Hydrate Pore Habits Research Articles

Maximum Sizes of Fluid-Occupied Pores within Hydrate-Bearing Porous Media Composed of Different Host Particles

Hydraulic properties of hydrate-bearing sediments are largely affected by the maximum size of pores occupied by fluids. However, effects of host particle properties on the maximum size of fluid-occupied pores within hydrate-bearing sediments remain elusive, and differences in the maximum equivalent, incircle, and hydraulic diameters of fluid-occupied pores evolving with hydrate saturation have not been well understood. In this study, numerical simulations of grain-coating and pore-filling hydrate nucleation and growth within different artificial porous media are performed to quantify the maximum equivalent, incircle, and hydraulic diameters of fluid-occupied pores during hydrate formation, and how maximum diameters of fluid-occupied pores change with hydrate saturation is analyzed. Then, theoretical models of geometry factors for incircle and hydraulic diameters are proposed based on fractal theory, and variations of fluid-occupied pore shapes during hydrate formation are discussed. Results show that host particle properties have obvious effects on the intrinsic maximum diameters of fluid-occupied pores and introduce discrepancies in evolutions of the maximum pore diameters during hydrate formation. Pore-filling hydrates reduce the maximum incircle and hydraulic diameters of fluid-occupied pores much more significantly than grain-coating hydrates; however, hydrate pore habits have minor effects on the maximum equivalent diameter reduction. Shapes of fluid-occupied pores change little due to the presence of grain-coating hydrates, but pore-filling hydrates lead to much fibrous shapes of fluid-occupied pores.

Four-Dimensional Dynamic Synchrotron Microcomputed Tomography Imaging of Gas-Water Interface at High Pressure and Low Temperature

It is challenging to separate water from gas phases in computed tomography images of three-phase granular materials because water and most gases have close attenuation coefficients for x-ray. This article presents two techniques for three-dimensional (3D) imaging using synchrotron microcomputed tomography (SMT). Monochromatic x-ray beam that can be tuned for a specific energy level was used for a dual energy SMT that takes advantage of a sudden change in attenuation at the absorption edge of iodine. A solution of 4 % by weight potassium iodide (KI) and distilled water was used as a doping agent to saturate a column of sand as a test sample. The article focuses on how the technique was employed to image a column of sand as the degree of saturation changes. Water and air were separated easily, and the degree of saturation was calculated for the sand column at different drainage conditions. The article also presents a description of a high-pressure, low-temperature flow cell suitable for SMT imaging for dynamic monitoring of gas hydrate formation and dissociation. High photon flux beam (pink beam) enabled fast 4D imaging (3D plus time) of xenon gas hydrate formation. Hydrate specific area increased initially with increasing hydrate saturation and began to decrease after a threshold, which is evidence of Ostwald Ripening. For hydrate saturation less than 10 %, the predominant pore-habit was surface coating. Cementing pore-habit was observed at 15 % hydrate saturation, and pore-filling hydrate pore-habit was observed with further increase in hydrate saturation.

Simultaneous measurement of water permeability and methane hydrate pore habit using a two-dimensional glass micromodel

In this study, we developed an in situ chamber to measure water permeability as a function of the methane hydrate (MH) habit in pore space using a two-dimensional glass micromodel by adding a methane-dissolved water source unit to prevent MH dissociation. This unit enabled us to adjust the amount of methane dissolved in the water by controlling the pressure and temperature. We simultaneously observed MH crystallization behavior and measured the water permeability of the porous media. The growth rate of MH and the pore habit formation changed with subcooling, ΔT. As ΔT increased, the shape of the pattern transformed from a hexagonal plate to a dendrite and hexagonal plate, and finally, to a dendrite. The glass pillar played a role in inhibiting the growth of dendritic patterns. The plugging process of the porous media following MH formation was also observed. We compared our results with various water permeability models of MH sediments and found that the nonempirical relative permeability (NRP) models showed relatively good agreement. This was likely because the NRP models enhanced the effect of the gas phase. However, a gap remains between the NRP model predictions and our experimental results. On the other hand, there was no possibility of agreement other than the NRP models because the gas phase was not included in the equation.

