Methane Transport Research Articles

Microscopic study on the memory effect of methane hydrate in the presence of silica nanoparticles: Ⅰ. Dissociation mechanism & guest supersaturated hypothesis

As a key issue emerged in the exploitation of combustible ice resources, the memory effect inducing hydrate reformation in sand-containing dissociated-water system is still ambiguous. Among them, methane hydrate dissociation kinetics and guest supersaturated hypothesis for methane hydrate reformation are the primary issues to be addressed. A molecular dynamics simulation system where methane hydrate interacts with surface-hydroxylated silica nanoparticles was established to simulate dissociation process, which is necessary to construct hydrate reformation systems for further microscopic study on hydrate memory effect. The transportation mechanism of methane during hydrate dissociation in sand-containing aqueous system was elucidated. Based on this, hydrate-dissociated systems with methane supersaturated were captured, and molecular dynamics simulations were carried out to further study hydrate reformation mechanism regarding the guest supersaturated hypothesis. By analyzing the distribution and transportation of methane, hydrate clusters, and silica nanoparticles, it can be concluded that the hydrate-like orderly arrangement of methane that are dissolved in the solution or on the surface of nanobubbles are necessary to trigger hydrate memory effect by inducing the reformation of hydrate clusters, while the silica nanoparticles can inhibit the reformation of hydrate clusters by disturbing the arrangement of methane molecules and water molecules. Thence, the microscopic analysis indicated that supersaturated guest molecules is vital to the occurrence of hydrate memory effect and its effect varies between the supersaturated states.

Theoretical Analysis of Landfill Gas Migration in Capillary Barrier Covers Considering Effects of Waste Temperature

The high-temperature and high-humidity conditions arising from the biochemical degradation of landfill waste result in significant temperature gradients within the landfill cover. The effects of waste temperature on landfill gas transport and microbial aerobic methane oxidation are not fully understood. In this study, a fully coupled theoretical model was developed to simulate the interactions of moisture, heat, and gas transport within a capillary barrier cover. A series of parametric studies were carried out to investigate the influence of the combined effects of temperature gradient, initial soil moisture content, and landfill gas generation rate on methane transport, oxidation, and emissions. The simulated results indicated that increasing waste temperature intensified the temperature gradient, leading to higher surface evaporation rates and variations in methane oxidation efficiencies. Additionally, variations in initial soil moisture content and landfill gas generation rates were found to significantly impact gas migration and methane oxidation in the cover. This study demonstrates the critical role of waste temperature in landfill gas migration within landfill cover systems, providing technical methodologies for the optimized design of soil cover systems.

Methane Adsorption and Transport in Tortuous Slit-like Nanochannels: A Molecular Simulation Study.

Tortuosity is a crucial characteristic of porous materials, such as the shale matrix where shale gas is stored. The presence of tortuous nanochannels significantly affects the adsorption and transport of nanoflows. In this research, we use molecular dynamics simulation (MD) to study the adsorption and transport properties of shale gas (methane) in a curved slit-like nanochannel constructed from bent graphene sheets. Our findings reveal that the curvature of the tortuous channel influences methane adsorption: convex surfaces exhibit stronger adsorption, while concave surfaces exhibit weaker adsorption; the discrepancy is amplified by the nanoflow. Additionally, nanoflow velocity is heterogeneously distributed within the curved channel, with higher tangential flow velocities observed near the entrance and the outer surface. We also identify a "bouncing effect", where the nanoflow not only moves tangentially along the channel but also bounces between the inner and outer walls. Furthermore, methane in narrower channels exhibits higher tangent flow velocity and higher bouncing frequency but smaller flux, whereas larger curvature results in shorter channel length and smaller tortuosity, but the transport tangent velocity and flux are both reduced. The findings of this study can help in the better understanding of shale gas nanoflow properties in tortuous media and provide insights for simulating more general nonstraight nanoflows.

