Methane Hydrate Research Articles

Rapid Impact Crater Relaxation Caused by an Insulating Methane Clathrate Crust on Titan

Titan’s impact craters are hundreds of meters shallower than expected, compared to similar-sized craters on Ganymede. Only 90 crater candidates have been identified, the majority of which have low certainty of an impact origin. Many processes have been suggested to shallow, modify, and remove Titan’s craters, including fluvial erosion by liquid from rainfall, aeolian sand infill, and topographic relaxation induced by insulating sand infill. Here we propose an additional mechanism: topographic relaxation due to an insulating methane clathrate crustal layer in Titan’s upper ice shell. We use finite element modeling to test whether a clathrate crust 5, 10, 15, or 20 km thick could warm the ice shell and relax craters to their currently observed depths or remove them completely. We model the viscoelastic evolution of crater diameters 120, 100, 85, and 40 km, with two initial depths based on depth−diameter trends of Ganymede’s craters. We find that all clathrate crustal thicknesses result in rapid topographic relaxation, despite Titan’s cold surface temperature. The 5 km thick clathrate crust can reproduce nearly all of the observed shallow depths, many in under 1000 yr. A 10 km thick crust can reproduce the observed depths of the larger craters over geologic timescales. If relaxation is the primary cause of the shallow craters, then the clathrate thickness is likely 5–10 km thick. Topographic relaxation alone cannot remove craters; crater rims and flexural moats remain. To completely remove craters and reproduce the observed biased crater distribution, multiple modification processes must act together.

CH4 hydrate dissociation and CH4 leakage characteristics: Insights from laboratory investigation based on stratified environment reconstruction of natural gas hydrate reservoir

Submarine natural gas hydrates (NGHs) are one of the largest methane reservoirs on Earth, offering huge potential as an alternative energy source and serving as a crucial global carbon sink. However, the substantial risk of methane leakage during NGH development seriously threatens marine and global ecological and environmental safety, presenting a major challenge for commercial NGH exploitation. Focusing on the unknown leakage mechanisms, this study employed a new simulation device to construct a stratified environment and to investigate the characteristics of hydrate dissociation and methane leakage during depressurization production, under conditions of varied fracturing in overlying sediment. A movable module was used to dynamically isolate and connect the hydrate reservoir with the overlying layer. The results showed that the intrusion of overlying water decelerated the reservoir depressurization rate, leading to a mass of hydrate reformation. The invasion locations and flow paths of the overlying water were influenced by the fracture scale of the overlying sediment. Benefiting from the additional sensible heat and reservoir space occupation of the overlying water in the later production stages, the methane recovery ratio in the fracture-containing systems were not significantly affected. However, the leakage methane increased as fracture channels enlarged, reaching up to 9.90 % of the total methane content in the hydrate reservoir. The leakage mechanism primarily involved local overpressure, buoyancy effects, and diffusion. The research, for the first time, experimentally revealed the response relationship between methane leakage and hydrate dissociation, providing foundational data and theoretical support for the safe and efficient NGH development.

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.

Optimization of energy efficiency in gas production from hydrates assisted by geothermal energy enriched in the deep gas

Scaled-up production from natural gas hydrates is still facing the significant issues of limited gas yield and unsustainable hydrate dissociation. In this work, the deep gas with huge reserves and abundant geothermal energy was used to enhance the hydrate production efficiency. Results showed that the geotherm-assisted gas production was significantly increased by 178.22 %. Surprisingly, the hydrate dissociation rate was slightly weakened by 3.66 % due to the hindered fugacity of the gas from hydrate decomposition as a result of the fast deep gas upwelling. Besides, the energy flow analysis showed that up to 40.67 % of the deep gas injection energy was dissipated to the surroundings, with only 8.28 % utilized for the hydrate decomposition. Consequently, the multi-well deployment was used to regulate the deep gas injection rate. It was found that the multiple wells weakened the sealing effect of hydrate on migration channels, preventing the violent gas upwelling while increasing the hydrate decomposition amount under geothermal stimulation. Then, prolonging crossflow distance of deep gas in the hydrate layer enabled the sediment to absorb more injected energy, resulting in the minimum wasted energy ratio. Not limited to this, the more stable gas production throughout the whole process effectively guaranteed the safety of exploitation. Finally, the hydrate decomposition rate in the depressurization and constant pressure stages was found to be positively correlated with the utilization ratio of the injected energy and the injected rate, respectively. The results could help guide the formulation of the multi-gas joint production scenarios in the field tests to balance production efficiency and cost.

