Methane Diffusion Research Articles

Methane Desorption-Diffusion Behaviors in Micropores of Coal under Different Water Displacement Pressures.

Hydraulic fracturing not only enhances the flow conductivity of coal seams but also transforms the CH4 adsorbed in coal seams into free CH4 and then outputs it via the desorption-diffusion process, thus improving the output quantity and efficiency of CH4. In this paper, taking the coal from Changping mine in Shanxi as the research object, the 3D macromolecule model of coal was established by using analytical test experiments, and the molecular dynamics simulation method of desorption and diffusion was applied to study the characteristics of methane desorption rate and diffusion behaviors under different driving water pressures through the parameters of gas-water concentration distribution, desorption and diffusion rates, and the interaction energies between the coal and the gas-liquid. The results show that the water drive can increase the desorption rate of methane. With the increase of methane adsorption pressure, the desorption effect of water drive becomes stronger and then weaker. The desorption effect of water drive was best when the methane adsorption pressure was 5 MPa and the pressure difference was 2 MPa. Generally, the water drive promoted the methane diffusion, but if the water drive time was too long, it formed a water plug, and the water drive methane inhibited the diffusion. In shallow reservoirs, water drive can obviously promote the desorption-diffusion of methane. The binding energy between CH4 molecules is mainly composed of the repulsive force, while that between water molecules is mainly the adsorption force. In the binding energy between CH4 molecules and coal structures, the van der Waals (VDW) force accounts for 99% of the effect; in the binding energy between water molecules and coal structures, the electrostatic force contributes 84% to ∼88% thereto. The VDW force is significantly influenced by the pressure, while the electrostatic force is slightly affected. As the water displacement differential pressure is increased, the binding energy between CH4 molecules and coal structures decreases.

Analytical simulation of the simultaneous adsorption process of methane and water vapor in shales

ABSTRACT Investigations on the diffusion – adsorption of methane and water vapour in shale nanopores are essential for developing shale gas extraction. A kinetic model considering diffusion and different adsorption mechanisms was proposed. An analytical solution to the model was obtained through the integral transformation method and used to predict the distributions of methane and water within a shale particle. The results suggest that the reversible adsorption caused by the dispersion force is not the only adsorption mechanism; irreversible adsorption caused by hydrogen bonding or other types of intermolecular forces is more prominent, lengthening the delay to reach equilibrium. The presence of water strongly affects shale, considerably decreasing the diffusivity and adsorption capacity as well as the swelling of the shale matrix caused by the increase in the methane pressure. The diffusion and adsorption process expands to the shale particle surface after the pores near the particle centre are filled. The transport and storage of water vapour are more sensitive to the pore structure than those of methane. In the initial stage of the methane diffusion‒adsorption process, a large number of water molecules enter the particles, and the adsorbed water hinders methane molecules from contacting the shale surface.

Investigation into the Simulation and Mechanisms of Metal-Organic Framework Membrane for Natural Gas Dehydration.

Natural gas dehydration is a critical process in natural gas extraction and transportation, and the membrane separation method is the most suitable technology for gas dehydration. In this paper, based on molecular dynamics theory, we investigate the performance of a metal-organic composite membrane (ZIF-90 membrane) in natural gas dehydration. The paper elucidates the adsorption, diffusion, permeation, and separation mechanisms of water and methane with the ZIF-90 membrane, and clarifies the influence of temperature on gas separation. The results show that (1) the diffusion energy barrier and pore size are the primary factors in achieving the separation of water and methane. The diffusion energy barriers for the two molecules (CH4 and H2O) are ΔE(CH4) = 155.5 meV and ΔE(H2O) = 50.1 meV, respectively. (2) The ZIF-90 is more selective of H2O, which is mainly due to the strong interaction between the H2O molecule and the polar functional groups (such as aldehyde groups) within the ZIF-90. (3) A higher temperature accelerates the gas separation process. The higher the temperature is, the faster the separation process is. (4) The pore radius is identified as the intrinsic mechanism enabling the separation of water and methane in ZIF-90 membranes.

