures, with organic pores occasionally visible. The pore size is mostly within 0.4–250 nm range but dominated by micropores and mesopores less than 20 nm, with pore numbers peaking at pore sizes of 0.5 nm, 0.6 nm, 0.82 nm, 3 nm, and 10 nm, respectively. The pores are poorly connected and macropores are rarely seen, which may explain the low porosity and low permeability of the samples. Samples with high content of organic matter and felsic minerals are potential reservoirs for oil and gas with their favorable physical properties and high connectivity. The pores less than 5 nm contribute significantly to the specific surface area and serve as important storage space for adsorbed gas.展开更多
The petroleum paleo-productivity and generative potential of the Nkporo and Awgu shales in the Lower Benue Trough (LBT) were studied. Major oxides were determined using Spectro Ciros Inductively-coupled plasma optical...The petroleum paleo-productivity and generative potential of the Nkporo and Awgu shales in the Lower Benue Trough (LBT) were studied. Major oxides were determined using Spectro Ciros Inductively-coupled plasma optical emission spectrometer (ICP-OES) while trace and rare earth elements were determined using an ELAN 9000 Inductively-coupled plasma mass spectrometer (ICP-MS). The shales have Co/Ni ratios greater than 0.1 suggesting oil source rocks with more marine source input due to brief marine incursion in the transition zone after deposition. The very low Ni values and moderate V values, and a lack of correlation between the TOC and sulphur content, suggests that the organic matter is of terrestrial Type Ⅲ;and the very low paleo-productivity (Ba/Al and P/Ti ratios) suggests that the organic matter is of terrestrial origin. The low V/Ni values of the Nkporo and Awgu shales (Av. ≈ 4) and the high metal concentrations indicate a matured status. From the K/Rb ratios of the Nkporo (191–259) and Awgu shales (198–261), it can be deduced that the organic matter within the shales experienced a considerable loss of K and the shales are mature to generate gaseous hydrocarbons.展开更多
基金jointly funded by the National Key Laboratory of Oil and Gas Reservoir Geology and Exploitation(PLC20210104)China Geological Survey(DD20221661)China National Science and Technology Major Project“Test and Application of Shale Gas Exploration and Evaluation Technology(2016ZX05034004)”。
文摘Upper Ordovician-Lower Silurian Wufeng-Longmaxi Formation is the most developed strata of shale gas in southern China.Due to the complex sedimentary environment adjacent to the Kangdian Uplift,the favorable area for organic-rich shale development is still undetermined.The authors,therefore,focus on the mechanism of accumulation of organic matter and the characterization of the sedimentary environment of the Wufeng-Longmaxi Shales to have a more complete understanding and new discovering of organic matter enrichment and favorable area in the marginal region around Sichuan Basin.Multiple methods were applied in this study,including thin section identification,scanning electron microscopy(SEM)observations and X-ray diffraction(XRD),and elemental analysis on outcrop samples.Five lithofacies have been defined according to the mineralogical and petrological analyses,including mudstone,bioclastic limestone,silty shale,dolomitic shale,and carbonaceous siliceous shale.The paleo-environments have been reconstructed and the organic enrichment mechanism has been identified as a reduced environment and high productivity.The Wufeng period is generally a suboxic environment and the early Longmaxi period is a reducing environment based on geochemical characterization.High dolomite content in the study area is accompanied by high TOC,which may potentially indicate the restricted anoxic environment formed by biological flourishing in shallower water.And for the area close to the Kangdian Uplift,the shale gas generation capability is comparatively favorable.The geochemical parameters implied that new favorable areas for shale gas exploration could be targeted,and more shale gas resources in the mountain-basin transitional zone might be identified in the future.
