High-pressure Methane Adsorption Research Articles

Methane adsorption effect of cyclodextrin-based metal-organic frameworks and ultra-fine water mist composite system in closed container

Natural gas, predominantly composed of methane, is a widely used energy source. Methane is prone to leakage during storage and usage, posing environmental risks. Currently, effective strategies to capture methane leaked in urban environments are lacking. This study investigates the synthesis of a non-toxic Cyclodextrin-based Metal-Organic Framework (CD-MOF) and its adsorption capacity for leaked methane in an ultrafine water mist composite solution system. CD-MOFs, utilizing β-cyclodextrin as the organic ligand and alkali metal potassium as the metal ion, were synthesized via solvothermal and methanol vapor diffusion method. The morphology, functional groups, and thermal properties of CD-MOFs were characterized by multiple techniques. The BET specific surface area, pore structure, and high-pressure methane adsorption capacity of the samples were investigated. Furthermore, CD-MOF, surfactant, and castor oil were combined to create a composite solution absorbent. The methane absorption efficacy of this ultra-fine water mist of absorbent was tested using a closed-container methane spray adsorption apparatus, and the compound solution ratio was optimized. The results indicate that CD-MOFs retain the parent cyclodextrin structure, and the methane adsorption capacity under high-pressure (35 bar) of CD-MOF synthesized by the sodium dodecyl sulfate-assisted solvothermal method reached 216.13 cm3/g. The composite solution with an appropriate proportion of surfactant, castor oil, and CD-MOF reached a methane absorption capacity of 5.7 % vol in enclosed spaces. The successful synthesis of CD-MOFs and the application of composite solutions with ultra-fine water mist offer innovative approaches and theoretical guidance for the emergency absorption and non-toxic disposal of leaked methane.

A Comprehensive Study on Methane Adsorption Capacities and Pore Characteristics of Coal Seams: Implications for Efficient Coalbed Methane Development in the Soma Basin, Türkiye

This study represents a comprehensive assessment of methane adsorption capacity and pore characteristics for the coal seams of the Soma Basin in Western Türkiye, with a focus on their implications for coalbed methane potential. Twenty-one exploration wells were utilized to obtain coal samples from the kP1 and kM2 coal seams in the Kınık coalfield of the Soma Basin. High-pressure methane adsorption experiments using the indirect gravimetric method were conducted to quantify the storage capacities of these coal seams. Results revealed a wide range of methane adsorption capacities, ranging from 10.5 to 28.3 m3/t (air-dry basis), indicating significant methane storage potential for the kP1 and kM2 coal seams. The gas contents, ranging from 1.1 to 4.3 m3/t (as-received basis), suggested that the coal seams were undersaturated. Low-pressure N2/CO2 adsorption tests, along with standard proximate and gross calorific value analyses, were performed to investigate the influence of coal quality and pore characteristics on methane adsorption capacities. The findings demonstrated correlations between coal quality parameters and adsorption capacity, with ash yield showing a moderately negative correlation and fixed carbon content and gross calorific values exhibiting moderately positive correlations. Microporosity was identified as the critical factor governing methane adsorption, with a strong positive correlation observed between micropore surface areas and volumes and adsorption capacity. These results highlight the significant methane storage capacities of the coal seams in the Soma Basin and underscore the importance of micropores in determining methane adsorption capacity. The findings provide valuable insights for optimizing methane extraction and utilization in the region and offer important considerations for reservoir characterization and development strategies in similar low-rank coal deposits.HighlightsExtensive evaluation of methane adsorption and pore characteristics in Soma Basin coals, uncovering substantial potential for coalbed methane.The study reveals a diverse range of methane adsorption capacities, indicating highly promising methane storage capabilities.Correlation between coal quality parameters and methane adsorption, offering valuable insights into gas storage influenced by coal composition.Emphasis on the crucial role of micropores in methane storage, underscoring their significance as primary adsorption sites.Practical implications for optimizing methane extraction and utilization, guiding reservoir development in low-rank coal deposits like Soma Basin.