Non-steady flow decomposition behaviors of heat and mass transfer on intrinsic kinetics for methane hydrate particles transported in pipelines

The differential equations governing the decomposition rate and activation energy, convective mass transfer, methane diffusion and fugacity, as well as heat conduction and enthalpy change were derived by integrating thermal convection, heat conduction, mass transfer and intrinsic kinetics. Mathematical models for decomposition kinetics and thermodynamics in a non-steady field were solved using a radial logarithmic grid for node division and discretization of the equations. The study elucidated the heat and mass transfer processes as well as decomposition kinetics in pipelines by analyzing the impacts of particle size, temperature, pressure, flow rate and activation energy on decomposition rate. The results indicated that compared with the isothermal decomposition of the intrinsic kinetic model and static experimental decomposition, the complex non-steady multiphase flow model offers a more accurately simulation of hydrate decomposition as well as associated heat and mass transfer processes. Hydrate decomposition is characterized as a non-isothermal dynamic ablation process with heat transfer rate and intrinsic kinetics dominating during the preliminary stage and the stable stage, respectively. An increasing in the slurry temperature, temperature fluctuation and flow rate accelerated the heat transfer rate capacity, enhanced convective heat transfer capacity and facilitated hydrate decomposition, with the mass transfer rate exhibiting lesser influence. The particle surface area and slurry temperature exhibited the most significant influence on hydrate decomposition, which was followed by flow rate. Upon increasing particle size from 1 mm to 5 mm and the temperature from 293 K to 313 K, the decomposition rate increased by 20.7 times and 13.5 times, respectively. Furthermore, enhancing temperature and flow rate while decreasing particle size and pressure decreased both the decomposition time and the duration required for the decomposition rate to reach its peak. Additionally, the decomposition rate and its constant vary with the activation energy.

Insight into the micro-mechanism of hydrate-based methane storage from active ice

Gas hydrate formation in active ice holds significant potential for solidified natural gas storage, while the deep understanding of its micro-mechanism is required for the futural application of such a technology. In this study, the kinetics and micro-properties of methane hydrate formation enhanced by active ice (porous ice containing an unfrozen solution layer of sodium dodecyl sulfate) were investigated via experiments and molecular dynamics (MD) simulations. Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray diffraction (XRD) differential scanning calorimetry (DSC) characterization, and in-situ visual observation confirmed the formation of sI methane hydrate in the active ice system and the occurrence of single-crystal hydrate, and also indicated the occurrence of active water near the surface of porous active ice during the active ice formation. A sensitivity analysis of the hydrate kinetics experiments suggested that temperature is the primary driver of rapid methane hydrate formation in the active ice system. The shortest induction time and t90 for hydrate formation were recorded at 5 s and 5.5 min, respectively. Furthermore, MD simulations indicated that the direct hydrate nucleation and growth in the active water, heat transfer from gas hydrate to ice, and the diffusion of active water (1.24 × 10-9 m2/s) and methane (7.10 × 10-8 m2/s) into the porous ice structure are the primary mechanism that enhances hydrate formation kinetics and methane storage capacity. This work provides an essential microscopic mechanism of the “active ice → active water → gas hydrate” circulation that contributes to the deep understanding and futural application of the efficient hydrate-based solidified methane storage in active ice system.

Molecular simulation of CO2/N2 injection on CH4 adsorption and diffusion

As an efficient and clean energy, coalbed methane development and utilization have deep significance in promoting energy conservation and emission reduction, reducing greenhouse gas emissions. Therefore, molecular simulation was utilized to study the influence of N2/CO2 on the adsorption and diffusion of methane in coal under different gas injection methods and to elucidate the influence of varying gas injection methods on the efficiency of coalbed methane extraction, which provides a basis for the efficient development of coalbed methane. The results show that the adsorption effect of gases in coal decreases with the increase of temperature and increases with the rise of pressure, and the adsorption performance of the three gases in coal shows the law of CO2 > CH4 > N2. In addition, the injection of CO2/N2 had an obvious inhibition effect on CH4 adsorption, and the inhibition effect of CO2 was more significant, and the inhibition effect on CH4 adsorption reached the maximum when the two gases were mixture injected. In terms of diffusion, compared with separate injection, mixed injection of N2 + CO2 promotes CH4 diffusion more effectively, which can be reflected in the relative concentration distribution and velocity distribution. The injection of N2 helps to increase the porosity of coal, and the injection of CO2 and N2 + CO2 will lead to the decrease of porosity, but the mixed gas injection has less effect than the injection of CO2 alone.

Heat-dependent properties of methane diffusion in coal: an experimental study and mechanistic analysis.