基金supported by the projects of the China Geological Survey(DD20230043,DD20240048)the project of the National Natural Science Foundation of China(42102123)。
文摘Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential energy and mineral resources for the development of human society.They also record the evolution process of the earth and improve the understanding of the earth.This review focuses on the diagenesis and formation mechanisms of black shales sedimentation,composition,evolution,and reconstruction,which have had a significant impact on the formation and enrichment of shale oil and gas.In terms of sedimentary environment,black shales can be classified into three types:Marine,terrestrial,and marine-terrestrial transitional facies.The formation processes include mechanisms such as eolian input,hypopycnal flow,gravity-driven and offshore bottom currents.From a geological perspective,the formation of black shales is often closely related to global or regional major geological events.The enrichment of organic matter is generally the result of the interaction and coupling of several factors such as primary productivity,water redox condition,and sedimentation rate.In terms of evolution,black shales have undergone diagenetic evolution of inorganic minerals,thermal evolution of organic matter and hydrocarbon generation,interactions between organic matter and inorganic minerals,and pore evolution.In terms of reconstruction,the effects of fold deformation,uplift and erosion,and fracturing have changed the stress state of black shale reservoirs,thereby having a significant impact on the pore structure.Fluid activity promotes the formation of veins,and have changed the material composition,stress structure,and reservoir properties of black shales.Regarding resource effects,the deposition of black shales is fundamental for shale oil and gas resources,the evolution of black shales promotes the shale oil and gas formation and storage,and the reconstruction of black shales would have caused the heterogeneous distribution of oil and gas in shales.Exploring the formation mechanisms and interactions of black shales at different scales is a key to in-depth research on shale formation and evolution,as well as the key to revealing the mechanism controlling shale oil and gas accumulation.The present records can reveal how these processes worked in geological history,and improve our understanding of the coupling mechanisms among regional geological events,black shales evolution,and shale oil and gas formation and enrichment.
基金supported by the project of the China Geological Survey for shale gas in Southern China(DD20221852)the National Natural Science Foundation of China(42242010,U2244208)。
文摘China is home to shales of three facies:Marine shale,continental shale,and marine-continental transitional shale.Different types of shale gas are associated with significantly different formation conditions and major controlling factors.This study compared the geological characteristics of various shales and analyzed the influences of different parameters on the formation and accumulation of shale gas.In general,shales in China’s several regions exhibit high total organic carbon(TOC)contents,which lays a sound material basis for shale gas generation.Marine strata generally show high degrees of thermal evolution.In contrast,continental shales manifest low degrees of thermal evolution,necessitating focusing on areas with relatively high degrees of thermal evolution in the process of shale gas surveys for these shales.The shales of the Wufeng and Silurian formations constitute the most favorable shale gas reservoirs since they exhibit the highest porosity among the three types of shales.These shales are followed by those in the Niutitang and Longtan formations.In contrast,the shales of the Doushantuo,Yanchang,and Qingshankou formations manifest low porosities.Furthermore,the shales of the Wufeng and Longmaxi formations exhibit high brittle mineral contents.Despite a low siliceous mineral content,the shales of the Doushantuo Formation feature a high carbonate mineral content,which can increase the shales’brittleness to some extent.For marine-continental transitional shales,where thin interbeds of tight sandstone with unequal thicknesses are generally found,it is recommended that fracturing combined with drainage of multiple sets of lithologic strata should be employed to enhance their shale gas production.
基金This work was financially supported by the National Natural Science Foundation of China(41972123,41922015)the Natural Science Foundation of Shandong Province(ZR2020QD036).
文摘The occurrence characteristics of shale oil are of great significance to the movability of shale oil.In this study,the occurrence characteristics of oil in the shale matrix at Funing Formation shale in Subei Basin were quantitatively evaluated by organic geochemistry and microscopic pore structure characterization experiments.The Multiple Isothermal Stages Pyrolysis(MIS)experiment results show that the content of total oil,adsorbed oil,and free oil in the shales are 3.15-11.25 mg/g,1.41-4.95 mg/g,and 1.74-6.51 mg/g,respectively.among which the silicon-rich shale has the best oil-bearing.The relative content of free oil shows an increasing trend in pores with pore diameters greater than 3 nm.When the relative content of free oil reaches 100%,the pore size of silicon-rich shale is about 200 nm,while that of calcium-rich shale,clay-rich shale,and siliceous mixed shale is about 10 nm.The occurrence law of adsorbed oil is opposite to that of free oil,which indicates that shale oil will occur in the pores and fractures in a free state in a more extensive pore size range(>200 nm).This study also enables us to further understand the occurrence characteristics of shale oil under the interaction of occurrence state and occurrence space.
