Quantitative characterizations of anisotropic dynamic properties in organic-rich shale with different kerogen content

Understanding the quantitative responses of anisotropic dynamic properties in organic-rich shale with different kerogen content(KC)is of great significance in hydrocarbon exploration and development.Conducting controlled experiments with a single variable is challenging for natural shales due to their high variations in components,diagenesis conditions,or pore fluid.We employed the hot-pressing technique to construct 11 well-controlled artificial shale with varying KC.These artificial shale samples were successive machined into prismatic shape for ultrasonic measurements along different directions.Observations revealed bedding perpendicular P-wave velocities are more sensitive to the increasing KC than bedding paralleling velocities due to the preferential alignments of kerogen.All elastic stiffnesses except C_(13)are generally decreasing with the increasing KC,the variation of C_(1) and C_(33)on kerogen content are more sensitive than those of C_(44)and C_(66).Apparent dynamic mechanical parameters(v and E)were found to have linear correlation with the true ones from complete anisotropic equations independent of KC,which hold value towards the interpretation of well logs consistently across formations,Anisotropic mechanical parameters(ΔE and brittlenessΔB)tend to decrease with the reducing KC,withΔB showing great sensitivity to KC variations.In the range of low KC(<10%),the V_(P)/V_(S) ratio demonstrated a linearly negative correlation with KC,and the V_(P)/V_(S) ratio magnitude of less than 1.75may serve as a significant characterization for highly organic-rich(>10%)shale,compilation of data from natural organic rich-shales globally verified the similar systematic relationships that can be empirically used to predict the fraction of KC in shales.

Extractable and kerogen-bound hopanoids from typical Eocene oil shales in China

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.

Quantitative effect of kerogen type on the hydrocarbon generation potential of Paleogene lacustrine source rocks,Liaohe Western Depression,China

Kerogen types exert a decisive effect on the onset and capacity of hydrocarbon generation of source rocks.Lacustrine source rocks in the Liaohe Western Depression are characterized by thick deposition,high total organic carbon(TOC)content,various kerogen types,and a wide range of thermal maturity.Consequently,their hydrocarbon generation potential and resource estimation can be misinterpreted.In this study,geochemical tests,numerical analysis,hydrocarbon generation kinetics,and basin modeling were integrated to investigate the differential effects of kerogen types on the hydrocarbon generation potential of lacustrine source rocks.Optimized hydrocarbon generation and expulsion(HGE)models of different kerogen types were established quantitatively upon abundant Rock-Eval/TOC/vitrinite reflectance(R_(o))datasets.Three sets of good-excellent source rocks deposited in the fourth(Es4),third(Es3),and first(Es1)members of Paleogene Shahejie Formation,are predominantly types I-II_(1),II_(1)-II_(2),and II-III,respectively.The activation energy of types I-II_(2)kerogen is concentrated(180-230 kcal/mol),whereas that of type III kerogen is widely distributed(150-280 kcal/mol).The original hydrocarbon generation potentials of types I,II_(1),II_(2),and III kerogens are 790,510,270,and 85 mg/g TOC,respectively.The Ro values of the hydrocarbon generation threshold for type I-III source rocks gradually increase from 0.42%to 0.74%,and Ro values of the hydrocarbon expulsion threshold increase from 0.49%to 0.87%.Types I and II_(1)source rocks are characterized by earlier hydrocarbon generation,more rapid hydrocarbon expulsion,and narrower hydrocarbon generation windows than types II_(2)and III source rocks.The kerogen types also affect the HGE history and resource potential.Three types(conventional,tight,and shale oil/gas)and three levels(realistic,expected,and prospective)of hydrocarbon resources of different members in the Liaohe Western Depression are evaluated.Findings suggest that the Es3 member has considerable conventional and unconventional hydrocarbon resources.This study can quantitatively characterize the hydrocarbon generation potential of source rocks with different kerogen types,and facilitate a quick and accurate assessment of hydrocarbon resources,providing strategies for future oil and gas exploration.

