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Abstract The permeability of porous media containing gas hydrates is of crucial importance in predicting the fluid flow behavior and gas production capacity during the exploitation of gas hydrate resource. Gas hydrates are generally unevenly distributed in the natural samples, the inhomogeneity of which could have significant impacts on the permeability properties. So here we extend our study on the permeability of heterogeneous hydrate-bearing porous media using pore network models combined with X-ray computed tomography (CT). The effects of varying pore/throat radii, non-even distribution of hydrates and fluid flow directions on the absolute and relative permeability are discussed. It is indicated that the rather high water saturation would significantly impact the gas permeation, which is not favorable for gas production. The microstructures of pores and throats would likely differ even under similar porosities; some pores may not have sufficient throats connected to them, limiting the fluid flow. The absolute permeability could also significantly vary with flow directions; the direction favorable for gas flow may not be true for water flow. This finding can be of help in case a preferential gas production is more required rather than water in the field test. Highlights • The effect of inhomogeneity on permeability of hydrate-bearing sediments is studied. • The micro-connection of pores and throats would differ even under similar porosities. • Some pores may not have sufficient throats connected to them, limiting the fluid flow. • The direction favorable for gas flow may not be true for water flow. [ABSTRACT FROM AUTHOR]

• An anisotropy of gas hydrate growth was in-situ characterized through X-ray technique. • Themotactic habit of hydrate growth towards a low temperature region was proposed. • The hydrate morphology can be controlled via regulating the heat transfer scheme. Promoting hydrate formation kinetics is considered a major challenge hindering the application of hydrate-based techniques. Surfactants are thus widely used for a better gas solution and water conversion. Yet significant issues involving an uncontrolled morphology and foaming are encountered. In this work, a unique anisotropic behavior of gas hydrate formation was identified through in-situ X-ray technique with the rate of vertical growth 5 times higher than the lateral. This was ascribed to the varying driving force of hydrate nucleation at the wall surface where the reaction heat could be more easily dissipated. Consequently, a thermotactic habit of gas hydrate growth was proposed: the nucleation and growth would preferentially proceed towards a low temperature region to release the reaction heat. Hence through regulating the temperature and thereby the heat transfer scheme one can design the behavior and morphology of hydrate formation. Specifically, a surprisingly fast hydrate formation was observed when freezing the surfactant-containing solution prior to warming-up and pressurization. The melting ice consuming large amount of heat enabled a sequential transformation of water into hydrate tracing the thawing front. This thermotactic behavior was also consolidated in a more macroscopic process. The findings could provide new insights into the kinetics of gas hydrate formation coupling the heat-associated phase transition; the results could also be of help in the up-scale of the hydrate-based techniques where a concentrated transformation is highly required. [ABSTRACT FROM AUTHOR]

Thermal properties of gas hydrate-bearing sediments directly govern the heat transfer process during hydrate decomposition which couples with phase transitions and multiphase flows. The effective thermal conductivity of a multiphase system represents the composite capacity to conduct heat. Here we report on point heat source measurements of the effective thermal conductivity of methane hydrate-bearing sediments through a thermistor-based method combining with X-ray CT observations. Methane hydrates were formed at different saturations, with various initial water contents, and in porous matrices simulated by grains with differing thermal conductivities. It is indicated that the effective thermal conductivity of sediments negatively correlated with the hydrate saturation, while an increase of initial water contents and thermal conductivity of grains has a positive impact on the elevation of the effective thermal conductivity. Moreover, the effective thermal conductivity was found to slightly increase with the proceeding of hydrate decomposition. Typical effective medium models were evaluated with the measurements of this study, and a hybrid fitting model combining three forms of self-consistent models was proposed, with the optimal weighting parameters determined via the genetic algorithm. The effective prediction of the measurements in this work and results in literatures corroborates the feasibility of the model. This study could help in understanding the evolutions of sediment thermal properties during gas production and their effects on large-scale hydrate decomposition when expanded to field scale tests. [ABSTRACT FROM AUTHOR]

