Excess Adsorption Capacity Research Articles

Helium expansion revisited: Effects of accessible volume on excess adsorption in kerogen matrices

Enhancing our understanding of the excess adsorption capacity in shale gas reservoirs is paramount for accurately predicting production capabilities and refining extraction processes. A significant factor in this calculation is the accessible volume, which can only be measured indirectly using helium as a proxy. In this study, hybrid grand canonical Monte Carlo/molecular dynamics (GCMC/MD) simulations were employed to scrutinize the accessible volume and quantify the excess adsorption capacities of various gases in kerogen matrices, characterized by diverse micropore distributions at 363.15 K (90 °C) and pressures up to 50 MPa. We evaluated multiple approaches to determine accessible volume in simulations, emphasizing the importance of selecting a probe size that reflects the actual size of the adsorbate. The simulation outcomes reveal that accessible volumes derived from the helium expansion method, mimicking the traditional experimental techniques, tend to be overestimated by around a factor of two. This finding challenges the reliability of such measurements and suggests a need for their recalibration based on computer simulation models. Furthermore, when our simulations were compared with various theoretical adsorption isotherm models, the more advanced Supercritical Dubinin-Radushkevich and Supercritical Brunauer-Emmett-Teller models demonstrated better accuracy in predicting absolute adsorption values compared to the more conventional Langmuir model. However, neither model accurately predicted the absolute adsorption quantities, indicating room for improvement. Finally, the simulations underscore the significant adsorption capacity of CO2 compared to other gases, highlighting its promising role in facilitating enhanced gas recovery and geological sequestration within shale formations.

New insight into CH4 adsorption mechanism in coal based on modeling analysis of different adsorption theories

Based on the principle of Gibbs excess adsorption measurement, high-pressure isothermal adsorption and desorption experiments of CH4 were performed on fractured coal samples, and CH4 adsorption phase density was obtained by the intercept method according to the experimental data. The Langmuir model, BET model, DA model, and their corrected model, the supercritical adsorption models were used for the fitting analysis of CH4 excess adsorption capacity. A hybrid model of different adsorption theories was developed based on CH4 adsorption phase density and theoretical adsorption capacity predicted by the intercept method. The transition in the occurrence pattern and control mechanism of CH4 in coal were investigated. The fitting of the Langmuir model, BET model, DA model, and their corrected models, the SBET model, the SDA model, and the SDA-L model to the CH4 excess adsorption capacity in coal shows that all multilayer adsorption theory model is not suitable for fitting the CH4 excess adsorption capacity in coal. The uncorrected Langmuir model and DA model are only suitable for fitting the CH4 excess adsorption capacity in coal in the low-pressure stage (pressure below 10 MPa). The corrected Langmuir model, the corrected DA model, the SDA model, and the SDA-L model can be used to fit the CH4 excess adsorption capacity in coal, but they show some bias in predicting the theoretical CH4 adsorption capacity and the CH4 adsorption phase density. The fitting of the three main adsorption theory models suggests that there may be simultaneous monolayer adsorption and microporous filling adsorption. The fitting results of the hybrid model based on monolayer adsorption and microporous filling adsorption theory depend on showing that with the increase of temperature, the occurrence of CH4 in coal gradually changes from mainly monolayer adsorption to mainly microporous filling adsorption, and the transformation of occurrence mode is related to temperature and the development of pores in coal.

Modeling of Supercritical CO2 Adsorption for Low-Permeability Coal Seam of Huainan-Huaibei Coalfield, China.

