Yusuke Jin

Experimental evaluation of the gas recovery factor of methane hydrate in sandy sediment

Gas production tests have been conducted on artificial sandy sediments saturated by methane hydrate and water using a unique apparatus referred to as High-pressure Giant Unit for Methane-hydrate Analyses (HiGUMA), which is the worlds largest reservoir simulating vessel intended for gas hydrate analysis. The gas recovery factor was investigated at various depressurization schemes, including one-step depressurization, multistep depressurization, and depressurization below the quadruple point of methane hydrate. The gas production rate increased during the depressurization process with sediment temperature reduction; however, the rate decrease and stabilized at a very low level after the temperature reached a newly established equilibrium condition. This result indicates that an appropriate heat of the hydrate-bearing sediments is a crucial factor for driving hydrate dissociation. The potential economic recovery factor was 14% for 4.6 MPa of production pressure in the one-step depressurization. In the multistep depressurization, the recovery factor was increased with a reduction in production pressure and showed values of 13%, 31%, and 40% for 4.0 MPa, 3.1 MPa, and 2.5 MPa, respectively. However, depressurization above the quadruple point could not dissociate all the existing hydrate due to the lack of heat. In contrast, it was determined that 65% of the in-place methane could be produced when the production pressure was decreased to 2.1 MPa, which is below the quadruple point, because the latent heat of ice formation was efficiently used for hydrate dissociation. The results show that intentional ice formation by adjusting production pressure can potentially enhance methane hydrate recovery at a comparable level of conventional natural gas production.

Near-infrared spectroscopic study of water at high temperatures and pressures

Near-infrared absorption of the OH stretching overtone transition of water has been measured at temperatures and pressures in the ranges of 373–673 K and 20–400 bar, respectively. The absorption profile at 673 K and 400 bar retains a mark of rotational structure, indicating that an appreciable proportion of water molecules can rotate quite freely. The molar absorption intensity decreases linearly with increasing pressure in the low-pressure region. Enthalpy for dimerization has been estimated to be 15±3 kJ/mol from the temperature dependence of the slopes. Plots of the molar absorption intensity against molar concentration are observed to be located on a single curve irrespective of the temperature. This fact indicates that the ratio of hydrogen-bond formation is largely dependent on the molar density only. A good correlation between the molar absorption intensity and the first moments of the band has been found out; this will be useful in the study of aqueous mixtures.

Structural investigation of methane hydrate sediments by microfocus X-ray computed tomography technique under high-pressure conditions

The structure of natural gas hydrate sediments was observed by microfocus X-ray computed tomography (CT). A newly developed high-pressure vessel for the microfocus X-ray CT system was applied to observe the sediments at a temperature above 273 K and under high-pressure conditions. The obtained two-dimensional CT images clearly showed the spatial distribution of the free-gas pore, sand particles, water, and hydrates. These results demonstrated that microfocus X-ray CT can be effective for studying natural gas hydrate sediment samples.

New Method of Assessing Absolute Permeability of Natural Methane Hydrate Sediments by Microfocus X-ray Computed Tomography

The structure of natural-gas hydrate sediments was studied using a microfocus X-ray computed-tomography (CT) system. The free-gas spaces, sand particles, and hydrates or ices were identified from the obtained three-dimensional (3-D) images. We used CT data to analyze a continuous pore, which allows gas and water flow. The absolute permeability of sediment samples correlated well with horizontal-channel density in terms of direction. The grain-size distribution in sediment samples depended on the spread of flow channels. The average area and length of a channel evidently have little effect on absolute permeability. We determined that absolute permeability increased with the ratio of horizontal- to vertical-channel numbers. It was clear that the number ratio of the horizontal to vertical channels is a predominant factor that determines absolute permeability in similar porosity ranges. These results indicate that the pore network in sediments can be useful for assessing permeability.

Multiple-pressure-tapped core holder combined with X-ray computed tomography scanning for gas–water permeability measurements of methane-hydrate-bearing sediments

We present a novel setup for measuring the effective gas-water permeability of methane-hydrate-bearing sediments. We developed a core holder with multiple pressure taps for measuring the pressure gradient of the gas and water phases. The gas-water flooding process was simultaneously detected using an X-ray computed tomography scanner. We successfully measured the effective gas-water permeability of an artificial sandy core with methane hydrate during the gas-water flooding test.

