Methane Adsorption Research Articles

Adsorption of methane by modified-biochar aiming to improve the gaseous fuels storage/transport capacity: process evaluation and modeling.

The CH4 storage by adsorption on activated carbons for natural gas handling has gained interest due to the appearance of lightweight materials with large surface areas and pore volumes. Consequently, kinetic parameters estimation of the adsorptive process can play a crucial role in understanding and scaling up the system. Concerning its versatility, banana peel (BP) is a biomass with potential for obtaining different products, such as biochar, a solid residue from the biomass' thermal decomposition of difficult disposal, where through an activation process, the material porous features are taken advantage to application as adsorbent of gaseous substances. This research reported data for the CH4 adsorption kinetic modeling by biochar from BP pyrolysis. The activated biochar textural characterization showed particles with fine mesoporous structure (pore diameter ranging between 29.39 and 55.62Å). Adsorption kinetic analysis indicated that a modified pseudo-first-order model was the most suitable to represent the experimental data, with equilibrium adsorption of 28mgg-1 for the samples activated with 20.0% vol wt.-1 of H3PO4 and pyrolysis at 500°C. The equilibrium constant was consistent with the Freundlich isotherm model, suggesting a physisorption mechanism, and led to a non-ideal, reversible, and not limited to monolayer CH4 adsorption.

Monte Carlo Calculation of the Thermodynamic Characteristics of Methane and Ethane Adsorption on Graphite

Monte Carlo Calculation of the Thermodynamic Characteristics of Methane and Ethane Adsorption on Graphite

Effect of Tectonic Deformation on the Pore System and Methane Adsorption of Anthracite Coal.

Tectonic deformation significantly alters the physical structure of coals, holding great importance to the coal mining industry and coalbed methane. In this study, eight anthracite coal samples with varying degrees of deformation were collected to investigate the effects of tectonic deformation on the pore system and CH4 adsorption of anthracite coals. In addition, low-temperature gas adsorption (N2 and CO2), Raman spectroscopy, and CH4 isothermal experiments were performed. The results revealed that coal samples with higher degrees of deformation exhibited larger ratios of D-band intensity to G-band intensity (I D/I G), indicating increased molecular defects induced by tectonic deformation. As the deformation degree of the coal samples increased, the mesopore volume increased from 0.00044 cm3/g (primary coal) to 0.0019 cm3/g (scaly coal). Conversely, the micropore volume tended to decrease with the increasing deformation degree of the coal samples. Moreover, the impact of deformation degree on the CH4 adsorption capacity of anthracite coals was complex. With the deformation degree increasing, the Langmuir volume initially decreased from 32.0 to 24.55 cm3/g and then rose to 30.14 cm3/g. This complexity arose from the differential effects of tectonic deformation on various pore types, where micropores and mesopores collectively determined the CH4 adsorption capacity of anthracite coals. This study analyzed the influence of tectonic deformation on the pore structure and CH4 adsorption capacity at the molecular level, providing valuable insights for evaluating the in situ CH4 content in anthracite coal seams.

Reservoir Characteristics of Marine–Continental Transitional Taiyuan Formation Shale and Its Influence on Methane Adsorption Capacity: A Case Study in Southern North China Basin

To further study the reservoir characteristics and adsorption capacity of the Taiyuan Formation shale in the South North China Basin (SNCB), the pore structure and adsorption capacity of shale are discussed using various analysis tests, including elemental geochemistry, organic geochemistry, mineral composition, low-temperature nitrogen adsorption (LTNA), and methane adsorption experiments. The results indicate that the Taiyuan Formation shale formed in a poor oxygen and anaerobic sedimentary environment in still water. The average value of total organic carbon (TOC) content is 2.37%. The organic matter type mainly consists of type III kerogen. The vitinite reflectance (Ro) ranges from 3.11% to 3.50%. The clay mineral content varies greatly, averaging at 40.7%, while the quartz content averages at 37.7%. The Taiyuan Formation shale mainly develops interparticle (InterP) pores, followed by organic pores, intraparticle (IntraP) pores, solution pores, and microfractures. BET specific surface area (SSA) is between 9.47 m2/g and 22.14 m2/g, while pore volume (PV) ranges from 0.0098 cm3/g to 0.022 cm3/g, indicating favorable conditions for shale gas storage. According to the results of the CH4 adsorption experiment, Langmuir volume from Taiyuan Formation shales exhibits 1.35~4.30 cm3/g, indicating excellent adsorption capacity. TOC content shows a positive correlation with both Langmuir volume and BET SSA from Taiyuan Formation shales, suggesting that TOC plays a crucial role in controlling microscopic pores and gas adsorption capacity. Organic matter enhances the shale adsorption capacity by providing abundant pore SSA. Due to formation compaction, the pore size of clay minerals decreases, leading to an increase in pore SSA, while kaolinite exhibits weak hydrophilic ability. Consequently, with the increase in clay minerals and kaolinite content, the shale adsorption capacity is enhanced to a certain extent. However, an increase in the carbonate mineral content may result in a decrease in the proportion of clay minerals, therefore reducing the CH4 adsorption capacity of shale.

