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.

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.

Effective control of gas hydrate dissociation above the melting point of ice.

Direct measurements of the dissociation behaviors of pure methane and ethane hydrates trapped in sintered tetrahydrofuran hydrate through a temperature ramping method showed that the tetrahydrofuran hydrate controls dissociation of the gas hydrates under thermodynamic instability at temperatures above the melting point of ice.

Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

Spectroscopic study of water-NaCl-benzene mixtures at high temperatures and pressures.

Near-infrared and ultraviolet spectra of water-NaCl-benzene mixtures have been measured in the 473-573 K and 100-400 bar range and 373-498 K and 50-300 bar range, respectively. Concentrations of water in the benzene-rich phase and benzene in the water-rich phase were estimated from integrated intensities of the absorption bands. It is found that addition of NaCl in the aqueous phase suppresses transfer of water into the benzene-rich phase, and the relative decrease in water solubility in benzene exhibits good correlation with an increase in density of the aqueous NaCl solution relative to that of neat water. The salting-out constant for the water-NaCl-benzene system, which is estimated from a relative decrease in benzene solubility in the aqueous phase by addition of sodium chloride, increases significantly with increasing temperature. It is suggested that the effect of sodium chloride on the water-benzene mutual solubilities can be explained by ion-induced electrostriction of the aqueous phase.

Spectroscopic study of mutual solubilities of water and benzene at high temperatures and pressures.

Near-infrared and ultraviolet absorption of water-benzene mixtures has been measured at temperatures and pressures in the ranges of 323-673 K and 50-400 bar, respectively. Concentrations of water and benzene in both the water-rich phase and the benzene-rich phase of the mixtures were obtained from absorption intensities of near-infrared bands of water and benzene and ultraviolet bands of benzene. Mutual solubilities in molar fractions increase remarkably with increasing temperature at pressures in the two-liquid-phase coexistence region, and are consistent with previously reported values. It proves that the solubility of benzene in water is an order of magnitude smaller than that of water in benzene throughout the two-phase region. In addition, it is found that effect of pressure on the solubilities is opposite between water in benzene and benzene in water. These solubility properties are discussed on the basis of a cavity-based solvation model. It is suggested that the asymmetry in the mutual solubility and the opposite direction of the pressure effect are caused by difference in molecular size and difference in thermal compressibility, respectively, between water and benzene.

Near infrared study of water-benzene mixtures at high temperatures and pressures.

Near-infrared absorption of water-benzene mixtures has been measured at temperatures and pressures in the ranges of 473-673 K and 100-400 bar, respectively. Concentrations of water and benzene in the water-rich phase of the mixtures were obtained from the integrated absorption intensities of the OH stretching overtone transition of water and the CH stretching overtone transition of benzene, respectively. Using these concentrations, the densities of the water-rich phase were estimated and compared with the average densities before mixing, which were calculated from literature densities of neat water and neat benzene. It is found that anomalously large volume expansion on the mixing occurs in the region enclosed by an extended line of the three-phase equilibrium curve and the one-phase critical curve of the mixtures, and the gas-liquid equilibrium curve of water. Furthermore, magnitude of the relative volume change increases with decreasing molar fraction of benzene in the present experimental range. It is suggested that dissolving a small amount of benzene in water induces a change in the fluid density from a liquidlike condition to a gaslike condition in the vicinity of the critical region.

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.