Influence of tectonic preservation conditions on the nanopore structure of shale reservoir:A case study of Wufeng-Longmaxi Formation shale in western Hubei area,south China

Tectonism is one of the dominant factors affecting the shale pore structure.However,the control of shale pore structure by tectonic movements is still controversial,which limits the research progress of shale gas accumulation mechanism in the complex tectonic region of southern China.In this study,34 samples were collected from two exploratory wells located in different tectonic locations.Diverse experiments,e.g.,organic geochemistry,XRD analysis,FE-SEM,low-pressure gas adsorption,and high-pressure mercury intrusion,were conducted to fully characterize the shale reservoir.The TOC,Ro,and mineral composition of the shale samples between the two wells are similar,which reflects that the shale samples of the two wells have proximate pores-generating capacity and pores-supporting capacity.However,the pore characteristics of shale samples from two wells are significantly different.Compared with the stabilized zone shale,the porosity,pore volume,and specific surface area of the deformed zone shale were reduced by 60.61%,64.85%,and 27.81%,respectively.Moreover,the macroscopic and fine pores were reduced by 54.01%and 84.95%,respectively.Fault activity and uplift denudation are not conducive to pore preservation,and the rigid basement of Huangling uplift can promote pore preservation.These three factors are important reasons for controlling the difference in pore structure between two wells shales.We established a conceptual model of shale pores evolution under different tectonic preservation conditions.This study is significant to clarify the scale of shale gas formation and enrichment in complex tectonic regions,and helps in the selection of shale sweet spots.

Hydrodynamic resistance of pore–throat structures and its effect on shale oil apparent permeability

Oil transport is greatly affected by heterogeneous pore–throat structures present in shale.It is therefore very important to accurately characterize pore–throat structures.Additionally,it remains unclear how pore–throat structures affect oil transport capacity.In this paper,using finite element(FE)simulation and mathematical modeling,we calculated the hydrodynamic resistance for four pore–throat structure.In addition,the influence of pore throat structure on shale oil permeability is analyzed.According to the results,the hydrodynamic resistance of different pore throat structures can vary by 300%.The contribution of additional resistance caused by streamline bending is also in excess of 40%,even without slip length.Fur-thermore,Pore–throat structures can affect apparent permeability by more than 60%on the REV scale,and this influence increases with heterogeneity of pore size distribution,organic matter content,and organic matter number.Clearly,modeling shale oil flow requires consideration of porous–throat structure and additional resistance,otherwise oil recovery and flow capacity may be overestimated.

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.

Evolution of pore systems in low-maturity oil shales during thermal upgrading--Quantified by dynamic SEM and machine learning

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.

Shales in the Qiongzhusi and Wufeng–Longmaxi Formations:a rock-physics model and analysis of the effective pore aspect ratio

The shales of the Qiongzhusi Formation and Wufeng-Longmaxi Formations at Sichuan Basin and surrounding areas are presently the most important stratigraphic horizons for shale gas exploration and development in China. However, the regional characteristics of the seismic elastic properties need to be better determined. The ultrasonic velocities of shale samples were measured under dry conditions and the relations between elastic properties and petrology were systemically analyzed. The results suggest that 1） the effective porosity is positively correlated with clay content but negatively correlated with brittle minerals, 2） the dry shale matrix consists of clays, quartz, feldspars, and carbonates, and 3） organic matter and pyrite are in the pore spaces, weakly coupled with the shale matrix. Thus, by assuming that all connected pores are only present in the clay minerals and using the Gassmann substitution method to calculate the elastic effect of organic matter and pyrite in the pores, a relatively simple rock-physics model was constructed by combining the self-consistent approximation （SCA）, the differential effective medium （DEM）, and Gassmann＇s equation. In addition, the effective pore aspect ratio was adopted from the sample averages or estimated from the carbonate content. The proposed model was used to predict the P-wave velocities and generally matched the ultrasonic measurements very well.