Preparation and regulation of high-strength and high-permeability porous ceramic/PDMS composite membranes for gas-liquid separation

Methane detection is crucial in identifying combustible ice within the energy sector. The gas–liquid separation membrane, a key component of methane sensors, plays a critical role in effectively separating methane and water. It significantly enhances the efficiency and stability of detecting methane concentration in situ. However, the related permeability and mechanical property present conflicting requirements in order to achieve optimal membrane performance. This work proposes an investigation into the mass transfer performance of a high-strength composite membrane, utilizing PDMS as the functional layer and porous ceramics as the supporting layer. By adjusting the pore distribution of the porous ceramics, particularly through the use of spherical graphite as a porogen, the study examines the impact of spherical graphite (SG) on the support layer’s morphology and its ability to regulate pore structure. Results indicate that incorporating spherical graphite with a porogen content of 10 wt% and a particle size of 25 μm enhances connections between ceramic grains, resulting in a flexural strength of 56.36 MPa and a permeability coefficient of 1861.57 barrer. This configuration demonstrates good waterproof and breathable performance. Overall, this research presents a novel approach for fabricating methane-water separation membranes, offering valuable insights for underwater methane detection efforts.

Hydrate Technologies for CO2 Capture and Sequestration: Status and Perspectives.

CO2 capture and sequestration based on hydrate technology are considered supplementary approaches for reducing carbon emissions and mitigating the greenhouse effect. Direct CO2 hydrate formation and CH4 gas substitution in natural gas hydrates are two of the main methods used for the sequestration of CO2 in hydrates. In this Review, we introduce the crystal structures of CO2 hydrates and CO2-mixed gas hydrates and summarize the interactions between the CO2 molecules and clathrate hydrate/H2O frames. In particular, we focus on the role of diffraction techniques in analyzing hydrate structures. The kinetic and thermodynamic properties then are introduced from micro/macro perspectives. Furthermore, the replacement of natural gas with CO2/CO2-mixed gas is discussed comprehensively in terms of intermolecular interactions, influencing factors, and displacement efficiency. Based on the analysis of related costs, risks, and policies, the economics of CO2 capture and sequestration based on hydrate technology are explained. Moreover, the difficulties and challenges at this stage and the directions for future research are described. Finally, we investigate the status of recent research related to CO2 capture and sequestration based on hydrate technology, revealing its importance in carbon emission reduction.

Formation and evolution of nanobubbles in CH4-H2O-Alcohol system: Insight into the effect of alcohol chain length from molecular dynamics simulations