A semi-analytical model for coupled flow in stress-sensitive multi-scale shale reservoirs with fractal characteristics

A large number of nanopores and complex fracture structures in shale reservoirs results in multi-scale flow of oil. With the development of shale oil reservoirs, the permeability of multi-scale media undergoes changes due to stress sensitivity, which plays a crucial role in controlling pressure propagation and oil flow. This paper proposes a multi-scale coupled flow mathematical model of matrix nanopores, induced fractures, and hydraulic fractures. In this model, the micro-scale effects of shale oil flow in fractal nanopores, fractal induced fracture network, and stress sensitivity of multi-scale media are considered. We solved the model iteratively using Pedrosa transform, semi-analytic Segmented Bessel function, Laplace transform. The results of this model exhibit good agreement with the numerical solution and field production data, confirming the high accuracy of the model. As well, the influence of stress sensitivity on permeability, pressure and production is analyzed. It is shown that the permeability and production decrease significantly when induced fractures are weakly supported. Closed induced fractures can inhibit interporosity flow in the stimulated reservoir volume (SRV). It has been shown in sensitivity analysis that hydraulic fractures are beneficial to early production, and induced fractures in SRV are beneficial to middle production. The model can characterize multi-scale flow characteristics of shale oil, providing theoretical guidance for rapid productivity evaluation.

Shale porosity measurement by the saturated oil method: Removing the contribution from oils dissolved in kerogen

Shale porosity measurements have crucial scientific and economical applications in unconventionalpetroleum systems. As a standard technique, liquid saturation methods, including water saturation (WS)and oil saturation (OS), have been widely used to measure the porosity of many rock types. For clay-richshale reservoirs with high organic matter content, it is well known that the WS method may cause clayswelling and induce structural changes in the pore system. The OS method affects the accuracy ofporosity measurements because of some of the oil being dissolved by kerogen within the shale;however,this has not received sufficient research attention. In this study, we compare the previously reported andnewly tested OS porosities with helium (He) expansion porosity. Results show that OS porosity generallyexceeds the He porosity. Furthermore, the higher the total organic carbon (TOC) content and lower thematurity of shale, the greater the difference between the OS and helium porosities. When using the OSmethod, the effect of kerogen-dissolved oil causes an overestimation of the shale porosity by ~30%. To thebest of our knowledge, this is the first time to note the kerogen-dissolve oil effects on OS porosity. Herein,we propose a new, simple, and effective correction method for estimating OS porosity that involvessubtracting the kerogen-dissolved oil content from raw OS porosity. In addition, the quantification modelof kerogen-dissolved oil capacity is established, taking into account the abundance and maturity oforganic matter. Taking the He porosity as the benchmark, the absolute error of the corrected OS porositydoes not exceed 1% and the average relative error is only ~10%. The obtained results can help improve theaccuracy of shale porosity evaluation methods.

Effect of fracture fluid flowback on shale microfractures using CT scanning

The field data of shale fracturing demonstrate that the flowback performance of fracturing fluid is different from that of conventional reservoirs,where the flowback rate of shale fracturing fluid is lower than that of conventional reservoirs.At the early stage of flowback,there is no single-phase flow of the liquid phase in shale,but rather a gas-water two-phase flow,such that the single-phase flow model for tight oil and gas reservoirs is not applicable.In this study,pores and microfractures are extracted based on the experimental results of computed tomography(CT)scanning,and a spatial model of microfractures is established.Then,the influence of rough microfracture surfaces on the flow is corrected using the modified cubic law,which was modified by introducing the average deviation of the microfracture height as a roughness factor to consider the influence of microfracture surface roughness.The flow in the fracture network is simulated using the modified cubic law and the lattice Boltzmann method(LBM).The results obtained demonstrate that most of the fracturing fluid is retained in the shale microfractures,which explains the low fracturing fluid flowback rate in shale hydraulic fracturing.

Biodegradation of occluded hydrocarbons and kerogen macromolecules of the Permian Lucaogou shales,Junggar Basin,NW China