Numerical Analysis of the Influence of Preadsorbed Water on Methane Transport in Crushed Shale

Summary Methane migration in shale is affected by preadsorbed water. To understand this effect, we examined several key parameters, including the effective pore diameter Le, the pore volume distribution of Le, the effective porosity ϕe, the equivalent particle diameter da, and the water film thickness h. Using these parameters, we established an equivalent relationship linking the particle packing da and the Le and the ϕe of the capillary pores within a unit-length cuboid of particles. Based on this relationship, a conceptual model was developed to simulate methane adsorption and transport in partially saturated crushed shale, incorporating parameter estimation for the tangential momentum adjustment factor δ and methane desorption rate coefficient kd, where δ characterizes the slip flow intensity and kd is related to the Langmuir adsorption constant. The finite element method was used to calculate the methane permeability ke, Knudsen diffusion coefficient Dke, surface diffusion coefficient Ds, and adsorption phase transition rate Rm, which are all affected by adsorbed water. The model’s numerical results were validated through comparison with the results from adsorption experiments. These results revealed three distinct regions in the trend of the variation in δ with Le: a rapid increase in Region I (Le < 10 nm), a slowing increase in Region II (10 ≤ Le ≤ 100 nm), and a gradual increase in Region III (Le > 100 nm). In addition, kd is positively correlated with da. kd is also correlated with water saturation S; specifically, kd decreases when S ≤ 12%, increases when S = 12% to 45.8%, and decreases again when S exceeds 45.8%. The results also reveal overall negative correlations between h and ke, Dke, Ds and Rm. Furthermore, the rates of change in ke, Dke, Ds and Rm with increasing ε (ε is the bending coefficient associated with adsorbed water) range from 7.5% to 49.4%. Similarly, ke, Dke, and Ds increase by factors of 0.73–7.19 with increasing χ (χ is the coverage rate of the adsorbed water film). Additionally, as the adsorption time t increases, Ds initially increases rapidly, followed by a gradual increase. Between t = 500 seconds and 1,500 seconds, the rate of change in Ds decreases by 20%. Rm shows a three-stage relationship with t, namely, a rapid decrease from t = 0 seconds to 500 seconds, a steady decrease from 500 seconds to 1,000 seconds, and a stabilization from 1,000 seconds to 1,500 seconds, with Rm ranging from 1.10×10-11 mol/(m3·s) to 9.45×10-11 mol/(m3·s) overall. Ds increases with the adsorption amount ratio Ed (Ed is the ratio of the adsorption amount at t to the equilibrium adsorption amount). As Ed ranges from 0.2 to 0.6, the rate of change in Ds increases by 87% to 100%. Furthermore, Rm is negatively linearly correlated with Ed.

Analysis of dominant flow in tectonic coal during coalbed methane transport

Diffusion and seepage are the main flow forms of coal seam gas transport, and are one of the key factors in the selection of gas extraction improvement methods. Changes in the physical structure of tectonic coal make gas transport more complex during coalbed methane extraction. In this paper, we develop a multi-field coupled model of methane transport in coal seams, taking into account the effects of tectonics, and theoretically analyze the dominant flow patterns for methane extraction. Then, the evolution of gas dominated flow is analyzed for different initial pressures, initial permeabilities, and initial diffusion coefficients of tectonic and intact coal seams. The results show that the amount of daily methane seepage in tectonic coal increases with the initial pressure of the coal reservoir, but decreases with the initial diffusion coefficient of the coal reservoir. Methane seepage in tectonic coal has a longer control time than in intact coal at different initial pressures, initial permeabilities, and initial diffusion coefficients of the coal reservoir. For different coal reservoir initial pressures, coal reservoir initial permeabilities, and coal reservoir initial diffusion coefficients, the maximum seepage control time for tectonic coal is 20, 17, and 15 times longer than for intact coal, respectively. Finally, the discrepancies of methane dominant flow in tectonic coal and intact coal during methane extraction were analyzed by using the double bottleneck flow model, and methods for methane enhanced extraction in tectonic coal and intact coal were discussed. The results presented in this paper may provide a theoretical reference for the extraction of differentiated gas in coal seams.

