| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,3-9(2002) |
| ガスハイドレートの高圧物性 Gas Hydrates under High Pressure |
| 清水 宏晏 Hiroyasu SHIMIZU |
| The fundamental properties of gas hydrates are reviewed; classification and type, structure and composition, formation and stability, and occupancy of guest molecules. Recent Raman studies on the properties of cage-occupancy are discussed by considering the C-H vibrations of their guest molecules for methane, methane-ethane mixed (structural phase transition), ethane, and cyclopropane (pressure-induced small cage occupancy) hydrates. Finally, I give an overview of very recent x-ray (neutron) diffraction and Raman scattering studies of phase transitions in the methane hydrate at high pressures, and discuss the inconsistent results by investigating the experimental details. [gas hydrates, methane hydrate, Raman scattering, phase transition, cage structure, DAC] |
| 〒501-1193 岐阜市柳戸1の1 岐阜大学工学部，大学院環境エネルギーシステム Department of Electronics, and Environmental and Renewable Energy Systems, Gifu University , 1-1 Yanagido, Gifu 501-1193 shimizu@cc.gifu-u.ac.jp |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,10-15(2002) |
| 特異な条件下でのガスハイドレートの形成 - 129Xe NMR によるキャラクタリゼーション - Formation of Gas Hydrate under Curious Conditions as Probed by 129Xe NMR |
| 中山 尋量 尾身 洋典 江口 太郎 D.D. Klug J.S. Tse C.I. Ratcliffe J.A. Ripmeester Hirokazu NAKAYAMA Hironori OMI Taro EGUCHI Denis D. KLUG John S. TSE Chris I. RATCLIFFE John A. RIPMEESTER |
| In this article, recent research works on the formation process of gas hydrate were reviewed. We describe how efficiently a solid-state 129Xe NMR technique was applied to monitor the formation processes of gas hydrates, together with a short review of 129Xe NMR. Especially, the formation process from an amorphous mixture of Xe and H2O was described precisely. [129Xe NMR, Xe hydrate, amorphous mixture, in-situ high pressure NMR probe] |
| 〒658-8558 神戸市東灘区本山北町 4-19-1 神戸薬科大学 Kobe Pharmaceutical University, 4-19-1 Motoyamakitamachi, Higashinada-ku, Kobe 658-8558 hiro@kobepharma-u.ac.jp 〒560-0043 豊中市待兼山町 1-16 大阪大学大学院理学研究科 Graduate School of Science, Osaka University, 1-16 Machikaneyamacho, Toyonaka 560-0043 National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 Canada |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,16-21(2002) |
| 高圧ブリュアン散乱によるメタンハイドレートの弾性的性質 Elastic Properties of Methane Hydrate Studied by High-Pressure Brillouin Spectroscopy |
| 佐々木 重雄 熊崎 達也 久米 徹二 清水 宏晏 Shigeo SASAKI Tatsuya KUMAZAKI Tetsuji KUME Hiroyasu SHIMIZU |
| The elastic properties of structure I (sI) methane hydrate (MH) determined by high-pressure Brillouin spectroscopy up to 0.6 GPa at 23℃ are reviewed by comparing them with those of ice-Ih. The pressure dependence of adiabatic elastic moduli of sI-MH is similar to that of ice-Ih except for C11. Elastic moduli and bulk modulus indicate that sI-MH is slightly more compressive than ice-Ih, and acoustic velocities show nearly isotropic behaviors with respect to the crystal orientation. The C44 of sI-MH is less sensitive to pressure and smaller than C11 and C12, which implies the sI-MH is becoming less stable against the shear stress under high pressures. These results are useful to investigate the dynamic stability and the estimated amount of MH in the deep-sea sediments. [methane hydrate, DAC, adiabatic elastic modulus, acoustic velocity, Brillouin scattering] |
| 〒501-1193 岐阜市柳戸1-1 岐阜大学大学院 環境エネルギーシステム専攻 Environmental and Renewable Energy Systems, Gifu University, 1-1 Yanagido, Gifu 501-1193 ssasaki@cc.gifu-u.ac.jp |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,22-27(2002) |
| ハイドレート中の分子間相互作用とダイナミクス Molecular Interactions and Rotational Dynamics in Clathrate Hydrate |
| 竹林 良浩 大竹 勝人 Yoshihiro TAKEBAYASHI Katsuto OTAKE |
| The guest-host interactions and the rotational dynamics in the clathrate hydrates of acetone and THF are discussed in comparison with those in the supercooled aqueous solutions by measuring the 13C NMR chemical shift and the 2D spin-lattice relaxation time as functions of the temperature. When the temperature is decreased, the guest-water hydrogen bond is discontinuously reduced upon the clathrate cage formation. Due to the reduced friction with surrounding waters, the guest molecule reorients much faster in the clathrate cage than in the aqueous solution. On the other hand, the remaining guest-water interaction fluctuates the reorientational motion of the cage water. We also review the structural similarity between the clathrate hydrate and the aqueous solution. [clathrate hydrate, supercooled aqueous solution, hydrogen bonding interaction, rotational dynamics, cage structure, NMR, chemical shift, spin-lattice relaxation time] |