Investigating the coal adsorption behavior on supercritical CO2 (ScCO2) is crucial for long-term CO2 geological storage. In this paper, low-permeability coal samples from the Huainan-Huaibei coalfields in China were selected. The high-pressure isothermal adsorption of CO2 was carried out at 36, 42, and 48 °C. The results of adsorption experiments were analyzed by fitting 9 types of modified adsorption models, including three different adsorption theories. Considering that different adsorption mechanisms may exist for CO2 in coal, 14 mixed adsorption models were established. The accuracy of the coefficient of determination (R2) and root-mean-square error (RMSE) for ScCO2 excess adsorption capacity was analyzed, mainly focusing on the accuracy of the key model parameters such as the adsorption phase density and the theoretical adsorption capacity. These parameters were discussed, combined with the predicted adsorption phase density of CO2 based on the intercept method. The results indicate that among the 9 types of modified adsorption considered, based on the adsorption phase density screening, the deviation of the predicted adsorption capacity from the experimental value was then considered. The Dubinin-Radushkevich (DR) model can effectively fit the adsorption behavior of CO2 at low pressure (<7.5 MPa). The Langmuir (L), Langmuir-Freundlich (LF), Extended-Langmuir (EL), and TOTH models can effectively fit the adsorption behavior of CO2 at high pressure (7.5-20 MPa), while the multimolecular layer models were unsuitable for fitting ScCO2 adsorption. The model fitting results showed that only the monomolecular layer and micropore-filled adsorption models were suitable for fitting the ScCO2 adsorption capacity. The DR-LF model best fits the adsorption data based on its key parameters of adsorption phase density and theoretical adsorption capacity. The established mixed model DR-LF fitting results showed that the CO2 in coal was dominated by microporous filling adsorption. The higher the temperature, the greater the contribution of microporous filling adsorption to the total adsorption. There still exists deviation in the adsorption phase density and theoretical adsorption capacity. The contribution percentage of different adsorption mechanisms of CO2 in coal needs to be further investigated.

Isothermal adsorption characteristics of various phases of CO2 and CH4 in different rank coals

ABSTRACT Using the remaining coal seams of closed coal mines for CO2 geological storage can effectively slow down the greenhouse effect and realize the redevelopment and utilization of closed coal mines. The burial depth of coal seams in closed coal mines in China covers an extensive range, and CO2 and CH4 could exist in various phases in the coal. The existing experimental objects for CO2 adsorption in coal are mainly associated with the supercritical and gaseous phases, and a research gap comparison between the CO2 adsorption characteristics in the liquid phase and those of other phases is very obvious. Herein, the isotherm adsorption experiments of CO2 and CH4 in different phases on different rank coal samples are methodically conducted in the pressure range of 0-12MPa. The experimental results indicate that the excess adsorption capacity of gaseous CO2 and CH4 (gas pressure <4MPa) rapidly raises with the growth of the adsorption pressure; however, a significant difference for the case of the medium- and high-pressure stage (>4MPa) is detectable. With the growth of the adsorption pressure, the excess adsorption capacity of the supercritical CH4 gradually reaches the maximum value and then remains stable, where the maximum experimental value is 1.009 mmol/g. While the excess adsorption capacity of CO2 near the critical pressure of liquid and supercritical state rapidly reduces and then tends to be stable. The maximum adsorption capacity is capable of touching 2.096 mmol/g, which is stable around 0.5 mmol/g. The analysis indicates that the change in the excess adsorption amount of CO2 near the critical pressure corresponds to the change in its density. The absolute adsorption capacity of CO2 and CH4 monotonically grows in the pressure range of 0-12MPa, and the absolute adsorption capacity of the same coal sample follows the following order: liquid CO2 > supercritical CO2 > CH4. The maximum adsorption capacity values for these substances in order are 2.493, 2.345, and 1.296 mmol/g. With the growth of the coal rank, the Gibbs free energy, specific surface area, and adsorption capacity of the understudied coal samples exhibit a U-shape relationship as a function of their coal ranks.

Impact of Adsorption Swelling and Slippage Effects on Changes in Coal’s Permeability at Different Temperatures