Gas hydrate is a nonstoichiometric crystal compound formed from water and gas. Most nonvisual studies on gas hydrate are unable to detect how much water is converted to hydrates, and thus, the hydrate stoichiometry calculations are inaccurate. This study investigated the CO2 hydrate formation process in porous media directly and quantitatively. The characteristics of the time‐variable consumption of hydrate formation indicated a two‐stage formation, hydrate enclathration and continuous occupancy. The enclathration stage occurred in the first 20 min of the formation when considerable heat is released. The continuous occupancy stage lasted longer than the hydrate enclathration because the empty cages in previously formed hydrates would also be occupied. The higher formation pressures can accelerate water consumption and increase cage occupancy. The compositions of completely formed CO2 hydrates at 2.7, 3.0, and 3.3 MPa and 275.15 K were determined as CO2·6.90H2O, CO2·6.70H2O, and CO2·6.49H2O, respectively. [ABSTRACT FROM AUTHOR]

[Display omitted] Gas hydrates have gained great interest in the energy and environmental field as a medium for gas storage and transport, gas separation, and carbon dioxide sequestration. The presence of small doses of surfactants in the aqueous phase has been reported to enhance hydrate formation; however, the underlying mechanisms remain poorly understood. Thus, in situ high-resolution X-ray computed tomography measurements were performed to monitor the upward water migration and the resulting hydrate nucleation and growth. It was found that the presence of hydrate crystals at the gas–liquid–solid contact line triggered the enhanced growth of hydrates on the reactor wall. A time delay was observed between the disappearance of the bulk water reservoir and its transformation into hydrate. The lower interfacial tension between the hydrate surface and the solution facilitated its adsorption onto the reactor wall once a thin film of hydrate nucleated on the solid wall surface. These hydrate layers present on the reactor wall were found to be porous, wherein the porosity decreased with increased subcooling. These fundamental results will be of value in understanding the mechanism of hydrate growth in the presence of surfactants and its potential application in hydrate-based technologies. [ABSTRACT FROM AUTHOR]

[Display omitted] • MEG alters hydrate growth pattern, preventing hydrate film formation at interface. • MEG induces loose and low-saturation hydrate in solution, followed by solidification. • MEG leads to the formation of dense surface hydrate blocks at under-inhibition. • MEG concentration below 20 % does not exhibit significant self-inhibition of hydrate formation. Natural gas hydrate blockages pose a major risk to deepwater oil and gas development. Thermodynamic under-inhibition is a cost-effective hydrate management strategy, but the impact of mono ethylene glycol (MEG) on hydrate formation kinetics and mass transfer at the gas–water interface requires further understanding for hydrate-related flow assurance. This study investigates the kinetics and morphology of hydrate growth from MEG solutions using in situ micro X-ray CT and a macro transparent reactor. MEG concentration emerged as the primary factor influencing hydrate growth morphology. Findings revealed that MEG alters the growth morphology of gas hydrates by inhibiting the formation of a hydrate film at the gas–liquid interface and inducing flocculent hydrate growth within the solution. MEG can also induce the formation of low-saturation hydrates, with no significant self-inhibition observed at concentrations below 20 %. Over time, a dense hydrate shell tended to form on the surface of the hydrate lump, increasing the risk of blockage. Additionally, it was observed that subcooling also affects the hydrate growth morphology; higher subcooling accelerates the hydrate growth rate and increases the density of the formed hydrate. This research explored the mechanisms underlying hydrate formation in under-inhibited systems, aiming to extend the safe operational boundary for oil and gas transportation and provide theoretical support for deepwater hydrate management. [ABSTRACT FROM AUTHOR]

Increasing the efficiency of gas production from marine gas hydrate still faces significant problems. Based on the geological survey of marine reservoirs, gas hydrates are generally associated with underlying free gas layers with high temperature and water saturation. Here the effect of this gas layer and its characteristics on the gas and water production from the hydrate layer are studied. It was found that a large temperature difference existed between the two layers during gas production due to the different heat demand and consumption in each layer. Slower gas production rate was observed in case of dense distribution of hydrates in the hydrate-bearing layer and the resulting sluggish gas permeation and enormous heat supply. Notably, this was not present when the free gas layer was more water-saturated. The resulting maximum gas production rate could be effectively enhanced by 41 % at most as well. This was attributed to the increased sensible heat available from the pore water and the interbedded heat exchange. It was thus indicated that a hydrate reservoir with an underlying water-rich layer could be more favorable for gas production in terms of heat supply. • Joint exploitation through pre-embedding compartment device and vertical well. • A significant temperature difference between the two layers during exploitation. • Highly water-saturated underlying shallow gas layer enhance hydrate decomposition. [ABSTRACT FROM AUTHOR]