Storms and convection on Uranus and Neptune: Impact of methane abundance revealed by a 3D cloud-resolving model

Context. Uranus and Neptune have atmospheres dominated by molecular hydrogen and helium. In the upper troposphere (between 0.1 and 10 bar), methane is the third main molecule, and it condenses, yielding a vertical gradient in CH4 . As this condensable species is heavier than H2 and He, the resulting change in mean molecular weight due to condensation serves as a factor countering convection, which is traditionally considered as governed by temperature only. This change in mean molecular weight makes both dry and moist convection more difficult to start. As observations also show latitudinal variations in methane abundance, one can expect different vertical gradients from one latitude to another. Aims. In this paper, we investigate the impact of this vertical gradient of methane and the different shapes it can take, including on the atmospheric regimes and especially on the formation and inhibition of moist convective storms in the troposphere of ice giants. Methods. We developed a 3D cloud-resolving model to simulate convective processes at the required scale. This model is nonhydrostatic and includes the effect of the mean molecular weight variations associated with condensation. Results. Using our simulations, we conclude that typical velocities of dry convection in the deep atmosphere are rather low (on the order of 1 m/s) but sufficient to sustain upward methane transport and that moist convection at the methane condensation level is strongly inhibited. Previous studies derived an analytical criterion on the methane vapor amount above which moist convection should be inhibited in saturated environments. In ice giants, this criterion yields a critical methane abundance of 1.2% at 80 K (this corresponds approximately to the 1 bar level). We first validated this analytical criterion numerically. We then showed that this critical methane abundance governs the inhibition and formation of moist convective storms, and we conclude that the intensity and intermittency of these storms should depend on the methane abundance and saturation. In the regions where CH4 exceeds this critical abundance in the deep atmosphere (at the equator and the middle latitudes on Uranus and at all latitudes on Neptune), a stable layer almost entirely saturated with methane develops at the condensation level. In this layer, moist convection is inhibited, ensuring stability. Only weak moist convective events can occur above this layer, where methane abundance becomes lower than the critical value. The inhibition of moist convection prevents strong drying and maintains high relative humidity, which favors the frequency of these events. In the regions where CH4 remains below this critical abundance in the deep atmosphere (possibly at the poles on Uranus), there is no such layer. More powerful storms can form, but they are also a bit rarer. Conclusions. In ice giants, dry convection is weak, and moist convection is strongly inhibited. However, when enough methane is transported upward, through dry convection and turbulent diffusion, sporadic moist convective storms can form. These storms should be more frequent on Neptune than on Uranus because of Neptune’s internal heat flow and larger methane abundance. Our results can explain the observed sporadicity of clouds in ice giants and help guide future observations that can test the conclusions of this work.

High-Order Models for Gas Transport in Multiscale Coal Rock.

The coal reservoirs exhibit great heterogeneity and strong anisotropy in multiscale pore/fracture structures. Developing highly accurate multiscale models for real-time prediction of microgaseous flow in complicated porous media with pronounced contrast in transport coefficients is crucial but not yet available, which is time-consuming, expensive, and even computationally impossible. In this study, a multiscale approximate solution of the gas flow and pressure field is derived in this paper for predicting coalbed methane (CBM) transport in macro-microscopic two-scale porous media of typical coal rocks in Guizhou Province, China, and the detailed finite element algorithm is established. The multiscale approximate solutions are constructed from the first- and second-order auxiliary cell functions and low- or high-order derivatives of the homogenized pressure field, which can accurately approximate the solution of the original problem to a certain extent. The numerical accuracy and validity of the multiscale approximate solutions under various working conditions are analyzed in detail by comparing and verifying the results with the direct numerical simulation results of fine-mesh high-precision finite elements. The results show that the homogenized approximate solution can only roughly capture the characteristics of the macroscopic pressure evolution, the first-order approximate solution can partially reproduce the macro-microscopic pressure oscillation phenomenon, and the second-order approximate solution can accurately predict the pressure profile and its evolution law with time in porous media with macro-micro configuration under various complex conditions. The second- and high-order two-scale approximate solutions constructed in this paper exhibit high numerical accuracy and excellent computational efficiency. We also develop multiscale approximate solutions for predicting microgaseous flow at a low reservoir pressure where the slippage effects are very pronounced. Potential applications of our high-order models to the coal reservoirs with a hierarchical matrix and fractures are discussed. The developed multiscale models exhibit excellent applicability to investigating the crossflow effects and coupling mechanisms between the matrix and cleats or fractures with multiple configurations in the CBM and shale gas reservoirs, which is crucial for the effective implementation of hydraulic fracturing technology. This study provides a fundamental understanding of gas transport in multiscale matrix-fracture networks, which helps to improve the optimization design of hydraulic fracturing in tight reservoirs.

