Masato Kida

National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki, Japan

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Publications (49)104.34 Total impact

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    ABSTRACT: In this study, we measured the hydrate equilibrium conditions for simple methane, ethane, propane, and krypton hydrates formed from liquid/solid deuterium oxide in order to understand the effect of deuterium replacement in the host framework on the gas hydrate equilibrium conditions. We obtained the equilibrium conditions by recording pressure and temperature for gas hydrate formation and dissociation under deuterium oxide-rich conditions in the pressure range of (0.142 to 5.49) MPa and the temperature range of (263.4 to 282.3) K. The hydrate equilibrium pressure for deuterium oxide systems at a fixed temperature decreases in the order of methane, krypton, ethane, and propane. The hydrate equilibrium temperatures for all liquid deuterium oxide systems increase compared with those for its usual liquid water systems at fixed pressure. The deuterium isotopic effect of host water molecules on hydrate equilibrium temperatures for the three phases including liquid water at a fixed pressure becomes greater in the order of methane, ethane, krypton, and propane. The hydrate equilibrium conditions for all solid deuterium oxide systems are approximately consistent with those for its usual liquid water systems. The gas hydrate crystals formed from deuterium oxide were characterized by 13C NMR spectroscopy.
    Journal of Chemical & Engineering Data 05/2015; 60(6). DOI:10.1021/acs.jced.5b00276 · 2.05 Impact Factor
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    ABSTRACT: In this report, we describe the effects of ice on the restriction of methane diffusion during the dissociation of pressurized methane hydrate grains using two deuterium-labelling approaches with D2O. Direct measurements of the dissociation behaviors of the methane hydrate samples labelled by a temperature ramping method at temperatures of 253.0–293.0 K were carried out. The deuterium-labelling approaches demonstrated that water molecules in the host framework of methane hydrate predominantly contribute to ice formation, which restricts methane release from the decomposing hydrate framework more than ice coexisting with methane hydrate. The shielding effect of ice in intimate contact with methane hydrate particles on methane diffusion during the decomposition of the hydrate framework depends on the ratio of preexisting ice in the methane hydrate sample.
    Japanese Journal of Applied Physics 05/2015; 54(6):065502. DOI:10.7567/JJAP.54.065502 · 1.06 Impact Factor
  • Canadian Journal of Chemistry 04/2015; DOI:10.1139/cjc-2014-0539 · 1.01 Impact Factor
  • Yusuke Jin, Masato Kida, Jiro Nagao
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    ABSTRACT: In this study, we characterized structure H (sH) clathrate hydrates (hydrates) containing nitrogen (N2) and 2,2-dimethylbutane (neohexane, hereafter referred to as NH) molecules. Based on the powder X-ray diffraction profile, we estimated the unit cell dimensions of the sH hydrate of N2 + NH to be a = 1.22342(15) nm and c = 0.99906(17) nm at 153 K. The c axis of this hydrate was slightly shorter (i.e., 0.00584 nm) than that of CH4 + NH, whereas we observed no difference in the a axis between these two hydrates. We successfully observed a symmetric N–N stretching (N–N vibration) Raman peak with two bumps, and determined that the N–N vibrational mode in the 512 and 435663 cages occurred at approximately 2323.8 and 2323.3 cm−1, respectively. We found the cage occupancy ratio of the 435663/512 cages (θM/θS) of the sH hydrate of N2 + NH to be approximately 1.30. From a comparison of the N–N vibrational modes in the 512, 435663, 51262, and 51264 cages of the sI, sII, and sH hydrates, we determined that N2 molecules in the distorted 435663 cages experience more attractive guest-host interaction than those in spherical 51264 cages, whereas the guest/cage diameter ratio of 435663 cages is larger than that of 51264 cages. We determined the L1–L2–H–V four-phase equilibrium pressure–temperature conditions in the N2–NH–water system in the temperature range of 274.36–280.71 K. Using the Clausius–Clapeyron equation, we estimated the dissociation enthalpies of the sH hydrates of N2 + NH to be 388.4 and 395.9 kJ·mol−1 (per one molar of N2 molecules) in the experimental temperature range.