Coalbed methane thermodynamic extraction, as an emerging ECBM recovery method, can effectively improve gas recovery rates. And clarifying methane diffusion and migration law in coal under thermal stimulation is crucial for the selection of its process parameters. Based on laboratory methane adsorption-release experiments, the evolution law of methane diffusion characteristics with temperature and pressure was studied, and the control mechanism of heat-dependent methane diffusion behavior was explored. The results show that both thermal stimulation and high adsorption pressure accelerated the methane diffusion rate in coal. Adsorption pressure had little effect on methane diffusion percentage, but thermal stimulation promoted a significant increase in diffusion percentage and improved the net methane yield. The influence mechanisms of adsorption pressure and thermal stimulation on methane diffusion characteristics are elucidated in relation to the amount and proportion of methane-activated molecules in the diffusion process. The constant diffusion coefficient of methane is heat-dependent, based on which a diffusion model is derived to accurately predict the methane release process in coal. Additionally, temperature has a more important effect on transient diffusion coefficient than pressure. Thermal stimulation leads to a net increase rather than a decrease in diffusion coefficient in the early diffusion stages and can also accelerate the attenuation of diffusion coefficient, with this intensifying effect becoming more pronounced at higher temperatures. The research results can provide some reference for the determination of coal seam gas content and the selection of heat injection process parameters.

Assessment of a PAH-based soot production model in laminar coflow methane diffusion flames doped by gasoline surrogate fuels

This article assesses the capability of the PAH-based soot model developed by the authors and validated in ethylene non-premixed flames to predict soot production in flames fueled with gasoline surrogates. The soot model was coupled to a flamelet model and the Rank-Correlated Full-Spectrum k model to simulate laminar coflow nitrogen-diluted methane/air diffusion flames doped with n-heptane/toluene and iso-octane/toluene mixtures. Consistent with our previous studies, the simulation was conducted using the Kaust Mechanism 1, pyrene as soot precursor, and the same set of model parameters. The model reproduced reasonably-well the peak soot volume fraction. However, the soot production onset was predicted much earlier than measurements owing to the early formation of pyrene induced by the presence of toluene. These discrepancies can be partially corrected by selecting a larger PAH than pyrene with a similar level of concentrations as soot precursor. For the present mechanism, anthanthrene was found to be the best candidate. Model results show that different mechanisms dominate the soot mass growth in ethylene and gasoline surrogate flames. While the HACA is more important in the former, PAH condensation largely prevails in the latter. This suggests that ethylene may be not the most relevant reference fuel for developing semi-empirical soot models for fires. Further investigations are required to confirm this conjecture.

Solvent effects on methane diffusion in gas hydrates: A RxDFT study

Methane hydrate, a promising green energy reservoir located at the seafloor, holds potential for mitigating environmental pollution. The current study uses Reaction Density Functional Theory (RxDFT) to calculate the diffusion energy of methane hydrate in aqueous solution as a function of temperature, pressure, and the confinement provided by graphene channels. Study of changes in activation energy and the fluctuations in solvent water molecule density around the solute molecules suggests that the methane diffusion increases with higher reaction temperatures and lower reaction pressure. Furthermore, the activation energy for methane diffusion peaks at a width of 32 Å in the graphene channel, reaching its maximum value of 40.95 kcal mol−1. This elucidates the intricate interactions between solvent molecules and hydrates, providing insights into the diffusion mechanism.

Free volume theory of self-diffusion in zeolites: Molecular simulation and experiment

Neutron scattering and molecular dynamics are used to unravel the microscopic mechanisms that govern methane diffusion in MFI zeolite (silicalite-1). First, using neutron scattering for silicalite-1 loaded with different methane amounts, we analyze the experimental dynamic structure factor S(q,ω) in terms of molecular rotations and translations. While the rotational diffusion is found to be nearly independent of the zeolite loading, the translational diffusivity drastically decreases with the adsorbed amount. To gain insights into the diffusion mechanisms, trajectories obtained using molecular dynamics simulations are analyzed by determining mean square displacements 〈Δr2(t)〉 and incoherent scattering functions F(q,t). We also determine how anisotropy affects diffusion by considering independently the x, y and z directions. While the activation energy for diffusion is found to be weakly dependent on methane loading, the self-diffusivity decreases as the loading increases. Both the experimental and molecular simulation results suggest that steric repulsion between confined molecules – which increases as the loading increases – drastically affects diffusion. Using a free volume theory, we provide a simple formalism to predict consistently diffusion in the internal porous network of MFI zeolite. To demonstrate the applicability of this simple yet robust framework, we show that the free volume theory accurately captures diffusion in each direction of space but also when the size of the adsorbate molecule is arbitrarily increased.