Pore-scale evidence of ion exclusion during methane hydrate growth and evolution of hydrate pore-habit in sandy sediments

Hydrate-bearing sediments constitute complex hydrological systems, within which the pore habit of hydrate significantly affects all physical properties. However, there is scarce pore-scale evidence of the evolution of hydrate growth in porous media and the influence of water salinity in the micro-morphology of hydrate. In this paper, we used X-ray computed micro-tomography (CT) to monitor three experiments of methane hydrate growth in sand partially saturated with either NaBr or KI brine under excess-gas conditions. Gas, brine and hydrate are observed to co-exist at the pore-scale during the evolution of hydrate pore-habit towards three-phase equilibrium. The experiments and data analysis reveal that (1) hydrate forms as a porous medium mixed with inclusions of brine and gas, where hydrate and brine evolve gradually into separate phases as hydrate cages exclude salt ions, (2) hydrate growth mobilizes water over fairly long distances resulting in heterogeneous hydrate distribution, and (3) hydrate can exhibit interconnecting pore-habit at local hydrate saturations higher than ~50%, even if grown under excess-gas conditions. The results imply that hydrate micro-morphology and pore habit evolve during hydrate formation and, we suggest, so do the physical properties of hydrate-bearing sediments. Our findings provide new insights into the micro-morphology of hydrate and evolution of the properties of hydrate-bearing sediments synthesized in the laboratory and in natural systems.

Methane hydrate-bearing sediments: Pore habit and implications

Abstract Hydrate-bearing sediments are relevant to the organic carbon cycle, seafloor instability, and as a potential energy resource. Sediment characteristics affect hydrate formation, gas migration and recovery strategies. We combine the physics of granular materials with robust compaction models to estimate effective stress and capillary pressure in order to anticipate the pore habit of methane hydrates as a function of the sediment characteristics and depth. Then, we compare these results to an extensive database of worldwide hydrate accumulations compiled from published studies. Results highlight the critical role of fines on sediments mechanical and flow properties, hydrate pore habit and potential production strategies. The vast majority of hydrate accumulations (92% of the sites) are found in fines-controlled sediments at a vertical effective stress between σ′z = 400 kPa and 4 MPa, where grain-displacive hydrate pore habit prevails in the form of segregated lenses and nodules. While permeation-based gas recovery by depressurization is favored in clean-coarse sediments, gas recovery from fines-controlled sediments could benefit from enhanced transmissivity along gas-driven fractures created by thermal stimulation.

3D measurements of hydrate surface area during hydrate dissociation in porous media using dynamic 3D imaging

A better understanding of the kinetics of hydrate dissociation is essential to reliably predict gas production potential from natural hydrate reservoirs. Most hydrate dissociation models assume hydrates to be a constant number of equal-sized spheres dissociating at a constant rate. This paper uses dynamic 3D synchrotron micro-computed tomography (SMT) imaging to study hydrate surface area evolution during Xenon hydrate dissociation. Hydrates are formed inside a high-pressure low-temperature cell filled with partially saturated ASTM 20-30 Ottawa sand. Hydrate dissociation is initiated through depressurization in the first experiment and through thermal stimulation in the second experiment. During dissociation, continuous full 3D SMT images were acquired where each scan took 45 s to complete. A combination of cementing, pore-filling, and surface coating pore habits were observed for the depressurization experiment and pore-filling for the thermal stimulation experiment. Surface coating hydrates dissociate faster than hydrates with pore-filling pore habit due to the higher specific area which allows for more surface for hydrates to dissociate it. Direct measurements of hydrate volume and hydrate surface area suggest that even with a combination of hydrate pore habits formed within the 3D porous media, estimation of hydrate surface area as a linear relation with (hydrate volume)2/3 is best for hydrate saturation less than a threshold value depending on the dissociation method and driving force. (hydrate volume)2 and (hydrate volume)3 were found to better estimate hydrate interfacial area in comparison to (hydrate volume)2/3 for the depressurization experiment and thermal stimulation experiment, respectively.