High-Pressure adsorption of supercritical methane and carbon dioxide on Coal: Analysis of adsorbed phase density

The occurrence of supercritical CH4 and CO2 in coal is significant for both coalbed methane recovery and CO2 storage. Adsorption isotherms of CH4 and CO2 on two coals have been measured at three temperatures up to pressures of 25 MPa. Three modified supercritical adsorption models (SL-V, SBET-V, and SDR-V) were used to describe the excess adsorption behavior, with the pressure-independent adsorbed phase volume being considered. The adsorbed phase density (APD) and absolute adsorption amount were calculated based on the modified models and compared with those estimated by previous models. The results indicate that SDR-V is the most suitable for CH4 adsorption due to the dominant role of filling of micropores by CH4, while SBET-V is the most appropriate model for CO2 adsorption because of multilayer adsorption of CO2 in both micropores and meso-macropores. The APD increases with pressure until reaching a maximum value but decreases as temperature increases following a Langmuir-style trend. The previous models, which use a fixed APD, seriously underestimate the absolute adsorption, the extent of which increases with increasing pressure and temperature, leading to significant errors in deep formations with high temperature and pressure conditions. Furthermore, as burial depth increases, the adsorption process can be divided into three stages based on changes in APD and free phase density (FPD). These findings contribute to a comprehensive understanding of the behavior and occurrence of CH4 and CO2 within deep coal seams, enhancing the applicability of CO2-ECBM (CO2 Geological Storage Enhanced Coalbed Methane Recovery).

Water distribution in pore systems and its influences on gas-bearing property of deep shale: A case study of the Longmaxi Formation in the Luzhou area, southern Sichuan Basin

The deeply-buried (>3500 m) Longmaxi Formation (LMX) shale in the southern Sichuan Basin, China, has become an attractive target for shale gas exploration owing to its huge resource potential. Exploration shows that the deep shale has a wide range of gas-in-place (GIP) contents, with variable gas yields, but the reason remains unclear, especially the impact of pore water on gas-bearing property lacks systematic research. In the present study, a suite of deep LMX shale samples was collected from the well FB1 in the Luzhou area of the southern Sichuan Basin, and techniques such as the pore water content measurements, low-pressure gas (CO2 and N2) adsorption and high-pressure methane adsorption experiments of the moist and dry samples were employed to investigate the distribution of water in the nanopores and its effects on the gas-bearing property. The results show that the deep shale is characterized by a high water content, with a high water saturation (average up to 69.80%), and the water occurs in both the inorganic and organic pores. The water reduces the effective specific surface area and pore volume of the shale averagely by 79.01% and 22.56%. Consequently, the water results in the decrease of methane adsorption capacity averagely by 45.13%. The GIP content models of two typical shale samples indicate that their total gas content is < 3 m3/t under the actual conditions, without development potential, and it will increase significantly to >3 m3/t with decreasing water saturation to <40–50%, especially under overpressure conditions. The gas-bearing property of deep LMX shale reservoirs in the complex faulted zones or structural-complex zones would mainly depend on the pore water content except for the properties of shale itself (e.g., maturity, TOC content, mineral composition, porosity and pore structure).

Microwave irradiation-induced alterations in physicochemical properties and methane adsorption capability of coals: An experimental study using carbon molecular sieve

In order to comprehend the applicability of microwave irradiation for recovering coalbed methane, it is necessary to evaluate the microwave irradiation-induced alterations in coals with varying levels of metamorphism. In this work, the carbon molecular sieve combined with KMnO4 oxidation was selected to fabricate carbon molecular sieve with diverse oxidation degrees, which can serve as model substances toward coals. Afterwards, the microwave irradiation dependences of pores, functional groups, and high-pressure methane adsorption characteristics of model substances were studied. The results indicated that microwave irradiation causes rearrangement of oxygen-containing functional groups, which could block the micropores with a size of 0.40–0.60 nm in carbon molecular sieve; meanwhile, naphthalene and phenanthrene generated by macro-molecular structure pyrolysis due to microwave irradiation could block the micropores with a size of 0.70–0.90 nm. These alterations in micropore structure weaken the saturated methane adsorption capacity of oxidized carbon molecular sieve by 2.91%–23.28%, suggesting that microwave irradiation could promote methane desorption. Moreover, the increased mesopores found for oxidized carbon molecular sieve after microwave irradiation could benefit CH4 diffusion. In summary, the oxidized carbon molecular sieve can act as model substances toward coals with different ranks. Additionally, microwave irradiation is a promising technology to enhance coalbed methane recovery.