Research on the molecular dynamics of coalbed methane diffusion and adsorption in reservoir pores under different factors

Research on the molecular dynamics of coalbed methane diffusion and adsorption in reservoir pores under different factors

Experimental research on the flow field and flame geometry of free buoyant diffusion flames with low dimensionless heat release rates

The flame geometry of turbulent diffusion flames is dominated by the turbulent mixing between the gaseous fuel and the entrained air. The significant variations of the power law for the mean flame height regarding the dimensionless heat release rate (Q˙*) in different Q˙* ranges implied that the turbulent mixing characteristics would change greatly among these Q˙* regimes. This paper presents a combined experimental and analytical study to reveal the turbulent transport properties and flame shape of free turbulent buoyant diffusion flames of relatively low Q˙* prevalent in large-scale fires. The instantaneous velocity fields of free buoyant methane diffusion flames (burner diameter: d = 0.30 m, Q˙*= 0.22–0.40) were measured by the stereo particle image velocimetry (SPIV) technique. The results indicate that the radial profiles of the time-averaged axial velocity, axial normal stress, radial normal stress, shear stress, and turbulent kinetic energy exhibited self-similarity at different heights under all the heat release rates. The turbulent flow in the buoyant flame was found to be anisotropic. Based on the gradient transport approximation, the mean turbulent viscosity within the mean flame height (νt=) was scaled by g1/2d3/2, where g is the gravitational acceleration. The semi-physical correlations for the mean flame height and width were derived based on the concepts of turbulent mixing and equal axial convection and radial diffusion times, respectively. The two correlations agreed reasonably with the experimental data of this work.

Modelling of physical and chemical properties of activated carbons which affect methane adsorption mechanisms

Effect of important physical and chemical properties of activated carbons which affect the way methane adsorbs were studied. The Grand Canonical Monte Carlo (GCMC) simulations were used to study how the curvature and size of the platelets affect the mechanisms of methane adsorption process; and which role is played by the amount of oxygen present in activated carbons. Furthermore, Molecular dynamic (MD) simulations were carried out to study the effect of those properties on motion behavior of methane molecules during adsorption. The two simulations are very vital because they were able to exploit mechanisms which are difficult to obtain by using experiments alone. It was found that oxygen content, degree of curvature of platelets and size of basic structural units affected the availability of suitable methane binding sites in activated carbons and hence total methane adsorbed amount. Furthermore, the studied parameters were found to have impacts to the energy of interaction between activated carbons and methane, methane diffusion characteristics and amount of heat generated during adsorption process. It is concluded that the studied activated carbon properties hugely affect the way methane adsorbs and should be given attention during designing of the optimal adsorbent for methane adsorption.

Grid study on methane diffusion law in confined space of working face

AbstractThe layout of methane sensors in the working face cannot meet the needs for monitoring methane concentrations within confined spaces, and it is challenging to determine the precise locations for manual inspections. Therefore, the working face is firstly divided into different areas and grids. Then combined with the characteristics of methane emissions and the measured data on site, the boundary conditions of simulation experiments are set up and the research is carried out on the diffusion law of methane in the confined space of the working face under different conditions. The experimental results show that methane emission intensity from coal walls affects its distribution. As emission intensity rises, methane nearer the coal wall decreases, while methane further away increases. Among coal mining points, point 2 shows the widest methane diffusion range. Rising wind speeds decrease methane diffusion from the coal wall, increasing vertical diffusion distance. Methane from the coal wall shifts to the air inlet, while methane from the mining point diffuses increasingly to the downwind side. The location of the maximum methane concentration generated from falling coal and its transportation process is only related to the location of the coal mining point. The key areas for methane monitoring in confined spaces of the working face should be the overlapping locations of the vertical‐3 and vertical‐4 areas and the horizontal‐1 and horizontal‐3 areas. The key areas for manual inspection should be the overlapping locations of the vertical‐2 and vertical‐3 areas and the horizontal‐1 area.

A Comparison Between Water Addition and CO2 Addition to a Diffusion Coflow Flame

ABSTRACT This work compares the effects of adding water vapor and CO2 as diluent to fuel for a diffusion flame at different ambient pressures. The approach of this research is to study numerically a methane diffusion flame with various amounts of water vapor and CO2 added to the fuel, and to compare the flame behaviors with various percentages of water vapor and CO2 content (0% to 65%). This work uses a coflow burner in the PeleLM numerical framework for simulating the flame and computing the combustion behavior. The flame was simulated with pressures of 1.0, 1.4, 5.7, and 11.1 atm. The results extracted and analyzed include temperature profiles at fixed heights and various species mole fractions compared with their values at an equilibrium state condition. The results show that most of the diluent impact does not involve changes in flame chemistry but primarily changes to heat release and heat capacity in the flames. The results also show that the diluent amount has a much larger impact on flame behavior than do changes in pressure.