As a critical parameter, coal’s permeability influences the coalbed’s methane (CBM) production efficiency, which, in turn, is affected by a slippage effect, adsorption swelling, and effective stress in the CBM exploitation process. In this paper, an isothermal adsorption experiment under various temperatures, including seepage tests comprising CH4 and He in coal at different temperatures under constant effective stress, was carried out separately. We established a modified Shi&Duruca (S&D) model that considered constant effective stress and a modified adsorption model, in which the effect of excess adsorption capacity and temperature was considered. The results revealed that swelling deformation occurred when coal adsorbed CH4, which would result in the permeability of CH4 being lower than that of He under similar conditions. With an increase in pore pressure, coal’s permeability decreased gradually under the combined effects of slippage and adsorption swelling. Temperature is an important factor that affects the movement and storage of gas. Any change in temperature and pore pressure would result in coal’s permeability being comprehensively affected by thermal expansion, thermal cracking, and adsorption swelling, including the effects of slippage. Thermal expansion and thermal cracking increase coal’s permeability under low pressure and decrease coal’s permeability under high pressure. The modified adsorption model and permeability model could better characterize the adsorption and permeability properties of coal. The calculation results illustrated that the slippage effect and adsorption swelling are two important factors affecting permeability, with its permeability increment sharing a similar change trend with changes in permeability. Under the condition of low pressure, the adsorption swelling effect was dominant, and the contributary rate of the slippage effect on permeability would increase, obviously, with an increase in temperature.

High-pressure hydrogen adsorption in clay minerals: Insights on natural hydrogen exploration

Natural hydrogen has been widely detected in many environments. However, up to date, the knowledge about the occurrence of hydrogen in the geological formation is very limited. Clay minerals with large adsorption capacities due to their huge specific surface area are widely distributed in the subsurface. In order to find whether the hydrogen can be adsorbed on the clay minerals, 6 types of clay minerals (montmorillonite, chlorite, sepiolite, palygorskite, kaolinite and illite) were used for the hydrogen adsorption analysis at various temperatures (0, 25, 45, and 75 °C) and pressures (up to 18 MPa). In addition, multi-scale simulations via density functional theory (DFT) and grand canonical Monte Carlo (GCMC) were carried out to further explore the hydrogen adsorption mechanism of clay minerals in bulk phase. The results show that the excess adsorption capacities of sepiolite and palygorskite are much higher than those of montmorillonite and chlorite, and the excess adsorption capacities of illite and kaolinite are very low, nearly reaching the detection limit. The variation of hydrogen adsorption capacity (HAC) in different clays is attributed to the difference in their pore structures (i.e., specific surface area). A more complex pore structure and a larger specific surface area could provide more sorption sites for hydrogen molecules. HAC increases with pressure and decreases with temperature irrespective of the clay mineral types. This study highlights the features of hydrogen adsorption in clay minerals, contributes to a better understanding of natural hydrogen occurrence and storage in the subsurface, providing the potential application for geological hydrogen exploration.

Thermodynamic analysis of the difference in adsorption characteristics of CH4 and CO2 on continental shale

In order to explain the difference in adsorption characteristics of CH4 and CO2 on continental shale from the perspective of thermodynamics, the isothermal adsorption experiments of CH4 and CO2 adsorbed by shale in Yanchang Formation in Ordos Basin were carried out, and the excess adsorption capacity was corrected to absolute adsorption capacity. Then the Clausius-Clapeyron equation was used to analyze the isosteric heat of adsorption of CH4 and CO2 on shale. The results show that, for calculating the absolute adsorption capacity, Ozawa empirical formula or Van der Waals approximation method should be used to calculate the adsorption phase density. The absolute adsorption capacity should be selected as the basic data for calculating the isosteric heat of adsorption. The reason is that the excess isosteric heat of adsorption has a negative value in the low adsorption capacity stage, which is contradictory to the fact that the adsorption process is exothermic, and is significantly higher than the absolute isosteric heat of adsorption. There is a good linear positive correlation between the isosteric heat of adsorption and the adsorption amount of CH4 and CO2 adsorbed by continental shale, and the isosteric heat of adsorption of CH4 is greater than that of CO2. The absolute initial isosteric heat of adsorption of CH4 and CO2 adsorbed by shale is 52.04 kJ/mol and 27.71 kJ/mol, indicating that the adsorption force of CH4 on Yanchang Formation shale is stronger than that of CO2.

Study on Adsorption Characteristics of Deep Coking Coal Based on Molecular Simulation and Experiments.

