Review of natural gas hydrates as an energy resource: Prospects and challenges ☆

[1] Methane gas hydrates, crystalline inclusion compounds formed from methane and water, are found in marine continental margin and permafrost sediments worldwide. This article reviews the current understanding of phenomena involved in gas hydrate formation and the physical properties of hydrate-bearing sediments. Formation phenomena include pore-scale habit, solubility, spatial variability, and host sediment aggregate properties. Physical properties include thermal properties, permeability, electrical conductivity and permittivity, small-strain elastic P and S wave velocities, shear strength, and volume changes resulting from hydrate dissociation. The magnitudes and interdependencies of these properties are critically important for predicting and quantifying macroscale responses of hydrate-bearing sediments to changes in mechanical, thermal, or chemical boundary conditions. These predictions are vital for mitigating borehole, local, and regional slope stability hazards; optimizing recovery techniques for extracting methane from hydrate-bearing sediments or sequestering carbon dioxide in gas hydrate; and evaluating the role of gas hydrate in the global carbon cycle.

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Physical properties of hydrate-bearing sediments

[1] Review of the literature reveals that the nature of pore-scale interactions between gas hydrates and porous media remains a matter of controversy. To clarify the situation, nuclear magnetic resonance (NMR) measurements have been made on methane hydrate-bearing sandstones. The samples were synthetically prepared within the gas hydrate stability zone, at or near the seafloor in Monterey Bay, California. The method simulated natural hydrate deposition by gas flows that are not in thermodynamic equilibrium with the surrounding earth. The efficiency of hydrate production was variable, as has been observed elsewhere. When substantial hydrate saturations were achieved, NMR relaxation time measurements indicated that hydrate tended to replace water in the largest pore spaces. The relative permeability to water, as determined by an NMR-based correlation, was significantly reduced. The magnitude of this reduction was also consistent with formation of hydrate in the centers of pores, rather than with hydrate coating the grains. The growth habit suggested by these results is consistent with creation of hydrate nodules and lenses in coarse, unconsolidated sediments. It is also consistent with scenarios in which methane gas is delivered efficiently to the atmosphere as a result of seafloor slope failure, thereby strengthening global warming feedback mechanisms.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2003JB002389

Deep sea NMR: Methane hydrate growth habit in porous media and its relationship to hydraulic permeability, deposit accumulation, and submarine slope stability

Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties.

Fundamentals and Applications of Gas Hydrates

[1] The mechanical behavior of hydrate-bearing sediments subjected to large strains has relevance for the stability of the seafloor and submarine slopes, drilling and coring operations, and the analysis of certain small-strain properties of these sediments (for example, seismic velocities). This study reports on the results of comprehensive axial compression triaxial tests conducted at up to 1 MPa confining pressure on sand, crushed silt, precipitated silt, and clay specimens with closely controlled concentrations of synthetic hydrate. The results show that the stress-strain behavior of hydrate-bearing sediments is a complex function of particle size, confining pressure, and hydrate concentration. The mechanical properties of hydrate-bearing sediments at low hydrate concentration (probably 50% of pore space), the behaviorbecomesmoreindependentofstressbecausethehydratescontrolbothstiffnessand strength and possibly the dilative tendency of sediments by effectively increasing interparticle coordination, cementing particles together, and filling the pore space. The cementation contribution to the shear strength of hydrate-bearing sediments decreases with increasing specific surface of soil minerals. The lower the effective confining stress, the greater the impact of hydrate formation on normalized strength.

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Mechanical properties of sand, silt, and clay containing tetrahydrofuran hydrate

We offer a first-principle-based effective medium model for elastic-wave velocity in unconsolidated, high porosity, ocean bottom sediments containing gas hydrate. The dry sediment frame elastic constants depend on porosity, elastic moduli of the solid phase, and effective pressure. Elastic moduli of saturated sediment are calculated from those of the dry frame using Gassmann's equation. To model the effect of gas hydrate on sediment elastic moduli we use two separate assumptions: (a) hydrate modifies the pore fluid elastic properties without affecting the frame; (b) hydrate becomes a component of the solid phase, modifying the elasticity of the frame. The goal of the modeling is to predict the amount of hydrate in sediments from sonic or seismic velocity data. We apply the model to sonic and VSP data from ODP Hole 995 and obtain hydrate concentration estimates from assumption (b) consistent with estimates obtained from resistivity, chlorinity and evolved gas data.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/1999GL900421

Elastic‐wave velocity in marine sediments with gas hydrates: Effective medium modeling

[1] We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, sI methane hydrate, and sII methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from −20 to −5°C and 22.4 to 32.8 MPa for ice Ih, −20 to 15°C and 30.5 to 97.7 MPa for sI methane hydrate, and −20 to 10°C and 30.5 to 91.6 MPa for sII methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2008JB006132

Elastic wave speeds and moduli in polycrystalline ice Ih, sI methane hydrate, and sII methane-ethane hydrate

Estimating the in situ methane hydrate volume from seismic surveys requires knowledge of the rock physics relations between wave speeds and elastic moduli in hydrate/sediment mixtures. The elastic moduli of hydrate/sediment mixtures depend on the elastic properties of the individual sedimentary particles and the manner in which they are arranged. In this chapter, we present some rock physics data currently available from literature. The unreferenced values in Table I were not measured directly, but were derived from other values in Tables I and II using standard relationships between elastic properties for homogeneous, isotropic material. These derivations allow us to extend the list of physical property estimates, but at the expense of introducing uncertainties due to combining property values measured under different physical conditions. This is most apparent in the case of structure II (sII) hydrate for which very few physical properties have been measured under identical conditions.

Introduction to Physical Properties and Elasticity Models

Simultaneous measurements of compressional and shear wave speeds through polycrystalline methane hydrate have been made. Methane hydrate, grown directly in a wave speed measurement chamber, was uniaxially compacted to a final porosity below 2%. At 277 K, the compacted material had a compressional wave speed of 3,650 ± 50 m/s. The shear wave speed, measured simultaneously, was 1,890 ± 30 m/s. From these wave speed measurements, we derive Vp/Vs, Poisson's ratio, bulk, shear, and Young's moduli.

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Laboratory Measurements of Compressional and Shear Wave Speeds through Methane Hydrate

Simultaneous measurements of compressional and shear wave speeds through polycrystalline methane hydrate have been made. Methane hydrate, grown directly in a wave speed measurement chamber, was uniaxially compacted to a final porosity below 2%. At 277 K, the compacted material's compressional wave speed was 3650 {+-} 50 m/s. The shear wave speed, measured simultaneously, was 1890 {+-} 30 m/s. From these wave speed measurements, we derive Vp/Vs, Poisson's Ratio, bulk, shear and Young's moduli.

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M. B. Helgerud

Papers

Elastic‐wave velocity in marine sediments with gas hydrates: Effective medium modeling

Elastic wave speeds and moduli in polycrystalline ice Ih, sI methane hydrate, and sII methane-ethane hydrate

Introduction to Physical Properties and Elasticity Models

Laboratory Measurements of Compressional and Shear Wave Speeds through Methane Hydrate

Laboratory measurements of compressional and shear wave speeds through methane hydrate