    The Journal of Physical Chemistry C 04/2015; 119:9069-9075. DOI:10.1021/acs.jpcc.5b00529 · 4.84 Impact Factor
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    ABSTRACT: Effective and absolute permeability are among the most important factors affecting the productivity of hydrate-bearing sediments during gas recovery operations. In this study, effective and absolute permeability have been measured using natural sediment cores obtained from a methane hydrate reservoir in the Eastern Nankai Trough off the shore of Japan. The cores were recovered under pressure and shaped cylindrically with liquid nitrogen (LN2) spray after rapid pressure release. The cylindrical core was inserted into a core holder for flooding tests in order to apply a near in situ effective stress. The results indicated that effective and absolute permeability depend on sediment lithology, effective porosity, and hydrate saturation. The effective permeability of water in the hydrate-bearing sandy sediment was 47 millidarcies (md) with a hydrate saturation of 70%. After hydrate dissociation, the absolute permeability was estimated to be 840 md. Other test results showed that the absolute permeability of the hydrate-free sediments was estimated to be tens of microdarcies for clayey sediments, tens of md for silty sediments, and up to 1.5 darcy for sandy sediments. Absolute permeability showed a strong correlation with sediment grain size in log–log plots. In addition, the effective permeability of hydrate-bearing sandy sediments and the absolute permeability of hydrate-free sandy sediments correlated with the effective porosity. To understand the effective permeability of the hydrate reservoir at this location, we compared measured data to other experimental data using pressure cores recovered from the same well and wireline pressure tests from a well near the coring well. The results are consistent with each other. At this location, we found that the effective permeability for hydrate-bearing sandy sediments was in the range of 1–100 md, which was 2–3 orders of magnitude higher than conventional estimates. Finally, the change of permeability, potentially caused by depressurization-induced gas production, was analyzed. It was found that the high effective stress owing to depressurization and fresh water generation originating from hydrate dissociation caused reduction in absolute permeability. However, the magnitude of reduction depends on the sediment lithology. The results of this study can be used for future reservoir modeling and will make it possible to predict gas production behaviors.
    Marine and Petroleum Geology 03/2015; DOI:10.1016/j.marpetgeo.2015.02.020 · 2.47 Impact Factor
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    ABSTRACT: Bulk sediment mineralogy was measured from a gas hydrate-bearing Middle Pleistocene deepwater turbidite interval at the offshore production test site of the Eastern Nankai Trough area. We used a cores recovered from a 60-m-long section of the borehole to obtain samples for analysis of mineral and organic contents to ascertain the sediment mineralogy of the gas hydrate reservoir. Powder X-ray diffraction analysis, ignition loss test, and field-emission scanning electronic microscopy revealed the following: (i) ten bulk minerals vary in concentration and most of them have good exponential correlation with median grain size; (ii) the upper muddy section is dominated by coccolith-rich hemipelagites, whereas the middle and lower sections are characterized by relatively coccolith-poor, probably humic-rich alterations of sand and mud; and (iii) the common occurrence of authigenic gypsum, siderite, and framboidal pyrite indicates early diagenesis in anoxic and high salinity conditions probably associated with gas hydrate formation in some degree. Such mineralogical data can provide useful information on evaluation of thermal properties, geomechanical characteristics, effective permeability, and early diagenetic mechanism to characterize and exploit gas hydrate reservoirs.