To study the effect of high temperature and high pressure on the adsorption characteristics of coking coal, Liulin coking coal and Pingdingshan coking coal were selected as the research objects, and isotherm adsorption curves at different temperatures and pressures were obtained by combining isotherm adsorption experiments and molecular dynamics methods. The effect of high temperature and high pressure on the adsorption characteristics of coking coal was analyzed, and an isothermal adsorption model suitable for high-temperature and high-pressure conditions was studied. The results show that the adsorption characteristics of deep coking coal can be well characterized by the molecular dynamics method. Under a supercritical condition, the excess adsorption capacity of methane decreases with the increase of temperature. With the increase of pressure, the excess adsorption capacity rapidly increases in the early stage, temporarily stabilizes in the middle stage, and decreases in the later stage. Based on the classical adsorption model, the adsorption capacity of coking coal under high-temperature and high-pressure environments is fitted. The fitting degree ranges from good to poor. The order is D-R > D-A > L-F >BET > Langmuir, and combined with temperature gradient, pressure gradient, and the D-R adsorption model, it can be seen that after 800 m deep in Liulin Mine and 400 m deep in Pingdingshan Mine, the adsorption capacity of coking coal to methane decreases with the increase of depth.

Experimental study on coal seam permeability enhancement and CO2 permeability caused by supercritical CO2

Permeability is one of the most important parameters for characterizing fluid flow and production from reservoirs. In this paper, experimental studies on the percolation, permeability, and adsorption of supercritical CO2 in coal seams were carried out, taking into account the effects of injection pressure and temperature, comparing the changes in longitudinal wave velocity of specimens before and after the tests, and analyzing the permeability effect of supercritical CO2 on raw coal specimens. The test results showed that when the volume stress was 36 MPa, the permeability of supercritical CO2 in coal increased by 93%, on average, compared with that of CO2. The modified D-R model was used to fit the adsorption data, and it was found that the excess adsorption capacity of supercritical CO2 by coal decreased with increased pressure, with a maximum value of approximately 8 MPa. When the temperature increased by 10°C, the adsorption capacity decreased by 8.3%, on average. In the subcritical CO2 state, the trend of excess CO2 adsorption in coal was consistent with that of absolute adsorption, which was 16% higher than that of excess adsorption, on average. After the action of supercritical CO2, the propagation velocity of the longitudinal wave in the sample decreased significantly, indicating that supercritical CO2 can effectively promote the development of pores and fractures in the coal sample, with an obvious anti-reflection effect on the coal seam and the best permeability enhancement effect at 35°C.

Quantitative characterization of methane adsorption in shale using low-field NMR

Quantification of methane content in shales is a critical parameter for estimation of their potential gas production capacity. Traditional gravimetric methods for estimation of this quantity are sensitive only to adsorbed methane and are difficult to apply either to intact shale rock cores or via field measurements. Here non-invasive low-field nuclear magnetic resonance (LF-NMR) is applied to quantify excess methane adsorption capacity in two intact shale rock plugs at pressures up to 150 bar; validation is provided against destructive gravimetric methods performed on fragments from the same shale rock plugs. The resultant NMR transverse relaxation time (T2) distributions contain three distinct peaks (referred to as peaks P1 – P3) which are allocated to adsorbed methane in organic pores, methane constrained to inorganic pores and bulk methane located predominately in fractures, respectively. The area of peak P1 is observed to increase with pressure up to 100 bar, after which it reaches a plateau, whilst the area of peaks P2 and P3 both increase linearly with pressure up to 150 bar. The most accurate estimate of excess methane adsorption capacity is obtained via a combination of an overall system mass balance and the methane located in inorganic pores and fractures (peaks P2 and P3, respectively), where excellent agreement is produced with corresponding gravimetric measurements for both shale samples studied.