Nanopore structure comparison between shale oil and shale gas:examples from the Bakken and Longmaxi Formations

In order to analyze and compare the differences in pore structures between shale gas and shale oil formations, a few samples from the Longmaxi and Bakken Formations were collected and studied using X-ray diffraction, LECO TOC measurement, gas adsorption and field-emission scanning electron microscope. The results show that samples from the Bakken Formation have a higher TOC than those from the Longmaxi Formation. The Longmaxi Formation has higher micropore volume and larger micropore surface area and exhibited a smaller average distribution of microsize pores compared to the Bakken Formation. Both formations have similar meso-macropore volume. The Longmaxi Formation has a much larger meso-macropore surface area, which is corresponding to a smaller average meso-macropore size. CO_2 adsorption data processing shows that the pore size of the majority of the micropores in the samples from the Longmaxi Formation is less than 1 nm, while the pore size of the most of the micropores in the samples from the Bakken Formation is larger than 1 nm. Both formations have the same number of pore clusters in the 2–20 nm range, but the Bakken Formation has two additional pore size groups with mean pore size diameters larger than 20 nm. Multifractal analysis of pore size distribution curves that was derived from gas adsorption indicates that the samples from the Longmaxi Formation have more significant micropore heterogeneity and less meso-macropore heterogeneity. Abundant micropores as well as mesomacropores exist in the organic matter in the Longmaxi Formation, while the organic matter of the Bakken Formation hosts mainly micropores.

The Influence of Extractable Organic Matter on Pore Development in the Late Triassic Chang 7 Lacustrine Shales, Yanchang Formation, Ordos Basin, China

To investigate the influence of extractable organic matter （EOM） on pore evolution of lacustrine shales, Soxhlet extraction, using dichloromethane, was performed on a series of Chang 7 shale samples （Ordos Basin, China） with vitrinite reflectance of 0.64% to 1.34%. Low-pressure gas adsorption experiments were conducted on the samples before and after extraction. The pore structure parameters were calculated from the gas adsorption data. The results show complex changes to the pore volumes and surface areas after extraction. The pore development of both the initial and extracted samples is strongly controlled by total organic carbon （TOC） content. Micropores developed mainly in organic matter （OM）, while mesopores and macropores predominantly developed in fractions other than OM. The influence of EOM on micropores is stronger than on mesopores and macropores. Organic solvents with a higher boiling point should be used to explore the effect of EOM on pore structure in the future.

Comparison of pore characteristics in the coal and shale reservoirs of Taiyuan Formation, Qinshui Basin, China

Coal and shale are both unconventional gas reservoirs. Comparison of pore characteristics in shale and coal would help understand organic pore structure in shale and investigate co-exploration of shale gas and coalbed methane in coal bearing strata. In this study, five shale samples and three coal samples of Taiyuan Formation were collected from Qinshui Basin, China. High pressure mercury injection, scanning electronic microscopy, and fractal theory have been used to compare pore characteristics in shale and coal. The results show that pore volumes in coal are much larger than that in shale, especially pores 3-100 nm. In coal, there are many semi-closed pores in micro pores （〈10 nm） and transition pores （10-100 nm）. On the contrary, micro pores and transition pores are mainly with open pores in shale. The fractal curves show that pores larger than 65 nm in coal and shale reservoir both have obvious self-similarity and the fractal dimension values in shale and coal are similar. But the fractal characteristics of pores smaller than 65 nm in shale reservoir are quite different from that in coal.