    Marine and Petroleum Geology 03/2015; DOI:10.1016/j.marpetgeo.2015.02.039 · 2.47 Impact Factor
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    ABSTRACT: This study describes the chemical and crystallographic properties of natural gas hydrates recovered from a methane production test site in the eastern Nankai Trough. Gases released from the hydrate-bearing sediments contain methane as the main hydrocarbon component. The hydrate-bound gas includes small amounts of ethane and heavier hydrocarbons (less than ∼300 ppm). Concentrations of minor hydrocarbon components decrease in sediment cores recovered from shallower subseafloor depths. Molecular and isotopic analyses suggest a microbial origin for the natural gas distributed at this site. The 13C NMR and Raman spectra provide evidence that methane molecules are encaged in two distinct polyhedral cages of the structure I hydrate with a hydration number of 6.1. The powder X-ray diffraction profile shows that the crystal type of the gas hydrate is structure I (sI), with lattice constants estimated at 1.1841(2) nm at 83 K. At widely varying temperatures, the lattice constants of the pore-space natural gas hydrate crystals agree well with those of massive natural gas hydrate and artificial methane hydrate, suggesting that the mode of hydrate occurrence does not significantly affect the physical dimensions of the crystal lattice. The small amounts of ethane and heavier hydrocarbons that form sI hydrate have no influence on the lattice expansion of the pore-space hydrate. The density of the natural gas hydrate crystals in the hydrate-bearing sediment sample is estimated at 0.95 g/cm3 at 83 K.
    Marine and Petroleum Geology 03/2015; DOI:10.1016/j.marpetgeo.2015.02.019 · 2.47 Impact Factor
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    ABSTRACT: Sediment cores containing methane hydrate were obtained under pressure from the Eastern Nankai Trough offshore Japan, and they have been analyzed to investigate the relationship between compressional wave velocity (P-wave velocity), methane hydrate saturation, and pore space hydrate morphology. P-wave velocities of pressure cores were measured at near in-situ pressures, thus preventing hydrate dissociation. After the measurement of P-wave velocity, the cores were cut, under pressure, into separate P-wave velocity intervals. Each core interval was depressurized while measuring the evolved gas volume to quantify methane hydrate saturation. The results show that P-wave velocity correlates well with hydrate saturation; the P-wave velocity varied from less than 1700 m/s in the hydrate-free section to greater than 2300 m/s in the section with the highest hydrate saturation of 72%. The measured P-wave velocities were correctly reproduced by the sediment frame component model by adjusting model parameters such as sand-clay ratio and effective stress. It was found that all core data plotted within the model predictions assuming zero effective stress and assuming in situ effective stress. This may indicate that the cores were in the process of relaxing from their in situ effective stress at the time of measurement. By using pressure cores and pressure core analysis technology, the relationship between P-wave velocity and methane hydrate saturation has been directly obtained nondestructively. The observed relationship in high-resolution core-scale specimens enables estimation of the hydrate morphology and is expected to be more accurate than cross-plot data in well logging.
    Marine and Petroleum Geology 03/2015; DOI:10.1016/j.marpetgeo.2015.02.021 · 2.47 Impact Factor
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    ABSTRACT: Gas hydrate-bearing sediments from the eastern Nankai Trough, Japan, are characterized in terms of their lithology, interpreted processes and paleoenvironments of deposition, and various geometric parameters of their grain size distribution. These data are used to determine the relative influence of each characteristic on gas hydrate saturation within the sedimentary column. Four lithologies have been identified in a single turbidite sequence that can be attributed to hyperpycnal flow deposits, Tc or Td divisions of a turbidite sequence, a Te division of a turbidite sequence, and hemipelagic mud. Facies association indicates that the sediment core can be vertically divided into units that are characteristic of three depositional environments: a lowermost channel-fill turbidite sequence, an intervening sheet-like turbidite sequence, and an uppermost basin floor sequence. The channel-fill turbidite and sheet-like turbidite sequences are the best hydrate reservoirs, as evidenced by the high levels of gas hydrate contained within them. The relationships between gas hydrate saturation and the grain size distribution parameters of median grain size, sand content, and skewness show that the latter can be useful tools with which to assess the quality of the gas hydrate reservoir in the eastern Nankai Trough area. This result provides useful criteria for assessing reservoir quality in the eastern Nankai Trough area.
