Impact of volcanism on the formation and hydrocarbon generation of organic-rich shale in the Jiyang Depression, Bohai Bay Basin, China

Globally,most organic-rich shales are deposited with volcanic ash layers.Volcanic ash,a source for many sedimentary basins,can affect the sedimentary water environment,alter the primary productivity,and preserve the organic matter(OM)through physical,chemical,and biological reactions.With an increasing number of breakthroughs in shale oil exploration in the Bohai Bay Basin in recent years,less attention has been paid to the crucial role of volcanic impact especially its influence on the OM enrichment and hydrocarbon formation.Here,we studied the petrology,mineralogy,and geochemical characteristics of the organic-rich shale in the upper submember of the fourth member(Es_(4)^(1))and the lower submember of the third member(Es_(3)^(3))of the Shahejie Formation,aiming to better understand the volcanic impact on organic-rich shale formation.Our results show that total organic carbon is higher in the upper shale intervals rich in volcanic ash with enriched light rare earth elements and moderate Eu anomalies.This indicates that volcanism promoted OM formation before or after the eruption.The positive correlation between Eu/Eu*and Post-Archean Australian Shale indicates hydrothermal activity before the volcanic eruption.The plane graph of the hydrocarbon-generating intensity(S1+S2)suggests that the heat released by volcanism promoted hydrocarbon generation.Meanwhile,the nutrients carried by volcanic ash promoted biological blooms during Es_(4)^(1 )and Es_(3)^(3) deposition,yielding a high primary productivity.Biological blooms consume large amounts of oxygen and form anoxic environments conducive to the burial and preservation of OM.Therefore,this study helps to further understand the organic-inorganic interactions caused by typical geological events and provides a guide for the next step of shale oil exploration and development in other lacustrine basins in China.

Experimental investigation on pyrolysis products and pore structure characteristics of organic-rich shale heated by supercritical carbon dioxide

The efficient pyrolysis and conversion of organic matter in organic-rich shale,as well as the effective recovery of pyrolysis shale oil and gas,play a vital role in alleviating energy pressure.The state of carbon dioxide(CO_(2))in the pyrolysis environment of shale reservoirs is the supercritical state.Its unique supercritical fluid properties not only effectively heat organic matter,displace pyrolysis products and change shale pore structure,but also achieve carbon storage to a certain extent.Shale samples were made into powder and three sizes of cores,and nitrogen(N_(2))and supercritical carbon dioxide(ScCO_(2))pyrolysis experiments were performed at different final pyrolysis temperatures.The properties and mineral characteristics of the pyrolysis products were studied based on gas chromatography analysis,Xray diffraction tests,and mass spectrometry analysis.Besides,the pore structure characteristics at different regions of cores before and after pyrolysis were analyzed using N_(2) adsorption tests to clarify the impact of fracturing degree on the pyrolysis effect.The results indicate that the optimal pyrolysis temperature of Longkou shale is about 430℃.Compared with N_(2),the oil yield of ScCO_(2) pyrolysis is higher.The pyrolysis oil obtained by ScCO_(2) extraction has more intermediate fractions and higher relative molecular weight.The ScCO_(2) can effectively improve the pore diameter of shale and its effect is better than that of N_(2).The micropores are produced in shale after pyrolysis,and the macropores only are generated in ScCO_(2) pyrolysis environments with temperatures greater than 430℃.The pore structure has different development characteristics at different pyrolysis temperatures,which are mainly affected by the pressure holding of volatile matter and products blocking.Compared to the surface of the core,the pore development effect inside the core is better.With the decrease in core size,the pore diameter,specific surface area,and pore volume of cores all increase after pyrolysis.

Investigation of gas content of organic-rich shale:A case study from Lower Permian shale in southern North China Basin,central China