A developed dual-site Langmuir model to represent the high-pressure methane adsorption and thermodynamic parameters in shale

Comprehending the mechanism of methane adsorption in shales is a crucial step towards optimizing the development of deep-buried shale gas. This is because the methane adsorbed in shale represents a significant proportion of the subsurface shale gas resource. To properly characterize the methane adsorption on shale, which exhibits diverse mineral compositions and multi-scale pore sizes, it is crucial to capture the energy heterogeneity of the adsorption sites. In this paper, a dual-site Langmuir model is proposed, which accounts for the temperature and pressure dependence of the density of the adsorbed phase. The model is applied to the isothermals of methane adsorption on shale, at pressures of up to 30 MPa and temperatures ranging from 40 to 100 °C. The results show that the proposed model can describe the adsorption behavior of methane on shale more accurately than conventional models, which assume a constant value for the density of adsorbed phase. Furthermore, the proposed model can be extrapolated to higher temperatures and pressures. Thermodynamic parameters were analyzed using correctly derived equations. The results indicate that the widely used, but incorrect, equation would underestimate the isosteric heat of adsorption. Neglecting the real gas behavior, volume of the adsorbed phase, and energy heterogeneity of the adsorption sites can lead to overestimation of the isosteric heat of adsorption. Furthermore, the isosteric heat evaluated from excess adsorption data can only be used to make a rough estimate of the real isosteric heat at very low pressure.

Reservoir characteristics of different shale lithofacies and their effects on the gas content of Wufeng-Longmaxi Formation, southern Sichuan Basin, China

Various shale lithofacies differ significantly in terms of gas content and pore structure characteristics. In this study, FE-SEM, low-pressure gas adsorption (LPGA), in-situ reservoir water saturation restoring, and high-pressure (0–51Mpa) methane adsorption were conducted to systematically characterize pore structure and evaluate the gas content of different shale lithofacies in the Wufeng-Longmaxi Formation, southern Sichuan Basin. The mineral compositions identified four shale lithofacies, and pores are abundant in siliceous shale and mixed shale. Siliceous shale has the largest pore volume (PV) and specific surface area (SSA), averaging 0.0310 cm3/g and 25.827 m2/g, respectively. However, the PV and SSA are lowest in argillaceous shale, averaging 0.0217 cm3/g and 18.734 m2/g, respectively. Water saturation is positively correlated with clay minerals, and argillaceous shale possess the highest water saturation of 60% due to the highest clay content. The supercritical Dubinin-Astakhov (S-DA) excess adsorption model predictions deviated less from the measured data and fitted well. The shale adsorption capacity are dominated by TOC content and total SSA. However, water and temperature have an inhibitory activity on adsorption capacity, with the adsorption capacity of water-bearing shales decreasing by 28%∼81% at a water saturation of 30%∼65% compared to dry shales. As the temperature increased from 40 °C to 80 °C, the methane adsorption capacity decreased from 3.95 to 2.79 m3/t, a 29% decrease. The shale gas content prediction models were established and extrapolated into the functions of reservoir depth. Deep shale gas reservoirs are dominated by free gas, accounting for over 90% at 5000 m. Siliceous shale has the highest gas content, followed by mixed shale, argillaceous-siliceous shale, and argillaceous shale. It is estimated that siliceous shale has a three-fold higher gas content than argillaceous shale. Siliceous and mixed shale are favorable reservoirs for shale gas exploration and development due to their high gas contents and low water saturation.