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

Analysis of methane diffusion on permeability rebound and recovery in coal reservoirs: Implications for deep coalbed methane-enhanced extraction

A proper understanding of the effect of methane diffusion on coal reservoir permeability rebound and recovery is essential, as coal reservoir permeability is the key parameter influencing the efficiency of coalbed methane migration and computational research on it is lacking. In this paper, the multifield coupling model for methane migration was established. Then, two parameters, the influence coefficient of diffusion on permeability rebound (DPRB) and the influence coefficient of diffusion on permeability recovery (DPRC), were proposed to quantify the effect of methane diffusion on rebound and recovery of coal reservoir permeability. Subsequently, we used COMSOL software to study the variation rules of the coal reservoir permeability rebound time, permeability recovery time, and permeability rebound value, DPRB, and DPRC for different geologic parameters. The results shown that the permeability rebound time and recovery time are proportional to the coal seam initial pressure, but inversely proportional to the initial permeability and initial diffusion coefficient. The rebound value decreases with increasing coal seam initial pressure and initial permeability, but ascends with rising initial diffusion coefficient. DPRB declines with increasing coal seam initial pressure, initial permeability, and initial diffusion coefficient, but they are all greater than 0.7, indicating that methane diffusion has a significant effect on permeability rebound. The DPRC values for different coal seam initial pressures, initial permeabilities, and initial diffusion coefficients are above 0.98, which implies that methane diffusion dominates the permeability recovery process. Finally, a conceptual model was presented to research the mechanism of diffusion influence on rebound and recovery of coal reservoir permeability, and the implications for enhanced drainage of deep coalbed methane were discussed. Therefore, the results of this paper can provide a theoretical foundation for deep coalbed methane-enhanced extraction.

Self‐Made Equipment for Automatic Methane Diffusion and Ebullition Measurements From Aquatic Environments

AbstractFreshwater ecosystems are believed to account for about half of global methane emissions, but this estimate is uncertain due to few measurements in some geographical regions and most important for our purposes, large local variations. We propose a simple, cheap (<200€), and effective solution to the urgent need for equipment that can provide accurate data on methane emission at high spatial and temporal resolution for many days, across many ecosystems and regions, and with limited inspection. A low‐cost metal oxide semiconductor sensor, placed in a floating chamber equipped with an air pump to flush the chamber's headspace at regular intervals, provides frequent and accurate high‐resolution measurements of diffusive and ebullitive methane emissions from lakes and rivers. We made several improvements that yield more useful data and enable the setup to operate for several days without visual inspection. To test the accuracy of the equipment, we compared its measurements of methane emission to parallel measurements by an expensive, commercially available laser sensor. The correspondence was excellent (R2 ≥ 0.94) and the deviation of measurements was minimal at fluxes within ranges encountered in the field. We also designed an R‐package (FluxSeparator), which associates the large sensor‐generated data sets with diffusive and ebullitive flux activity. Both the sensor setup and the R‐package are flexible and have been made publicly available to encourage others to use and further improve the equipment and calculations.

Dissolved Methane Diffusion Drives Hydrate-Bearing Pressure Core Degradation during Long-Term Storage in Water

Dissolved Methane Diffusion Drives Hydrate-Bearing Pressure Core Degradation during Long-Term Storage in Water

Molecular Dynamics Simulation of Methane Adsorption and Diffusion

To study the adsorption and diffusion mechanism of low-rank coal at the microscopic level, samples of Fukang low-rank coal were collected, and the elemental composition, carbon type distribution and functional group type of the Fukang low-rank coal structure were determined by elemental analysis (Ea), Fourier-transform interferometric radiometer (FTIR), X-ray photoelectron spectroscopy (XPS) and 13C nuclear magnetic resonance (13C NMR) experiments to construct a 2D molecular structure of the coal and a 3D macromolecular structure model. The adsorption and diffusion characteristics of methane were researched by giant regular Monte Carlo (GCMC) and molecular dynamics (MD) simulation methods. The results showed that the excess adsorption amount of methane increased and then decreased with the increase in pressure. The diffusion of methane showed two stages with increasing pressure: a sharp decrease in the diffusion coefficient from 0.5 to 5.0 MPa and a slow decrease in the diffusion coefficient from 5.0 to 15.0 MPa. The lower the pressure, the larger the effective radius of the CH4 and C atoms, and the higher the temperature, the more pronounced the diffusion and the larger the effective radius.