Measuring gas content is an essential step in estimating the commerciality of gas reserves. In this study,eight shale core samples from the Mouye-1 well were measured using a homemade patented gas desorption apparatus to determine their gas contents. Due to the air contamination that is introduced into the desorption canister, a mathematical method was devised to correct the gas quantity and quality.Compared to the chemical compositions of desorbed gas, the chemical compositions of residual gas are somewhat different. In residual gas, carbon dioxide and nitrogen record a slight increase, and propane is first observed. This phenomenon may be related to the exposure time during the transportation of shale samples from the drilling site to the laboratory, as well as the differences in the mass, size and adsorptivity of different gas molecules. In addition to a series of conventional methods, including the USBM direct method and the Amoco Curve Fit(ACF) method, which were used here for lost gas content estimation, a Modified Curve Fit(MCF) method, based on the 'bidisperse' diffusion model, was established to estimate lost gas content. By fitting the ACF and MCF models to gas desorption data, we determined that the MCF method could reasonably describe the gas desorption data over the entire time period, whereas the ACF method failed. The failure of the ACF method to describe the gas desorption process may be related to its restrictive assumption of a single pore size within shale samples. In comparison to the indirect method, this study demonstrates that none of the three methods studied in this investigation(USBM, ACF and MCF) could individually estimate the lost gas contents of all shale samples and that the proportion of free gas relative to total gas has a significant effect on the estimation accuracy of the selected method. When the ratio of free gas to total gas is lower than 45%, the USBM method is the best for estimating the lost gas content, whereas when the ratio ranges from 45% to 75% or is more than 75%, the ACF and MCF methods, are the best options respectively.

The petrological characteristics and signif icance of organic-rich shale in the Chang 7 member of the Yanchang Formation,south margin of the Ordos basin,central China

The organic-rich shale of the Chang 7 member is the most important source rock in the Ordos basin.The sedimentary environment and the controlling factors of organic matter enrichment,however,are still in contention.In this investigation,the Yishicun outcrop,located on the south margin of the Ordos basin,has been considered for the study.X-ray diffraction,polarizing microscopy,field emission scanning electron microscopy and cathodoluminescence(CL)were used to investigate the petrological features of the organic-rich shale.The content of volcanic ash and the diameter of pyrite framboid pseudocrystals were measured to illustrate the relationship between oxygen level,ash content and the enrichment of organic matter.It has been found that the diameter of pyrite framboid pseudocrystals has a strong correlation with the total organic carbon,demonstrating that the redox status degree of the water column has a positive impact on the enrichment of organic matter.Additionally,with an increase in the ash content,the content of organic matter increased at first and then decreased,and reached a maximum when the ash content was about 6%,illustrating that the ash input has a double effect on the enrichment of organic matter.

Organic-rich rocks;Paleoenvironment;Lucaogou Formation;Jimusar Sag;Junggar Basin

The Lucaogou Formation in the Jimusar Sag of the eastern Junggar Basin is an important sedimentary stratum accumulating huge amounts of lacustrine tight oil in China, where organic-rich rocks are commonly observed. Focusing on the Lucaogou Formation, a precise analysis of the inorganic and organic petrology and the inorganic geochemistry characteristics was conducted. The paleoclimate and paleoenvironment during sedimentation of the Lucaogou Formation were established,and the key factors that were controlling the accumulation of organic matter during this time were identified. The results of this study suggest that during the sedimentation of the Lucaogou Formation, the paleoclimate periodically changed from a humid environment to an arid environment. As a result, the salinity of the water and the redox environment fluctuated.During the sedimentation period, the lake showed su cient nutrient supplies and a high primary productivity. The interval studies in the Lucaogou Formation were divided into five sedimentary cycles, where the first, second, and fifth sedimentary cycles consisted of cyclical paleoclimate fluctuations varied from a humid environment to an arid environment and shifted back to a humid environment with levels of salinity from low to high and decreased again. The third and fourth cycles have cyclical fluctuations from a humid to an arid environment and corresponding salinity variation between low and high levels.During the period when organic-rich rocks in the Lucaogou Formation deposited in the Jimusar Sag, the paleoclimate and the water body were suitable for lower aquatic organisms to flourish. As a result, its paleoproductivity was high, especially during the early period of each cycle. A quiet deep water body is likely to form an anoxic environment at the bottom and is also good for accumulation and preservation of organisms. Fine-grained sediments were accumulated at a low deposition rate, with a low dilution of organic matter. Therefore, high paleoproductivity provided a su cient volume of organisms in the studied area in a quiet deep water body with an anoxic environment and these were the key factors controlling formation of organic-rich rocks.