    Marine and Petroleum Geology 02/2015; DOI:10.1016/j.marpetgeo.2015.02.022 · 2.47 Impact Factor
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    ABSTRACT: The study of mechanical properties of marine sediments is essential for the prediction of the occurrence of geohazards (e.g., subsea landslides and seafloor subsidence) and the design of submarine structures for offshore industry. In this study, triaxial compression tests of gas-hydrate-bearing sandy sediments and clayey-silty sediments were conducted. The sediments were recovered by pressure coring in the Eastern Nankai Trough, the area of the first Japanese offshore production test. Soil index properties were measured and revealed porosity of 40% to 50%, with porosity decreasing gradually with greater depth below the seafloor. The mean particle size was less than 10 μm for clayey-silty sediments and approximately 100 μm for sandy sediments. Permeability, estimated by a consolidation process of triaxial testing and with X-ray diffraction analysis, depended on the content of fines, which consisted chiefly of mica, kaolinite, and smectite. The results of undrained compression tests for clayey-silty sediments showed positive excess pore pressure under all test conditions. This mechanical behavior indicates that the core samples are normally consolidated sediments. Drained compression tests showed that the strength and stiffness of sandy sediments increase with hydrate saturation. Furthermore, the volumetric strain of hydrate-bearing sediments changed from compression to dilative. This result was obtained for hydrate saturation values (Sh) of more than 70%. The shear strength of hydrate-bearing turbidite sediments of the Eastern Nankai Trough is shown to be a function of the confining pressure.
    Marine and Petroleum Geology 02/2015; DOI:10.1016/j.marpetgeo.2015.02.029 · 2.47 Impact Factor
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    ABSTRACT: Geomechanical and geotechnical properties are essential for evaluating the stability of deep seabed and subsea production systems for gas hydrate extraction from marine sediments. In this study, natural gas hydrate-bearing sediment was subjected to triaxial compression tests (shearing) using a newly developed triaxial testing system (TACTT) to investigate the geomechanical behavior of sediments recovered from below the seafloor in the eastern Nankai Trough, where the first Japanese offshore production test was conducted in 2013. The sediments were recovered using a hybrid pressure coring system, with pressure cores cut using onboard pressure core analysis tools. The pressure cores were subsequently transferred to our shore-based laboratory and subsampled using pressure core non-destructive analysis tools (PNATS) for the TACTT system. Pressure and temperature conditions were maintained within the hydrate stability boundary during coring and laboratory testing. An image processing technique was used to capture deformation of the sediment sample within the transparent acrylic test cell, and digital photographs were obtained for each 0.1% strain level experienced by the sample during the triaxial compression test. Analysis of the digitized images showed that sediments with 63% hydrate saturation exhibited brittle failure, whereas hydrate-free sediments exhibited ductile failure. The increase in shear strength with increasing hydrate saturation in natural gas hydrates is in agreement with previous data from sediments containing synthetic gas hydrates.
    Marine and Petroleum Geology 02/2015; DOI:10.1016/j.marpetgeo.2015.02.028 · 2.47 Impact Factor
  • Yusuke Jin, Masato Kida, Jiro Nagao
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    ABSTRACT: Phase equilibrium pressure–temperature (pT) boundaries of structure-H clathrate hydrates (sH hydrates) with rare gas (Kr and Xe)-bromide large molecule guest substances (LMGSs: bromocyclohexane, BrCH and bromocyclopentane, BrCP) were measured. The phase boundaries for the sH hydrates in the Kr–LMGS–water systems shifted to lower pressures than those for the pure Kr hydrate in the temperature range of (273.2 to 279.3) K. In this study, sH hydrate formation was not confirmed in the Xe–BrCP–water system, but sH hydrates were found in the Xe–BrCH–water system. At temperatures below 277 K, equilibrium conditions were observed at lower pressures for the Xe–BrCH–water system than for the pure Xe hydrate. However, the equilibrium pT curve for the Xe–BrCH–water system crossed over the equilibrium pT curve for the Xe hydrate at around 277 K. Intersections between the equilibrium pT curves for the Xe hydrates and the sH hydrates (Xe + LMGS) have also been found in Xe–methylcyclohexane–water systems. Using the Kr–and Xe–bromide LMGS–water systems showed that the sH hydrate phase stabilities are strongly related to the encaptured LMGS.