Dynamic 3D imaging of gas hydrate kinetics using synchrotron computed tomography

The availability of natural gas hydrates and the continuing increase in energy demand, motivated researchers to consider gas hydrates as a future source of energy. Fundamental understanding of hydrate dissociation kinetics is essential to improve techniques of gas production from natural hydrates reservoirs. During hydrate dissociation, bonds between water (host molecules) and gas (guest molecules) break and free gas is released. This paper investigates the evolution of hydrate surface area, pore habit, and tortuosity using in-situ imaging of Xenon (Xe) hydrate formation and dissociation in porous media with dynamic three-dimensional synchrotron microcomputed tomography (SMT). Xe hydrate was formed inside a high- pressure, low-temperature cell and then dissociated by thermal stimulation. During formation and dissociation, full 3D SMT scans were acquired continuously and reconstructed into 3D volume images. Each scan took only 45 seconds to complete, and a total of 60 scans were acquired. Hydrate volume and surface area evolution were directly measured from the SMT scans. At low hydrate saturation, the predominant pore habit was surface coating, while the predominant pore habit at high hydrate saturation was pore filling. A second-degree polynomial can be used to predict variation of tortuosity with hydrate saturation with an R2 value of 0.997.

Hydrate growth in quartzitic sands and implication of pore fractal characteristics to hydraulic, mechanical, and electrical properties of hydrate-bearing sediments

Gas hydrate pore habits significantly impact the pore-scale structure within hydrate-bearing sediments, and thus, play a central role in the physical property evolution. Characterization and quantification of the effective pore space within hydrate-bearing sediments at different hydrate saturations have not been well offered. This study performs random simulations of hydrate nucleation and growth in quartzitic sands to understand effects of hydrate saturation and hydrate pore habits on fractal characteristics of the effective pore space. Normalized pore-size fractal dimension and normalized maximal pore diameter are characterized and found to decrease with increasing hydrate saturation. In order to predict hydrate saturation dependent pore fractal characteristics, theoretical and empirical models are proposed and further extended to give implications to hydraulic, mechanical, and electrical properties of hydrate-bearing sediments during hydrate dissociation. Implications include that hydrate dissociation facilitates the absolute permeability and the electrical conductivity, and enhances first and then reduces the saturation exponent of Archie's law; hydrate dissociation also lowers the capillary pressure, and this promotes relative permeability to gas but inhibits relative permeability to water even the water saturation remains as a constant; shear strength of unsaturated hydrate-bearing sediments drops down due to the decreasing capillary pressure as hydrate dissociation. These implications all meet with conclusions in previous literatures.

Pore habit of methane hydrate and its evolution in sediment matrix – Laboratory visualization with phase-contrast micro-CT

Abstract Describing the pore habit of methane hydrate in sediment matrices is essential for understanding natural distribution of methane hydrate, methane trace (transport and solidification) in the hydrate stability zone, physical properties of hydrate-bearing sediments, and the associated influence on potential gas production. Pore habit visualization in natural media at pore scale even with laboratory synthesized cores has been challenging due to the similar densities of methane hydrate from pore liquid. In this work, we used phase-contrast assisted micro-CT with potassium iodine-doped brine to visualize four phases: sand particles, pore fluid, methane hydrate and methane gas. This study visualizes the pore habit of methane hydrate at various stages including during hydrate formation in excess-gas systems, its evolution after brine injection to replace pore fluid, and hydrate formation in excess-water systems. Hydrate tends to adopt round and smooth surfaces when in contact with water while exhibits relatively angular interfaces when in contact with methane gas. Hydrate formation in excess-gas systems results in a partial cementing and partial mineral-coating pore habit, while hydrate in excess-water systems develops mainly as pore-filling, and locally cementing or mineral-coating where big gas pockets exist at the initial state. Pore liquid replacement from methane gas to brine triggers a shift of hydrate pore habit towards pore-filling. Methane hydrate evolution over time produces bigger hydrate particles but with less contact area with sand particles. The effects of hydrate pore habit become less important as hydrate particle size exceeds the pore size. Additionally, hydrate formation could trap residual methane gas and brine as inclusions.

Multistage Triaxial Tests on Laboratory‐Formed Methane Hydrate‐Bearing Sediments

AbstractA sound understanding of the geomechanical behavior of hydrate‐bearing sediments (HBSs) is essential not only for assessing reservoir and wellbore stability during methane gas production but also for projecting the impact of global warming on the stability of geological settings that contain hydrates. This study experimentally investigated the geomechanical responses of laboratory‐formed methane‐HBS to triaxial shearing under drained conditions. The hydrate pore habit formed in the sediments is noncontact‐cementing, which is different from contact‐cementing or grain‐coating hydrate pore habits formed when the excessive gas method is used. The multistage triaxial test method, which shears a single specimen under different confinements, was employed to examine its applicability in measuring geomechanical properties of the HBS. Conventional single‐stage triaxial tests were also performed to serve as baselines. The results show that both the strength and stiffness of HBS increase with increased hydrate saturation and confining stress. Shear dilatancy increases with increased hydrate saturation and decreased confining stress. The peak strength and peak/postpeak shear dilation measured using the multistage tests are comparable to those using the single‐stage tests. However, the stiffness measured in later stress stages in the multistage tests was enhanced by the stress‐strain history of earlier stages. Therefore, the multistage test offers an efficient way of measuring the strength and volumetric response of the HBS with a much smaller number of specimens than the single‐stage test. This benefits the geomechanical characterization of the HBS, as obtaining the pressure cores is extremely costly and preparing lab samples is usually sophisticated and time consuming.

