Investigations of methane adsorption characteristics on marine-continental transitional shales and gas storage capacity models considering pore evolution

Methane adsorption is a critical assessment of the gas storage capacity(GSC)of shales with geological conditions.Although the related research of marine shales has been well-illustrated,the methane adsorption of marine-continental transitional(MCT)shales is still ambiguous.In this study,a method of combining experimental data with analytical models was used to investigate the methane adsorption characteristics and GSC of MCT shales collected from the Qinshui Basin,China.The Ono-Kondo model was used to fit the adsorption data to obtain the adsorption parameters.Subsequently,the geological model of GSC based on pore evolution was constructed using a representative shale sample with a total organic carbon(TOC)content of 1.71%,and the effects of reservoir pressure coefficient and water saturation on GSC were explored.In experimental results,compared to the composition of the MCT shale,the pore structure dominates the methane adsorption,and meanwhile,the maturity mainly governs the pore structure.Besides,maturity in the middle-eastern region of the Qinshui Basin shows a strong positive correlation with burial depth.The two parameters,micropore pore volume and non-micropore surface area,induce a good fit for the adsorption capacity data of the shale.In simulation results,the depth,pressure coefficient,and water saturation of the shale all affect the GSC.It demonstrates a promising shale gas potential of the MCT shale in a deeper block,especially with low water saturation.Specifically,the economic feasibility of shale gas could be a major consideration for the shale with a depth of<800 m and/or water saturation>60%in the Yushe-Wuxiang area.This study provides a valuable reference for the reservoir evaluation and favorable block search of MCT shale gas.

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.

Behavior and controlling factors of methane adsorption in Jurassic continental shale,northeastern Sichuan Basin

The behavior and controlling factors of natural gas adsorption in the Jurassic continental shale in the northeastern Sichuan Basin are studied based on the organic geochemical features,mineral compositions and pore structure parameters through a series of experiments on samples from the shale.Results show that the total gas content of the shale measured on-site is 0.1-5.3 cm^(3)/g,with an average of 0.7 cm^(3)/g.The methane isothermal adsorption curves show a trend of increasing first and then decreasing,indicating an obvious excessive adsorption.The shale has a maximum adsorption capacity(V^(L))of 0.44-3.59 cm^(3)/g,with an average of 1.64 cm^(3)/g,lower than that of marine shale in the same basin.The organic matter content and pore structure characteristics are identified as the two main factors controlling the adsorption capacity of the shale.Micropores in the shale are the main storage space for gas to be adsorbed.Due to well developed shell laminae and interlayers in the shale,calcite plays a more important role than clay minerals in affecting the adsorption of gas to the rock.The formation temperature and water content also significantly inhibit the gas adsorption to the shale.Compared with marine shale in the basin,the Jurassic continental shale is more heterogeneous and lower in TOC values.Furthermore,with a more widely developed clayey shale lithofacies and shell limy shale lithofacies as well as relatively less developed organic pores and micropores,the continental shale is inferior to marine shale in terms of gas adsorption capacity.

Molecular Simulation of Methane Adsorption in Different Micro Porous Activated Carbons at Different Temperatures

We employed the previously developed micro porous activated carbon models of different pore sizes ranges of 9-11?,10-12?,and 13-16?that were constructed by molecular simulation method based on a random packing of platelets of carbon sheets,functionalized with oxygen containing groups,to study the adsorption behavior of methane molecules.In studying methane adsorption behavior,we used Grand Canonical Monte Carlo and Molecular Dynamics methods at different temperatures of 273.15,298.15 and303.15 K.Adsorption isotherms,isosteric heats of adsorption,adsorption energy distributions and porosity changes of the models during adsorption process were analyzed and discussed.Furthermore,radial distribution Functions,relative distribution and diffusion coefficients of methane molecules in activated carbon models at different temperatures were studied.After the analysis,the main results indicated that large micro pores activated carbons were favorable for storing methane at lower temperatures and small micro pores were the most favorable for adsorbing methane molecules at higher temperatures.Interestingly,the developed model structures showed high capacities to store methane molecule at ambient temperatures and low pressure.