Investigation of cryo-adsorption hydrogen storage capacity of rapidly synthesized MOF-5 by mechanochemical method

Comparisons were made between the samples mechanochemically (MOF-5(M)) and solvothermally (MOF-5(S)) prepared for the development of efficient hydrogen storage medium. Synthesized samples were undergone structural characterization as well as adsorption equilibrium measurements of hydrogen at temperature-pressure range 77 K–87 K and 0.1–10 MPa. Grand Canonical Monte Carlo (GCMC) simulations were further conducted to study the behaviors of hydrogen molecules adsorbed on MOF-5. It shows that, besides the advantage of large scale synthesis and a lower cost, mechanochemical method respectively brings about 207% and 90.5% increments in the specific surface area and the maximum excess adsorption capacity of hydrogen at 77 K within pressure range 0–10 MPa. Results also reveal that the crystal within MOF-5(M) is regular and distributing uniformly with a mean size only one tenth of that of the MOF-5(S); at 77 K within pressure range 0–10 MPa, Toth equation can predict the adsorption equilibrium data of hydrogen on two MOF-5 samples with a mean relative error less than 1.5%. It suggests that MOF-5(M) is more promising for hydrogen storage by adsorption for practical applications.

Thermodynamic characteristics of high-pressure CH4 adsorption on longmaxi shale subjected to supercritical CO2-water saturation

The shale-CH4 interaction after supercritical CO2 (ScCO2) injection can be well interpreted by adsorption thermodynamics study. Using a gravimetric method, the methane adsorption experiments over wide range of pressure (up to 35 MPa) and temperature (30–90 °C) were conducted on Longmaxi shale before and after ScCO2-water saturation (60days/20Mpa/70°C). In addition, low-temperature CO2 and N2 adsorption experiments were performed to analyze the variations of pore structure of shale. Results indicates that the high-pressure CH4 adsorption curves of shale exhibit obvious excess adsorption characteristics, and the excess adsorption capacity of shale to CH4 decreased after ScCO2-water saturation, which is mainly caused by the decrease of the specific surface area of shale. Comparing to Brunauer-Emmett-Teller, Dubinin-Radushkevich and Ono-Kondo models, the excess adsorption data can be well-fitted by Langmuir model through combining Henry equation. Additionally, the thermodynamic parameters of shale-CH4 adsorption pair, including the isosteric heat of adsorption, enthalpy change, Gibbs free energy change and entropy change, displayed strong dependence on adsorption capacity and temperature, and altered in varying degrees after ScCO2-water saturation, demonstrating that the shale gas recovery can be enhanced by ScCO2-water-shale interaction from the perspective of thermodynamics. This study provides a reference for CO2 enhanced shale gas recovery.

Insight into difference in high-pressure adsorption-desorption of CO2 and CH4 from low permeability coal seam of Huainan-Huaibei coalfield, China

This study aimed to investigate the differential characteristics of high-pressure adsorption-desorption of supercritical CO2 and CH4 at main temperatures of 36 ℃, 42 ℃, and 48 ℃ and the pressure of 0–20 MPa in low permeability coal, a case from the tectonic coal area of Huainan-Huaibei coalfield, eastern China. Combining the variation characteristics of adsorption capacity with pressure, gas free phase density, the prediction of CO2 adsorbed phase density, the correction method of gas adsorption capacity, the sequestration capacity of CO2 in low permeability coal, and the adsorption hysteresis index of adsorbed gas were assessed. The controlling factors of gas adsorption capacity were revealed based on the general discussion of the relation between the gas adsorption capacity and the conditions such as temperature, pressure, coal maceral, coal quality, and pore structure. The results show that the lowest equilibrium pressure associated with the CH4 excess adsorption peak is 9 MPa, which is larger than most of the experimental pressures for the CH4 isothermal adsorption test. CO2 excess adsorption capacity of the different coal samples has characteristic of an obvious peak at the experimental pressure near 6 MPa under different experimental temperatures, all CO2 excess adsorption capacity changes with CO2 free phase density in a two-step pattern, CH4 or CO2 adsorbed phase density can be predicted by the truncation method. Desorption of CH4 or CO2 in coal has an obvious "hysteresis loop", the cumulative adsorption hysteresis index (CAHI) and the incremental adsorption hysteresis index (IAHI) of CH4 based on the calculation of CH4 excess adsorption capacity are controlled by the temperature and pressure, it has the obvious rise during the stage of low pressure (less than 4 MPa), whether IAHI or CAHI of CO2, it shows characteristics of complex changes. Variations in CAHI and IAHI for CH4 or CO2 are governed by the development of pore structure in coal, and the temperature. Coal maceral, coal quality, and coal grade have an effect on gas adsorption in coal by affecting the growth, filling, and deformation of pores in coal; the adsorption capacity of the gas depends both on the surface area of the pores and the pore volume of the pores in the coal. The differential mechanism for the gas adsorption capacity from the low permeability coal requires further understanding.