Investigations on Supercritical Methane Adsorption and Storage in the Lower Longmaxi Shale of Nanchuan Area, Southeast Sichuan Basin

A series of high-pressure methane adsorption measurements were performed at various temperatures on whole shale and kerogen samples collected from the Lower Longmaxi shale in the Nanchuan area, southeast Sichuan Basin, to investigate supercritical methane adsorption properties and evaluate in-place methane storage capacity as a function of burial depth. The results show that the supercritical Dubinin–Radushkevich (SDR) model fits the excess adsorption isotherms marginally better than the supercritical Langmuir model. However, the fitted adsorbed methane density of kerogens obtained from the SDR model may be greater than the liquid methane density at the atmospheric boiling point (0.423 g/cm3). The proposed multiple regression fitting carried out in this work illustrates that approximately 57.59% (34.51–85.45%) and 37.60% (10.74–59.52%) of the methane adsorption capacity at 333.15 K can be attributed to organic matter (OM) and clay minerals (CMs), respectively, for whole shales investigated. According to thermodynamic analyses, the significant contribution of OM to the methane adsorption capacity can be attributed to the stronger affinity between kerogens and methane molecules in contrast to that between CMs and whole shales. The methane storage capacity estimated as a function of burial depth showed that the adsorbed gas storage capacity declines with increasing burial depth between 2000 and 5000 m, while the free gas storage capacity shows the opposite trends. Gas accumulation pressure primarily exerts a significant effect on the free gas storage capacity rather than adsorbed gas storage capacity, and adsorbed gas storage capacity begins to exceed free gas storage capacity at shallow burial depths for normally pressured gas accumulations. Normally pressured shale gas accumulations at shallow burial depths, which are widely distributed in the residual syncline of the study area, should be given more attention due to their relatively low development costs and relatively high storage capacity for adsorbed gas.

The Characteristic Development of Micropores in Deep Coal and Its Relationship with Adsorption Capacity on the Eastern Margin of the Ordos Basin, China

The accurate description of micro-/nanopores in deep coal reservoirs plays an important role in evaluating the reservoir properties and gas production capacity of coalbed methane (CBM). This work studies nine continuous samples of high–rank coal from the Daning–Jixian area of the Ordos Basin. Maceral analysis, proximate analysis, field emission scanning electron microscopy (FE-SEM), low-pressure CO2 adsorption (LPA), low-temperature N2 adsorption (LTA) and high-pressure methane adsorption (HPMA) experiments were conducted for each sample. The fractal dimension (D) of the LPA data was calculated by using the micropore fractal model. The characteristics of the deep coal reservoir pore structure, proximate analysis, relationship between maceral and fractal dimensions, and gas adsorption capacity of the micropores are discussed. The results showed that the combination of LPA with nonlocalized density functional theory (NLDFT) models and LTA with NLDFT models can more accurately determine the pore size distribution of the micropores. The pore volume (PV) and specific surface area (SSA) of the coals were distributed in the ranges of 0.059~0.086 cm3/g and 204.38~282.42 m2/g, respectively. Although the degree of micropore development varies greatly among different coal samples, the pore distribution characteristics are basically the same, and the PV and SSA are the most developed in the pore size range of 0.4–0.7 nm. Ash content (Ad) and mineral composition are two major factors affecting micropore structure, but they have different impacts on the fractal dimension. The higher the vitrinite content, moisture content (Mad) and Ad are, the larger the micropore fractal dimension (D) and the stronger the heterogeneity of the pore structure. Micropores account for 99% of the total SSA in coal, and most methane can be adsorbed in micropores. The fractal dimension of micropores can be used to evaluate the pore structure characteristics. The larger the fractal dimension, the smaller the micro-SSA and micro-PV of the coal sample. Fractal analysis is helpful to better understand the pore structure and adsorption capacity of CBM reservoirs.

Pore structure and fractal characteristics of Wufeng–Longmaxi formation shale in northern Yunnan–Guizhou, China