Isotopic fractionation of methane on Mars via diffusive separation in the subsurface

Many processes have been identified in the Martian subsurface which may produce or release methane that eventually can be emitted into the atmosphere. Given the wide range of isotopic values for source carbon reported on Mars and the importance of atmospheric methane isotopologues as a tracer for subsurface processes, it is critical to quantify the level of isotopic fractionation that can occur during subsurface transport. On Earth, isotopic fractionation occurs when methane transport is dominated by Knudsen diffusion through small pores. However, unlike the Earth, on Mars the low atmospheric pressure and commensurate longer mean free path suggest that most subsurface transport of methane occurs in the Knudsen regime, amplifying this effect. Here, we report on simulations of diffusion through the martian subsurface and report on the level of fractionation that would be expected under two end-member scenarios. For Interplanetary Dust Particles (IDPs) incorporated in near-surface sediments in which methane is released quickly upon generation, atmospheric emissions of methane are expected to be representative of the reservoir isotopic ratio. However, for deeper sources in which methane accumulates as trapped gas, subsurface transport will result in depletions of 13CH4 compared to reservoir concentrations by approximately −31‰. Over time, both the reservoir and the emitted gas will evolve to become isotopically enriched in 13CH4 compared to a standard of constant isotopic ratio. This necessitates temporal measurements of emitted methane to understand the δ13C of the reservoir and depth of the release, preferably with hourly or better frequency. Finally, a seasonal cycle in δ13C with an amplitude of 5.3‰ is expected with adsorption acting to create small temporary reservoirs that are filled and emptied over the year by the subsurface thermal wave. This effect may provide a way to probe near-surface thermophysical properties.

Complete organelle genomes of the threatened aquatic species Scheuchzeria palustris (Scheuchzeriaceae): Insights into adaptation and phylogenomic placement.

Scheuchzeria palustris, the only species in the Scheuchzeriaceae family, plays a crucial role in methane production and transportation, influencing the global carbon cycle and maintaining ecosystem stability. However, it is now threatened by human activities and global warming. In this study, we generated new organelle genomes for S. palustris, with the plastome (pt) measuring 158,573 bp and the mitogenome (mt) measuring 420,724 bp. We predicted 296 RNA editing sites in mt protein-coding genes (PCGs) and 142 in pt-PCGs. Notably, abundant RNA editing sites in pt-PCGs likely originated from horizontal gene transfer between the plastome and mitogenome. Additionally, we identified positive selection signals in four mt-PCGs (atp4, ccmB, nad3, and sdh4) and one pt-PCG (rps7), which may contribute to the adaptation of S. palustris to low-temperature and high-altitude environments. Furthermore, we identified 35 mitochondrial plastid DNA (MTPT) segments totaling 58,479 bp, attributed to dispersed repeats near most MTPT. Phylogenetic trees reconstructed from mt- and pt-PCGs showed topologies consistent with the APG IV system. However, the conflicting position of S. palustris can be explained by significant differences in the substitution rates of its mt- and pt-PCGs (p < .001). In conclusion, our study provides vital genomic resources to support future conservation efforts and explores the adaptation mechanisms of S. palustris.