Competitive formation of 10- and 7-membered hydrogen-bonded rings of proline-containing model peptides

Intramolecularly hydrogen-bonded structures of proline-containing model peptides with a sequence of N-tert-butoxycarbonyl-prolyl-Xaa-NHCH3 [Xaa = Gly (glycyl), Ala (alanyl), Phe (phenylalanyl), Leu (leucyl), Ile (isoleucyl), and Val (valyl)] were studied by proton nuclear magnetic resonance and infrared spectroscopy. Variation of chemical shifts of amide protons with composition change of DMSO-d6/CDCl3 mixed solvents were found to be a good measure of intramolecular hydrogen bonding of peptides in CDCl3 solution. It has been shown that 10- and 7-membered hydrogen-bonded rings, which should have the beta- and gamma-turn like structures in proteins, respectively, form competitively with each other. It is suggested that the equilibrium between the two hydrogen-bonded rings is determined by steric hindrance due to a side chain of the Xaa residue. Free energies for formation of the 10- and 7-membered hydrogen-bonded rings, deltaG10 and deltaG7, were estimated from the solvent composition-dependent change of the chemical shifts. A good correlation between deltaG10 and the occurrence frequencies of residues Xaa at the (i + 2)th position for the beta-turns in proteins has been found.

Strengthening mechanism of cemented hydrate‐bearing sand at microscales

On the basis of hypothetical particle-level mechanisms, several constitutive models of hydrate-bearing sediments have been proposed previously for gas production. However, to the best of our knowledge, the microstructural large-strain behaviors of hydrate-bearing sediments have not been reported to date because of the experimental challenges posed by the high-pressure and low-temperature testing conditions. Herein, a novel microtriaxial testing apparatus was developed, and the mechanical large-strain behavior of hydrate-bearing sediments with various hydrate saturation values (Sh = 0%, 39%, and 62%) was analyzed using microfocus X-ray computed tomography. Patchy hydrates were observed in the sediments at Sh = 39%. The obtained stress-strain relationships indicated strengthening with increasing hydrate saturation and a brittle failure mode of the hydrate-bearing sand. Localized deformations were quantified via image processing at the submillimeter and micrometer scale. Shear planes and particle deformation and/or rotation were detected, and the shear band thickness decreased with increasing hydrate saturation.

On the water dimer contribution to the OH stretching absorption band profile in pressurized water vapour

The present paper considers the density effect on the water vapour absorption profile in the OH stretch range. The density evolution of the water vapour OH fundamental band shape is interpreted in terms of the monomer–dimer equilibrium. In contrast to previous works we adopt experimental values for the frequencies and IR intensities of the dimer vibrations in the vicinity of 3µm. This made it possible to reduce the number of unknown parameters required in the course of our spectral fit.

Pressurized subsampling system for pressured gas-hydrate-bearing sediment: Microscale imaging using X-ray computed tomography

A pressurized subsampling system was developed for pressured gas hydrate (GH)-bearing sediments, which have been stored under pressure. The system subsamples small amounts of GH sediments from cores (approximately 50 mm in diameter and 300 mm in height) without pressure release to atmospheric conditions. The maximum size of the subsamples is 12.5 mm in diameter and 20 mm in height. Moreover, our system transfers the subsample into a pressure vessel, and seals the pressure vessel by screwing in a plug under hydraulic pressure conditions. In this study, we demonstrated pressurized subsampling from artificial xenon-hydrate sediments and nondestructive microscale imaging of the subsample, using a microfocus X-ray computed tomography (CT) system. In addition, we estimated porosity and hydrate saturation from two-dimensional X-ray CT images of the subsamples.

A Pore-Scale Numerical Simulation Method for Estimating the Permeability of Sand Sediment

A numerical method system to estimate the permeability of sand sediments, at a microscopic scale, was developed. Initially, 3D geometrical representations of the sand grains are reconstructed from a series of 2D X-ray CT scans of real sand grains. 2D cross-sectional slices of the grain outlines are combined together to produce 3D objects via spherical harmonics series expansions. Then, the reconstructed sand grains are packed randomly inside a cubic, microscopic, domain by a combination of a growth method and a simulated annealing method to achieve a predefined porosity. Finally, a single-phase water flow within the domain was simulated numerically, using the lattice Boltzmann method. The calculated permeability of these systems compares well with the values provided by conventional theoretical models. One of the contributions of this study is to show that it is possible to predict the permeability of sand sediments of variable porosities, using sand grains from CT images with changing size distributions and orientations.