In this study, the microscopic pore characteristics of shale in marine strata are evaluated. Based on field emission scanning electron microscopy (FE-SEM), low-temperature N2 adsorption (LT-N2GA), low-pressure CO2 adsorption (LP-CO2GA) and high-pressure methane adsorption (HPMA) experiments, the pore characteristics of 12 shales from the Wufeng–Longmaxi Formations in northern Yunnan and Guizhou are characterized qualitatively and quantitatively. Fractal Frenkel–Halsey–Hill (FHH) theory is used to analyse the fractal characteristics, and the adsorption pore characteristics of shale are discussed. The correlation between the fractal dimension and pore structure and adsorption performance is determined. The results show that the total organic carbon (TOC) contents of the 12 shales are in the middle–low level, ranging from 0.43% to 5.42%, and the shales are generally in the highly mature to overmaturity stage (vitrinite reflectance (Ro) values between 1.80% and 2.51%). The mineral composition is mainly quartz and clay minerals. The average clay mineral content is 40.98% (ranging from 24.7% to 63.3%), and the average quartz content is 29.03% (ranging from 16.8% to 39.6%), which are consistent with those of marine shale in the Sichuan Basin. FE-SEM and LT-N2GA isotherms reveal a complex shale pore structure and open pore style, mainly ink bottle-shaped and parallel plate-like pores. The total pore volumes (PVs) range from 0.012–0.052 cm3/g, and the specific surface area (SSA) values range from 18.112–38.466 m2/g. All shale samples have abundant micropores and mesopores, accounting for &amp;gt;90% of the total SSA. The fractal dimensions, D1 and D2, were obtained from N2 adsorption data, with different adsorption characteristics at 0–0.5 and 0.5–1.0 relative pressures. The fractal dimensions increase with increasing BJH PV and BET SSA and decrease with decreasing average pore diameter (APD). The fractal dimensions are positively correlated with the TOC and clay mineral contents and negatively correlated with the quartz content. The fractal dimension can be used to evaluate the methane adsorption capacity; the larger the fractal dimension is, the larger the methane adsorption capacity is. Fractal analysis is helpful to better understand the pore structure and adsorption capacity of shale gas reservoirs.

Gas-Bearing Property in Deep Marine Shale and Its Micro Controlling Factors: Evidence from the Lower Silurian Longmaxi Formation in Southern Sichuan, China

Abstract The gas content in shale reservoirs is often determined by the micro storage and sealing capacities of the reservoir. Deep shale reservoirs are in the high- or over-thermale maturity stage and have complex pore structure and connectivity, which are highly heterogeneous in vertical distribution. Research on the gas-bearing property of deep shale reservoirs is limited by these complex microscopic conditions. To analyze the gas-bearing characteristics of deep shale reservoirs, this work collected and summarized data on total organic carbon content, mineral composition, porosity, water saturation, and gas content measured on-site for the Longmaxi Formation in the Sichuan Basin in southern Sichuan, China. Then, experimental methods, such as X-ray photoelectron spectroscopy, transmission electron microscope, low-pressure N2 adsorption, spontaneous imbibition, and high-pressure methane adsorption, were used to analyze the micro storage and sealing capacities of the deep shale reservoirs. The results show that, different from shallow shale reservoirs (&amp;lt;3500 m), deep shale reservoirs have a higher graphitization degree and water saturation. An abundance of graphite structures often leads to weak resistance of organic matter to compression, deformation, or even collapse of pores in organic matter and severe damage to the gas storage space. However, a higher degree of graphitization can enhance the ability of the shale reservoirs to adsorb gas and self-sealing. The high water saturation in the reservoirs can interact with clay minerals and negatively affect the gas accumulation, storage, and transmission capacities of the shale reservoirs. However, the upper shale reservoirs with higher water saturation can seal the lower shale reservoirs, helping it preserve shale gas. Based on the vertical distribution of graphite structure, clay minerals contents, lithofacies, and water content in deep shale reservoirs, the essential microscopic conditions for deep shale reservoirs to have high gas content were proposed. This paper provides a detailed explanation and evaluation of deep shale’s storage and sealing capacities at the microscopic scale and can serve as a reference for further identifying the patterns for high-yield and rich shale gas reservoirs and improving deep shale gas exploration technologies.