Three kerogen samples(JJZG-1,JJZG-2 and JJZG-3)isolated from the Permian Lucaogou shales of varying biodegradation levels(BLs≈0,3 and 7,respectively)were subjected to sequential stepwise pyrolysis combined with on-line detection of gas chromatography-mass spectrometry(GC-MS).Occluded fractions(bitumenⅡ)released at low-temperature steps(≥410℃)show consistent biodegradative signatures with that reported for solvent-extracted fractions(bitumenⅠ)of the original shales,e.g.,broad range of abundant n-alkanes,isoprenoids and regular hopanes for the non-biodegraded JJZG-1;trace n-alkanes and abundant hopanes for the moderately biodegraded JJZG-2;and no n-alkanes but still prominent hopanes including the microbially produced 25-nohopanes for the severely biodegraded JJZG-3.This consistency between bitumenⅡand bitumenⅠfractions indicates the biodegradability of the kerogenoccluded bitumenⅡwith limited protection from host kerogen.A minor level of protection was suggested by the trace distribution of n-alkanes in the bitumenⅡof JJZG-2,whereas the bitumenⅠhad no nalkanes.The kerogen itself was more resistant to biodegradation as reflected by the persistence of high abundances of both n-alkanes and hopanes in the high temperature(≥460℃)products of all three kerogen samples.However,the relative abundances of these product groups did show some evidence of biodegradation alteration,e.g.,ratios of n-C_(15)alkene/C_(27)hop-17(21)-ene at 510℃pyrolysis decreased by order of magnitude from the non-biodegraded(JJZG-1=27.4)to highly biodegraded(0.3 for JJZG-3)samples.The reduced biodegradation impact on the kerogen fraction(Cf.bitumen fractions)was also evident by the absence of 25-norhopanes in the high-temperature analysis of the JJZG-3 kerogen.

Development review and the prospect of oil shale in-situ catalysis conversion technology

As an unconventional resource, oil shale possesses abundant reserves and significant potential for industrial applications. The rational and efficient development of oil shale resources holds immense importance in reducing national energy demand. In-situ catalytic technology, characterized by its high efficiency, low pollution, and minimal energy consumption, represents a key direction for future oil shale development. This paper provides a comprehensive review of research progress in in-situ oil shale mining technology, oil shale pyrolysis catalysts, the pyrolysis mechanism of kerogen, and the compatibility of different heating processes and catalysts. Furthermore, the paper proposes future research directions and prospects for oil shale in-situ catalytic technology, including reservoir modification, highefficiency catalyst synthesis, injection processes, and high-efficiency heating technology. These insights serve as valuable technical references for the advancement of oil shale in-situ catalytic technology.

Geological conditions and reservoir characteristics of various shales in major shalehosted regions of China

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.

Geologic characteristics,exploration and production progress of shale oil and gas in the United States:An overview

We present a systematic summary of the geological characteristics,exploration and development history and current state of shale oil and gas in the United States.The hydrocarbon-rich shales in the major shale basins of the United States are mainly developed in six geological periods:Middle Ordovician,Middle-Late Devonian,Early Carboniferous(Middle-Late Mississippi),Early Permian,Late Jurassic,and Late Cretaceous(Cenomanian-Turonian).Depositional environments for these shales include intra-cratonic basins,foreland basins,and passive continental margins.Paleozoic hydrocarbon-rich shales are mainly developed in six basins,including the Appalachian Basin(Utica and Marcellus shales),Anadarko Basin(Woodford Shale),Williston Basin(Bakken Shale),Arkoma Basin(Fayetteville Shale),Fort Worth Basin(Barnett Shale),and the Wolfcamp and Leonardian Spraberry/Bone Springs shale plays of the Permian Basin.The Mesozoic hydrocarbon-rich shales are mainly developed on the margins of the Gulf of Mexico Basin(Haynesville and Eagle Ford)or in various Rocky Mountain basins(Niobrara Formation,mainly in the Denver and Powder River basins).The detailed analysis of shale plays reveals that the shales are different in facies and mineral components,and"shale reservoirs"are often not shale at all.The United States is abundant in shale oil and gas,with the in-place resources exceeding 0.246×10^(12)t and 290×10^(12)m^(3),respectively.Before the emergence of horizontal well hydraulic fracturing technology to kick off the"shale revolution",the United States had experienced two decades of exploration and production practices,as well as theory and technology development.In 2007-2023,shale oil and gas production in the United States increased from approximately 11.2×10^(4)tons of oil equivalent per day(toe/d)to over 300.0×10^(4)toe/d.In 2017,the shale oil and gas production exceeded the conventional oil and gas production in the country.In 2023,the contribution from shale plays to the total U.S.oil and gas production remained above 60%.The development of shale oil and gas has largely been driven by improvements in drilling and completion technologies,with much of the recent effort focused on“cube development”or“co-development”.Other efforts to improve productivity and efficiency include refracturing,enhanced oil recovery,and drilling of“U-shaped”wells.Given the significant resources base and continued technological improvements,shale oil and gas production will continue to contribute significant volumes to total U.S.hydrocarbon production.