Natural gas hydrates are a potential future energy modality with the advantages of clean burning and large resource reserves and have attracted worldwide attention. Natural gas hydrates formation and dissociation impact the skeletal structure and mechanical properties of porous media sediments. In addition, there is a synergistic effect between the migration of fine clay particles in porous media and hydrate behavior. In this study, methane hydrate was examined in-situ using a low-field nuclear magnetic resonance system in the presence of two suspensions of clay particles with different stability. The results showed that clay particles impacted methane hydrate formation and dissociation and the pore structure of porous media. Hydrate nucleated preferentially in large pores, causing them to split into smaller pores; the presence of clay particles, especially illite, improved the water conversion rate. The results indicated that water content in large pores increased after hydrate dissociation but was discontinuous among different pores. When illite was present, the distribution was more continuous; when montmorillonite was present, the water distribution of the large pores was similar to that of the original state. This work increases our understanding of the kinetics, water migration, and pore structure alteration of methane hydrate formation and dissociation in sediments with clay particles and provides support for the safe and efficient development of natural gas hydrates. • Clay particles impacted methane hydrate formation and dissociation • Hydrate nucleated preferentially in large pores • Clay particles, especially illite, improved the water conversion rate • Water content in large pores increased after hydrate dissociation but was discontinuous among different pores [ABSTRACT FROM AUTHOR]

The gas production from marine gas hydrate has always been plagued by low productivity; the complex geological environment poses a significant obstacle to its commercialization. Horizontal wells are thus getting increasing attention due to their advantages in facilitating pressure propagation. Here a pre-embedded dual horizontal well was used to probe its effects in the local temperature distribution and gas production behavior. By doubling the number of boreholes, the flow channels of gas were increased enlarging the decomposition zone. Specifically, this was found to raise the reservoir temperature from −1 °C in a single well to approximately 0 °C. The temperature decline was more moderate due to a weakened Joule-Thomson effect. Consequently, almost 90% of the cumulative gas yield was produced before the lowest temperature occurred, compared to ∼30% in the single vertical well case. This indicates that the gas production from a dual well case was proceeding at a relatively higher temperature, potentially benefitting an enhanced gas production efficiency. An enlarged depressurization region was thus suggested in the field test for a controlled temperature decline to make more use of the sensible heat of the reservoir. • Simulation of horizontal wells by the scheme of pre-embedding. • Increase the minimum temperature during gas production by the dual horizontal wells. • Multiple gas flow paths can alleviate the rapid drop in reservoir temperature. [ABSTRACT FROM AUTHOR]

Among deep-sea oil and gas transportation, kinetic inhibitors of gas hydrates are widely added in transportation pipelines to prevent gas hydrates from clogging pipelines. Unfortunately, the micro-and nano-sized clay particles will enter the wellbore to adsorb the practical components of the inhibitors, thereby weakening the inhibitory effect of the inhibitors on hydrates. This work shows that 1:1-type layered silicates can only adsorb inhibitors through the surface, while 2:1-type layered silicates can adsorb inhibitors through both surface and intercalation. The clay particles with adsorbed inhibitors tend to be aggregated and settled because the surface charge density and the potential energy between the particles are reduced. Meanwhile, the inhibitors adsorbed on the surface of the clay lose their inhibitory effect on gas hydrates. Therefore, the suppression effect of layered silicate minerals on inhibitors should be considered in clay-rich oil and gas transportation pipelines. • Inhibitory effect of different clays on polyvinyl caprolactam hydrate was studied. • The inhibitory effects were weakened in the presence of clas due to adsorption. • The inhibitor adsorption ability of 2:1 clay is stronger than that of 1:1 clay. [ABSTRACT FROM AUTHOR]