Potential of Phenylalanine‐, Tryptophan‐, and Tyrosine‐MOF‐5 Composites for Selective Carbon Dioxide and Methane Adsorption

Potential of Phenylalanine‐, Tryptophan‐, and Tyrosine‐MOF‐5 Composites for Selective Carbon Dioxide and Methane Adsorption

Influence of Tectonically Deformed Coal-Based Activated Carbon and Its Surface Modification on Methane Adsorption.

A series of coal-based activated carbons (CACs) were synthesized from mylonitized fat coal, a type of tectonically deformed coal (TDC) and symbiotic primary structural coal (PSC), followed by oxidative modification. The pore structure, surface oxygen-containing functional groups, and their influence on methane adsorption by CAC as the simplified coal model were investigated by using low-temperature nitrogen adsorption, Fourier transform infrared spectroscopy, Boehm titration, and X-ray photoelectron spectroscopy. The results showed that tectonic deformation fostered smaller pores, particularly ultramicropores in TDC, dominating methane adsorption. Acid-modified TDC-based activated carbons (ACs) showed higher pore parameters and oxygen-containing functional groups than those of PSC-based ACs. Nitric acid introduced abundant carboxyl groups concurrently increasing the pore volume and specific surface area (SSA), while sulfuric acid-ammonium persulfate treatment resulted in increased lactone groups and a partial collapse/blockage of nanopores. Methane adsorption experiments confirmed the importance of micropores and revealed a significant decrease in capacity owing to increased oxygen-containing functional groups as the primary role, with pore wall corrosion playing a secondary role. Thus, the study highlights the surface effects of TDC on methane adsorption and the potential for producing high-performance methane storage materials from China's tectonic coal resources.

Characterizing competitive adsorption and diffusion of methane and carbon dioxide in kerogen type-III slit model

Characterizing competitive adsorption and diffusion of methane and carbon dioxide in kerogen type-III slit model

Effect and mechanism of ionic liquid-polymer composite coating on enhancing hydrogen embrittlement resistance of X80 pipeline steel for hydrogen blended natural gas transportation

Blending hydrogen into existing natural gas pipelines is a cost-effective method for large-scale hydrogen transportation. However, high hydrogen ratios cause hydrogen embrittlement in pipeline steel, limiting transportation efficiency. Due to complex structures and harsh application conditions, existing coatings are difficult to apply on pipelines. To tackle such issues, we propose an ionic liquid-polymer composite coating using epoxy resin as coating substrate, based on the competitive adsorption of methane and hydrogen on pipeline steel. Ionic liquids with high methane selectivity were selected via quantum chemical calculation. The protective effect of coatings was characterized using hydrogen pre-charging constant strain tensile tests. Simulation and experimental results demonstrate that epoxy resin coatings reduce hydrogen embrittlement in X80 steel. Modified with selective CH4/H2 permeability ionic liquids, the epoxy resin coating enhances methane and hydrogen competitive adsorption on the steel surface, improving hydrogen embrittlement resistance. This novel coating offers a viable solution for achieving safe and high ratio hydrogen blended transportation in natural gas pipeline.