文摘Deep shale reservoirs(3500–4500 m)exhibit significantly different stress states than moderately deep shale reservoirs(2000–3500 m).As a result,the brittleness response mechanisms of deep shales are also different.It is urgent to investigate methods to evaluate the brittleness of deep shales to meet the increasingly urgent needs of deep shale gas development.In this paper,the quotient of Young’s modulus divided by Poisson’s ratio based on triaxial compression tests under in situ stress conditions is taken as SSBV(Static Standard Brittleness Value).A new and pragmatic technique is developed to determine the static brittleness index that considers elastic parameters,the mineral content,and the in situ stress conditions(BIEMS).The coefficient of determination between BIEMS and SSBV reaches 0.555 for experimental data and 0.805 for field data.This coefficient is higher than that of other brittleness indices when compared to SSBV.BIEMS can offer detailed insights into shale brittleness under various conditions,including different mineral compositions,depths,and stress states.This technique can provide a solid data-based foundation for the selection of‘sweet spots’for single-well engineering and the comparison of the brittleness of shale gas production layers in different areas.
基金Supported by the National Natural Science Foundation of China(42272117,42002116).
文摘Thin section and argon-ion polishing scanning electron microscope observations were used to analyze the sedimentary and diagenetic environments and main diagenesis of the Permian Fengcheng Formation shales in different depositional zones of Mahu Sag in the Junggar Basin,and to reconstruct their differential diagenetic evolutional processes.The diagenetic environment of shales in the lake-central zone kept alkaline,which mainly underwent the early stage(Ro<0.5%)dominated by the authigenesis of Na-carbonates and K-feldspar and the late stage(Ro>0.5%)dominated by the replacement of Na-carbonates by reedmergnerite.The shales from the marginal zone underwent a transition from weak alkaline to acidic diagenetic environments,with the early stage dominated by the authigenesis of Mg-bearing clay and silica and the late stage dominated by the dissolution of feldspar and carbonate minerals.The shales from the transitional zone also underwent a transition from an early alkaline diagenetic environment,evidenced by the formation of dolomite and zeolite,to a late acidic diagenetic environment,represented by the reedmergnerite replacement and silicification of feldspar and carbonate minerals.The differences in formation of authigenic minerals during early diagenetic stage determine the fracability of shales.The differences in dissolution of minerals during late diagenetic stage control the content of free shale oil.Dolomitic shale in the transitional zone and siltstone in the marginal zone have relatively high content of free shale oil and strong fracability,and are favorable“sweet spots”for shale oil exploitation and development.
基金funded by the Natural Science Foundation of China(No.42373028,No.42072154).
文摘This study conducted a comparative analysis of extractable hopanoid hydrocarbons and those released via stepwise pyrolysis of typical Eocene immature oil shales in China,namely the Huadian,Maoming,and Fushun shales.Both the Huadian and Maoming shales exhibit immature indicators in extractable and kerogen-bound hopanoids(notably,high abundance of C_(29)to C_(32)17β,21β-hopanes and unsaturated hopenes).In contrast,the Fushun oil shale's hopanoids from extracts and pyrolyzates suggest a higher maturity level.The absence of neohopenes in the pyrolyzates of the shales underpins that the kerogenbound hopanoid skeletons resist rearrangement.However,the Huadian oil shale's asymmetric distribution of C_(29)and C_(30)hopenes and neohopenes hints at the presence of an additional source.Novel unsaturated hopenes,such as hop-20(21)-enes,identified in pyrolyzates of the three kerogens at various pyrolysis temperatures,reveal the occurrence of double bonds in kerogen-bound hopanoid skeletons without methyl rearrangements.The absence of hop-20-(21)-ene in extracts suggests that it might act as an intermediate of these novel hopenes during the epimerization of hopanoid skeletons within kerogen.The extractable and pyrolytic hopanoids'stereochemical alignment indicates that epimerization may occur in both ring systems and alkyl side chains of kerogen-bound hopanoid skeletons.Sequential stepwise pyrolysis proves to be a quick screening method for geological hopanoids without causing any significant alteration to the original skeletons even when cracking multiple covalent bonds is necessary.