Nanobubbles (NBs) which are gas filled cavities of nanometre dimensions present in liquids attracted increasing attention in the recent years due to their application in various fields such as chemistry, biology, medicine etc. An important aspect of NB research is the study of effect of additives on formation and evolution of these bubbles. The present study examined by applying molecular dynamics simulations, the formation and evolution of methane NBs in the CH4-H2O-Alcohol system, which is known to form during alcohol induced dissociation of CH4 hydrates in the natural gas extraction process. The effect of alcohol type and concentration on NB formation and evolution was examined through simulations of CH4-H2O-CH3OH, CH4-H2O-C2H5OH and CH4-H2O-nC3H7OH systems. The study revealed that increase in both concentration and the alkyl chain length of alcohols promoted NB formation. Alcohol molecules are found to enhance NB nucleation through accumulation near the NB-liquid interface resulting in a decrease in the surface tension (γ) at the interface. These effects become more pronounced as the alkyl chain length increases which explains the enhanced NB formation in systems containing nC3H7OH and C2H5OH compared to those containing CH3OH. The mechanism of formation and evolution of NBs is found to significantly depend on the type of alcohol present. NBs are found to nucleate at multiple locations in the systems containing nC3H7OH and C2H5OH which eventually coalesce to form a single large stable NB. In the presence of NBs which vary significantly in size, bubble growth was also found to occur through Ostwald ripening which involves transfer of CH4 from smaller NB to the larger one. In contrast, in the CH4-H2O-CH3OH system, primarily a single NB nucleated which grew in size through absorption of CH4 molecules dissolved in the liquid, rather than through coalescence or Ostwald ripening. The observed influence of alcohol type on the process of NB evolution is explained by examining the influence of alkyl chain length on γ and diffusivity of CH4 molecules. Due to the role of NBs on methane hydrate regeneration from the hydrate melt, we examined the influence of NB in the CH4-H2O-Alcohol system on the organization of water molecules (HSWs) present in the hydration shell of dissolved CH4. The value of F4 order parameter of HSWs and the number of hydrogen bonded water rings in the hydration shell of CH4 were analysed. The value of F4 order parameter indicate that the hydrophobic alkyl chain of alcohol induced hydrate like arrangement of HSWs, which is more pronounced in the case of alcohol with longer alkyl chain. However, alcohol molecules are also found to dislodge HSWs around CH4 resulting in a decrease in the number of water rings around dissolved CH4 which is not conducive to hydrate formation. These observations are consistent with the reported dual effect of alcohol on hydrate formation with alcohol promoting hydrate formation at low concentrations and inhibiting at high concentrations.

Analysis on a five-spot well for enhancing energy recovery from silty natural gas hydrate deposits in the South China Sea

The five-spot well is a promising technique for enhancing the inherent low gas production rate from silty natural gas hydrate (NGH) reservoirs with low permeability in the South China Sea (SCS). However, the production characteristics and the responses to key geological and engineering factors are still unclear and warrants investigation. Herein, we first establish a three-dimensional reservoir model based on the SH2 NGH deposits at SCS with the implementation of a five-spot well. We systematically examine the gas production enhancement effect and the unexpected well-to-well interaction induced by long-term depressurization. A sensitivity analysis on the effects of bottomhole pressure (Pbtm), permeability (k) and hydrate saturation (SH) is conducted to elucidate the key factors controlling the gas production enhancement. Our results reveal that the five-spot well significantly improves the gas productivity with cumulative gas production increased to 4.12 times that of a single well over 10 years. The well interference on gas production is not significant in the early stage but becomes more significant as depressurization sustains. Due to the relatively slow pressure propagation at the inner well, contribution to gas production from the inner well decreases over time while the outer wells increase. Based on the sensitivity analysis, gas production increases with decreasing Pbtm, increasing k, and decreasing SH with Pbtm and k as the key controlling factors. The findings provide valuable design basis for the adoption of a multi-well system in enhancing gas production for targeted NGH reservoirs in the next field production trial at SCS.

Spatial evolution of CO2 storage in depleted natural gas hydrate reservoirs and its synergistic efficiency analysis

Carbon neutrality is now a common strategic target worldwide, with geological storage seen as the mainstream scheme to address CO2 emissions and the greenhouse effect. Depleted natural gas hydrate reservoirs (DNHR), with their high-pressure, low-temperature environment, could capture CO2 in the form of hydrates, being an innovative way for carbon storage. A lab-scale reactor was used in this work to simulate CO2 injection into the reservoir after gas hydrate exploitation. As expected, it was found that the low-temperature environment of the depleted reservoir at the end of gas production provided a high driving force and accelerated the rate of CO2 hydrate formation. Consequently, the maximum gas storage capacity was increased by 66% by optimizing the injection timing and reducing the gas injection flow rate to enable enough hydrate formation. Besides, the formation of CO2 hydrate in the DNHR could also help stabilize the reservoir to achieve a more efficient CH4 production and CO2 storage. This study provides a novel strategy for gas hydrate exploitation as well as subsequent geological storage of CO2 in depleted natural gas hydrate reservoirs by making full use of their favorable conditions.