“Component flow”conditions and its effects on enhancing production of continental medium-to-high maturity shale oil

Based on the production curves,changes in hydrocarbon composition and quantities over time,and production systems from key trial production wells in lacustrine shale oil areas in China,fine fraction cutting experiments and molecular dynamics numerical simulations were conducted to investigate the effects of changes in shale oil composition on macroscopic fluidity.The concept of“component flow”for shale oil was proposed,and the formation mechanism and conditions of component flow were discussed.The research reveals findings in four aspects.First,a miscible state of light,medium and heavy hydrocarbons form within micropores/nanopores of underground shale according to similarity and intermiscibility principles,which make components with poor fluidity suspended as molecular aggregates in light and medium hydrocarbon solvents,such as heavy hydrocarbons,thereby decreasing shale oil viscosity and enhancing fluidity and outflows.Second,small-molecule aromatic hydrocarbons act as carriers for component flow,and the higher the content of gaseous and light hydrocarbons,the more conducive it is to inhibit the formation of larger aggregates of heavy components such as resin and asphalt,thus increasing their plastic deformation ability and bringing about better component flow efficiency.Third,higher formation temperatures reduce the viscosity of heavy hydrocarbon components,such as wax,thereby improving their fluidity.Fourth,preservation conditions,formation energy,and production system play important roles in controlling the content of light hydrocarbon components,outflow rate,and forming stable“component flow”,which are crucial factors for the optimal compatibility and maximum flow rate of multi-component hydrocarbons in shale oil.The component flow of underground shale oil is significant for improving single-well production and the cumulative ultimate recovery of shale oil.

The influences of perforating phase and bedding planes on the fracture deflection in laminated shale

The perforating phase leads to complex and diverse hydraulic fracture propagation behaviors in laminated shale formations. In this paper, a 2D high-speed imaging scheme which can capture the interaction between perforating phase and natural shale bedding planes was proposed. The phase field method was used to simulate the same conditions as in the experiment for verification and hydraulic fracture propagation mechanism under the competition of perforating phase and bedding planes was discussed.The results indicate that the bedding planes appear to be no influence on fracture propagation while the perforating phase is perpendicular to the bedding planes, and the fracture propagates along the perforating phase without deflection. When the perforating phase algins with the bedding planes, the fracture initiation pressure reserves the lowest value, and no deflection occurs during fracture propagation. When the perforating phase is the angle 45°, 60°and 75°of bedding planes, the bedding planes begin to play a key role on the fracture deflection. The maximum deflection degree is reached at the perforating phase of75°. Numerical simulation provides evidence that the existence of shale bedding planes is not exactly equivalent to anisotropy for fracture propagation and the difference of mechanical properties between different shale layers is the fundamental reason for fracture deflection. The findings help to understand the intrinsic characteristics of shale and provide a theoretical basis for the optimization design of field perforation parameters.

Influences of shale microstructure on mechanical properties and bedding fractures distribution

The difference in microstructure leads to the diversity of shale mechanical properties and bedding fractures distribution patterns.In this paper,the microstructure and mechanical properties of Longmaxi marine shale and Qingshankou continental shale were studied by X-ray diffractometer(XRD),field emission scanning electron microscope(FE-SEM)with mineral analysis system,and nanoindentation.Additionally,the typical bedding layers area was properly stratified using Focused Ion Beam(FIB),and the effects of microstructure and mechanical properties on the distribution patterns of bedding fractures were analyzed.The results show that the Longmaxi marine shale sample contains more clay mineral grains,while the Qingshankou continental shale sample contains more hard brittle mineral grains such as feldspar.For Longmaxi marine shale sample,hard brittle minerals with grain sizes larger than 20μm is18.24%and those with grain sizes smaller than 20μm is 16.22%.For Qingshankou continental shale sample,hard brittle minerals with grain sizes larger than 20μm is 40.7%and those with grain sizes smaller than 20μm is 11.82%.In comparison to the Qingshankou continental shale sample,the Longmaxi marine shale sample has a lower modulus,hardness,and heterogeneity.Laminated shales are formed by alternating coarse-grained and fine-grained layers during deposition.The average single-layer thickness of Longmaxi marine shale sample is greater than Qingshankou continental shale sample.The two types of shale have similar bedding fractures distribution patterns and fractures tend to occur in the transition zone from coarse-grained to fine-grained deposition.The orientation of the fracture is usually parallel to the bedding plane and detour occurs in the presence of hard brittle grains.The fracture distribution density of the Longmaxi marine shale sample is lower than that of the Qingshankou continental shale sample due to the strong heterogeneity of the Qingshankou continental shale.The current research provides guidelines for the effective development of shale reservoirs in various sedimentary environments.

