Masato Kida

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

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Publications (37)62.93 Total impact

  • 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. · 2.00 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.
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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; · 2.77 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. · 1.85 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. · 1.85 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. · 2.00 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. · 2.00 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. · 3.83 Impact Factor
  • Tsutomu Uchida, Masato Kida, Jiro Nagao
    ChemPhysChem 06/2011; 12(9):1652-6. · 3.35 Impact Factor
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    ABSTRACT: Experimental NMR measurements for (13)C chemical shifts of propane molecules encaged in 16-hedral cages of structure II clathrate hydrate were conducted to investigate the effects of guest-host interaction of pure propane clathrate on the (13)C chemical shifts of propane guests. Experimental (13)C NMR measurements revealed that the clathrate hydration of propane reverses the (13)C chemical shifts of methyl and methylene carbons in propane guests to gaseous propane at room temperature and atmospheric pressure or isolated propane, suggesting a change in magnetic environment around the propane guest by the clathrate hydration. Inversion of the (13)C chemical shifts of propane clathrate suggests that the deshielding effect of the water cage on the methyl carbons of the propane molecule encaged in the 16-hedral cage is greater than that on its methylene carbon.
    The Journal of Physical Chemistry A 02/2011; 115(5):643-7. · 2.77 Impact Factor
  • ChemPhysChem 10/2010; 11(14):3070-3. · 3.35 Impact Factor
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    ABSTRACT: 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.
    The Journal of Physical Chemistry A 09/2010; 114(35):9456-61. · 2.77 Impact Factor
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    ABSTRACT: We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ13C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ13C signatures at two sites where ethane δ13C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which 13C and deuterium were both highly depleted (mean δ13C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C2 δ13C–δD classification for hydrate-bound gas in either freshwater or marine environments.
    Geo-Marine Letters 06/2010; 30(3):321-329. · 1.85 Impact Factor
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    ABSTRACT: We report on the isotopic composition of dissolved inorganic carbon (DIC) in pore-water samples recovered by gravity coring from near-bottom sediments at gas hydrate-bearing mud volcanoes/gas flares (Malenky, Peschanka, Peschanka 2, Goloustnoe, and Irkutsk) in the Southern Basin of Lake Baikal. The δ13C values of DIC become heavier with increasing subbottom depth, and vary between −9.5 and +21.4‰ PDB. Enrichment of DIC in 13C indicates active methane generation in anaerobic environments near the lake bottom. These data confirm our previous assumption that crystallization of carbonates (siderites) in subsurface sediments is a result of methane generation. Types of methanogenesis (microbial methyl-type fermentation versus CO2-reduction) were revealed by determining the offset of δ13C between dissolved CH4 and CO2, and also by using δ13C and δD values of dissolved methane present in the pore waters. Results show that both mechanisms are most likely responsible for methane generation at the investigated locations.
    Geo-Marine Letters 06/2010; 30(3):427-437. · 1.85 Impact Factor
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    ABSTRACT: Natural gas hydrates are crystalline clathrate compounds, which encage a large amount of natural gas. The crystallographic structure of natural gas hydrates depends on the encaged natural gas components. In addition, the amount of hydrate-bound natural gas is attributed to the crystallographic structure. Massive and pore-space natural gas hydrates were obtained from the eastern Nankai Trough area during Japan's Methane Hydrate R&D Program conducted by the Ministry of Economy, Trade and Industry (METI) of Japan, aboard the RV JOIDES Resolution. In this study, hydrate-bound gas, crystal structure, and cage occupancies, and hydration number of the natural gas hydrates were characterized. The pore-space natural gas hydrates recovered from the eastern Nankai Trough area existed in pore-spaces of sandy sediments with median diameters of approximately 80-180 mum. The PXRD profiles of the massive and pore-space natural gas hydrates revealed that the crystallographic structures of the all natural gas hydrates studied were structure I. The lattice constants of the pore-space natural gas hydrates were ranging from 1.183-1.207 nm, depending on the content of fine sediment particles less than 40 mum in the sandy samples. All samples contained CH4 as a main hydrocarbon component, indicating that the natural gas in marine sediment at the study areas is mainly CH4. The hydrocarbon compositions agreed well with those reported for microbial (CO2 reduction) natural gas in gas hydrate-bearing sediments recovered previously from the eastern Nankai Trough area. In this study, on the other hand, although almost all samples contained small amounts of C2H6 (less than 200 ppm), C3H8 (less than 50 ppm), and i-C4H10 (less than 20 ppm), large concentrations of heavier hydrocarbons such as C3H8 or i-C4H10 were found in three of 15 samples. 