Long‐range transport of littoral methane explains the metalimnetic methane peak in a large lake

AbstractIn large and stratified lakes, substantial methane stocks are often observed within the metalimnion. The origin of the methane (CH4) accumulated in the metalimnion during stratification, which can sustain significant emissions during convective mixing, is still widely debated. While commonly attributed to the transport of methane produced anaerobically ex situ, recent evidence suggests that oxic in situ methane production could also contribute to metalimnetic methane peaks. Here, we assessed the origin, that is, pelagic CH4 production or transport of sublittoral CH4 through the interflow, of metalimnetic methane in Lake Geneva, the largest lake in Western Europe. Microbial diversity data do not support the hypothesis of oxic methane production in the metalimnion. In contrast, both spatial and temporal surveys of methane show that maxima occur at depths and sites most affected by the Rhône River inflow. Methane δ13C values point to an anaerobic sublittoral methane source, within a biogeochemical hotspot close to the river delta region, and an efficient transport across several kilometers in a vertically well‐constrained metalimnion. Our current findings emphasize the indirect role of river interflows for the long‐range transport of CH4 produced in sediment biogeochemical hotspots, even for large lakes where sublittoral habitats represent a fairly limited fraction of the lake volume.

Carbon isotope fractionation during methane transport through tight sedimentary rocks: Phenomena, mechanisms, characterization, and implications

The phenomenon of carbon isotopic fractionation, induced by the transport of methane in tight sedimentary rocks through processes primarily involving diffusion and adsorption/desorption, is ubiquitous in nature and plays a significant role in numerous geological and geochemical systems. Consequently, understanding the mechanisms of transport-induced carbon isotopic fractionation both theoretically and experimentally is of considerable scientific importance. However, previous experimental studies have observed carbon isotope fractionation phenomena that are entirely distinct, and even exhibit opposing characteristics. At present, there is a lack of a convincing mechanistic explanation and valid numerical model for this discrepancy. Here, we performed gas transport experiments under different gas pressures (1–5 MPa) and confining pressures (10–20 MPa). The results show that methane carbon isotope fractionation during natural gas transport through shale is controlled by its pore structure and evolves regularly with increasing effective stress. Compared with the carbon isotopic composition of the source gas, the initial effluent methane is predominantly depleted in 13C, but occasionally exhibits 13C enrichment. The carbon isotopic composition of effluent methane converges to that of the source gas as mass transport reaches a steady state. The evolution patterns of the isotope fractionation curve, transitioning from the initial non-steady state to the final steady state, can be categorized into five distinct types. The combined effect of multi-level transport channels offers the most compelling mechanistic explanation for the observed evolution patterns and their interconversion. Numerical simulation studies demonstrate that existing models, including the Rayleigh model, the diffusion model, and the coupled diffusion-adsorption/desorption model, are unable to describe the observed complex isotope fractionation behavior. In contrast, the multi-scale multi-mechanism coupled model developed herein, incorporating diffusion and adsorption/desorption across multi-level transport channels, effectively reproduces all the observed fractionation patterns and supports the mechanistic rationale for the combined effect. Finally, the potential carbon isotopic fractionation resulting from natural gas transport in/through porous media and its geological implications are discussed in several hypothetical scenarios combining numerical simulations. These findings highlight the limitations of carbon isotopic parameters for determining the origin and maturity of natural gas, and underscore their potential in identifying greenhouse gas leaks and tracing sources.

Design of eco-friendly antifreeze peptides as novel inhibitors of gas-hydration kinetics.

In this study, peptides designed using fragments of an antifreeze protein (AFP) from the freeze-tolerant insect Tenebrio molitor, TmAFP, were evaluated as inhibitors of clathrate hydrate formation. It was found that these peptides exhibit inhibitory effects by both direct and indirect mechanisms. The direct mechanism involves the displacement of methane molecules by hydrophobic methyl groups from threonine residues, preventing their diffusion to the hydrate surface. The indirect mechanism is characterized by the formation of cylindrical gas bubbles, the morphology of which reduces the pressure difference at the bubble interface, thereby slowing methane transport. The transfer of methane to the hydrate interface is primarily dominated by gas bubbles in the presence of antifreeze peptides. Spherical bubbles facilitate methane migration and potentially accelerate hydrate formation; conversely, the promotion of a cylindrical bubble morphology by two of the designed systems was found to mitigate this effect, leading to slower methane transport and reduced hydrate growth. These findings provide valuable guidance for the design of effective peptide-based inhibitors of natural-gas hydrate formation with potential applications in the energy and environmental sectors.