Phase equilibrium data for semiclathrate hydrates formed with n-propyl, tri-n-butylammonium bromide and tri-n-butyl, n-pentylammonium bromide under methane, carbon dioxide and nitrogen gas pressure

Semiclathrate hydrates are water-based materials formed from aqueous solutions of ionic substances. To enhance the gas capture performance of these materials, it is necessary to direct focus on the cation, which is a key part of construction of the hydrogen-bonding framework. In this paper, we focus on the partly-asymmetric cations, i.e., the n-propyl, tri-n-butylammonium bromide (N3444Br) and tri-n‑butyl, n-pentylammonium bromide (N4445Br), which are yet to be subjected to gas hydrate formation. The three phase equilibrium (gas–hydrate–liquid) conditions for the systems of (N3444Br or N4445Br) + H2O + (CH4, CO2 or N2) in the range of the pressure and mass fractions of the aqueous solutions between 1 and 11 MPa and 0.10–0.40, respectively, are reported. In all the systems, the semiclathrate hydrates were successfully formed under gas pressure. It was demonstrated that both the N3444Br and N4445Br salts promoted hydrate formation under these gases, while in the case with lean aqueous solutions N3444Br acted as an inhibitor of methane hydrate formation in pure water system. The present data are compared with the literature data, and the effect of the side chain length on the phase behavior of the semiclathrate hydrate phase is discussed.

Methane hydrate formation in amino acids / sodium montmorillonite systems

To understand the occurrence of natural gas hydrates in seabed sediments, it is crucial to examine the mechanisms of methane (CH4) hydrate formation in sodium montmorillonite (Na-Mt) systems in the presence of amino acid. Accordingly, this study employed kinetics experiments and molecular dynamics simulations to investigate CH4 hydrate nucleation and growth in an Na-Mt system containing alanine (Ala), leucine (Leu), and phenylalanine (Phe), respectively. Kinetics and Raman experiments showed that, compared with Ala, Leu and Phe enhanced hydrogen bonding between water molecules surrounding Na-Mt. This enhancement was due to the long carbon chain of Leu and the phenyl ring of Phe and facilitated CH4 hydrate formation. Moreover, in the Na-Mt system, Ala reduced CH4 consumption, whereas Leu and Phe increased CH4 consumption. Molecular dynamics simulations revealed that the strength of electrostatic interactions between the negatively charged Na-Mt surface and the functional groups of amino acids affected the distribution of amino acids, thereby altering CH4 aggregation and CH4 hydrate nucleation processes. The strong interaction between Na-Mt and Ala significantly disrupted interfacial interactions between Na-Mt and water molecules. In contrast, the weaker interactions between Na-Mt and Leu and Phe, respectively, meant that these amino acids affected CH4 hydrate nucleation in the bulk-like solution by influencing the arrangement of water molecules. These findings indicate that interfacial interactions between Na-Mt and amino acids play a crucial role in CH4 hydrate formation. Overall, this study generated insights into the formation kinetics and nucleation properties of CH4 hydrates in clay mineral–amino acid complexes that may increase understanding about the occurrence of natural gas hydrates in marine sediments.

Mechanical properties and cage transformations in CO2-CH4 heterohydrates: a molecular dynamics and machine learning study

Abstract The substitution of natural gas hydrates with CO2 offers a compelling dual advantage by enabling the extracting of CH4 while simultaneously sequestering CO2. This process, however, is intricately tied to the mechanical stability of CO2-CH4 heterohydrates. In this study, we report the mechanical properties and cage transformations in CO2-CH4 heterohydrates subjected to uniaxial straining via molecular dynamics (MD) simulations and machine learning (ML). Results indicate that guest molecule occupancy, the ratio of CO2 to CH4 and their spatial arrangements within heterohydrate structure greatly dictate the mechanical properties of CO2–CH4 heterohydrates including Young’s modulus, tensile strength, and critical strain. Notable, the introduction of CO2 within clathrate cages, particularly within 512 small cages, weakens the stability of CO2–CH4 heterohydrates in terms of mechanical properties. Upon critical strains, unconventional clathrate cages form, contributing to loading stress oscillation before fracture of heterohydrates. Intriguingly, predominant cage transformations, such as 51262–4151063 or 425864 and 512–425861 cages, are identified, in which 4151062 appears as primary intermediate cage that is able to transform into 4151063, 425862, 425863, 512 and 51262 cages, unveiling the dynamic nature of heterohydrate structures under straining. Additionally, ML models developed using MD data well predict the mechanical properties of heterohydrates, and underscore the critical influence of the spatial arrangement of guest molecules on the mechanical properties. These newly-developed ML models serve as valuable tools for accurately predicting the mechanical properties of heterohydrates. This study provides fresh insights into the mechanical properties and cage transformations in heterohydrates in response to strain, holding significant implications for environmentally sustainable utilization of CO2–CH4 heterohydrates.