A rock physics model for the characterization of organic-rich shale from elastic properties

Kerogen content and kerogen porosity play a significant role in elastic properties of organic-rich shales. We construct a rock physics model for organic-rich shales to quantify the effect of kerogen content and kerogen porosity using the Kuster and Toks6z theory and the selfconsistent approximation method. Rock physics modeling results show that with the increase of kerogen content and kerogen-related porosity, the velocity and density of shales decrease, and the effect of kerogen porosity becomes more obvious only for higher kerogen content. We also find that the Poisson＇s ratio of the shale is not sensitive to kerogen porosity for the case of gas saturation. Finally, for the seismic reflection responses of an organic-rich shale layer, forward modeling results indicate the fifth type AVO re- sponses which correspond to a negative intercept and a positive gradient. The absolute values of intercept and gradient increase with kerogen content and kerogen porosity, and present predictable variations associated with velocities and density.

The application of machine learning under supervision in identification of shale lamina combination types——A case study of Chang 7_(3)sub-member organic-rich shales in the Triassic Yanchang Formation,Ordos Basin,NW China

Organic rich laminated shale is one type of favorable reservoirs for exploration and development of continental shale oil in China.However,with limited geological data,it is difficult to predict the spatial distribution of laminated shale with great vertical heterogeneity.To solve this problem,taking Chang 73 sub-member in Yanchang Formation of Ordos Basin as an example,an idea of predicting lamina combinations by combining'conventional log data-mineral composition prediction-lamina combination type identification'has been worked out based on machine learning under supervision on the premise of adequate knowledge of characteristics of lamina mineral components.First,the main mineral components of the work area were figured out by analyzing core data,and the log data sensitive to changes of the mineral components was extracted;then machine learning was used to construct the mapping relationship between the two;based on the variations in mineral composition,the lamina combination types in typical wells of the research area were identified to verify the method.The results show the approach of'conventional log data-mineral composition prediction-lamina combination type identification'works well in identifying the types of shale lamina combinations.The approach was applied to Chang 73 sub-member in Yanchang Formation of Ordos Basin to find out planar distribution characteristics of the laminae.

Factors controlling organic-rich shale development in the Liushagang Formation,Weixinan Sag,Beibu Gulf Basin:Implications of structural activity and the depositional environment

The mechanisms of lacustrine organic-rich shale formation have attracted attention due to its association with global shale oil and shale gas exploration.Samples of general-quality and excellent-quality source rocks,and oil shale from the Beibu Gulf Basin were analyzed to investigate their organic geochemistry,palynofacies,and trace elements.Hydrocarbon potential was higher in the oil shale(29.79 mg/g)than in the general-quality source rock(3.82 mg/g),and its kerogen type wasⅠ-Ⅱ2.Hydrogen-rich liptinite(cutinite and sporinite)components derived from terrigenous higher plants provided most of the hydrocarbon potential of excellent-quality source rock and oil shale.Under the influence of depressioncontrolling fault activity,a deeper subsidence center promotes the deposition of excellent-quality source rock and oil shale in brackish-hypoxic bottom water.A shallower subsidence center,due to subsag-controlling fault activity,promotes the formation of excellent-quality source rock under freshbrackish and weak oxidation-weak reducing conditions.The local uplift and shallow-slope led to the formation of general-quality source rock,under freshwater weak-oxidation conditions.A model was established for organic matter(OM)accumulation in organic-rich shales,accounting for fault activity,terrigenous hydrogen-rich OM,and the preservation conditions,to predict the development of excellent-quality source rock from areas with low levels of exploration.

China organic-rich shale geologic features and special shale gas production issues

The depositional environment of organic-rich shale and the related tectonic evolution in China are rather different from those in North America. In China, organic-rich shale is not only deposited in marine environment, but also in non-marine environment： marine-continental transitional environment and lacustrine environment. Through analyzing large amount of outcrops and well cores, the geologic features of organic-rich shale, including mineral composition, organic matter richness and type, and li- thology stratigraphy, were analyzed, indicating very special characteristics. Meanwhile, the more complex and active tectonic movements in China lead to strong deformation and erosion of organic-rich shale, well-development of fractures and faults, and higher thermal maturity and serious heterogeneity. Co-existence of shale gas, tight sand gas, and coal bed methane （CBM） proposes a new topic： whether it is possible to co-produce these gases to reduce cost. Based on the geologic features, the primary pro- duction issues of shale gas in China were discussed with suggestions.