    Journal of Chemical & Engineering Data 04/2014; 59(5):1704–1709. DOI:10.1021/je500216u · 2.05 Impact Factor
  • Japanese Journal of Applied Physics 01/2014; 53(1):018003. DOI:10.7567/JJAP.53.018003 · 1.06 Impact Factor
  • Yusuke Jin, Masato Kida, Jiro Nagao
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    ABSTRACT: This study characterized new structure H (sH) clathrate hydrates with bromide large-molecule guest substances (LMGSs) bromocyclopentane (BrCP) and bromocyclohexane (BrCH), using powder X-ray diffraction (PXRD) and Raman spectroscopy. The lattice parameters of sH hydrates with (CH4 + BrCP) and (CH4 + BrCH) were determined from their PXRD profiles. On the basis of their Raman spectra, the M-cage to S-cage occupancy ratio (435663 and 512 cages, respectively), θM/θS, was estimated to be approximately 1.3, and the Raman shift of the symmetric C–H vibrational modes of CH4 in S- and M-cages was 2911.1 and 2909.1 cm–1, respectively. The phase-equilibrium conditions of sH hydrates with (CH4 + BrCP) and (CH4 + BrCH) were determined by an isochoric method. A comparison between the equilibria of sH hydrates with BrCP and BrCH and those with other typical nonpolar and polar LMGSs (methylcyclopentane, MCP; methylcyclohexane, MCH; neohexane, NH; and tert-butyl methyl ether, TBME) at the same temperature revealed that the equilibrium pressure increased in the order NH < MCH < BrCH < TBME MCP < BrCP. The phase stabilities of sH hydrates can be determined by not only molecular geometry but also their polar properties, which affect guest–host interactions.
    The Journal of Physical Chemistry C 10/2013; 117(45):23469–23475. DOI:10.1021/jp403430z · 4.84 Impact Factor
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    ABSTRACT: The solid-state 13C NMR spectra of various guest hydrocarbons (methane, ethane, propane, adamantane) of clathrate hydrates were measured to elucidate local structural environments around hydrocarbon molecules isolated in guest-host frameworks of clathrate hydrates. Results show that, depending on the cage environment, trends in the 13C chemical shift and in the line width change as a function of temperature. Shielding around the carbons of the guest normal alkanes in looser cage environments tends to decrease with increasing temperature, although shielding in tighter cage environments tends to increase continuously with increasing temperature. Furthermore, the 13C NMR line widths suggest that the local structures, because of the reorientation of the guest alkanes in structure II, are more averaged than those in structure I. Differences between structures I and II tend to be remarkably large in the lower temperature range examined in this study. The 13C NMR spectra of adamantane guest molecules in structure H hydrate show that the local structures around adamantane guests trapped in structure H hydrate cages are averaged at the same level as the phase α solid adamantane.
    The Journal of Physical Chemistry A 04/2013; 117(20). DOI:10.1021/jp312130c · 2.78 Impact Factor
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    ABSTRACT: Thermal measurements and hydrate mapping in the vicinity of the K-2 mud volcano in Lake Baikal have revealed a particular type of association of thermal anomalies (29–121 mW m–2) near hydrate-forming layers. Detailed coring within K-2 showed that hydrates are restricted to two distinct zones at sub-bottom depths exceeding 70–300 cm. Temperature data from stations with hydrate recovery and degassing features all display low thermal gradients. Otherwise, the thermal gradients within the mud volcano are generally increased. These findings imply a more complicated thermal regime than often assumed for mud volcanoes, with important roles for both fluids and hydrates. The coexistence of neighbouring low and high thermal anomalies is interpreted to result from discharging and recharging fluid activity, rather than hydrate thermodynamics. It is suggested that hydrates play a key role in controlling the fluid circulation pattern at an early stage. At a later stage, the inflow of undersaturated lake water would favour the dissolution of structure I hydrates and the formation of structure II hydrates, the latter having been observed on top of structure I hydrates in the K-2 mud volcano.