基金jointly supported by the Science and Technology Department of Shanxi Province,China (20201101003)the National Natural Science Foundation of China (U1810201)the China Scholarship Council (202206400012)。
文摘Methane adsorption is a critical assessment of the gas storage capacity(GSC)of shales with geological conditions.Although the related research of marine shales has been well-illustrated,the methane adsorption of marine-continental transitional(MCT)shales is still ambiguous.In this study,a method of combining experimental data with analytical models was used to investigate the methane adsorption characteristics and GSC of MCT shales collected from the Qinshui Basin,China.The Ono-Kondo model was used to fit the adsorption data to obtain the adsorption parameters.Subsequently,the geological model of GSC based on pore evolution was constructed using a representative shale sample with a total organic carbon(TOC)content of 1.71%,and the effects of reservoir pressure coefficient and water saturation on GSC were explored.In experimental results,compared to the composition of the MCT shale,the pore structure dominates the methane adsorption,and meanwhile,the maturity mainly governs the pore structure.Besides,maturity in the middle-eastern region of the Qinshui Basin shows a strong positive correlation with burial depth.The two parameters,micropore pore volume and non-micropore surface area,induce a good fit for the adsorption capacity data of the shale.In simulation results,the depth,pressure coefficient,and water saturation of the shale all affect the GSC.It demonstrates a promising shale gas potential of the MCT shale in a deeper block,especially with low water saturation.Specifically,the economic feasibility of shale gas could be a major consideration for the shale with a depth of<800 m and/or water saturation>60%in the Yushe-Wuxiang area.This study provides a valuable reference for the reservoir evaluation and favorable block search of MCT shale gas.
基金financially supported by the National Key Research and Development Program of China(Grant No.2022YFE0129800)the National Natural Science Foundation of China(Grant No.42202204)。
文摘In-situ upgrading by heating is feasible for low-maturity shale oil,where the pore space dynamically evolves.We characterize this response for a heated substrate concurrently imaged by SEM.We systematically follow the evolution of pore quantity,size(length,width and cross-sectional area),orientation,shape(aspect ratio,roundness and solidity)and their anisotropy—interpreted by machine learning.Results indicate that heating generates new pores in both organic matter and inorganic minerals.However,the newly formed pores are smaller than the original pores and thus reduce average lengths and widths of the bedding-parallel pore system.Conversely,the average pore lengths and widths are increased in the bedding-perpendicular direction.Besides,heating increases the cross-sectional area of pores in low-maturity oil shales,where this growth tendency fluctuates at<300℃ but becomes steady at>300℃.In addition,the orientation and shape of the newly-formed heating-induced pores follow the habit of the original pores and follow the initial probability distributions of pore orientation and shape.Herein,limited anisotropy is detected in pore direction and shape,indicating similar modes of evolution both bedding-parallel and bedding-normal.We propose a straightforward but robust model to describe evolution of pore system in low-maturity oil shales during heating.
基金funded by the subproject of the National Science and Technology Major Project(No.2017ZX05036004).
文摘Through microscopic analyses(e.g.,organic macerals,thin section observation,scanning electron microscope(SEM)imaging of fresh bedding planes via argon ion milling,and energy spectrum tests)combined with Rock-Eval analyses,this study systematically investigated the organic matter and pyrites in the continental shales in the 3^(rd)submember of the Chang 7 Member(Chang 7^(3)submember)in the Yanchang Formation,Ordos Basin and determined their types and the formation and evolutionary characteristics.The results are as follows.The organic matter of the continental shales in the Chang 7^(3)submember is dominated by amorphous bituminites and migrabitumens,which have come into being since the early diagenetic stage and middle diagenetic stage A,respectively.The formation and transformation of organic matter is a prerequisite for the formation of pyrites.The Ordos Basin was a continental freshwater lacustrine basin and lacked sulphates in waters during the deposition of the Chang 7 Member.Therefore,the syndiagenetic stage did not witness the formation of large quantities of pyrites.Since the basin entered early diagenetic stage A,large quantities of sulfur ions were released as the primary organic matter got converted into bituminites and,accordingly,pyrites started to form.However,this stage featured poorer fluid and spatial conditions compared with the syndepositional stage due to withdraw of water,the partial formation of bituminites,and a certain degree of compaction.As a result,large quantities of pyrrhotite failed to transition into typical spherical framboidal pyrites but grew into euhedral monocrystal aggregates.In addition,pyrites are still visible in the migrabitumens in both microfractures and inorganic pores of mudstones and shales,indicating that the pyrite formation period can extend until the middle diagenetic stage A.