Nanoscale pore morphology and distribution of lacustrine shale reservoirs:Examples from the Upper Triassic Yanchang Formation,Ordos Basin

Pore structure plays an important role in the gas storage and flow capacity of shale gas reservoirs. Fieldemission environmental scanning electron microscopy（FE-SEM） in combination with low-pressure carbon dioxide gas adsorption（CO2GA）,nitrogen gas adsorption（N2GA）,and high-pressure mercury intrusion（HPMI） were used to study the nanostructure pore morphology and pore-size distributions（PSDs） of lacustrine shale from the Upper Triassic Yanchang Formation,Ordos Basin. Results show that the pores in the shale reservoirs are generally nanoscale and can be classified into four types： organic,interparticle,intraparticle,and microfracture. The interparticle pores between clay particles and organic-matter pores develop most often,l with pore sizes that vary from several to more than 100 nm. Mercury porosimetry analysis shows total porosities ranging between 1.93 and 7.68%,with a mean value of 5.27%. The BET surface areas as determined by N2 adsorption in the nine samples range from 10 to 20 m2/g and the CO2 equivalent surface areas（2 nm）vary from 18 to 71 m2/g. Together,the HPMI,N2 GA,and CO2 GA curves indicate that the pore volumes are mainly due to pores 100 nm in size. In contrast,however,most of the specific surface areas are provided by the micropores. The total organic carbon（TOC） and clay minerals are the primary controls of the structures of nanoscale pores（especially micropores and mesopores）. Micropores are predominantly determined by the content of the TOC,and mesopores are possibly related to the content of clay minerals,particularly the illite-montmorillonite mixed-layer content.

Controlling Factors of Organic Nanopore Development: A Case Study on Marine Shale in the Middle and Upper Yangtze Region, South China

The Upper Ordovician Wufeng-Lower Silurian Longmaxi and the Lower Cambrian Qiongzhusi shales are the major targets for shale gas exploration and development in China.Although the two organic-rich shales share similar distribution ranges and thicknesses,they exhibit substantially different exploration and development results.This work analyzed the nanopore structures of the shale reservoirs in this region.Pore development of 51 shale samples collected from various formations and locations was compared using the petromineralogical,geochemical,structural geological and reservoir geological methods.The results indicate that the reservoir space in these shales is dominated by organic pores and the total pore volume of micropores,mesopores,macropores in different tectonic areas and formations show different trends with the increase of TOC.It is suggested that organic pores of shale can be well preserved in areas with simple structure and suitable preservation conditions,and the shale with smaller maximum ancient burial depth and later hydrocarbongeneration-end-time is also more conducive to pore preservation.Organic pore evolution models are established,and they are as follows:①Organic matter pore development stage,②Early stage of organic matter pore destruction,and③late stage of organic matter pore destruction.The areas conducive to pore development are favorable for shale gas development.Research results can effectively guide the optimization and evaluation of favorable areas of shale gas.

Full-Sized Pore Structure and Fractal Characteristics of Marine-Continental Transitional Shale: A Case Study in Qinshui Basin, North China

Based on 10 shale samples collected from 4 wells in Qinshui Basin,we investigate the full-sized pore structure and fractal characteristics of Marine-Continental transitional shale by performing organic geochemistry,mineralogical composition,Nitrogen gas adsorption(N2 adsorption)and Nuclear Magnetic Resonance(NMR)measurements and fractal analysis.Results show that the TOC content of the shale samples is relatively high,with an average value of 2.44wt%,and the thermal evolution is during the mature-over mature stage.The NMR T2 spectrum can be used to characterize the fullsized pore structure characteristics of shale.By combining N2 adsorption pore structure parameters and NMR T2 spectrums,the surface relaxivity of samples are calculated to be between 1.7877 um/s and 5.2272 um/s.On this basis,the T2 spectrums are converted to full-sized pore volume and surface area distribution curves.The statistics show that the pore volume is mainly provided by mesopore,followed by micropore,and the average percentages are 65.04%and 30.83%respectively;the surface area is mainly provided by micropore,followed by mesopore,and the average percentages are 60.8004%and 39.137%respectively;macropore contributes little to pore volume and surface area.The pore structure characteristics of shale have no relationship with TOC,but strong relationships with clay minerals content.NMR fractal dimensions Dmicro and Dmeso have strong positive relationships with the N2 adsorption fractal dimensions D1 and D2 respectively,indicating that Dmicro can be used to characterize the fractal characteristics of pore surface,and Dmeso can be used to characterize the fractal characteristics of pore structure.The shale surface relaxivity is controlled by multiple factors.The increasing of clay mineral content,pore surface area,pore surface fractal dimension and the decreasing of average pore size,will all lead to the decreasing of shale surface relaxivity.