Experimental measurements of CO2 adsorption on Indonesian low-rank coals under various conditions

In this study, the CO2 adsorption capacity was measured on Indonesian low-rank coals in the raw and dry conditions in powder and block states using different coal sample preparation to estimate CO2 sequestration and storage potential. Coal sample specimens were taken from three different areas in the South Sumatra Basin, Indonesia. The adsorption experiments were performed using the volumetric method at a temperature of 318.15 K and pressure up to 3 MPa. The CO2 excess adsorption capacity of powder coal is always higher than block coal. Moreover, decreasing moisture content by the drying process increases CO2 adsorption capacity on coal. Based on fitted CO2 adsorption experimental data with the Langmuir and Freundlich isotherm model, the adsorption occurs on monolayer and multilayer at various conditions. Langmuir volume capacity and pressure show drying and crushing process increased adsorption capacity. However, the drying process affects more the capability of coal to adsorb CO2 than the powdered sample, especially in low-rank coal. It was also observed adsorption capacity is directly proportional to huminite content in the coal. Due to lower moisture and higher huminite contents, the dried WB coal powder had the highest CO2 adsorption capacity over the other coal samples in similar sample conditions. Altogether, this study may provide a better understanding in CO2 adsorption on low-rank coal with different coal sample preparation resulting in different CO2 adsorption capacity.

Predicting adsorbed gas capacity of deep shales under high temperature and pressure: Experiments and modeling

Temperature and pressure conditions of deep shale are beyond experiment range, and the amount of adsorbed gas is difficult to determine. To predict the adsorbed gas content of deep shales under formation conditions, isothermal adsorption experiments and model building were conducted on shale samples from Longmaxi Formation in China. A temperature-dependent adsorption model based on the Langmuir equation is proposed, which can be well-fitted by observed isotherms with a high correlation coefficient. Based on the fitted parameters at 303.15 K, the isothermal adsorption curves at 333.15 K, 363.15 K, and 393.15 K are predicted, showing a good agreement with experimental curves available. Compared with previous prediction methods, the biggest advantage of the proposed method is that it can be carried out only based on one-time isothermal adsorption experiment. Based on the predictions, the downward trend of the excess adsorption curves will slow down under high temperature and pressure conditions, and when the pressure reaches a certain level (&gt; 80 MPa), the temperature has little effect on the excess adsorption capacity. While for absolute adsorption, the gas adsorption reaches saturation much slowly at high temperature, it can also reach saturation under formation pressure. Under the burial depth of marine shale, temperature plays a major role in controlling the adsorbed gas, resulting in the decrease of adsorbed gas content in deep shale, and its ratio will further decrease as the depth increases. Cited as: Zhou, S., Wang, H., Li, B., Li, S., Sepehrnoori, K., Cai, J. Predicting adsorbed gas capacity of deep shales under high temperature and pressure: Experiments and modeling. Advances in Geo-Energy Research, 2022, 6(6): 482-491. https://doi.org/10.46690/ager.2022.06.05

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%).

Hydrogen storage potential of coals as a function of pressure, temperature, and rank