文摘The Saghro massif constitutes a vast metallogenic province with numerous deposits and shows of base metals (lead, zinc, copper) and precious metals (gold and silver), besides various useful substances (talc, pyrophyllite, barite, fluorite). Silver/lead occurrences are concentrated along the Cryogenian Imiter series and moderately at Boumalne and Sidi Flah. Copper occupies the plutonic intrusions and intrusive rocks of the East-Central Saghro while barite deposits are widespread throughout the Cambrian cover of the East Saghro in contact with the Ediacaran basement. To justify this distribution, the new contributions of the cartography and the organic geochemistry of the black shales of Jbel Saghro have clearly shown the particularity of the Imiter black shales in terms of the richness in organic matter (TOC = 0.18%), the blackish color and the friability. The Boumalne and Sidi Flah groups present some similarities with the Imiter group, such as the sub-equatorial structuring, the friable pelites and the richness in organic matter (Boumalne TOC = 0.11% and SidiFlah TOC = 0.16%), which is a quite good show that requires to reinforce the exploration works. For Western Saghro in the Iknioun and Qalaa’t M’Gouna groups, the variations in the thickness of the volcanic cover show an irregular paleotopography with hard, greenish, organic-poor pelitic sediments (TOC = 0.01 to 0.04%). We can conclude that the formation of Imiter-type silver concentrations requires the combination of the sedimentological, the volcanic and structural factors. For Imiter-type silver these factors are: a fine pelitic and argillic casing deposited in a confined environment, a basic volcanism source of metals and other intermediate to acid generated by the hydrothermalism and heat, a convenable paleotopography and a network of fracturations to trap the mineralizations.
基金funded by the National Natural Science Foundation of China(Project 42090025 and 42202152)Heilongjiang Province open competition projects:“Research on the shale oil phase state,seepage mechanism,and integrated geologicalengineering stimulation technology in the Gulong Sag”and“Research on the diagenetic dynamic evolution process and its coupling relationship with pores and fractures”.
文摘Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sag,Songliao Basin is a classic lacustrine pure shale reservoir that contains abundant shale oil resources.The predicted geological reserves of the shale are 1.268×10^(9) t.In this study,field emission scanning electron microscope(FE-SEM),the modular automated processing system(MAPS),pyrolysisgas chromatography(Py-GC),low-pressure nitrogen gas adsorption(LPNA),Soxhlet extraction,pyrolysis,and 2-D nuclear magnetic resonance(NMR)were integrated to describe the shale oil components,microscopic occurrence,mobility,and the effective pore size distribution.Meanwhile,the related controlling factors are discussed.The shale oil in the Qingshankou Fm exists dominantly in the matrix pores of the clay minerals,with small amounts distributed in the intergranular pores of terrigenous clastic grains,intercrystalline pores of pyrite,intragranular pores of ostracod shells,and micro-fractures.Shale oil is distributed in the pore spaces of variable sizes in different lithofacies.The clay mineral-laminated shales are characterized by the broadest range of pore size and largest volume of pore spaces with shale oil distribution,while the ostracod-laminated shales have limited pore spaces retaining oil.Furthermore,the proposed integrated analysis evaluates the shale oil molecules existing in two states:movable,and adsorbed oil,respectively.The result illustrates that movable oil takes up 30.6%e79.4%of the total residual oil.TOC,mineral composition,and pore structures of the shale joint together to control the states and mobility of the shale oil.TOC values are positively correlated with the quantities of shale oil regardless of the state of oil.The mineral components significantly impact the state of shale oil.Noticeable differences in the states of oil were observed following the changing types of minerals,possibly due to their difference in adsorption capacity and wettability.Clay minerals attract more adsorbed oil than movable oil.Felsic minerals generally decrease the occurrence of total and adsorbed oil.Carbonate plays a positive role in hydrocarbon retention of all the shale oil states.As for the pore structure,the average pore size exerts a critical impact on the total,movable,and adsorbed oil content.The total pore volume and specific surface area of shales play a principal role in controlling the total yields and amounts of adsorbed oil.This research improves the understanding of the occurrence characteristics and enrichment mechanisms of shale oil in terrestrial pure shales and provides a reference for locating favorable shale oil exploration areas.