A well-testing model for partially perforated wells in natural gas hydrate reservoirs

A well-testing model for partially perforated wells in natural gas hydrate reservoirs

Visual study of hydrate particles agglomeration and rolling characteristic in gas-oil-water phase using a flow loop

Natural gas hydrate blockage always leads to safety problems in oil and gas transportation pipelines. It is important to look for the characteristic of hydrate blockage process. The hydrate blockage was visually investigated under gas-oil-water multi-phase flow conditions in a flow loop in this study. The change of pressure drop with water conversion rate variations were detected. The hydrate particle movements were also observed in the visual pipes at different liquid loadings and water cuts. It was found that the hydrate particles may agglomerate and deposit with an obvious rolling process in low water cut conditions. The oil phase will accelerate particles agglomeration in the contact interface of oil, gas and water, and form a large number of flocculent hydrates. A theoretical hydrate particle rolling model was conducted to analysis the experiment results, and the hydrate particle velocity increases first and then decreases with the increase of particle diameter due to the comprehensive influence of van der Waals force and drag force. The results also confirmed the maximum of the pressure drop increased when the liquid loading increased. However, the hydrate formation and blockage speed also slow down due to small component of the gas phase in high liquid loading. In addition, comparing with 20 % and 80 % water cut, 50 % water cut has the fastest hydrate formation speed in different experimental conditions. Furthermore, the maximum water conversion rate increased with have a higher water cut. More hydrate will form in the condition, which will lead to the decrease of flow velocity in the pipeline.

Experimental study of mechanical properties of deep-sea hydrate-bearing sediments under multi-field coupling conditions

To ensure the long-term safety of hydrate-bearing sediments (HBSs) in the deep sea, it is necessary to conduct a comprehensive study of the mechanical properties of HBSs, which is closely related to the safe extraction of natural gas hydrates (NGH). In this study, a HBSs preparation method was proposed preparing HBSs artificially to meet the test requirement. A series of triaxial shear tests were carried out by the self-developed HBSs multi-field coupling intelligent triaxial test device to analyze the effects of different hydrate saturation and NaCl concentration on the mechanical properties of HBSs. The results show that HBSs have elastic-plastic properties under multi-field coupling conditions, and the stress-strain curves show a strain-hardening trend. Hydrate saturation affects the shear strength of hydrate-bearing sediment critically. When the hydrate saturation is Sh>35 %, the cohesion and internal friction angle is directly proportional to the hydrate saturation. When the NaCl concentration is low, the cohesion of HBSs is more affected by the NaCl concentration, and the shear strength and yield strength are proportional to NaCl concentration. When NaCl concentration is high, the internal friction angle of HBSs is more affected by NaCl concentration and the shear strength is inversely proportional to NaCl concentration. Under the condition of multi-field coupling, the influence of each factor on the mechanical properties of HBSs has an upper limit, which is not a purely linear relationship.