Laminae combination and shale oil enrichment patterns of Chang 73 sub-member organic-rich shales in the Triassic Yanchang Formation, Ordos Basin, NW China

The Chang 73 sub-member of Triassic Yanchang Formation in the Ordos Basin was taken as an example and the lamina types and combinations,reservoir space features and shale oil enrichment patterns in organic-rich shale strata were investigated using core observation,thin section analysis,XRF element measurement,XRD analysis,SEM,high solution laser Raman spectroscopy analysis,and micro-FTIR spectroscopy analysis,etc.According to the mineral composition and thickness of the laminae,the Chang 73 organic-rich shales have four major types of laminae,tuff-rich lamina,organic-rich lamina,silt-grade feldspar-quartz lamina and clay lamina.They have two kinds of shale oil-bearing layers,"organic-rich lamina+silt-grade feldspar-quartz lamina"and"organic-rich lamina+tuff-rich lamina"layers.In the"organic-rich+silt-grade feldspar-quartz"laminae combination shale strata,oil was characterized by relative high maturation,and always filled in K-feldspar dissolution pores in the silt-grade feldspar-quartz laminae,forming oil generation,migration and accumulation process between laminae inside the organic shales.In the"organic-rich+tuff-rich lamina"binary laminae combination shale strata,however,the reservoir properties were poor in organic-rich shales,the oil maturation was relatively lower,and mainly accumulated in the intergranular pores of interbedded thin-layered sandstones.The oil generation,migration and accumulation mainly occurred between organic-rich shales and interbedded thin-layered sandstones.

Geochemical characteristics and sedimentary environment of the Middle Devonian organic-rich shales in the Northwest of Guizhong Depression, Southwest China

In order to figure out the redox conditions and paleo-sedimentary environment of the Middle Devonian shales in the northwest of Guizhong Depression,the trace element analysis was conducted on the Middle Devonian cores(320.35–938.50 m)of the typical shale gas investigation well(GY-1)at a 1.50 m sampling interval through X-ray fluorescence spectroscopy(XRF)and inductively coupled plasma mass spectrometry(ICP-MS).According to the test result,the average values of V/(V+Ni),V/Cr and Ni/Co in Nabiao formation(Fm.)are larger than 0.67,4.65 and 7.71 respectively,and Nabiao Fm.is rich in biological assemblages such as tabasheer,ammonite,etc.These evidences indicate the rising sea level rose relatively in the sedimentation period of Nabiao Fm.and a deepwater shelf environment,which was favorable for the preservation of organic matters.The V/(V+Ni),V/Cr and Ni/Co in Luofu Fm.and Tangting Fm.are 0.38–0.65,0.73–4.10 and 3.70–6.72 respectively,indicating that the sea level dropped relatively in their sedimentation period,during which the water bodies became shallow,and the sedimentary environment was a weak oxidizing shallow water shelf environment.In addition,the variation of TOC has a high correlation with the enrichment degree of Ba element,indicating the favorable conditions for the enrichment and preservation of organic matters under an oxygen-deficient environment.Moreover,according to the identification of trace element indexes,the northwest of Guizhong Depression experienced the sedimentary cycle of relative rise to relative fall of sea level from bottom to top in the Middle Devonian sedimentation period.The relative sea level rose to the highest in the sedimentation period of Nabiao Fm.,in which the organic-rich shales with stable thickness and high organic content were deposited.Hence,the Nabiao Fm.could be regarded as the favorable exploration target interval in this area.

Types of biogenic quartz and its coupling storage mechanism in organic-rich shales: A case study of the Upper Ordovician Wufeng Formation to Lower Silurian Longmaxi Formation in the Sichuan Basin, SW China

Biogenic quartz in the Upper Ordovician Wufeng Formation to Lower Silurian Longmaxi Formation(WufengLongmaxi)shale layers in the Sichuan Basin and its periphery is qualitatively analyzed and quantitatively characterized by organic petrologic,mineralogic,and geochemical methods to find out the coupling effect between organic matter and quartz.(1)There are two types of biogenic quartz in the shale layers:Type I quartz is submicron quartz appearing in clusters around the organic matter.Type II quartz is in nano-scale grain size and floats in spherical shape on organic matter,with grains in point-to-point or surface-to-surface contact;this type of quartz is mainly biologic origin and slightly affected by hydrothermal activity in local parts.(2)The reservoirs in the Wufeng-Longmaxi formations is consistent in distribution with biogenic silica content in them,and mainly concentrated at the bottom of the Wufeng-Longmaxi formations,and is thinner in the Changning and Weiyuan regions,while thicker in the Fuling region.(3)The biogenic quartz in the Wufeng-Longmaxi shale worked through the entire evolution process of hydrocarbon generation.The presence of biogenic quartz can enhance the development of organic matter pores and microcracks,and can effectively preserve the organic matter pores and residual intergranular pores,forming"biological silicon intergranular pores,organic pores and micro-fractures".This would benefit later hydraulic fracturing and result in high production/stable production of well.The coupling effect between biogenic quartz development and organic matter evolution and hydrocarbon generation is a critical factor for high-quality shale reservoir development.