基金funding from the Department of Science and Technology(DST#/SR/S4/ES-528/2010)New Delhi and infrastructural facility from Department of Geology,University of Delhi.Research funding from the Council of Scientific and Industrial Research(CSIR#09/045(1021)/2010-EMR-I)the University of Delhi(Sch./UTA/2010/58053)is also gratefully acknowledged.
文摘With increase in shale gas exploration, inorganic and organic geochemical investigations of shale have become extremely important. Here, we explore the six argillaceous (shale) intervals (Arangi, Koldaha, Rampur, Bijaygarh, Rewa and Sirbu shale) from Son valley sector, Vindhyan Basin with an aim to understand provenance conditions, palaeoclimate, tectonic setting and hydrocarbon generation potential. Whole rock geochemistry indicates Vindhyan sediments derived from felsic source(s) except for Sirbu shale that indicates additional influx of mafic rocks with differentiated felsic source. A comparative study of Vindhyan shale rare earth elements (REEs) points to Mahakoshals and Chhotanagpur gneissic complex (CGC) as probable sediment provenance for Vindhyan sediments. CIA analysis, after necessary corrections for K-metasomatism, suggests evolution in weathering and palaeoclimate indicating a transformation from moderate weathering conditions with warm and humid climate during lower Vindhyan deposition to intense weathering conditions with hot and humid climate during upper Vindhyan deposition. Trace (La/Y vs. Sc/Cr) and REE analysis indicates passive margin setting for Vindhyan sediments whereas a wide range spanning passive to active continental margin setting is also inferred using (Th-Sc-Zr/10) and (Th–La-Sc) ternary diagrams. However, these tectonic discriminant diagrams lack in explaining rift- or sag-related origin of any intracratonic basin such as the Vindhyan Basin. The total organic carbon (TOC) content in Vindhyan shales ranges from 0.29% to 8.44%. The thermally liberated hydrocarbon (S1) values range from 0.01 to 0.18 mg HC/g rock (milligram hydrocarbon per gram of rock sample), whereas hydrocarbon from cracking of the kerogen (S2) shows values ranging from 0.04 to 0.47 mg HC/g rock. Based on modified Van Krevelen correlation (HI vs. Tmax) diagram, organic matter from Arangi and Bijaygarh shales is characterized as thermally mature, Type III kerogen of gas prone character indicating good to very good gas generation potential.
基金supported by Xinjiang Oilfield Company of China(No.2020-C4006).
文摘The Mesozoic and Cenozoic strata in the Junggar basin developed two sets of shallow to semi-deep lacustrine shale, namely, the Cretaceous Qingshuihe Formation (K_(1q)) and the Paleogene Anjihaihe Formation (E_(2-3a)). Through organic petrology and scanning electron microscope (SEM) observation, it is found that the primary hydrocarbon-generating organic matter (OM) in the two sets of strata is different. The biological precursor of the E_(2-3a) OM is mainly green algae (Pediastrum), while the precursor of K_(1q) kerogen is mainly cyanobacteria (Oscillatoria). Then, the E_(2-3a) green algae-rich shale and K_(1q) cyanobacteria-rich shale were subjected to hydrous pyrolysis and kinetic analysis, respectively. The results show that the evolution modes of hydrocarbon generation of the typical shales are very different. Green algae have the characteristics of a low oil generation threshold, heavy oil quality, and no prominent oil peak, while cyanobacteria have the characteristics of late oil generation, concentrated hydrocarbon generation, and relatively light oil quality. The characteristics of oil generation can also be well reflected in the composition evolution of the crude oil components. The carbon isotope of gas, kerogen, and extracts of the E_(2-3a) green algae-rich shale are significantly heavier than the K_(1q) cyanobacteria-rich shale, which may be related to the living habits of their biological precursors, carbon source usage, photosynthesis efficiency, and carbon fixation efficiency.
基金funded by a PetroChina Basic Technology Research Project(No.2021DJ1905).