[Display omitted] • An approach of warm brine injection to promote CH 4 /CO 2 replacement is proposed. • Warm brine injection provides a 2.0 times enhancement of the cumulative gas yield. • A potential risk of hydrate reformation is alleviated by increasing salinity. • Gas production is insensitive to injected heat as the significant heat loss. • Brine injection scheme should be optimized based on energy harvest and CO 2 storage. CH 4 /CO 2 replacement for natural gas hydrates (NGHs) exploitation is a promising method for CO 2 geological sequestration and energy recovery simultaneously. However, the puzzles of low replacement efficiency and slow reaction rate caused by the mass transfer obstacle of gas exchange are fatal bottlenecks for field application of gas replacement method. Therefore, we propose a method that uses warm brine injection during CH 4 /CO 2 replacement process to break the barrier of CO 2 diffusion and enhance CH 4 recovery as well as CO 2 storage. Benefiting from the synergistic influence of salt effect and thermal stimulation as well as water flow erosion, warm brine injection provides three dimensionally connected channels in hydrate for subsequent mass transfer, improving CH 4 /CO 2 replacement in the deep layer of hydrate. CO 2 sequestration efficiency of the newly proposed method reaches 76.46%, and the maximum amounts of CH 4 recovery is nearly treble than that achieved by single CO 2 replacement method. Notably, a potential risk of secondary hydrate formation could occur upon the pressure surge and fluid migration attached to warm brine injection, which could be effectively alleviated by increasing salinity to destabilize hydrate lattices by reducing water activity. The gas production is insensitive to the injected heat as the significant heat loss during the transportation of injected brine in pipelines and thermal diffusion through boundaries. The introduction of free water increases the complexity of the reactions in hydrate reservoirs, and the formulation of brine injection regimes should be synergistically optimized based on energy harvest, energy efficiency and CO 2 sequestration. This work extends the previous knowledge on CH 4 /CO 2 replacement and shows important practical significance for future field studies of NGHs exploitation and CO 2 geological sequestration. [ABSTRACT FROM AUTHOR]

• Presence of fine particle could block the pores and hinder gas production. • Water content determines the behavior of fine particle aggregation. • Distribution pattern of fine particles directly affects the gas production efficiency. Natural gas hydrates are widely distributed in silty marine sediments containing fine particles less than 75 μm in size. The effects of WC (water content) on the behavior of fine particle migration and their role in gas and water production do not appear well understood. This work found that the WC slightly affected the gas production pattern in uniform sandy reservoirs. Yet upon a mixture of coarse and fine particles, the fine particles would instantly aggregate at the nearby pore throat reducing the reservoir permeability and prolonging the production by more than 3 times. Surprisingly, 16% of the fine particles at the edge and 19% at the middle were found to migrate with the fluid flow upon increasing water content, resulting in a less hindered initial gas production but a following more complete blockage or even production failure. This behavior can be consolidated in the scenario of a sand-kaolin mixture. The findings could provide new knowledge on the particle migration behavior upon gas and especially water production and guide the strategy design on dealing with the sand problem in the field test. [ABSTRACT FROM AUTHOR]

• The long-term joint production from hydrate and shallow gas layer provides a 4.1 times enhancement of the cumulative gas yield. • The regulated layer-dependent scheme effectively alleviated the interbedded pressure difference by ∼70%, avoiding the interlayer instability. • An energy return on investment (EROI) analysis was carried out to evaluated the optimized joint production method. Recent field tests to recover natural gas from marine gas hydrate reservoirs in Japan and China have exhibited worldwide attention to this strategic energy form; significant challenges still remain in improving the accumulative gas yield for a better economic efficiency. According to the geological survey in marine hydrate reservoirs, there exists a concomitant free gas layer underlying the gas hydrate reservoir. Consequently, here we propose a new scheme to jointly produce the gases from hydrate layer and its underlying shallow gas layer. It was found that a dual horizontal well deployment respectively in the corresponding two layers could contribute to a 4.1 times cumulative gas yield comparing that of a single vertical well scenario. This implies a remarkable enhancement of gas productivity via making full use of the gases in the shallow gas layer. Notably, a potential risk of interlayer failure could occur upon the great interbedded pressure difference (maximum 10.7 MPa) arising from the varying behavior of pressure propagation in the layers. This can be effectively alleviated by separately controlling the depressurization scheme in different layers; a mild step-wise depressurization was suggested in the more permeable shallow gas layer while the hydrate layer with a lower permeability should experience a sharper pressure drop. This was found beneficial reducing the interbedded pressure difference by about 70% without intervening the gas production. An energy return on investment (EROI) analysis showed a promising positive energy harvest of our optimized layer-dependent pressure scheme. It could be therefore a potential method to be applied in the field tests in the South China Sea to improve the economic efficiency without disturbing the reservoir stability. [ABSTRACT FROM AUTHOR]