Pore Structure Heterogeneity of the Xiamaling Formation Shale Gas Reservoir in the Yanshan Area of China: Evaluation of Geological Controlling Factors

Micro-heterogeneity is an integral parameter of the pore structure of shale gas reservoir and it forms an essential basis for setting and adjusting development parameters.In this study,scanning electron microscopy,high-pressure mercury intrusion and low-temperature nitrogen adsorption experiments were used to qualitatively and quantitatively characterize the pore structure of black shale from the third member of the Xiamaling Formation in the Yanshan area.The pore heterogeneity was studied using fractal theory,and the controlling factors of pore development and heterogeneity were evaluated in combination with geochemical parameters,mineral composition,and geological evolution history.The results show that the pore structure of the reservoir was intricate and complicated.Moreover,various types of micro-nano scale pores such as dissolution pores,intergranular pores,interlayer pores,and micro-cracks are well developed in member 3 of the Xiamaling Formation.The average porosity was found to be 6.30%,and the mean value of the average pore size was 4.78 nm.Micropores and transition pores provided most of the storage space.Pore development was significantly affected by the region and was mainly related to the total organic carbon content,vitrinite reflectance and mineral composition.The fractal dimension,which characterizes the heterogeneity,is 2.66 on average,indicating that the pore structure is highly heterogeneous.Fractal dimension is positively correlated with maturity and clay mineral content,while it is negatively correlated with brittle mineral content and average pore size.These results indicate that pore heterogeneity is closely related to thermal history and material composition.Combined with the geological background of this area,it was found that the pore heterogeneity was mainly controlled by the Jurassic magmatism.The more intense the magma intrusion,the stronger the pore heterogeneity.The pore structure and its heterogeneity characteristics present today are a general reflection of the superimposed geological processes of sedimentary-diagenetic-late transformation.The influence of magmatic intrusion on the reservoir is the main geological factor that should be considered for detailed evaluation of the Xiamaling Formation shale gas reservoir in the Yanshan area.

Pore structure and heterogeneity of shale gas reservoirs and its effect on gas storage capacity in the Qiongzhusi Formation

Fine characterization of pore systems and heterogeneity of shale reservoirs are significant contents of shale gas reservoir physical property research. The research on micro-control factors of low productivity in the Qiongzhusi Formation(Fm.) is still controversial. The lower Cambrian Qiongzhusi Fm. in the Qujing, Yunnan was taken as the object to investigate the influence of mineral compositions on the physical properties of the reservoir and the heterogeneity of shale, using the algorithm to improve the characterization ability of Atomic Force Microscopy(AFM). The results showed that:(1) The pores are mainly wedge-shaped pores and V-shaped pores. The pore diameter of the main pore segment ranges from 5 to 10 nm. Mesopores are mainly developed in the Qiongzhusi Fm. shale in Well QD1, with the average pore diameter of 6.08 nm.(2) Microscopic pore structure and shale surface properties show strong heterogeneity, which complicates the micro-migration of shale gas and increases the difficulty of identifying high-quality reservoirs.(3) The increase of clay mineral content intensifies the compaction and then destroys the pores. Conversely, brittle minerals can protect pores. The support and protection of brittle minerals to pores space depend on their content, mechanical properties and diagenesis.(4)Compression damage to pores, large microscopic roughness and surface fluctuations and strong pore structure heterogeneity are the reasons for the poor gas storage capacity of the Qiongzhusi Fm., which will lead to poor productivity in the Qiongzhusi Fm.