Validated methane adsorption isotherms up to 7.5 MPa on a reference Na-Y zeolite at near ambient temperatures

Reference gas adsorption isotherms are useful for validating equilibrium data obtained from various techniques and for ensuring that experimental systems are operating correctly. In this work, we extend an interlaboratory study on a NIST reference zeolite (Na-Y, RM8850) to two additional temperatures above and below the original 298.15 K, validating the results via independent measurements using two different techniques. Volumetric experiments on a novel Adsorption Differential Volumetric Apparatus (ADVA-270) were carried out at The University of Edinburgh, and gravimetric experiments were performed at Hiden Isochema using a proprietary XEMIS microbalance. Both techniques provided highly accurate results and an excellent match between the two independent measurements using less than 150 mg of sample. Absolute equilibrium data were modelled using a Langmuir-virial isotherm to obtain an accurate concentration dependence of the heat of adsorption.

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.

In-situ exploration of divergent methane coupling pathways in dry and aqueous environments on silver and palladium heteropolyacid-titania photocatalysts

Methane, abundant but inert, contributes significantly to greenhouse gases, primarily through combustion, which emits vast amounts of CO2. Photocatalytic methane coupling at ambient temperature offers a method to convert it into ethane, a more versatile hydrocarbon. This study examines selective methane-to-ethane coupling using heterogeneous photocatalysts comprising silver and palladium salts dispersed on titania. Through a combination of ex-situ and in-situ techniques along with DFT simulations, distinct mechanisms and active phases in these catalysts are revealed. In silver catalysts, dispersed cationic Ag+ species are crucial for methane activation, while in palladium catalysts, palladium primarily exists in metallic form during coupling. Water strongly enhances coupling rates with both catalysts. DFT modeling identified methane adsorption sites, suggesting methane activation via •OH radicals, experimentally supported by EPR under in-situ conditions.

Shale gas‐bearing capacity and its controlling factors of Wufeng–Longmaxi formations in northern Guizhou, China

Great progress has been made in marine shale gas of Wufeng–Longmaxi formations in the Sichuan Basin. However, shale gas exploration in the complex structural belt around the Sichuan Basin still faces great challenges. In this study, shales of Wufeng–Longmaxi formations collected from the northern Guizhou were taken as the studied target, organic matter (OM) characteristics, mineral composition, pore structure, methane adsorption capacity and in situ desorption gas content were measured, and the controlling factors of shale gas content were further discussed. The results indicated that the sedimentary facies of Wufeng–Longmaxi formations in north Guizhou varies from shallow‐water shelf facies to deep‐water shelf facies from south to north, and organic‐rich shales are primarily distributed in Daozhen‐Xishui areas, with a maximum thickness of about 80–100 m. Organic‐rich shales are characterized by high total organic carbon (TOC) content, high thermal maturation and type I–II1 kerogens, which can be comparable with those in commercially produced shale gas field in Sichuan Basin. High‐quality shale gas reservoirs generally have a high content of brittle minerals, making them easier to be fractured. OM pores are the dominanted pore type in the studied shales, followed by intergranular pores associated with brittle minerals, dissolution pores within carbonate grains and microcracks, while clay mineral‐related pores are poorly developed. The Wufeng–Longmaxi Formation shales generally have strong methane adsorption capacities, but these vary greatly across different areas. Shale gas adsorption capacity is primarily controlled by TOC content and thermal maturation level. Similarly, total gas content, including desorption gas and lost gas, varies greatly in different areas, and it is obviously lower than that in Fuling and Luzhou shale gas field, due to the loss of shale gas and low‐pressure coefficient in the complex structural zone. It is worth explaining that shale gas is not always low in northern Guizhou, which is determined by burial depth and the distance of great fractures. Shale gas content is relatively high in LY1 well and DY1 well in Xishui‐Daozhen area, and it is extremely low in TY1 well and AY1 well in Tongzi‐Zheng'an area. Shale gas content in the same structural unit is primarily influenced by TOC content, OM pore development degree and water saturation. However, different structural units have different shale gas contents, due to the differences in preservation conditions. Shale reservoirs with good preservation conditions, that is, wide and gentle structure, far from a large fault and great burial depth, generally have high shale gas contents.

Micro-mesoporous carbons form non-porous zinc-organic coordination compounds: Synthesis, structure and gas adsorption properties

A series of non-porous zinc-containing coordination compounds with mono- and polydentate ligands has been used to produce carbon materials with a hierarchical porous structure. Adjustment of the carbonization mode enables to increase the target product yield by an average of three times. The obtained carbons have a combination of micro- and mesopores with a pronounced maximum at 3.5 nm. The gas-sorption behavior of the obtained carbons has been studied over a wide range of temperatures and pressures. It has been established that the amount of excess adsorption for hydrogen and methane reaches 2.7 and 15 wt%, respectively. The extension of the proposed approach to the use of simple bimetallic complexes as precursors may be promising for obtaining effective catalysts based on a carbon matrix with controlled porosity and encapsulated nanoscale particles of a catalytically active metal.