Methane absorption of coal-measure shales with and without pore water from the Qinshui Basin, North China: Based on high-pressure methane absorption experiments

The coal-measure shale in the Qinshui Basin, North China has a high thermal maturity and a huge shale gas resource, but studies related to its gas-bearing property (GBP) are lack. In this paper, shale samples taken from the carboniferous coal-measure strata in the Yangquan block of Qinshui Basin were mainly investigated on their pore water contents and occurrence characteristics, and their high-pressure methane adsorption capacities under the dry and moist conditions. The results show that the pore water in the shale is in an ultra-low saturation state, occurring mainly in clay minerals (91% on average), significantly decreases its effective pore structure parameters, especially the nonmicropore specific surface areas (by 70.21% on average), and reduces its methane adsorption capacity (by 33% on average at 30 °C), with the adsorbed methane occurring mainly in micropores and controlled by the TOC content. The adsorption of methane on the shale is an exothermic process, and both the shale adsorption capacity and adsorbed methane density are reduced with increasing temperature. Pore water not only has a competitive adsorption with methane, but also weakens the adsorbed methane inter-molecular interaction forces, decreasing the methane adsorption capacity, especially under the low temperature and pressure conditions. The GBP models of a selected shale under the dry and moist conditions further indicate that pore water also decreases the adsorbed gas percentage to some extent, especially at a burial depth < 1500 m, and the adsorbed gas is dominant in the shale. These GBP characteristics of coal-measure shale should pay a great attention in the future exploration and development of shale gas in the Qinshui Basin.

The Pore Structure of Marine to Continental Transitional Shales in the Permian Shanxi Formation on the East Margin of the Ordos Basin, China

The pore structure is an important factor in determining the storage capacity for shale gas development. Twelve samples were selected from the marine to continental transitional shales in the Shanxi Formations on the eastern margin of the Ordos Basin, and their nanoscale pore structure was investigated by a variety of low-temperature N2 adsorption (LT-N2GA) and low-pressure CO2 adsorption (LP-CO2GA) and high-pressure mercury intrusion (HPMI) experiments. The shale pores are complex and are mainly mesopores, which range mainly from 10 nm to 40 nm and greatly contribute to the pore volume (PV), whereas pores with a diameter less than 0.8 nm greatly contribute to the specific surface area (SSA) of the shale. The pore structure is affected by the TOC content, organic matter maturity, and illite/smectite (I/S) mixed layer content. The total PV increases with the increase in TOC content, organic matter maturity, and I/S mixed layer content. The effects of pores on the occurrence shale gas were determined by high-pressure methane adsorption experiments. The maximum adsorption amount of methane was positively correlated with the SSA of the micropores, indicating that the micropores have a large SSA, which controlled the adsorbed gas content of the shale. The mesopores provide the majority of the PV, which mainly corresponds to the volume of free gas in the shale, and the macropores are mainly micron-sized pores, which can form the main migration channels for shale gas.

Comparative study of methane adsorption of Middle-Upper Ordovician marine shales in the western Ordos Basin, NW China: Insights into impacts of moisture on thermodynamics and kinetics of adsorption

Impacts of water molecules on subsurface shale gas adsorption is a challenging topic in the assessment of shale gas resources and the selection of optimized exploitation plans. And scholars have recognized that water molecules occupy adsorption sites on hydrophilic pore walls. However, the impacts of water molecules on the thermodynamics and kinetics of methane adsorption in shales remains poorly understood. We document a series of high-pressure methane adsorption isotherms of dry and moisture-equilibrated samples of the Middle-Upper Ordovician Wulalike shale at 20–120 °C and up to 30 MPa. Quantitative analyses of the thermodynamic and kinetic characteristics are carried out. Results show that water molecules do not change the impacts of temperature and pressure on the trend of isotherms, thermodynamics, and kinetics of methane adsorption. The impacts of temperature, pressure, methane adsorption capacity, and water molecules on the methane adsorption are basically functioned by modifying the interactions between the adsorbate and the adsorbent. The presence of water molecules in shales leads to a decrease of ∼ 77.06% in the capacity of methane adsorption, an increase of ∼ 70.46% in the adsorption heat (Qst), a decrease of ∼ 96.62% in the standard entropy (△S0), and a decrease of ∼ 1/9 to 1/5 in the Bangham adsorption rate (kb). The impacts of water molecules on the decline of methane adsorption at high pressure is lower than that at low pressure, however, on the decrease of methane adsorption rate higher than that at low pressure. The study also reflects the methane adsorption into the three-dimensional network system of kerogen. This work can improve our understanding of subsurface supercritical adsorption under reservoir conditions.