Deformation mechanism and hydrocarbon significance of Eocene organic-rich fine-grained soft sediments in the Leijia Region,Liaohe Depression

The deformation structure of soft sediments has always been a research hotspot,which is of great significance for analyzing the tectonic and sedimentary evolution background of a basin,as well as the physical properties of reservoirs.Previous studies have reported that a large number of soft sediment deformation structures are developed in the western part of Liaohe depression.In this study,through core observation and thin section identification,various types of deformation structures are identified in the core samples which are collected from the upper Es4 in the Leijia region,western sag of Liaohe depression,such as liquefied dikes,liquefied breccia,convoluted laminae,annular bedding,synsedimentary faults,vein structures,etc.Based on the characteristics of core structure,single well profile and continuous well profile,combined with the regional background,this study clarifies that the deformation structure of soft sediments in the study area is mainly caused by seismic action.It is found that the permeability and porosity of deformation layers in the study area are higher than those of the undeformation layers,which proves that the deformation structure of soft sediments has a good effect on improving the physical properties of reservoirs.

Organic-rich formation and hydrocarbon enrichment of lacustrine shale strata:A case study of Chang 7 Member

Lacustrine shale is an important target for the exploration of unconventional oil and gas in China beyond marine shale gas.However,the formation environment of lacustrine shale differs from that of marine shale,resulting in a different reservoir composition,organic matter,oil and gas content,and hydrocarbon mobility.In this study,the Chang 7 shale of the Yanchang Formation in the Ordos Basin was used to analyze the effect of volcanic activity on the paleoproductivity and preservation conditions during the formation of lacustrine shale.The results show that algae and bacteria were developed before the eruption.After the eruption,the number of bacteria declined,but the increased prosperity of algae reflects that the volcanic activity enhanced ancient productivity.The sulfate generated by volcanic activity promotes bacterial sulfate reduction,and the produced H_(2)S leads to a strong reducing environment in the waterbody,which is conducive to the preservation of organic matter.Organic geochemical analysis shows that the black shale in the shale strata has a high total organic carbon(TOC)content and strong hydrocarbon generation potential,whereas the tuff has a low TOC content and can scarcely generate hydrocarbons,indicating that the tuff deposited by volcanic activity cannot be considered as effective source rock.In terms of storage space,shale is mainly laminar and dispersed,and it includes organic and inorganic pores.The development of organic pores is affected by thermal maturity,whereas inorganic pores mainly occur between detrital particles and crystals.Tuff is mainly supported by heterogeneous matrix and associated with alteration.Its pores include inter-and intragranular mineral pores.The development of tight sandstone pores is affected by compaction,cementation,and dissolution,which mainly consist of intra-and intergranular pores.The Chang 7 lacustrine shale generally contains oil,but different lithologies have different oil drainage efficiencies.Sandstone and shale exhibit the best and worst oil drainage efficiency,respectively.It is mainly affected by the pore size distribution,fluid properties,and rock wettability.Therefore,the development of shale oil should mainly focus on lacustrine shale formations with interbeds.The mutual dissolution of organic matter and hydrocarbons in the shale section leads to the poor mobility and difficult development of hydrocarbons.