We conducted measurements of hydrogen adsorption on three coal samples of varying ranks at high pressure (0 to 102 bar) and elevated temperatures (303 K to 333 K) to assess their hydrogen storage potential. The excess adsorption capacity increased with increasing pressure but decreased with increasing temperature irrespective of coal rank. The highest hydrogen adsorption recorded was 0.721 mol/kg for the anthracite coal at 303 K and 102 bar. Furthermore, the hydrogen adsorption capacity correlated positively with coal vitrinite and fixed carbon contents (i.e. the high-rank coal exhibited greater adsorption), while all samples depicted predominantly type-I adsorption behavior for the entire pressure range. Micropore analysis and Fourier-transform infrared spectroscopy measurements were conducted to explore the microstructural and surface chemistry associated with these adsorption trends. The micropore content of the three samples followed the order: anthracite > sub-bituminous > bituminous, while H2 adsorption followed the trend: anthracite > bituminous > sub-bituminous – i.e., no direct correlation between coal micropore content and its H2 adsorption capacity – attributable to high clay content of bituminous coal which lowered its micropore content. Moreover, bituminous, and sub-bituminous samples exhibited an abundance of oxygen-containing functional groups, while anthracite coal depicted notable aromatic content – suggesting that the H2 adsorption capacity is a complex function of coal surface chemistry and micropore content. Overall, high-rank coal seams at high pressure and temperature showed the largest hydrogen adsorption i.e., analogous to CO2 adsorption potential albeitat lower absolute values. These results, therefore, provide preliminary data on the hydrogen storage potential of coal seams and the associated scientific understanding of the mechanisms causing hydrogen adsorption.

Low-Field NMR Relaxation Analysis of High-Pressure Ethane Adsorption in Mesoporous Silicas.

Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) 1 H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25-50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g-1 of the observed ethane capacity. NMR relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis.

GCMC simulation of supercritical N&lt;sub&gt;2&lt;/sub&gt; adsorption in single-walled carbon nanotubes

The development of supercritical fluid technology is becoming more and more mature. The research on the adsorption behaviors of supercritical fluid in nanoporous materials has theoretical significance and application value for the development and application of supercritical fluid technology. In this paper, the grand canonical Monte Carlo (GCMC) method is used to simulate the adsorption behaviors of N&lt;sub&gt;2&lt;/sub&gt; in single-walled carbon nanotubes under supercritical condition and subcritical condition, and the isosteric heat of adsorption and integral molar enthalpy change in different adsorption systems are discussed. The results show that the adsorption isotherms of N&lt;sub&gt;2&lt;/sub&gt; in SWCNT do not strictly follow the layered adsorption mechanism under supercritical condition, as a result of the increase of molecular thermal motion, the degree of free mobility becomes higher, and it is easier for nitrogen molecule to intersperse and jump between different molecular layers. The nitrogen adsorption isotherm has a peak, which decreases gradually with the increase of temperature, while the critical pressure at peak increases with the temperature increasing. Around the critical point temperature (126 K), a small change in pressure can cause large fluctuations in the bulk gas phase density, resulting in a sharp drop in the adsorption isotherm after peaking. What is different from the subcritical condition is that the adsorption peak of local density distribution curve of the fluid under supercritical condition cannot represent the increase of excess adsorption capacity, and the influence of gas phase density on the adsorption process cannot be ignored. By studying the adsorption integral molar enthalpy under the supercritical condition, it is found that the excess integral molar enthalpy decreases with the pore size increasing; the adsorption integral molar enthalpy decreases with the augment of pore size at lower pressure, but due to a fact that the proportion of gas phase fluid in large-pore SWCNTs increases at higher pressure, on the contrary, it increases with the pore size at higher pressure increasing.

CO2 Adsorption Enhanced by Tuning the Layer Charge in a Clay Mineral.

Due to the compact two-dimensional interlayer pore space and the high density of interlayer molecular adsorption sites, clay minerals are competitive adsorption materials for carbon dioxide capture. We demonstrate that with a decreasing interlayer surface charge in a clay mineral, the adsorption capacity for CO2 increases, while the pressure threshold for adsorption and swelling in response to CO2 decreases. Synthetic nickel-exchanged fluorohectorite was investigated with three different layer charges varying from 0.3 to 0.7 per formula unit of Si4O10F2. We associate the mechanism for the higher CO2 adsorption with more accessible space and adsorption sites for CO2 within the interlayers. The low onset pressure for the lower-charge clay is attributed to weaker cohesion due to the attractive electrostatic forces between the layers. The excess adsorption capacity of the clay is measured to be 8.6, 6.5, and 4.5 wt % for the lowest, intermediate, and highest layer charges, respectively. Upon release of CO2, the highest-layer charge clay retains significantly more CO2. This pressure hysteresis is related to the same cohesion mechanism, where CO2 is first released from the edges of the particles thereby closing exit paths and trapping the molecules in the center of the clay particles.