文摘Deep shale gas(3500-4500 m)will be the important succeeding field for the growth of shale gas production in China.Under the condition of high temperature and high pressure in deep shale gas reservoirs,its gas occurrence characteristics are markedly different from those of medium and shallow layers.To elucidate the gas occurrence characteristics and controlling factors of deep shales in the Wufeng-Longmaxi Formation,methane adsorption,low-temperature N2,and cO2 adsorption experi-ments were conducted.The results show that in deep shales,the mesopores provide approximately 75%of the total specific surface area(SA)and 90%of the total pore volume(PV).Based on two hypotheses and comparing the theoretical and actual adsorption capacity,it is speculated that methane is adsorbed in deep shale in the form of micropore filling,and free gas is mainly stored in the mesopores.Correlation analysis demonstrated that ToC is the key material constraint for the adsorption capacity of deep shale,and micropore SSA is the key spatial constraint.Other minerals and mesopore parameters have limited effect on the amount of adsorbed gas.Moreover,the free gas content ranges from 2.72 m^(3)/t to 6.20 m^(3)/t,with an average value of 4.60 m^(3)/t,and the free gas content ratio is approximately 58%,suggesting that the deep shale gas reservoirs are dominated by free gas.This ratio may also increase to approximately 70%when considering the formation temperature effect on adsorbed gas.Gas density,porosity,and gas saturation are the main controlling factors of free gas content,resulting in significantly larger free gas content in deep shale than in shallower formations.
基金funded by the National Natural Science Foundation of China(41872128)Postdoctoral Foundation of China University of Petroleum(Beijing)(ZX20220102).
文摘The majority of oil and gas resources in the world are related to saline sediments, which mainly occur in sedimentary strata in the form of cap rocks or salt-associated shales. A large number of shale oil resources have been discovered in the saline shale sediments of the Cenozoic terrestrial lake basin in China. The hydrocarbon generation ability and the reservoir capacity of shale control the oil and gas generation. The reservoir capacity is mainly characterized by pore type, structure and porosity. Most of China’s shale oil and gas resources belong to salt-bearing formations. The role of gypsum-salt rocks in the formation and evolution of organic matter (OM) in such formations has received extensive attention. However, systematic understanding is lacking. Research on the pore formation and evolution in shale under the action of gypsum-salt rock sediments is especially weak. Taking the shales in the third member of the Shahejie Formation (Es_(3)) of the Bohai Bay Basin as an example, the influence of halite on the formation and evolution process of pores was studied in this paper. The results show that halite and gypsum minerals were associated with OM, which made them more likely to develop OM pores. The samples with a high halite mineral content (HC) are more developed regarding the pore volume and specific surface area than those with a low HC. The formation of thick salt rocks is influenced by factors of deep thermal brine upwelling, sea erosion and arid environments. The frequent alternation between humid and arid environments led to the outbreak and death of organisms and the precipitation of gypsum-salt rock, which formed the simultaneous deposition of OM and halite minerals. Finally, we have established a model of shale pore evolution under the participation of the gypsum-salt rock, and halite minerals contribute to pore development in both Stage II and Stage IV. This study provides strong microscopic evidence for the pore system formation and evolution in salt-bearing reservoirs.
基金Supported by the the National Natural Science Foundation of China(U22A201550).
文摘On the basis of sorting out current understanding of solid bitumen (SB) in shales and taking organic-rich shales in the first member of the Cretaceous Qingshankou Formation in the Songliao Basin as an example, the definition, classification, occurrence and evolution path of SB are systemtically studied, and the indicative significance of SB reflectance (Rob) on maturity and its influence on the development of reservoir space are discussed and summarized. The results show that the difference of primary maceral types is primarily responsible for the different evolution paths of SB. Most of the pre-oil bitumen is in-situ SB with only a small amount being of migrated SB, while most of the post-oil bitumen and pyrobitumen are migrated SB. From the immature to early oil maturity stage, bituminite, vitrinite, and inertinite can be distinguished from SB based on their optical characteristics under reflected light, and alginite can be differentiated from SB by their fluorescence characteristics. Under scanning electron microscope, in-situ SB and migrated SB can be effectively identified. Rob increases linearly with increasing vitrinite reflectance (Ro), as a result of a decrease of aliphatic structure and the enhancement of aromatization of SB. Within the oil window three types of secondary pores may develop in SB, including modified mineral pores, devolatilization cracks and bubble holes. At a high maturity stage spongy pores may develop in pyrobitumen. Scanning electron microscopy combined with in-situ SEM-Raman spectroscopy can further reveal the structral information of different types of SB, thus providing crucial data for understanding for understanding OM migration paths, dynamics, and distances at micro-scale.