Experimental and numerical simulation study on the erosion behavior of the elbow of gathering pipeline in shale gas field

During the production period of shale gas, proppant particles and rock debris are produced together,which will seriously erode the elbows of gathering pipelines. In response to this problem, this paper takes the elbow of the gathering pipeline in the Changning Shale Gas Field as an example to test the erosion rate and material removal mechanism of the test piece at different angles of the elbow through experiments and compares the four erosion models with the experimental results. Through analysis, it is found that the best prediction model for quartz sand-carbon steel erosion is the Oka model. Based on the Oka model, FLUENT software was used to simulate and analyze the law of erosion of the elbow of the gas gathering pipeline under different gas flow velocities, gas gathering pressure, particle size, length of L1,and bending directions of the elbow. And a spiral pipeline structure is proposed to reduce the erosion rate of the elbow under the same working conditions. The results show that this structure can reduce erosion by 34%.

Sedimentary Environment and Mineralization of the Black Shale Polymetallic Layer in the Early Cambrian,SW China:Constraints from in situ LA-ICP-MS Analysis of Pyrite

A polymetallic layer is usually developed at the bottom of the early Cambrian black shale in Guizhou Province.The mineral that makes up the polymetallic layer is related to the sedimentary facies.To analyze the differentiation mechanism between polymetallic deposits(Ni-Mo and V),the Zhijin Gezhongwu profile located in the outer shelf and the Sansui Haishan V deposit located in the lower slope are selected to study the in situ sulfur isotopes and trace elements of pyrite.The results show that δ^(34)S values of pyrite vary widely from−7.8‰to 28‰in the Gezhongwu profile,while the δ^(34)S values are relatively uniform(from 27.8‰to 38.4‰)in the Haishan profile.The isotopic S composition is consistent with the transition that occurs in the sedimentary phase from the shelf to the deep sea on the transgressive Yangtze platform;this indicates that the δ^(34)SO_(4)^(2−)values in seawater must be differently distributed in depositional environments.The sulfur in the Ni-Mo layer is produced after the mixing of seawater and hydrothermal fluid,while the V layer mainly originates from seawater.Overall,the Ni-Mo and V deposits have been differentiated primarily on the basis of the combined effect of continental weathering and hydrothermal fluid.

Hydraulic fracturing behaviors of shale under coupled stress and temperature conditions simulating different burial depths

Fracture propagation in shale under in situ conditions is a critical but poorly understood mechanical process in hydraulic fracturing for deep shale gas reservoirs. To address this, hydraulic fracturing experiments were conducted on hollow double-wing crack specimens of the Longmaxi shale under conditions simulating the ground surface(confining pressure σ_(cp)=0, room temperature(Tr)) and at depths of 1600 m(σ_(cp)=40 MPa, Ti=70 ℃) and 3300 m(σ_(cp)=80 MPa, high temperature Ti=110 ℃) in the study area.High in situ stress was found to significantly increase fracture toughness through constrained microcracking and particle frictional bridging mechanisms. Increasing the temperature enhances rather than weakens the fracture resistance because it increases the grain debonding length, which dissipates more plastic energy and enlarges grains to close microdefects and generate compressive stress to inhibit microcracking. Interestingly, the fracture toughness anisotropy in the shale was found to be nearly constant across burial depths, despite reported variations with increasing confining pressure. Heated water was not found to be as important as the in situ environment in influencing shale fracture. These findings emphasize the need to test the fracture toughness of deep shales under coupled in situ stress and temperature conditions rather than focusing on either in situ stress or temperature alone.

Further study on the genesis of lamellar calcite veins in lacustrine black shale--A case study of Paleogene in Dongying Depression, China