K_2S-activated carbons developed from coal and their methane adsorption behaviors

The main purpose of this work is to prepare various activated carbons by K2S activation of coal with size fractions of 60-80 meshes, and investigate the microporosity development and corresponding methane storage capacities. Raw coal is mixed with K2S powder, and then heated at 750 ℃-900 ℃ for 30 min-150 min in N2 atmosphere to produce the adsorbents. The texture and surface morphology are characterized by a N2 adsorption/desorption isotherm at 77 K and scanning electron microscopy （SEM）. The chemical properties of carbons are confirmed by ultimate analysis. The crystal structure and degree of graphitization are tested by X-ray diffraction and Raman spectra. The relationship between sulfur content and the specific surface area of the adsorbents is also determined. K2S activation is helps to bring about better development of pore texture. These adsorbents are microporous materials with textural parameters increasing in a range of specific surface area 72.27 m2/g-657.7 m2/g and micropore volume 0.035 cm3/g-0.334 cm3/g. The ability of activated carbons to adsorb methane is measured at 298 K and at pressures up to 5.0 MPa by a volumetric method. The Langmuir model fits the experimental data well. It is concluded that the high specific surface area and micropore volume of activated carbons do determine methane adsorption capacity. The adsorbents obtained at 800 ℃ for 90 min with K2S/raw coal mass ratios of 1.0 and 1.2 show the highest methane adsorption capacities amounting to 106.98 mg/g and 106.17 mg/g, respectively.

Methane adsorption effected by pore structure of overmature continental shale:Lower Cretaceous Shahezi Formation,Xujiaweizi Fault,Songliao Basin

Overmature continental shale is commonly developed,but few studies have given insight into its pore structure and sorption capacity.Various techniques,including SEM,helium porosity and permeability,N_(2)/CO_(2)adsorption,MICP,and NMR,were used to detect the pore structure of shale from the Shahezi Formation,Xujiaweizi Fault,Songliao Basin.The excess methane adsorption volumes were measured by the volumetric method and modeled by the Langmuir model.Based on the findings,the most developed pores are intraparticle pores in clay minerals,followed by the dissolution pores in feldspar,but organic pores are uncommon.The selected shales have low helium porosity(mean 1.66%)and ultralow permeability(mean 0.0498×10^(−3)μm^(2)).The pore throats are at the nanoscale,and the pore-throat size distributions are unimodal,with most less than 50 nm.The studied shales are characterized by the lower specific surface area(SSA)and pore volume(PV)but the larger average pore diameter.The total SSA is contributed by the micro-and mesopores,while the PV is dominated by meso-and macropores.The pore structures are more complex and controlled by multiple factors,such as mineral compositions and diagenesis,but organic matter is not critical.The maximum absolute adsorption methane volume(VL)is 0.97−3.58 cm^(3)/g(mean 1.90 cm^(3)/g),correlating well with the total SSA,SSA,and pore volume of micropores,which indicates that methane is mainly adsorbed and stored in micropores,followed by mesopores.

Methane Adsorption Capacity Reduction Process of Water-Bearing Shale Samples and Its Influencing Factors: One Example of Silurian Longmaxi Formation Shale from the Southern Sichuan Basin in China