Pore characteristics and formation mechanism of high-maturity organic-rich shale in Lower Cambrian Jiumenchong Formation,southern Guizhou

In order to investigate pore characteristics and formation mechanism in the high-maturity organic-rich shale of Lower Cambrian Jiumenchong Formation in southern Guizhou,the pore structure,pore type and storage properties are well studied through the rock thin section,total rock X-ray diffraction,lowtemperature nitrogen adsorption,high pressure mercury injection-adsorption test,helium porosity test,argon ion polishing-scanning electron microscope,thermal evolution and pore evolution history reconstruction,and based on the diagenesis and compaction as well as thermal evolution process,a microscopic pore formation and evolution model of high-maturity organic-rich shale are established.The result shows that the high-maturity organic-rich shale of Jiumenchong Formation has the average total specific surface area of 12.66m^(2)/g and the total pore volume of 11.54×10^(-3)cm^(3)/g,and the total specific surface area have a positive correlation with total pore volume;the total specific surface area and the total pore volume are slightly lower compared with the Lower Silurian shale.The pores are dominated by micropores and mesopores,while macropores are very rare.The pores of the organic-rich shale mainly are organic pores with small diameter usually less than 30 nm,and the pore boundary form is irregular,the inorganic mineral pores are not developed.Compared with the Silurian shale,the shale has poorer reservoir property,the average porosity is only 2.80%;the horizontal permeability is 1e3 times of the vertical permeability,indicating the horizontal lamellations are not developed.The formation and evolution of pores in high-maturity organic-rich shale is jointly influenced by the evolutionary process of intergranular pores of inorganic mineral under the control of the diagenesis and compaction,the organic pore formation process in the hydrocarbon generation-oil formation-oil and gas transformation sequence under the control of thermal evolution,and the natural gas loss-supply equilibration process under the condition of later pore preservation.

Sedimentary and geochemical characteristics of the Triassic Chang 7 Member shale in the Southeastern Ordos Basin,Central China

The Ordos Basin is the largest petroliferous basin in China, where the Chang 7 Member shale serves as the major source rock in the basin, with an area of more than 100,000 km^2 So far, sedimentary and geochemical characterizations have rarely been conducted on the shale in shallow(< 1000 m) areas in the southeastern part of the basin, but such characterizations can help identify the genesis of organic-rich shale and promote the prediction and recovery of shale oil. In this paper,several outcrop sections of the Chang 7 Member in the Tongchuan area were observed and sampled, and sedimentary and geochemical characterizations were conducted for the well-outcropped YSC section. The study results show that the Chang7 Member shale is widely distributed laterally with variable thickness. The organic-rich shale is 7-25 m thick in total and exhibits obvious horizontal variation in mineral composition. In the eastern sections, the shale contains organic matter of TypeⅡ_2-Ⅲ and is low in thermal maturity, with high clay mineral content, low K-feldspar content, and no pyrite. In the western sections, the shale contains Type Ⅱ_1 organic matter and is low in thermal maturity, with high clay mineral, K-feldspar, and pyrite contents. The YSC section reveals three obvious intervals in vertical mineral composition and organic abundance.The Chang 7 Member organic-rich shale(TOC > 10%) contains mainly sapropelite and liptinite, with Type Ⅱ kerogen. It is generally characterized by a hydrocarbon potential of more than 70 mg/g, low maturity, and shallow-semideep lacustrine facies. In the western sections, the shale, still in a low maturity stage, has a higher hydrocarbon potential and is optional for shale oil recovery. However, the Chang 7 Member shale in the study area is highly heterogeneous and its shale oil recovery is practical only in the organic-rich intervals.

Shale Gas Formation and Occurrence in China： An Overview of the Current Status and Future Potential

Shale gas is one of the most promising unconventional resources both in China and abroad. It is known as a form of self-contained source-reservoir system with large and continuous dimensions. Through years of considerable exploration efforts, China has identified three large shale gas fields in the ruling, Changning and Weiyuan areas of the Sichuan Basin, and has announced more than 540 billion m3 of proven shale gas reserves in marine shale systems. The geological theories for shale gas development have progressed rapidly in China as well. For example, the new depositional patterns have been introduced for deciphering the paleogeography and sedimentary systems of the Wufeng shale and Longmaxi shale in the Sichuan Basin. The shale gas storage mechanism has been widely accepted as differing from conventional natural gas in that it is adsorbed on organic matter or a mineral surface or occurs as free gas trapped in pores and fractures of the shale. Significant advances in the techniques of microstructural characterization have provided new insights on how gas molecules are stored in micro- and nano-scale porous shales. Furthermore, newly-developed concepts and practices in the petroleum industry, such as hydraulic fracturing, microseismic monitoring and multiwell horizontal drilling, have made the production of this unevenly distributed but promising unconventional natural gas a reality. China has 10-36 trillion m3 of promising shale gas among the world＇s whole predicted technically recoverable reserves of 206.6 trillion m3. China is on the way to achieving its goal of an annual yield of 30-50 billion m3 by launching more trials within shale gas projects.