Mapping the Sustainability of Waste-to-Energy Processes for Food Loss and Waste in Mexico—Part 1: Energy Feasibility Study

Mexico generated 8.9 Mt of food loss and waste (FLW) at food distribution and retail centers in the year 2022. Traditional management methods in Latin America primarily involve final disposal sites, contributing to national greenhouse gas emissions of 0.22 Mt CO2 eq y−1. This creates an urgent need for sustainable valorization strategies for FLW to mitigate environmental impacts. This comprehensive study analyzes the geographical distribution of FLW generation and proposes a valorization approach using WtE-AD plants. Geographic information systems were employed for geographical analysis, life cycle assessment was used for environmental evaluation, and circular economy business models were applied for sustainability assessment. The primary objective of this first part of the contribution is to evaluate the technical feasibility of implementing waste-to-energy anaerobic digestion (WtE-AD) plants for FLW management in Mexico considering their geographical locations. The results demonstrate that WtE-AD plants with treatment capacities exceeding 8 t d−1 can achieve positive energy balances and significantly reduce greenhouse gas emissions. Specific findings indicate that these plants are viable for large-scale implementation, with larger plants showing resilience to increased transport distances while maintaining energy efficiency. The results highlight the critical influence of methane yields and transport distances on plant energy performance. This study underscores the importance of strategically placing and scaling WtE-AD plants to optimize resource efficiency and environmental sustainability. These findings provide essential insights for policymakers and stakeholders advocating for the transition of Mexico’s food supply chain toward a circular economy. Future parts of this study will explore detailed economic analyses and the policy frameworks necessary for the large-scale implementation of WtE-AD plants in Mexico. Further research should continue to develop innovative strategies to enhance the techno-economic and environmental performance of WtE-AD processes, ensuring sustainable FLW management and energy recovery.

Transport and reactivity of nitrous oxide and methane in two contrasting subterranean estuaries

AbstractContinental groundwaters are commonly enriched in nitrous oxide (N2O) and methane (CH4), which can discharge into the coast. The contribution of this diffuse source to coastal N2O and CH4 emissions largely depends on the biogeochemical processes of coastal aquifer exit zones, known as subterranean estuaries. Here, we study the role of subterranean estuaries in modulating N2O and CH4 exports toward the coast. The two studied subterranean estuaries are located at Panxón and Ladeira beaches (Ría de Vigo, NW Iberian Peninsula) and had opposite oxygenation at their interior. Groundwater‐borne N2O was detected in the oxygenated subterranean estuary of Panxón Beach, although denitrification attenuated N2O before porewater was discharged into the coast. An N2O hotspot was detected at about 50 cm depth in this subterranean estuary, characterized by the presence of nitrate under suboxic conditions. This N2O also seems to be consumed along the flow path before discharging into the coast. The anoxic subterranean estuary of Ladeira Beach completely removed groundwater‐borne N2O. Yet, nitrification within its suboxic upper saline plume produced and exported N2O toward the coast, hiding the role of this subterranean estuary as an N2O sink. The anoxic subterranean estuary exported CH4 toward the coast. This CH4 was not sourced by continental groundwater, hence it was produced in situ fuelled by the accumulation of organic matter within the beach. The suboxic upper saline plume in Ladeira Beach and the oxygenated subterranean estuary of Panxón Beach acted as CH4 sinks.