Adsorption characteristics and controlling factors of marine deep shale gas in southern Sichuan Basin, China

Deep shale gas (3500–4500 m) is the important replacement field of shale gas production growth in the future China. The research on key parameters of deep shale-gas reservoir is critical to determine its basic geological characteristics and establish a suitable development mode. In order to clarify the adsorption characteristics and controlling factors of deep shale gas in Longmaxi Formation, the main tests such as high-pressure methane adsorption, low-temperature nitrogen and carbon dioxide adsorption coupled with the adsorption fitting model and comparative analysis were conducted. The results show that the adsorption isotherms of deep shale gas also have a downward trend in spite of the higher pressure, and there is no obvious difference in adsorption characteristics, which is mainly due to the similar characteristics of microscopic pore-structure between deep shale and shallower shale. It is found that different adsorption models can well fit the experimental adsorption curve of deep shale gas, but the absolute adsorption capacity converted from excess adsorption capacity shows the same fitting result, i.e., DA-LF model > DR model > Langmuir model. Furthermore, DR model based on micropore filling theory is more suitable for characterizing the adsorption law of deep shale gas combined with the correlation analysis between pore structure and adsorbed-gas capacity. In addition, TOC is the key material factor controlling the adsorption capacity, and specific surface area of micropore is the key spatial factor. Compared to shallower shale, the deep shale shows higher siliceous content, lower calcite content, lower TOC content and lower adsorbed-gas content (the proportion of adsorbed-gas is about 30%).

Methane Storage Capacity of Permian Shales with Type III Kerogen in the Lower Yangtze Area, Eastern China

Marine–terrestrial transitional Permian shales occur throughout South China and have suitable geological and geochemical conditions for shale gas accumulation. However, the Permian shales have not made commercial exploitation, which causes uncertainly for future exploration. In this study, high-pressure methane (CH4) adsorption experiments were carried out on the Permian shales in the Lower Yangtze area, and the influences of total organic carbon (TOC) content and temperature on adsorption parameters were investigated. The characteristics and main controlling factors of methane storage capacity (MSC) of the Permian shales are discussed. The results show that the maximum adsorption and the adsorbed phase density of these Permian samples are positively correlated with TOC contents but negatively correlated with temperatures. The pores of organic matter in shale, especially a large number of micropores and mesopores, can provide important sites for methane storage. Due to underdeveloped pore structure and poor connectivity, the methane adsorption capacities of the Permian shales are significantly lower than those of marine shales. Compared with the Longmaxi shales, the lower porosity and lower methane adsorption of the Permian shales are reasonable explanations for their lower gas-in-place (GIP) contents. It is not suitable to apply the index system of marine shales to the evaluation of marine–terrestrial transitional shales. The further exploration of Permian shales in the study area should be extended to overpressure stable reservoirs with high TOC contents (e.g., &gt;5%), high porosity (e.g., &gt;3%), and deep burial (e.g., &gt;2000 m).

Pore system and gas adsorption potential of lacustrine Yanchang Mudstone, Ordos Basin, China

Understanding the pore system and the geological factors controlling the adsorption of gas in mudstones and shales is a key element in predicting the gas accumulation potential of an unconventional reservoir. A series of integrated methods, including basic geochemistry, X-ray diffraction, scanning electron microscopy, low-pressure gas (CO2 and Ar) physisorption, and high-pressure methane adsorption were performed on a set of mudstones from the Triassic Yanchang Formation in Ordos Basin, to characterize the pore system and gas adsorption capacity and their geological controlling factors. The results show that the studied Yanchang Mudstones are mainly siliceous rocks with high total organic carbon concentration (average of 7.63%) and low to moderate thermal maturity (vitrinite reflectance of 0.55–0.92 %). The microscopic visible pores are mainly intergranular pores between organic matter and rigid mineral grains, while organic matter pores are less well-developed. The pore volume is mainly contained in micropores (diameter < 2 nm) and mesopores (diameter = 2–50 nm), while much of the specific surface area occurs in the micropores, mainly in the organic matter pores. The occurrence of rigid minerals can inhibit the compaction of the intergranular pores. The abundant organic matter can provide potential adsorption sites for gas molecules, while clays and rigid minerals also have a limited positive effect on adsorption capacity. The adsorbed methane is mainly stored in micropores, which accounts for about 55%–90% of the total adsorbed methane content.