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR, FT-IR, XRD and HRTEM

Kerogen plays an important role in shale gas adsorption,desorption and diffusion.Therefore,it is necessary to characterize the molecular structure of kerogen.In this study,four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation.Raman spectroscopy was used to determine the maturity of these kerogen samples.Highresolution transmission electron microscopy(HRTEM),13 C nuclear magnetic resonance(13 C NMR),X-ray diffraction(XRD)and Fourier transform infrared(FT-IR)spectroscopy were conducted to characterize the molecular structure of the shale samples.The results demonstrate that VReqv of these kerogen samples vary from 2.3%to 2.8%,suggesting that all the kerogen samples are in the dry gas window.The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic(fa’=0.56).In addition,the aromatic structural units are mainly composed of naphthalene(23%),anthracene(23%)and phenanthrene(29%).However,the aliphatic structure of the kerogen macromolecules is relatively low(fal*+falH=0.08),which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units.The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups(fac=0.23)and hydroxyl groups or ether groups(falO=0.13).The crystallite structural parameters of kerogen,including the stacking height(Lc=22.84?),average lateral size(La=29.29?)and interlayer spacing(d002=3.43?),are close to the aromatic structural parameters of anthracite or overmature kerogen.High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented,and more than 65%of the diffractive aromatic layers are concentrated in the main direction.Due to the continuous deep burial,the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted.However,the ductility and stacking degree of the aromatic structure increases during thermal evolution.This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods,which may contribute to an improved understanding of the organic pores in black shale.

Paleoenvironment and organic matter enrichment of the Carboniferous volcanic-related source rocks in the Malang Sag,Santanghu Basin,NW China

Volcanic activity was quite frequent during the deposition of the Late Carboniferous Ha’erjiawu Formation in the Santanghu Basin.The petrology and organic and inorganic geochemical indicators were used to investigate hydrocarbon potential,paleoenvironmental conditions and organic matter enrichment of the mudstones.The results show that the oil generation capacity of the Ha’erjiawu Formation mudstones,which has abundant oil-prone organic matter(TypeⅡkerogen with hydrogen index values mainly ranging from 250 to 550 mg HC/g TOC)in mature stage(Tmax values mainly ranging from 435 to 450℃),is considerable.The Ha’erjiawu Formation was deposited in a dysoxic,freshwater-mildly brackish,and warm-humid environment.During its deposition,the Ha’erjiawu Formation received hydrothermal inputs.The volcanic hydrothermal activities played an important role in the organic matter enrichment.In addition,the total organic carbon(TOC)is significantly positively correlated with the felsic mineral content,but it is negatively correlated with the carbonate mineral content and C27/C29 ratios,indicating that terrigenous organic matter input also contributed to the primary productivity in the surface water.Therefore,the formation of the high-quality source rocks in the Ha’erjiawu Formation was jointly affected by the hydrothermal activity and the terrigenous organic matter input.

Safe and Stable Lithium Metal Batteries Enabled by an Amide-Based Electrolyte

The formation of lithium dendrites and the safety hazards arising from flammable liquid electrolytes have seriously hindered the development of high-energy-density lithium metal batteries.Herein,an emerging amide-based electrolyte is proposed,containing LiTFSI and butyrolactam in different molar ratios.1,1,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropylether and fluoroethylene carbonate are introduced into the amide-based electrolyte as counter solvent and additives.The well-designed amide-based electrolyte possesses nonflammability,high ionic conductivity,high thermal stability and electrochemical stability(>4.7 V).Besides,an inorganic/organic-rich solid electrolyte interphase with an abundance of LiF,Li3N and Li-N-C is in situ formed,leading to spherical lithium deposition.The formation mechanism and solvation chemistry of amide-based electrolyte are further inves-tigated by molecular dynamics simulations and density functional theory.When applied in Li metal batteries with LiFePO4 and LiMn2O4 cathode,the amide-based electrolyte can enable stable cycling performance at room temperature and 60℃.This study provides a new insight into the development of amide-based electrolytes for lithium metal batteries.