Machine Learning Driven Sensitivity Analysis of E3SM Land Model Parameters for Wetland Methane Emissions

AbstractMethane (CH4) is globally the second most critical greenhouse gas after carbon dioxide, contributing to 16%–25% of the observed atmospheric warming. Wetlands are the primary natural source of methane emissions globally. However, wetland methane emission estimates from biogeochemistry models contain considerable uncertainty. One of the main sources of this uncertainty arises from the numerous uncertain model parameters within various physical, biological, and chemical processes that influence methane production, oxidation, and transport. Sensitivity Analysis (SA) can help identify critical parameters for methane emission and achieve reduced biases and uncertainties in future projections. This study performs SA for 19 selected parameters responsible for critical biogeochemical processes in the methane module of the Energy Exascale Earth System Model (E3SM) land model (ELM). The impact of these parameters on various CH4 fluxes is examined at 14 FLUXNET‐ CH4 sites with diverse vegetation types. Given the extensive number of model simulations needed for global variance‐based SA, we employ a machine learning (ML) algorithm to emulate the complex behavior of ELM methane biogeochemistry. We found that parameters linked to CH4 production and diffusion generally present the highest sensitivities despite apparent seasonal variation. Comparing simulated emissions from perturbed parameter sets against FLUXNET‐CH4 observations revealed that better performances can be achieved at each site compared to the default parameter values. This presents a scope for further improving simulated emissions using parameter calibration with advanced optimization techniques.

Exploring Methane Storage Capacities of M2(BDC)2(DABCO) Sorbents: A Multiscale Computational Study

A promising solution for efficient methane (CH4) storage and transport is a metal–organic framework (MOF)-based sorbent. Hence, searching for potential MOFs like M2(BDC)2(DABCO) to enhance the CH4 storage capacity in both gravimetric and volumetric uptakes is essential. Herein, we systematically elucidate the adsorption of CH4 in M2(BDC)2(DABCO) or M(DABCO) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn) MOFs using multiscale simulations that combined grand canonical Monte Carlo simulation with van der Waals density functional (vdW-DF) calculation. We find that, in the M(DABCO) series, Mg(DABCO) has the highest total CH4 adsorption capacities, with mtot= 231.39 mg/g at 298 K, for gravimetric uptake, and Vtot= 231.43 cc(STP)/cc, for volumetric uptake. The effects of temperature, pressure, and metal substitution on enhancing CH4 storage are evaluated, and we predict that the volumetric CH4 storage capacity on M(DABCO) could meet the DOE target at temperatures of ca. 238 K–268 K and pressures of 35–100 bar. The interactions between CH4 and M(DABCO) are dominated by the vdW interactions, as shown by the vdW-DF calculations. The Mg, Mn, Fe, Co, and Ni substitutions in M(DABCO) result in a stronger interaction and thus, a higher CH4 storage capacity, at higher pressures for Mg, Mn, Ni, and Co and at lower pressures for Fe. This work may provide guidance for the rational design of CH4 storage in M2(BDC)2(DABCO) MOFs.

Emerging trends in hydrogen and synfuel generation: a state-of-the-art review.

The current work investigated emerging fields for generating and consuming hydrogen and synthetic Fischer-Tropsch (FT) fuels, especially from detrimental greenhouse gases, CO2 and CH4. Technologies for syngas generation ranging from partial oxidation, auto-thermal, dry, photothermal and wet or steam reforming of methane were adequately reviewed alongside biomass valorisation for hydrogen generation, water electrolysis and climate challenges due to methane flaring, production, storage, transportation, challenges and opportunities in CO2 and CH4 utilisation. Under the same conditions, dry reforming produces more coke than steam reforming. However, combining the two techniques produces syngas with a high H2/CO ratio, which is suitable for producing long-chain hydrocarbons. Although the steam methane reforming (SMR) process has been industrialised, it is well known to consume significant energy. However, coke production via catalytic methane decomposition, the prime hindrance to large-scale implementation of these techniques for hydrogen production, could be addressed by coupling CO with CO2 conversion to alter the H2/CO ratio of syngas, increasing the reaction temperatures in dry reforming, or increasing the steam content fed in steam reforming. Optimised hydrogen production and generation of green fuels from CO2 and CH4 can be achieved by implementing these strategies.