Pore structure characterization and its effect on methane adsorption in shale kerogen

Pore structure characterization and its effect on methane adsorption on shale kerogen are crucial to understanding the fundamental mechanisms of gas storage,transport,and reserves evaluation.In this study,we use 3D scanning confocal microscopy,scanning electron microscopy(SEM),X-ray nano-computed tomography(nano-CT),and low-pressure N2 adsorption analysis to analyze the pore structures of the shale.Additionally,the adsorption behavior of methane on shales with different pore structures is investigated by molecular simulations.The results show that the SEM image of the shale sample obviously displays four different pore shapes,including slit pore,square pore,triangle pore,and circle pore.The average coordination number is 4.21 and the distribution of coordination numbers demonstrates that pores in the shale have high connectivity.Compared with the adsorption capacity of methane on triangle pores,the adsorption capacity on slit pore,square pore,and circle pore are reduced by 9.86%,8.55%,and 6.12%,respectively.With increasing pressure,these acute wedges fill in a manner different from the right or obtuse angles in the other pores.This study offers a quantitative understanding of the effect of pore structure on methane adsorption in the shale and provides better insight into the evaluation of gas storage in geologic shale reservoirs.

Graptolite-Derived Organic Matter and Pore Characteristics in the Wufeng-Longmaxi Black Shale of the Sichuan Basin and its Periphery

A key target of shale gas exploration and production in China is the organic-rich black shale of the Wufeng Formation-Longmaxi Formation in the Sichuan Basin and its periphery.The set of black shale contains abundant graptolites,which are mainly preserved as flattened rhabdosomes with carbonized periderms,is an important organic component of the shale.However,few previous studies had focused on the organic matter(OM)which is derived from graptolite and its pore structure.In particular,the contributions of graptolites to gas generation,storage,and flow have not yet been examined.In this study,focused ion beam-scanning electron microscope(FIB-SEM)was used to investigate the characteristics of the graptolite-derived OM and the micro-nanopores of graptolite periderms.The results suggested that the proportion of OM in the graptolite was between 19.7%and 30.2%,and between 8.9%and 14.4%in the surrounding rock.The total organic carbon(TOC)content of the graptolite was found to be higher than that of the surrounding rock,which indicated that the graptolite played a significant role in the dispersed organic matter.Four types of pores were developed in the graptolite periderm,including organic gas pores,pyrite moulage pores,authigenic quartz moldic pores,and microfractures.These well-developed micro-nano pores and fractures had formed an interconnected system within the graptolites which provided storage spaces for shale gas.The stacked layers and large accumulation of graptolites resulted in lamellation fractures openning easily,and provided effective pathways for the gas flow.A few nanoscale gas pores were observed in the graptolite-derived OM,with surface porosity lie in 1.5%–2.4%,and pore diameters of 5–20 nm.The sapropel detritus was determined to be rich in nanometer-sized pores with surface porosity of 3.1%–6.2%,and pore diameters of 20–80 nm.Due to the small amount of hydrocarbon generation of the graptolite,supporting the overlying pressure was difficult,which caused the pores to become compacted or collapsed.

Multifractal characteristics of shale and tight sandstone pore structures with nitrogen adsorption and nuclear magnetic resonance

Based on the experiments of nitrogen gas adsorption(N_2 GA) and nuclear magnetic resonance(NMR),the multifractal characteristics of pore structures in shale and tight s andstone from the Chang 7 member of Trias sic Yanchang Formation in Ordos Basin,NW China,are investigated.The multifractal spectra obtained from N2 GA and NMR are analyzed with pore throat structure parameters.The results show that the pore size distributions obtained from N2 GA and NMR are different,and the obtained multifractal characteristics vary from each other.The specific surface and total pore volume obtained by N2 GA experiment have correlations with multifractal characteristics.For the core samples with the similar specific surface,the value of the deviation of multifractal spectra Rd increases with the increase in the proportion of large pores.When the proportion of macropores is small,the Rd value will increase with the increase in specific surface.The multifractal characteristics of pore structures are influenced by specific surface area,average pore size and adsorption volume measured from N2 GA experiment.The multifractal characteristic parameters of tight sandstone measured from NMR spectra are larger than those of shale,which may be caused by the differences in pore size distribution and porosity of shale and tight sandstone.