13C NMR and Raman spectroscopic techniques were used to obtain molecular information on the encaged hydrocarbon molecules. The 13C NMR chemical shifts and Raman shifts of guest molecules showed that the primary component of guest molecule is CH4 and their crystallographic structure is structure I, supporting the PXRD data. The occupancies of small and large cages were evaluated from the 13C NMR and Raman spectra, which the pore-space gas hydrates had 0.83 small cage occupancy of CH4 and 0.97 large cage occupancy of CH4, indicating the large cages were almost fully occupied by CH4 molecules. The hydration number estimated from the obtained cage occupancies was 6.1-6.2, which resembled those of the massive NGHs studied. The obtained cage occupancies and hydration numbers are important parameters for estimation of amount of hydrocarbons in hydrate-bound natural gases in the eastern Nankai Trough area. This work was supported by funding from the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) planned by METI.
    05/2010;
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    ABSTRACT: Pore-space gas hydrates sampled from the eastern Nankai Trough area off of Japan were minutely characterized using several instrumental techniques. Gas chromatographic results indicated that the natural gas in the sediment samples studied comprises mainly CH4. The concentrations of minor components varied according to depth. The powder X-ray diffraction patterns showed that the pore-space hydrates were of structure I (sI); the lattice constants were 1.183−1.207 nm. Both 13C NMR and Raman spectra confirmed that CH4 molecules were encaged in sI hydrate lattice. The average cage occupancies were calculated, respectively, from the Raman data as 0.83 for small cages and 0.97 for large cages. The hydration numbers were determined as 6.1−6.2.
    Energy & Fuels - ENERG FUEL. 11/2009; 23(11).
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    ABSTRACT: We measured the isotopic compositions of methane (C1) and ethane (C2) of hydrate-bound gas and of dissolved gas in pore water retrieved from bottom sediments in Lake Baikal. Both structure I (sI:3%C2) and II (sII:14%C2) gas hydrates are observed in the same sediment cores in Kukuy K-2 mud volcano. We found that C2δD of sI gas hydrate is larger than that of sII, whereas C1δ13C, C1δD and C2δ13C values are practically the same in both hydrate structures. δ13C of C1 and C2 of hydrate-bound gas are several permil smaller than those in pore water, showing that the current pore water is not the source of gas hydrates. These findings lead to a new model where the sII gas hydrates were formed prior to the sI hydrates.
    Geophysical Research Letters 09/2009; 36(18). · 3.98 Impact Factor
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    ABSTRACT: The dissociation heat of gas hydrates is one of the important parameters that control the formation/dissociation speed of the gas hydrate. We investigated the effect of the ethane concentration on the dissociation heat of the mixed-gas (methane and ethane) hydrate. The dissociation heat of the mixed-gas hydrate [kJ mol–1] was within the range between the dissociation heat of pure methane hydrate and that of ethane hydrate, and it increased with the ethane concentration. Only several % of ethane composition was quite effective to increase the dissociation heat. The hydration number, which changed according to the crystal structure (sI/sII hydrates), determined the dissociation heat during the transition from hydrate to gas and water. The dissociation heat of the mixed-gas hydrate [kJ kg–1] was 6–30% greater than that of pure methane and ethane hydrates during the transition from hydrate to gas and ice, and 3–8% greater during the transition from hydrate to gas and water.
    Seppyo. 09/2009; 71(5):341-351.
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    ABSTRACT: Knowledge of cage occupancies and hydration numbers (n) of naturally occurring gas hydrate in a local environment is important for the improvement in global estimates of hydrate-bound natural gas. We report on local differences in cage occupancies and hydration number of gas hydrates from Lake Baikal. Natural gas hydrates of both structures I and II (sI and sII) and ranging in composition from pure CH4 to mixed gas hydrate containing up to 15% C2H6 are compared. The average hydration numbers are n = 6.1 for the sI CH4 hydrates recovered from the Malenky and Bolshoy mud volcanoes, n = 6.2 for the sI hydrates, containing 3–4% C2H6 recovered from the K-2 mud volcano, and n = 6.9 for the sII hydrate containing about 15% C2H6 recovered from the K-2 mud volcano. The differences in hydration number are due to the differences in the small cage occupancy of CH4 among the samples studied.
    Geochemistry Geophysics Geosystems 05/2009; 10(5). · 2.94 Impact Factor
  • Chigaku Zasshi (jounal of Geography). 03/2009; 118(1):194-206.

Publication Stats

102 Citations
62.93 Total Impact Points

Institutions

  • 2008–2013
    • National Institute of Advanced Industrial Science and Technology
      • Methane Hydrate Research Center
      Tsukuba, Ibaraki, Japan
  • 2005–2012
    • Kitami Institute of Technology
      Notsukeushi, Hokkaidō, Japan
  • 2011
    • Hokkaido University
      • Division of Applied Physics
      Sapporo-shi, Hokkaido, Japan
  • 2010
    • Ghent University
      Gand, Flanders, Belgium
    • Institut de Physique du Globe de Paris
      Lutetia Parisorum, Île-de-France, France