Application and Research of Multi-Scale Dynamic Diffusion Permeability Model in Different Coal Ranks

The spatial scale of coal mining and rock layer control is distributed between 10-10 and 107, spanning 17 orders of magnitude. There are multi-scale pore cracks from millimeter to micro and nanometers in the coal, and the pore size can reach one million times, which makes the coal permeability also show a multi-scale characteristics of millions and time. For the permeability of the coal seam, it is necessary to test and analyze the distribution of micro and nano pores and cracks in the coal [1]. CBM mining is accompanied by the dynamic change of adsorption pressure in coal and the complex deformation of multi-scale heterogeneous structure of coal, and the multi-scale deformation feature of pore fissure structure plays an important role in the transport of methane [2]. However, existing studies focus on treating coal as a homogeneous isotropic medium, without considering the influence of coal multiscale pore structure on permeability. The variation of heterogeneous degree of coal structure with structural scale and its influence on dynamic diffusion and permeability are rarely reported. Li Zhiqiang et al. [3] conducted an experimental-model-mechanism study of CBM gas micro-nano series multi-scale dynamic diffusion permeability. On this basis, the dynamic diffusion and permeability of different coal scales.

Water-bearing properties of high rank coal reservoir and the effect on multiphase methane

Coal reservoirs commonly exhibit the coexistence of gas and water, wherein the distribution of water plays a crucial role in influencing methane storage and transportation. The presence of water affects methane adsorption, and models predicting adsorbed methane that do not account for water conditions can introduce errors, posing challenges in meeting practical production needs. In this study, through a series of centrifugation experiments and nuclear magnetic resonance (NMR) adsorption experiments, the distribution characteristics of bound water and movable water in reservoirs and their influence on multiphase methane were assessed. The results indicate that under water-bearing conditions, there exists specific methane in the adsorption space, exhibiting properties similar to free methane. In terms of the relaxation characteristics, the presence of water affects both the peak area and morphology of the T2 spectra of multiphase methane. Based on the NMR response characteristics of adsorbed methane at different water saturations, we proposed and established a theoretical model for predicting the content and density of adsorbed methane under varying water saturations. Additionally, utilizing two-dimensional NMR technology, a simple identification spectrum for multiphase methane was established. The study suggests that the presence of water delays the time of adsorption equilibrium for methane. At low water saturations, water primarily inhibits the adsorption rate of methane. However, with increasing pressure and water saturation, water predominantly suppresses the adsorption capacity of methane. At low water saturations, the bound water has a significant effect on adsorbed methane. Conversely, as water saturations increase, movable water gradually occupies adsorption sites with weaker adsorption potential. It is worth noting that with an increase in water saturation, the content of adsorbed methane decreases, but the adsorption phase density may not necessarily decrease. These research findings provide new insights into the interaction mechanisms between water and methane in water-bearing coal reservoirs.

A Simulator Based on Coupling of Reaction Transport Model and Multiphase Hydrate Simulator and Its Application to Studies of Methane Transportation in Marine Sediments

Summary Methane emissions at seafloor are generally associated with the upward methane migration from the deeper sediments, partly from hydrate dissociation. The anaerobic oxidation of methane (AOM) occurring in the surface sediments acts as an important barrier to methane emissions, caused by the reaction between sulfate ions and dissolved methane molecules. However, the current hydrate simulators rarely consider the transport of sulfate and the subsequent AOM reaction. In this study, to investigate AOM effects in hydrate systems, a new simulator named Tough+Hydrate+AOM (THA) is developed by combining the reaction transport model (RTM) with the widely used Tough+Hydrate (T+H) simulator. The THA simulator is validated using the single-phase cases of the Dvurechenskii mud volcano in Black Sea since the results obtained are in good agreement with previous ones. This simulator is then applied to investigate the response of a hydrate reservoir offshore West Svalbard to seasonal seafloor temperature change and also to confirm its adaptability in multiphase hydrate systems. The results obtained suggest that the AOM filter efficiency is as low as 5%, meaning that the majority of methane released from hydrate dissociation in the deeper sediments will escape into the ocean. The THA simulator considering AOM is expected to be an important tool for assessing methane emissions caused by hydrate destabilization.