Due to the existence of water content in shale reservoir,it is quite meaningful to clarify the effect of water content on the methane adsorption capacity(MAC)of shale.However,the role of spatial configuration relationship between organic matter(OM)and clay minerals in the MAC reduction process is still unclear.The Silurian Longmaxi Formation shale samples from the Southern Sichuan Basin in China were prepared at five relative humidity(RH)conditions(0%,16%,41%,76%,99%)and the methane adsorption experiments were conducted on these water-bearing shale samples to clarify the MAC reduction process considering the spatial configuration relationship between clay minerals and OM and establish the empirical model to fit the stages.Total organic carbon(TOC)content and mineral compositions were analyzed and the pore structures of these shale samples were characterized by field-emission scanning electron microscopy(FE-SEM),N2 adsorption and high-pressure mercury intrusion porosimetry(HPMIP).The results showed that the MAC reduction of clay minerals in OM occurred at different RH conditions from that of clay minerals outside OM.Furthermore,the amount of MAC reduction of shale samples prepared at the same RH condition was negatively related with clay content,which indicated the protection role of clay minerals for the MAC of water-bearing shale samples.The MAC reduction process was generally divided into three stages for siliceous and clayey shale samples.And the MAC of OM started to decline during stage(1)for calcareous shale sample mainly because water could enter OM pores more smoothly through hydrophobic pathway provided by carbonate minerals than through hydrophilic clay mineral pores.Overall,this study will contribute to improving the evaluation method of shale gas reserve.

The role of volatiles and coal structural variation in coal methane adsorption

We investigated the role of volatiles in the porous structure of coal samples and the corresponding structural deformations that affect the coals＇ methane adsorption capacity. For this study, the volatiles in coal were gradually removed by extraction. Changes in the crystal, textural, and porous structures were identified by means of thermogravimetric analysis, X-ray diffraction, and N2 adsorption/desorption. Changes in the methane adsorption behavior before and after volatile removal were investigated. It was found that changes in methane adsorption could be attributed to volatile-related deformations in the coal＇s porous structure. Microstructural characterizations indicated that the volatiles could be found in two states within the coal, either trapped in the pores, or cross-linked in the network. The former played an important role in constructing the pore spaces and walls within the coal and affected the accessibility of gases. The latter cross-linked state retained the volatiles within the macromolecular coal structural network. This state affected coal-coal interactions, which was a factor that controlled the crystal structure of coal and contributed to the number of porous deformations.

Theoretical and Experimental Study on the Adsorption and Desorption of Methane by Granular Activated Carbon at 25℃

A theoretical and experimental study was conducted to accurately determine the amount of adsorption and desorption of methane by various Granular Activated Carbon （GAC） under different physical conditions. To carry out the experiments, the volumetric method was used up to 500 psia at constant temperature of 25℃. In these experiments, adsorption as well as desorption capacities of four different GAC in the adsorption of methane, the major constituent of natural gas, at various equilibrium pressures and a constant temperature were studied. Also, various adsorption isotherm models were used to model the experimental data collected from the experiments. The accuracy of the results obtained from the adsorption isotherm models was compared and the values for the regressed parameters were reported. The results shows that the physical characteristics of activated carbons such as BET surface area, micropore volume, packing density, and pore size distribution play an important role in the amount of methane to be adsorbed and desorbed.

Surface Modification of Bituminous Coal and Its Effects on Methane Adsorption

This paper studied the role of O-containing groups over the coal surface in methane adsorption. The coal was modified with H2SO4, （NH4）2S208 or H2SO4/（NH4）2S2Os）, respectively, to introduce O-containing functional groups, and characterized by proximate analysis, ultimate analysis, Boehm titration, X-ray photoelectron spectroscopy （XPS） and nitrogen adsorption. The results of ultimate analysis, Boehm titration and XPS indicate that there were increases in terms of both the content of oxygen and the quantities of O-containing groups over the modified coals surface, especially for the carboxyl. Nitrogen adsorption shows that the modified coals possessed higher surface area and pore volume than that of 0-XQ. The methane adsorption data were measured at 298 K at pressures up to 4.0 MPa by the volumetric method and fitted well by Langmuir model. Experimental results implied that O-containing groups and pore structure affected methane adsorption. The adsorption capacities decreased as increasing quantities of O-containing groups.