基金Supported by the PetroChina Science and Technology Project(2022KT1205).
文摘The relationship between fracture calcite veins and shale gas enrichment in the deep Ordovician Wufeng Formation-Silurian Longmaxi Formation (Wufeng-Longmaxi) shales in southern Sichuan Basin was investigated through core and thin section observations, cathodoluminescence analysis, isotopic geochemistry analysis, fluid inclusion testing, and basin simulation. Tectonic fracture calcite veins mainly in the undulating part of the structure and non-tectonic fracture calcite veins are mainly formed in the gentle part of the structure. The latter, mainly induced by hydrocarbon generation, occurred at the stage of peak oil and gas generation, while the former turned up with the formation of Luzhou paleouplift during the Indosinian. Under the influence of hydrocarbon generation pressurization process, fractures were opened and closed frequently, and oil and gas episodic activities are recorded by veins. The formation pressure coefficient at the maximum paleodepth exceeds 2.0. The formation uplift stage after the Late Yanshanian is the key period for shale gas migration. Shale gas migrates along the bedding to the high part of the structure. The greater the structural fluctuation is, the more intense the shale gas migration activity is, and the loss is more. The gentler the formation is, the weaker the shale gas migration activity is, and the loss is less. The shale gas enrichment in the core of gentle anticlines and gentle synclines is relatively higher.
基金funded by a National Science and Technology Major Project(No.2016ZX05007)Chinese Academy of Sciences(CAS)Strategic Leading Science&Technology Program(No.XDA14010000)CNPC's"Fourteenth Five-Year Plan"forward-looking basic strategic major scientific and technological project(No.2021DJ3102).
文摘Shale samples from the Ordovician Wulalike Formation at the western margin of the Ordos Basin are studied to define the types, microstructures and connectivity of pores as well as the relationships between the pore structures and gas content of the samples by using experimental techniques such as high-resolution field emission scanning electron microscopy (FESEM), mercury injection capillary pressure (MICP), low-temperature nitrogen adsorption (LTNA), CO_(2) adsorption, and focused ion beam scanning electron microscopy (FIB-SEM). The results show that the shale has 10 different lithofacies, typical mixed sedimentary characteristics, and poorly developed pores. The reservoir space mainly consists of intercrystalline pores, dissolution pores, intergranular pores, and micro-fissures, with organic pores occasionally visible. The pore size is mostly within 0.4–250 nm range but dominated by micropores and mesopores less than 20 nm, with pore numbers peaking at pore sizes of 0.5 nm, 0.6 nm, 0.82 nm, 3 nm, and 10 nm, respectively. The pores are poorly connected and macropores are rarely seen, which may explain the low porosity and low permeability of the samples. Samples with high content of organic matter and felsic minerals are potential reservoirs for oil and gas with their favorable physical properties and high connectivity. The pores less than 5 nm contribute significantly to the specific surface area and serve as important storage space for adsorbed gas.
文摘The petroleum paleo-productivity and generative potential of the Nkporo and Awgu shales in the Lower Benue Trough (LBT) were studied. Major oxides were determined using Spectro Ciros Inductively-coupled plasma optical emission spectrometer (ICP-OES) while trace and rare earth elements were determined using an ELAN 9000 Inductively-coupled plasma mass spectrometer (ICP-MS). The shales have Co/Ni ratios greater than 0.1 suggesting oil source rocks with more marine source input due to brief marine incursion in the transition zone after deposition. The very low Ni values and moderate V values, and a lack of correlation between the TOC and sulphur content, suggests that the organic matter is of terrestrial Type Ⅲ;and the very low paleo-productivity (Ba/Al and P/Ti ratios) suggests that the organic matter is of terrestrial origin. The low V/Ni values of the Nkporo and Awgu shales (Av. ≈ 4) and the high metal concentrations indicate a matured status. From the K/Rb ratios of the Nkporo (191–259) and Awgu shales (198–261), it can be deduced that the organic matter within the shales experienced a considerable loss of K and the shales are mature to generate gaseous hydrocarbons.