Shale Gas Nanofluid in the Curved Carbon Nanotube: A Molecular Dynamics Simulation Study.

Curved nanochannels are prevalent in porous and tortuous materials, with shale matrices being a noteworthy example. The tortuosity of shale matrices significantly influences the behavior of shale gas, holding crucial implications for gas recovery engineering. In this study, we employ molecular dynamics simulation (MD) to investigate the impact of curvature and radius in tortuous nanochannel formed by a curved single-walled carbon nanotube (SWCNT) on the adsorption and transport properties of methane gas fluid. Our findings reveal that the inner half surface of the SWCNT, characterized by negative curvature, exhibits enhanced methane adsorption. Methane in straighter and narrower channels displays higher flow velocities, while wider channels exhibit higher flow flux. The nonzero flow velocity alters adsorption strength, causing the outer half to surpass the inner half. Tangent and vertical velocities of the flow are heterogeneously distributed in the channel, with the outer half having higher tangent velocities. Additionally, a vertical velocity pulse near the entrance induces turbulent vortex flow, slowing down the tangent flow velocity. This research contributes to a deeper understanding of shale gas properties in matrices with bent and curved channels, offering insights into nanofluids in carbon nanotubes and porous media featuring curved nanochannels.

Scale translation yields insights into gas adsorption under nanoconfinement

This work describes a scale-translating simulation framework to investigate gas adsorption behavior in nanoconfined pores. The framework combines molecular simulations (MSs), equation of state (EoS), and lattice Boltzmann (LB) simulations. MSs reveal the physics of methane adsorption in nano-sized pores, where input values of fugacity coefficients are optimized based on EoS predictions. Then, an LB free-energy model, which incorporates a viral EoS, upscales intermolecular forces and estimates adsorption behavior via a proposed fluid–wall interaction model. Armed with the values of the LB interaction parameter as a function of pressure, the LB model is used to predict fluid behavior in irregular nanopores, and the results are validated against reference MS data. The LB model is then used to study adsorption behavior at a continuum scale in representative organic shale nanopores based on finely characterized Vaca Muerta shale samples. The results show that methane adsorption could significantly increase contained fluids by 10%–25% in pores smaller than 20 nm. However, in larger pores (40 nm to 90 nm), adsorption's impact diminishes to 2%–3%, suggesting sorption's negligible role beyond a 40 nm pore size.

Analysis of the Current Status and Hot Technologies of Carbon Dioxide Geological Storage

Carbon dioxide geological storage is one of the key measures to control and alleviate atmospheric carbon dioxide content. To better grasp the developmental dynamic and trend of carbon dioxide geological storage research over the world, promoting the research of CO2 storage theory and technology, 5052 related studies published in the past 22 years were collected from the Web Of Science database. The annual published articles on carbon dioxide geological storage research, partnerships, research hotspots, and frontiers were analyzed by using the knowledge map method of article analysis. The results show that the articles on the carbon dioxide geological storage are increasing yearly. The United States, China, and the United Kingdom are the most active countries; meanwhile, Tianfu Xu and Xiaochun Li from China are experts with the most achievements in the field of carbon dioxide geological storage. Although the theoretical and research frameworks for geological storage of CO2 are abundant, the field of enhanced gas formation recovery, shale gas extraction and subsurface storage, methane reservoirs, and methane adsorption are still challenging frontier science and technology topics.