Monte Carlo simulation of methane molecule adsorption on coal with adsorption potential

The paper presents a Monte Carlo simulation to study the adsorption characteristics of methane molecule on coal slit pores from different aspects.Firstly,a physical model of adsorption and desorption of methane molecules on micropores was established.Secondly,a grand canonical ensemble was introduced as the Monte Carlo simulation system.Thirdly,based on the model and system,the molecule simulation program was developed with VC++6.0 to simulate the isothermal adsorption relationship between the amount of molecule absorption and the factors affecting it.Lastly,the numerically simulated results were compared with measured results of adsorption coal samples of two different coal mines with a laboratory gas absorption instrument.The results show that the molecule simulations of the adsorption constants,the adsorption quantity,and the isothermal adsorption curve at the same and different coal temperatures were in good agreement with those measured in the experiments,indicating that it is feasible to use the established model and the Monte Carlo molecule simulation to study the adsorption characteristics of methane molecules in coal.

Effect of particle size on high-pressure methane adsorption of coal

Adsorbed gas cannot be neglected in the evaluation of coalbed methane and shale gas since a significant proportion of gas is stored in the form of adsorbed gas.Adsorbed methane of coal and shale has been widely studied by high-pressure methane adsorption experiment.In sample treatment of the experiment,the sample is crushed and sieved to a particular particle size range.However,how particle size influence high-pressure methane adsorption is still unclear.In this study,low-pressure nitrogen(N_(2))and high-pressure methane adsorption have been measured on coal samples with different particle size.According to N2 sorption analysis,pore volume and surface area increase with particle size reduction.Pore size distribution of small pores(<10nm)changes among varying particle size.Pore volume proportion of small pores(<10nm)increases and pore volume proportion of big pores(>10nm)decreases with decreasing particle size.Decreasing particle size by crushing sample introduces new connectivity for closed pores to the particle surface.The responses of isotherms of high-pressure methane adsorption are different with different particle size.Methane adsorption at initial pressure(145psi)increases with decreasing particle size.Adsorption increase rate at high pressure(435-870psi)decreases with particle size reduction.This can be explained that fine sample has more pore volume and higher pore volume proportion of small pores(<10nm).Sample with particle size of 150-250μm has the highest Langmuir volume.

Adsorption of methane onto mudstones under supercritical conditions: Mechanisms, physical properties and thermodynamic parameters

Since the mechanisms of methane-mudstone interactions are important for estimating shale gas reserves,methane adsorption under supercritical conditions of 30 MPa pressure and 303.15,333.15,363.15 K temperatures was studied to measure the excess methane adsorption in two mudstone samples from Yanchang Formation,Ordos Basin.Excess adsorption features inflection points where the amount of adsorbed gas changes from increasing to decreasing concentrations.Three methods(fixed,slope,and freely fitted density)were applied to calculate the adsorbed-phase density(rad),which was then used to fit the measured excess adsorption.Two criteria,the goodness-of-fit and whether the fitting can obtain reasonable absolute adsorption,were applied to determine the most accurate model.Results indicated that the supercritical Dubinin-Radushkevich(SDR)model with freely fitted rad was the most reasonable model.The volume of adsorbed methane at 363.15 K is close to the micropore(d<2 nm)volume of the corresponding mudstone.Considering the actual geological conditions,the adsorbed gas should be predominantly stored in micropores.Thermodynamic parameters reveal that the methane adsorption on mudstone is a physisorption process that is jointly controlled by the heterogeneity of,and interaction forces between the methane molecule and,the rock surface.

Effects of coal molecular structure and pore morphology on methane adsorption and accumulation mechanism