Lamellar calcite veins are prevalent in carbonate-rich,lacustrine dark shale.The formation mechanisms of these veins have been extensively debated,focusing on factors such as timing,depth,material source,and driving forces.This paper examines dark lacustrine shale lamellar calcite veins in the Paleogene strata of Dongying Depression,using various analytical techniques:petrography,isotope geochemistry,cathodoluminescence,inclusion thermometry,and electron probe micro-analysis.Two distinct types of calcite veins have been identified:granular calcite veins and sparry calcite veins.These two types differ significantly in color,grain structure,morphology,and inclusions.Through further investigation,it was observed that vein generation occurred from the shallow burial period to the maturation of organic matter,with a transition from granular calcite veins to sparry calcite veins.The granular calcite veins exhibit characteristics associated with the shallow burial period,including plastically deformed laminae and veins,the development of strawberry pyrite,the absence of oil and gas,weak fractionation in oxygen isotopes,and their contact relationship with sparry calcite veins.These granular calcite veins were likely influenced by the reduction of sulfate bacteria.On the other hand,sparry calcite veins with fibrous grains are antitaxial and closely linked to the evolution and maturation of organic matter.They contain oil and gas inclusions and show a distribution range of homogenization temperature between 90℃ and 120℃ and strong fractionation in oxygen isotopes,indicating formation during the hydrocarbon expulsion period.The carbon isotope analysis of the surrounding rocks and veins suggests that the material for vein formation originates from the shale itself,specifically authigenic micritic calcite modified by the action of methanogens.The opening of horizontal fractures and vein formation is likely driven by fluid overpressure resulting from undercompaction and hydrocarbon expulsion.Veins may form rapidly or through multi-stage composite processes.Early veins are predominantly formed in situ,while late veins are a result of continuous fluid migration and convergence.Furthermore,the veins continue to undergo modification even after formation.This study emphasizes that the formation of lamellar calcite veins in shale is a complex diagenetic process influenced by multiple factors:biology,organic matter,and inorganic processes,all operating at various stages throughout the shale's diagenetic history.

Analysis of CH_(4) and H_(2) Adsorption on Heterogeneous Shale Surfaces Using aMolecular Dynamics Approach

Determining the adsorption of shale gas on complex surfaces remains a challenge in molecular simulation studies.Difficulties essentially stem from the need to create a realistic shale structure model in terms of mineral heterogeneityand multiplicity.Moreover,precise characterization of the competitive adsorption of hydrogen andmethane in shale generally requires the experimental determination of the related adsorptive capacity.In thisstudy,the adsorption of adsorbates,methane(CH_(4)),and hydrogen(H_(2))on heterogeneous shale surface modelsof Kaolinite,Orthoclase,Muscovite,Mica,C_(60),and Butane has been simulated in the frame of a moleculardynamic’s numerical technique.The results show that these behaviors are influenced by pressure and potentialenergy.On increasing the pressure from 500 to 2000 psi,the sorption effect for CH_(4)significantly increasesbut shows a decline at a certain stage(if compared to H_(2)).The research findings also indicate that raw shalehas a higher capacity to adsorb CH_(4)compared to hydrogen.However,in shale,this difference is negligible.

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.

A novel responsive stabilizing Janus nanosilica as a nanoplugging agent in water-based drilling fluids for exploiting hostile shale environments

Thermo-responsive nanocomposites have recently emerged as potential nanoplugging agents for shale stabilization in high-temperature water-based drilling fluids(WBDFs). However, their inhibitory properties have not been very effective in high-temperature drilling operations. Thermo-responsive Janus nanocomposites are expected to strongly interact with clay particles from the inward hemisphere of nanomaterials, which drive the establishment of a tighter hydrophobic membrane over the shale surface at the outward hemisphere under geothermal conditions for shale stabilization. This work combines the synergistic benefits of thermo-responsive and zwitterionic nanomaterials to synchronously enhance the chemical inhibitions and plugging performances in shale under harsh conditions. A novel thermoresponsive Janus nanosilica(TRJS) exhibiting zwitterionic character was synthesized, characterized,and assessed as shale stabilizer for WBDFs at high temperatures. Compared to pristine nanosilica(Si NP)and symmetrical thermo-responsive nanosilica(TRS), TRJS exhibited anti-polyelectrolyte behaviour, in which electrolyte ions screened the electrostatic attraction between the charged particles, potentially stabilizing nanomaterial in hostile shaly environments(i.e., up to saturated brine or API brine). Macroscopically, TRJS exhibited higher chemical inhibition than Si NP and TRS in brine, prompting a better capability to control pressure penetration. TRJS adsorbed onto the clay surface via chemisorption and hydrogen bonding, and the interactions became substantial in brine, according to the results of electrophoretic mobility, surface wettability, and X-ray diffraction. Thus, contributing to the firm trapping of TRJS into the nanopore structure of the shale, triggering the formation of a tight hydrophobic membrane over the shale surface from the outward hemisphere. The addition of TRJS into WBDF had no deleterious effect on fluid properties after hot-treatment at 190℃, implying that TRJS could find potential use as a shale stabilizer in WBDFs in hostile environments.