The roles of different migration mechanisms in the transport of H2O–CH4 gas mixture in shales

Studying the roles of different migration mechanisms in shale matrix gas transport is beneficial for shale gas extraction and CO2 sequestration. The roles of different transport mechanisms in shale H2O–CH4 gas mixture transport were investigated considering their contributions to fluid flux. A permeability model coupling multiple gas migration mechanisms was developed by combining the pore network-related effective medium approximation, which was validated using process data from simultaneous H2O–CH4 transport in shales. The results showed that the gas transport mechanisms dominating methane and water vapor migration in shale differed. Slip flow and Knudsen diffusion contributed approximately 99% to methane migration. Water vapor surface diffusion as well as slip flow and Knudsen diffusion primarily contributed to the water vapor permeability before and after a time point, respectively. Water vapor and methane permeability generally decreased with time. The equilibrium water vapor and methane permeabilities ranged from 2.7699×10−22–12.312×10−22 m2 and 0.2640×10−21–4.9036×10−21 m2, respectively. The methane surface diffusion permeability increased slowly with time before approaching methane monolayer adsorption (before ∼100 s). An increase in relative humidity (approximately 300–3600 s) can promote the transport of water vapor. Water vapor and methane adsorption, especially the condensation of adsorbed water, could largely explain the decrease in shale gas permeability.

Investigation of methane adsorption mechanism in Low-Rank bituminous coal considering internal water Distribution: A molecular simulation and experimental study

The impact of high internal water in low-rank bituminous coal on methane adsorption properties has significant implications for the extraction and utilization of low-rank coalbed methane. Mercury-in-pressure (MIP), low-pressure N2/CO2 adsorption (LPNA/CA), low-field nuclear magnetic resonance (NMR), and isothermal adsorption of methane experiments were conducted on two types of low-rank bituminous coal from neighboring mines in the same region. Additionally, molecular dynamics simulations were performed by constructing a molecular model of the low-rank bituminous coal. Experimental and simulation results indicate that the unique internal water distribution characteristics of low-rank bituminous coal and the methane adsorption mechanism under its influence. The initial adsorption of water molecules occurs within the micropores of coal, forming a microporous filling. As relative humidity increases, water molecules migrate spontaneously to the macropores, but they do not seal the pores. This phenomenon is observed in low-rank bituminous coals. The internal water primarily affects the microporous filling of methane, yet it does not alter the absolute predominance of this form in adsorption, and the internal water spontaneously migrates to provide part of the filling site for the methane molecules with the increase in adsorption pressure. The results provide valuable insights into optimizing the extraction strategies for low-rank coalbed methane resources.

Effect of supercritical carbon dioxide on pore structure and methane adsorption of shale with different particle sizes

Supercritical carbon dioxide (SCCO2) fracturing significantly enhances shale gas recovery, which is influenced by particle size. We soaked shale in SCCO2 and investigated the impact of SCCO2 on different particle sizes. Large-particle shales showed the largest percentage changes in specific surface area and total pore volume (54.11 %, 87.87 %; 58.59 %, 76.32 %) followed by small-particle size shales. This trend was also observed in other pore structure parameters. The particle-size effect is: Large-particle shale, with abundant microfractures, enhances SCCO2 flow and pore alteration. Small-particle shale's high specific surface area facilitates SCCO2 penetration. Medium-particle shale is less affected due to balanced interactions of these factors. Methane is primarily found in large and medium pores and microfractures. Methane adsorption in shale mainly involves multi-layer adsorption. Following SCCO2 treatment, pore fractures narrowed, increasing the proportion of methane molecules adsorbed as a single-layer. This study is crucial for evaluating the fracturing effects on shale gas wells.

A Fractal Adsorption Model on Methane in Coal with Temperature Effect Dependence

The traditional Langmuir equation displays drawback in accurately characterizing the methane adsorption behavior in coal, due to it assuming the uniform surface of coal pores. Additionally, the decay law of gas adsorption capacity with an increasing coal reservoir temperature remains unknown. In this study, the fractal adsorption model is proposed based on the fractal dimension (Df) of coal pores and the attenuation coefficient (n) of the adsorption capacity. The principles and methods of this fractal adsorption model are deduced and summarized in detail. The results show that the pore structures of the two coal samples exhibit obvious fractal characteristics, with the values of fractal dimensions (Df) being 2.6279 and 2.93. The values of adsorption capacity attenuation coefficients (n) are estimated as −0.006 and −0.004 by the adsorption experiments with different temperatures. The proposed fractal adsorption model presents a greater theoretical significance and higher accuracy than that of the Langmuir equation. The accuracy of the fractal adsorption model with temperature effect dependence is verified, establishing a prediction method for methane adsorption capacity in deep coal reservoirs. This study can serve as a theoretical foundation for coalbed methane exploration and development, as well as provide valuable insights for unconventional natural gas exploitation.