The adsorption,diffusion,and aggregation of methane from coal are often studied based on slit or carbon nanotube models and isothermal adsorption and thermodynamics theories.However,the pore morphology of the slit model involves a single slit,and the carbon nanotube model does not consider the molecular structure of coal.The difference of the adsorption capacity of coal to methane was determined without considering the external environmental conditions by the molecular structure and pore morphology of coal.The study of methane adsorption by coal under single condition cannot reveal its mechanism.In view of this,elemental analysis,FTIR spectrum,XPS electron energy spectrum,13C NMR,and isothermal adsorption tests were conducted on the semi-anthracite of Changping mine and the anthracite of Sihe Mine in Shanxi Province,China.The grand canonical Monte Carlo(GCMC)and molecular dynamics simulation method was used to establish the coal molecular structure model.By comparing the results with the experimental test results,the accuracy and practicability of the molecular structure model are confirmed.Based on the adsorption potential energy theory and aggregation model,the adsorption force of methane on aromatic ring structure,pyrrole nitrogen structure,aliphatic structure,and oxygen-containing functional group was calculated.The relationship between pore morphology,methane aggregation morphology,and coal molecular structure was revealed.The results show that the adsorption force of coal molecular structure on methane is as follows:aromatic ring structure(1.96 kcal/mol)>pyridine nitrogen(1.41 kcal/mol)>pyrrorole nitrogen(1.05 kcal/mol)>aliphatic structure(0.29 kcal/mol)>oxygen-containing functional group(0.20 kcal/mol).In the long and narrow regular pores of semi-anthracite and anthracite,methane aggregates in clusters at turns and aperture changes,and the adsorption and aggregation positions are mainly determined by the aromatic ring structure,the positions of pyrrole nitrogen and pyridine nitrogen.The degree of aggregation is controlled by the interaction energy and pore morphology.The results pertaining to coal molecular structure and pore morphology on methane adsorption and aggregation location and degree are conducive to the evaluation of the adsorption mechanism of methane in coal.

Structure modeling of activated carbons used for simulating methane adsorption-A review

Activated carbons(ACs)are highly porous materials with a broad range of applications in industry such as gas storage,water and air purification,gas separation,and catalysis.The microstructure for ACs is still not clearly known in spite of their wide industrial uses.There have been efforts to describe the structure of activated carbons experimentally in relation to its methane adsorption characteristics.In this review,it is assumed that natural gas is sorely composed of CH_(4)for simplicity(because CH_(4)is the major component,>90%).Experimental means to unveil the microstructure and many other properties for these ACs have some limitations,to overcome these limitations,ACs structural modeling and simulation become very important to match the properties with the desired methane adsorption characteristics.The major challenge that methane adsorption simulation faces for so long,is the lack of realistic AC models.This paper reviews the current efforts to develop the realistic AC models for methane adsorption,most of the built models are based on experimental carbon structural findings from the previous studies.The structural parameters including pore size distribution(PSD),specific surface area(SSA),pore volume and extent of curvature in the carbon materials and their role to methane adsorption are discussed.The role of chemical properties,such as presence of functional groups and the nature of the functional groups to the adsorption properties of methane,are also introduced.Different pore morphologies(such as slit pore,platelet,spherical,etc.)are studied with their effect on methane adsorption and presented too.It is found that each of the mentioned parameters has its own bearing to methane adsorption.Furthermore,this work analyzes different current techniques used in modeling natural gas adsorption,and the mechanisms are able to reproduce the specific carbon materials for a certain desired set of adsorption characteristic.Some future works are also recommended in this area,so that better representations of ACs can be obtained for methane storage purposes.

Impact of methane adsorption on tight rock permeability measurements using pulse-decay

The permeability of the rock is usually measured by the injection of gas using Darcy's flow model(pulse-decay).For oil formations,helium and nitrogen are the most common gases used to measure the permeability of the rock.However,recent approaches are based on the use of methane as it minimizes the properties difference between the testing fluid and reservoir fluid.This work focused on the latter approach to compute the correction of gas adsorption.The most widely used model is Cui et al.model that is based on Langmuir adsorption isotherm.In this work,we introduced a modified model that is based on Freundlich isotherm.This model also includes the correction for gas adsorption such as Freundlich isotherms proved to be more appropriate for the adsorption on intact reservoir rock.The model is based on gas and rock properties and reduced pressure and temperature were used to accommodate the gas compressibility.The modified model can also capture effective porosity of adsorption(a)that can correct the pulse-decay storage capacity parameters a and b.The permeability estimation of ultra-tight samples using the modified approach is enhanced owing to the correction in the storage volume and rock porosity.Including the proper adsorption isotherm enhanced the porosity estimation because Langmuir isotherm yielded 11%porosity and Freundlich isotherm yielded 12%porosity.Similar results were obtained in the permeability estimation,Langmuir isotherm resulted in a 1.5%error compared to zero error in the Freundlich isotherm estimation.