Ostwald ripening changes the pore habit and spatial variability of clathrate hydrate

Clathrate hydrate is a solid crystalline compound that consists of water cages with trapped gas molecules. Methane hydrate in permafrost and marine sediments is estimated to contain 2 × 103 to 4 × 106 Gt of carbon, which makes it both a potential energy source and a liability to global warming. The transport and mechanical properties of hydrate bearing sediments (HBS), and therefore hydrate dissociation through depressurization, thermal stimulation, or CO2 injection, depend on hydrate pore habit and spatial distribution in sediments. However, the evolution of hydrate pore habit and spatial distribution in HBS are not well understood yet. Here we show experimental evidence of Ostwald ripening of gas hydrate crystals in pores and porous media. We find that (1) hydrate growth rate (under nearly isothermal conditions) versus the degree of overpressurization fits an Arrhenius-type equation, and (2) Ostwald ripening gradually changes hydrate pore habit from grain-attaching to pore-filling and increases hydrate saturation heterogeneity at both pore and core scales. The latter ultimately creates significant spatial variations of permeability and sediment strength. Our results provide insights into kinetics and pore-scale physics that determine the geophysical signature from HBS at various scales. Based on our findings of hydrate occurrence in both gas and gas-water interface, we argue that hydrate growth in natural HBS is not limited to the water liquid phase. Our observation of hydrate pore habit alteration by Ostwald ripening explains patchy saturation and heterogeneous distribution of hydrate in natural HBS, which gives physical insight to improve geophysical hydrate models in porous media.

Water permeability in hydrate‐bearing sediments: A pore‐scale study

AbstractPermeability is a critical parameter governing methane flux and fluid flow in hydrate‐bearing sediments; however, limited valid data are available due to experimental challenges. Here we investigate the relationship between apparent water permeability (k′) and hydrate saturation (Sh), accounting for hydrate pore‐scale growth habit and meso‐scale heterogeneity. Results from capillary tube models rely on cross‐sectional tube shapes and hydrate pore habits, thus are appropriate only for sediments with uniform hydrate distribution and known hydrate pore character. Given our pore network modeling results showing that accumulating hydrate in sediments decreases sediment porosity and increases hydraulic tortuosity, we propose a modified Kozeny‐Carman model to characterize water permeability in hydrate‐bearing sediments. This model agrees well with experimental results and can be easily implemented in reservoir simulators with no empirical variables other than Sh. Results are also relevant to flow through other natural sediments that undergo diagenesis, salt precipitation, or bio‐clogging.

Hydrate formation and growth in pores

Gas hydrates consist of guest gas molecules encaged in water cages. Methane hydrate forms in marine and permafrost sediments. In this study, we use optical, mechanical and electrical measurements to monitor hydrate formation and growth in small pores to better understand the hydrate pore habit in hydrate-bearing sediments. Hydrate formation in capillary tubes exposes the complex and dynamic interactions between nucleation, gas diffusion and gas solubility. The observation of hydrate growth in a droplet between transparent plates shows that the hydrate shell does not grow homogeneously but advances in the form of lobes that invade the water phase; in fact, the hydrate shell must be discontinuous and possibly cracked to justify the relatively fast growth rates observed in these experiments. Volume expansion during hydrate formation causes water to flow out of menisci; expelled water either spreads on the surface of water-wet substrates and forms a thin hydrate sheet, or remains next to menisci when substrates are oil-wet. Hydrate formation is accompanied by ion exclusion, yet, there is an overall increase in electrical resistance during hydrate formation. Hydrate growth may become salt-limited in trapped water conditions; in this case, aqueous brine and gas CH4 may be separated by hydrate and the three-phase system remains stable within the pore space of sediments.