Pore Characteristics and Factors Controlling Lacustrine Shales from the Upper Cretaceous Qingshankou Formation of the Songliao Basin,Northeast China:A Study Combining SEM,Low-temperature Gas Adsorption and MICP Experiments

To investigate pore characteristics and the factors controlling lacustrine shales,geochemical,mineralogical and petrophysical experiments were performed on 23 shale samples from the Qingshankou Formation of the Songliao Basin,China.A comparison of mercury injection capillary pressure(MICP)and low-temperature N2 adsorption pore-size distribution showed that MICP has a higher pore-size distribution(PSD)line in its overlapping pore diameter range,which may be elevated by the higher pressure of MICP.Therefore,in the overlapping range,low-temperature N2 adsorption data were preferred in pore characterization.Negative correlations were observed between pore volumes and TOC content,indicating organic matter pores are not well-developed in the studied samples.This may be related to their low grade of maturity and type I kerogens.There existed negative relationships between pore volumes and S1,which illustrated that liquid hydrocarbons occupied some pore space.Micropore volume had a better correlation with S1 than mesopore and macropore volumes,which suggests that liquid hydrocarbons preferentially occur in micropores.No obvious relationships between pore volumes and quartz or feldspar were observed,while pore volumes increased with the increasing clay mineral content.These relationships indicate that intraparticle pores in clay minerals represent the principal pore type.

Characterization of a Lacustrine Shale Reservoir and the Evolution of its Nanopores: A Case Study of the Upper Cretaceous Qingshankou Formation in the Songliao Basin, Northeastern China

The Songliao Basin is one of the most important petroliferous basins in northern China. With a recent gradual decline in conventional oil production in the basin, the exploration and development of unconventional resources are becoming increasingly urgent. The Qingshankou Formation consists of typical Upper Cretaceous continental strata, and represents a promising and practical replacement resource for shale oil in the Songliao Basin. Previous studies have shown that low-mature to mature Qingshankou shale mainly preserves type Ⅰ and type Ⅱ1 organic matter, with relatively high total organic carbon(TOC) content. It is estimated that there is a great potential to explore for shale oil resources in the Qingshankou Formation in this basin. However, not enough systematic research has been conducted on pore characteristics and their main controlling factors in this lacustrine shale reservoir. In this study, 19 Qingshankou shales from two wells drilled in the study area were tested and analyzed for mineral composition, pore distribution and feature evolution using Xray diffraction(XRD), scanning electron microscopy(SEM), low-pressure nitrogen gas adsorption(N2-GA), and thermal simulation experiments. The XRD results show that clay, quartz, and feldspar are the dominant mineral constituents of Qingshankou shale. The clay minerals are mostly illite/smectite mixed layers with a mean content of 83.5%, followed by illite, chlorite, and kaolinite. There are abundant deposits of clay-rich shale in the Qingshankou Formation in the study area, within which many mineral and organic matter pores were observed using SEM. Mineral pores contribute the most to shale porosity;specifically, clay mineral pores and carbonate pores comprise most of the mineral pores in the shale. Among the three types of organic matter pores, type B is more dominant the other two. Pores with diameters greater than 10 nm supply the main pore volume;most are half-open slits and wedge-shaped pores. The total pore volume had no obvious linear relationship with TOC content, but had some degree of positive correlation with the content of quartz + feldspar and clay minerals respectively. However, it was negatively correlated with carbonate mineral content. The specific surface area of the pores is negatively related to TOC content, average pore diameter, and carbonate mineral content. Moreover, it had a somewhat positive correlation with clay mineral content and no clear linear relationship with the content of quartz + feldspar. With increases in maturity, there was also an increase in the number of carbonate mineral dissolution pores and organic matter pores, average pore diameter, and pore volume, whereas there was a decrease in specific surface area of the pores. Generally, the Qingshankou shale is at a low-mature to mature stage with a TOC content of more than 1.0%, and could be as thick as 250 m in the study area. Pores with diameters of more than 10 nm are well-developed in the shale. This research illustrates that there are favorable conditions for shale oil occurrence and enrichment in the Qingshankou shale in the study area.