Study on the evolution of solid–liquid–gas in multi-scale pore methane in tectonic coal

The rich accumulation of methane(CH_(4))in tectonic coal layers poses a significant obstacle to the safe and efficient extraction of coal seams and coalbed methane.Tectonic coal samples from three geologically complex regions were selected,and the main results obtained by using a variety of research tools,such as physical tests,theoretical analyses,and numerical simulations,are as follows:22.4–62.5 nm is the joint segment of pore volume,and 26.7–100.7 nm is the joint segment of pore specific surface area.In the dynamic gas production process of tectonic coal pore structure,the adsorption method of methane molecules is“solid–liquid adsorption is the mainstay,and solid–gas adsorption coexists”.Methane stored in micropores with a pore size smaller than the jointed range is defined as solid-state pores.Pores within the jointed range,which transition from micropore filling to surface adsorption,are defined as gaseous pores.Pores outside the jointed range,where solid–liquid adsorption occurs,are defined as liquid pores.The evolution of pore structure affects the methane adsorption mode,which provides basic theoretical guidance for the development of coal seam resources.

Adsorption behavior of carbon dioxide and methane in bituminous coal:A molecular simulation study

The adsorption behavior of CO_2, CH_4 and their mixtures in bituminous coal was investigated in this study. First, a bituminous coal model was built through molecular dynamic(MD) simulations, and it was confirmed to be reasonable by comparing the simulated results with the experimental data. Grand Canonical Monte Carlo(GCMC)simulations were then carried out to investigate the single and binary component adsorption of CO_2 and CH_4with the built bituminous coal model. For the single component adsorption, the isosteric heat of CO_2 adsorption is greater than that of CH_4 adsorption. CO_2 also exhibits stronger electrostatic interactions with the heteroatom groups in the bituminous coal model compared with CH_4, which can account for the larger adsorption capacity of CO_2 in the bituminous coal model. In the case of binary adsorption of CO_2 and CH_4mixtures, CO_2 exhibits the preferential adsorption compared with CH_4 under the studied conditions. The adsorption selectivity of CO_2 exhibited obvious change with increasing pressure. At lower pressure, the adsorption selectivity of CO_2 shows a rapid decrease with increasing the temperature, whereas it becomes insensitive to temperature at higher pressure. Additionally, the adsorption selectivity of CO_2 decreases gradually with the increase of the bulk CO_2 mole fraction and the depth of CO_2 injection site.

New Evidences for the Adsorption of Methane over Oxide Surfaces

It is indicative of the TSR result that CH4 was strongly adsorbed on well degassed SrCO3 surface at high temperatUre.A desorption peak of CH4 was found in CH4TPD profile which appeared at ca. 310℃.The strong adsorption of CH4 over the surface of SrCO3 was attributed to the strong basicity of SrO sites resulted from decomposition of SrCO_3

Nanoporous carbons as promising novel methane adsorbents for natural gas technology

Nanoporous carbons were synthesized using furfuryl alcohol and sucrose as precursors and MCM-41 and mordenite as nanoporous templates.The produced nanoporous carbons were used as adsorbent for methane storage.The average pore diameter of the samples varied from 3.9 nm to 5.9 nm and the BET surface area varied from 320m2/g to 824m2/g.The volumetric adsorption experiments revealed that MCM-41 and sucrose had better performance compared with mordenite and furfuryl alcohol,correspondingly.Also,the effect of precursor to template ratio on the structure of nanoporous carbons and their adsorption capacities was investigated.The nanoporous carbon produced from MCM-41 mesoporous molecular sieve partially filled by sucrose shows the best methane adsorption capacity among the tested samples.