• 3D morphologies and time-dependent parameters of the hydrate shell are obtained. • Water is more mobile than gas in hydrates in the diffusion-controlled growth stage. • Protrusions growth on the outer surface of a hydrate shell is due to water permeation. • Effective diffusion coefficients of gas and water in hydrate are determined. Understanding the transport properties of water and guest molecules in dense hydrate structures is pivotal in controlling their formation and stability; this is nevertheless hindered by challenges in characterizing the time-varying diffusion and permeation process. This paper reports experimental results on the mass-transfer characteristics of water and guest molecules across hydrate shells during their formation from water droplets. The time-dependent 3D morphologies and parameters of hydrate shells were in-situ obtained via X-ray computed tomography to reveal the transport mechanism in hydrates. It was found that in the mass-transfer-limited stage, hydrate growth occurred primarily at the hydrate-gas interface, indicating a more mobile characteristic of water molecules in those hydrate shells than gas. The resulting outward permeation of water led to the growth of hydrate protrusions on the outer surface of the hydrate shell, suggesting a transition of the water transport schema through the hydrate shell from diffusion to permeation. Consequently, a diffusion-based shell growth model was developed to quantify the diffusivity of gas and water molecules in hydrates. Combining the measurements in the temperature range of 275.15–283.15 K, the effective diffusion coefficient of gas through the hydrates was estimated to be in the range of 1.34 × 10−14 − 1.90 × 10−13 m2/s, with that of interstitial water in the range of 2.87 × 10−12 − 3.83 × 10−11 m2/s. These results are of fundamental value in developing an improved understanding of the kinetics of hydrate formation from gas-water interfaces, which is essential in the optimization of hydrate-based techniques. [ABSTRACT FROM AUTHOR]

• Metabolic molecules significantly promote hydrate formation. • Protein macromolecules could act as kinetic inhibitor of hydrate nucleation. • Water in the macropores is preferentially consumed during hydrate formation. Numerous efforts have been made to mimic the natural marine environments to understand the behavior of hydrate formation and accumulation in the sediments under seafloor. Yet it is found that the role of organic matters in the kinetics of hydrate formation is largely veiled, which should be much enriched as a result of the activities of the marine ecosystem. Therefore in this study, the kinetic effects of protein macromolecules and metabolic small molecules on CH 4 hydrate formation were examined; the organic compounds were extracted from the samples gathered from the hydrate reservoir located in the South China Sea. A total of 2058 species classified into 10 types of protein macromolecules and metabolic molecules were identified. Low-field nuclear magnetic resonance technique was used to in-situ monitor the hydrate formation process. The results showed that the metabolic molecules could remarkably promote hydrate formation, with more water converted into hydrate within a shorter time. Proteins have been widely studied to inhibit hydrate formation; here it is for the first time confirmed that the proteins extracted from the natural samples drilled in the hydrate reservoir could act as kinetic inhibitor, lowering the possibility of hydrate nucleation. It was further indicated that hydrate formation majorly consumed the water in the macro pores; this was followed by a diffusion-limitation process with the hydrate shell acting as mass transfer barrier slowing down the water conversion. The water in the micropores was yet found to be very difficult to participate in the reaction, potentially resulting from the unavailable gas-water contact. The findings could provide insights into the kinetics of hydrate formation in the presence of organic matters abundant in natural sediments and expand the current understandings on the occurrence of natural gas hydrate under marine environments. [ABSTRACT FROM AUTHOR]