Porosity model and pore evolution of transitional shales:an example from the Southern North China Basin

The evolution of shale reservoirs is mainly related to two functions:mechanical compaction controlled by ground stress and chemical compaction controlled by thermal effect.Thermal simulation experiments were conducted to simulate the chemical compaction of marine-continental transitional shale,and X-ray diffraction(XRD),CO2 adsorption,N2 adsorption and high-pressure mercury injection(MIP)were then used to characterize shale diagenesis and porosity.Moreover,simulations of mechanical compaction adhering to mathematical models were performed,and a shale compaction model was proposed considering clay content and kaolinite proportions.The advantage of this model is that the change in shale compressibility,which is caused by the transformation of clay minerals during thermal evolution,may be considered.The combination of the thermal simulation and compaction model may depict the interactions between chemical and mechanical compaction.Such interactions may then express the pore evolution of shale in actual conditions of formation.Accordingly,the obtained results demonstrated that shales having low kaolinite possess higher porosity at the same burial depth and clay mineral content,proving that other clay minerals such as illite-smectite mixed layers(I/S)and illite are conducive to the development of pores.Shales possessing a high clay mineral content have a higher porosity in shallow layers(<3500 m)and a lower porosity in deep layers(>3500 m).Both the amount and location of the increase in porosity differ at different geothermal gradients.High geothermal gradients favor the preservation of high porosity in shale at an appropriate Ro.The pore evolution of the marine-continental transitional shale is divided into five stages.Stage 2 possesses an Ro of 1.0%-1.6%and has high porosity along with a high specific surface area.Stage 3 has an Ro of 1.6%-2.0%and contains a higher porosity with a low specific surface area.Finally,Stage 4 has an Ro of 2.0%-2.9%with a low porosity and high specific surface area.

A novel hybrid thermodynamic model for pore size distribution characterisation for shale

Scholars often see the gas adsorption technique as a straight-to-interpret technique and adopt the pore size distribution(PSD)given by the gas adsorption technique directly to interpret pore-structure-related issues.The oversimplification of interpreting shale PSD based on monogeometric thermodynamic models leads to apparent bias to the realistic pore network.This work aims at establishing a novel thermodynamic model for shale PSD interpretation.We simplified the pore space into two geometric types—cylinder-shaped and slit-shaped.Firstly,Low-temperature Nitrogen Adsorption data were analyzed utilizing two monogeometric models(cylindrical and slit)to generate PSD_(cyl).and PSD_(slit);Secondly,pore geometric segmentation was carried out using Watershed by flooding on typical SEM images to obtain the ratio of slit-shaped(∅_(s))and cylinder-shaped pores(∅_(c)).Combining the results of the two,we proposed a novel hybrid model.We performed pyrolysis,XRD,FE-SEM observation,quantitative comparison with the results obtained by the DFT model,and fractal analysis to discuss the validity of the obtained PSD_(Hybrid).The results showed that:the hybrid model proposed in this work could better reflect the real geometry of pore space and provide a more realistic PSD;compared with thermodynamic monogeometric models,PSD obtained from the hybrid model are closer to that from the DFT model,with an improvement in the deviation from the DFT model from 5.06%to 68.88%.The proposed hybrid model has essential application prospects for better interpretation of shale pore space.It is also worth noting that we suggest applying the proposed hybrid model for PSD analysis in the range of 5-100 nm.