    Geo-Marine Letters 12/2012; 32(5-6):407-417. DOI:10.1007/s00367-012-0292-0 · 2.06 Impact Factor
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    ABSTRACT: This study reports measurements of the Raman spectra of Lake Baikal gas hydrates and estimations of the hydration number of methane-rich samples. The hydration number of gas hydrates retrieved from the southern Baikal Basin (crystallographic structure I) was approx. 6.1. Consistent with previous results, the Raman spectra of gas hydrates retrieved from the Kukuy K-2 mud volcano in the central Baikal Basin indicated the existence of crystallographic structures I and II. Measurements of the dissociation heat of Lake Baikal gas hydrates by calorimetry (from the decomposition of gas hydrates to gas and water), employing the hydration number, revealed values of 53.7–55.5 kJ mol–1 for the southern basin samples (structure I), and of 54.3–55.5 kJ mol–1 for the structure I hydrates and 62.8–64.2 kJ mol–1 for the structure II hydrates from the Kukuy K-2 mud volcano.
    Geo-Marine Letters 12/2012; 32(5-6):419-426. DOI:10.1007/s00367-012-0285-z · 2.06 Impact Factor
  • Yusuke Jin, Masato Kida, Jiro Nagao
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    ABSTRACT: The dissociation temperature of clathrate hydrates in the krypton (Kr)–liquid hydrocarbon (methylcyclohexane, MCH and methylcyclopentane, MCP)–water systems was established in the temperature range of (273.2 to 285.6) K and pressure range of (0.5 to 2.4) MPa using optical scanning microscopy. From powder X-ray diffraction data, it was established that the clathrate hydrates formed in the Kr–MCH–water and Kr–MCP–water systems had the structure H (sH). The dissociation pressure–temperature (pT) conditions of the krypton–liquid hydrocarbon–water systems are milder than the pT conditions of Kr hydrate. Large guest molecules captured in the 51268 cage affect the phase stability of the sH hydrate when compared to the phase-equilibrium data in the Kr–neohexane–water system.
    Journal of Chemical & Engineering Data 08/2012; 57(9):2614–2618. DOI:10.1021/je300761q · 2.05 Impact Factor
  • Yusuke Jin, Masato Kida, Jiro Nagao
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    ABSTRACT: Phase equilibrium pressure–temperature (pT) conditions for the xenon (Xe)–tetra-n-butylammonium bromide (TBAB)–water system were characterized by an isochoric method in the pressure range from (0.05 to 0.3) MPa using TBAB solutions with mole fractions ranging from (0.0029 to 0.0137). The phase equilibrium pT conditions in the system appeared at a lower pressure and higher temperature than in the pure Xe hydrate. Furthermore, under atmospheric pressure, the dissociation temperature in the Xe–TBAB–water system shifted to a higher region than in the pure TBAB hydrate. In the experimental TBAB concentration range, the powder X-ray diffraction patterns of the Xe–TBAB–water system revealed that the TBAB clathrate hydrate is TBAB·38H2O.
    Journal of Chemical & Engineering Data 05/2012; 57(6):1829–1833. DOI:10.1021/je300299b · 2.05 Impact Factor
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    ABSTRACT: 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.
    Physical Chemistry Chemical Physics 09/2011; 13(41):18481-4. DOI:10.1039/c1cp21656b · 4.20 Impact Factor