Characterization of a fly ash-based hybrid well cement under different temperature curing conditions for natural gas hydrate drilling

This paper presents a study on the temperature effect (3°C, 10°C, and 50°C, in water bath) and activator effect on the characterization of a fly ash-based hybrid well cement, with a large fraction of fly ash (approximately 70 %), which has potential for natural gas hydrate drilling due to its low heat release. The mechanical strength, micro/nanostructure characteristics were investigated through various tests, including x-ray diffraction (XRD), thermogravimetry analysis (TGA-DTG), nuclear magnetic resonance (MAS NMR), and scanning electron microscope (SEM), to reveal the hydration mechanism of the fly ash-based hybrid well cement. The results indicate that the low curing temperatures (3°C, 10°C) inhibited both the hydration of the well cement and the pozzolanic reaction of fly ash in the cement system. However, the incorporation of solid Na2SO4 significantly contributed to the pozzolanic reaction during the hydration process by consuming more calcium hydroxide, promoting more ettringite formation and reducing the apparent activation energy of the blend cement (from 53.06 kJ·mol−1 to 41.23 kJ·mol−1), resulting in better compressive strength. MAS NMR results showed that the addition of solid Na2SO4 facilitated the substitution of Al with Si atoms, leading to the formation of more C-A-S-H and C-(N)-A-S-H gels in the system with a denser microstructure. Overall, the fly ash-based hybrid well cement can be developed as a cement system for natural gas hydrate drilling in the ocean. This cement not only exhibits low heat release but also shows improved strength development, with a 72-hour compressive strength of 8.05 MPa when cured at 10 °C.

Investigation of methane gas bubble dynamics and hydrate film growth during hydrate formation using 4-D time-lapse synchrotron X-ray computed tomography

Investigation of methane gas bubble dynamics and hydrate film growth during hydrate formation using 4-D time-lapse synchrotron X-ray computed tomography

Nucleation of Methane Hydrate in Surfactant Solutions in Cells Made of Teflon, Stainless Steel, and Glass

Nucleation of Methane Hydrate in Surfactant Solutions in Cells Made of Teflon, Stainless Steel, and Glass

Inversion of gas hydrate saturation and solid frame permeability in a gas hydrate-bearing sediment by Stoneley wave attenuation

Natural gas hydrate is a potential novel energy resource that is widely distributed globally. Acoustic logging can effectively provide information on the surrounding reservoir and plays an important guiding role in gas hydrate exploration and development. Natural gas hydrate-bearing sediments are composed of a solid frame with natural gas hydrates and water-filled pores. The borehole mode wave characteristics of two-phase porous media cannot be used to evaluate the parameters of such a multiphase porous medium. We explore factors that influence the monopole Stoneley wave in a borehole embedded in a multiphase porous medium containing two solids and one fluid and analyze the influence of each factor on monopole Stoneley wave attenuation systematically. The sensitivity analysis results indicate that the Stoneley wave attenuation is highly sensitive to solid frame permeability and gas hydrate saturation. Building upon this foundation, a method to invert for gas hydrate saturation and solid frame permeability is first developed using Stoneley wave attenuation. Synthetic logging data are used to demonstrate the feasibility of this method for inverting for gas hydrate-bearing sediment properties. Even in the presence of considerable noise added to the receiver signal arrays, the inversion method is stable, and reliably evaluates gas hydrate saturation and solid frame permeability.

Revealing the kinetic behaviors of hydrate formation on bubble surface with different pressure gradients in deep-sea methane seepage areas of the South China Sea

In the deep-sea methane seepage environment, hydrate formation on the methane bubbles is a crucial pathway for methane transformation, and plays an important role in determining whether seepage methane can enter the surface ocean. While how the pressure determines the hydrate formation process in different water depths remains unclear. In this study, we investigated the formation kinetic characteristics and microstructure evolution of methane hydrate on suspended gas bubbles within varied pressure conditions. The pressure range (4–14 MPa) was in the deep-sea methane seepage environment. The results indicated that pressure obviously affected the hydrate film formation characteristics. As pressure increased, the lateral growth rate of the hydrate film accelerated, the hydrate crystal particles became smaller, and the initial hydrate film surface became smoother. Raman spectroscopy results showed that pressure changes did not obviously alter the microporous evolution on the hydrate film surface, that the gas-phase/water-phase Raman peak area ratio exhibited similar trends. The dissolved methane concentration under different pressure conditions was not the primary factor affecting hydrate thickening, rather, it depended mainly on the driving force. This study is of great significance in revealing the characteristics of methane hydrate formation and methane transfer in the oceanic methane seepage environment.