Reservoir Characteristics of the Lower Permian Marine-Continental Transitional Shales: Example from the Shanxi Formation and Taiyuan Formation in the Ordos Basin

The pore types and pore structure parameters of the heterogenetic shale will affect the percolation and reservoir properties of shale; therefore, the research on these parameters is very important for shale reservoir evaluation. We used X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), low-pressure CO2 adsorption analysis, mercury injection capillary pressure (MICP), and high-pressure methane adsorption analysis to analyze the characteristics of different pore types and their parameters of the Lower Permian Shanxi Formation and Taiyuan Formation in the Ordos Basin. The influence of different mineral contents on the porosity and pore size is also investigated. The Shanxi Formation (SF) is composed of quartz (average of 38.4%), plagioclase, siderite, Fe-dolomite, calcite, pyrite, and clay minerals (average of 50.1%), while the Taiyuan Formation (TF) is composed of calcite (average of 37%), siderite, Fe-dolomite, quartz, pyrite, and clay minerals (average of 32.3%). The most common types of pores observed in this formation are interparticle pores (InterP pores), intraparticle pores (IntraP pores), interclay pores, intercrystalline pores (InterC pores), organic matter pores (OM pores), and microfractures. CO2 adsorption analysis demonstrates the type I physisorption isotherms, showing microporous solids having comparatively small external surfaces. The similar types of isothermal shapes of the Shanxi Formation (SF) and Taiyuan Formation (TF) suggest that both types have similar pore size distribution (PSD) within the measured pore range by the low-pressure CO2 adsorption experiment. The micropore pore size of the TF is larger than that of the SF. MICP shows the larger pores (&gt;50 nm), and most of the volume was adsorbed by macropores. Methane gas sorption capacity increases with increasing pressure. Clay minerals and quartz played an important role in providing adsorption sites for methane gas. The overall analysis of both formations shows that TF has good reservoir properties than SF.

Supercritical High-Pressure Methane Adsorption on the Lower Cambrian Shuijingtuo Shale in the Huangling Anticline Area, South China: Adsorption Behavior, Storage Characteristics, and Geological Implications

Supercritical high-pressure methane (CH4) adsorption analysis was performed to investigate the gas adsorption behavior and storage capacities of the Lower Cambrian Shuijingtuo Shale in the Huanglin...

Pore structural characteristics and methane adsorption capacity of transitional shale of different depositional and burial processes: a case study of shale from Taiyuan formation of the Southern North China basin

Pore structural characteristics and methane adsorption capacity are two significant aspects affecting shale gas potential, but the impact of deposition and burial processes on these two aspects is not clear. Hence, the shale samples of Taiyuan Formation deposited continuously and experienced multi-stage tectonic uplift in Fuyang-Bozhou area of Southern North China Basin were collected in this study. Based on the total organic carbon content analysis, mineral composition determination, low-pressure CO2 and N2 adsorption, high-pressure methane adsorption and argon ion polishing-field emission scanning electron microscope observation. The impact of depositional and burial processes variation on shale reservoir physical properties and adsorption performance is studied. The results display that the pore types of shale samples which were continues deposited and experienced multi-stage tectonic uplift have no obvious differences, while the pore volume as well as specific surface area (SSA) of micropores and mesopores of shale samples under multi-stage tectonic uplift are larger significantly. Meanwhile, the roughness of shale pores increases also. The decrease of loading pressure caused by multi-stage tectonic uplift may be the main factor for the pore structure changes of shale sample. Compared with the continuous deposited samples, the shale samples under multi-stage tectonic uplift have stronger methane adsorption capacity, which is relevant to the greater SSA of micropores as well as mesopores. This study provides an example and new revelation for the influence of depositional and burial processes on shale pore structure and methane adsorption capacity.