| 〒305-8565 茨城県つくば市東1-1-5 (独)産業技術総合研究所 環境調和技術研究部門 超臨界グループ National Institute of Advanced Industrial Science and Technology (AIST), 1-1-5 Higashi , Tsukuba, Ibaraki 305-8565 chikulin@ni.aist.go.jp |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,28-33(2002) |
| メタンハイドレートの高圧相転移 Phase Changes of Methane Hydrate under High Pressure |
| 平井 寿子 内原 弓佳子 Hisako HIRAI Yukako UCHIHARA |
| Recent high-pressure studies using diamond anvil cell of methane hydrate are reviewed. Three high-pressure phases of methane hydrate were observed by x-ray diffraction and Raman spectroscopy up to 8 GPa in the present authors' study. The well-known cubic phase I decomposed into a hexagonal phase A and fluid at 0.8 GPa. The phase A transformed into an orthorhombic phase B at 1.6 GPa, and the phase B further transformed into another orthorhombic phase C at 2.1 GPa which survived above 7.8 GPa. The fluid solidified as ice VI at 1.4 GPa, and the ice VI transformed to ice VII at 2.1 GPa. The bulk moduli, K0, for the phase I, phase A, and phase C were calculated to be 7.4, 9.8, and 25.0 GPa, respectively. Comparison of the highpressure studies and the description of these high pressure structures were described in detail. [methane hydrate, high pressure , phase change, cage occupancy, DAC] |
| 〒305-8571 つくば市天王台 1-1 筑波大学 地球科学系 Institute of Geoscience, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan hhirai@sakura.cc.tsukuba.ac.jp |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,34-39(2002) |
| 純粋ならびに混合ガスハイドレートの相平衡関係 Phase Behavior for Pure and Mixed Gas Hydrate Systems |
| 菅原 武 菅原 啓祐 大垣 一成 Takeshi SUGAHARA Keisuke SUGAHARA Kazunari OHGAKI |
| As a fundamental study of gas hydrates, which are key substances in the energy and environmental problems, the thermodynamic stability for the pure and mixed gas hydrate systems is investigated. The intermolecular vibration energy between the host water molecules and the intramolecular vibration energies of guest species are measured by means of laser Raman spectroscopy. The structural phase transition controlled on the equilibrium composition of the mixed gas is observed in the (methane + ethylene) mixed gas hydrate systems, while each pure hydrate has no structural phase transition in the whole range in this study. [gas hydrate, thermodynamic stability, structural phase transition, Raman Spectroscopy, phase behavior] |
| 〒560-8531 大阪府豊中市待兼山町1-3 大阪大学大学院基礎工学研究科化学系専攻化学工学分野 Department of Chemical Science and Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama,Toyonaka 560-8531 sugahara@cheng.es.osaka-u.ac.jp |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,40-49(2002) |
| CO2海洋隔離とCO2ハイドレート CO2 Ocean Sequestration and CO2 Hydrate |
| 綾 威雄 山根 健次 小島 隆志 波江 貞弘 Izuo AYA Kenji YAMANE Ryuji KOJIMA Sadahiro NAMIE |
| CO2 ocean sequestration, which is thought to be a promising measure to mitigate global warming, can be classified mainly into the dissolution and the storage methods. On the evaluation of these measures, CO2 hydrate plays an important role, because CO2 becomes a hydrate in the ocean deeper than 500 m (North Pacific Ocean)〜900 m (North Atlantic Ocean). The solubility of CO2 shows a dual nature (solid and liquid solubilities) in the hydrate forming region. Two types of unexpected hydrate membrane strength just below the dissociation temperature and in a CO2 saturated solution, and the rebuilding process under stressed conditions greatly influence the above two CO2 ocean sequestration methods. [CO2, ocean sequestration, dissolution method, storage method, solubility in hydrate region, hydrate membrane strength, rebuilding of hydrate] |
| 〒576-0034 交野市天野が原町 3-5-10 (独立行政法人) 海上技術安全研究所 大阪支所 Osaka Branch, Maritime Research Institute, 3-5-10 Amanogahara, Katano, Osaka 576-0034 aya@srimot.go.jp |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,50-55(2002) |
| メタンハイドレート層の掘削 −基礎試錐「南海トラフ」掘削実績− Exploration for Natural Hydrate in MITI Nankai-Trough Wells Offshore Japan* |
| 若月 基** 米澤 哲夫** 高橋 秀明*** 武富 義和**** Motoi WAKATSUKI Tetsuo YONEZAWA Hideaki TAKAHASHI Yoshikazu TAKEDOMI |
| Exploration for natural methane hydrate was carried out in the Nankai-Trough offshore Japan at a water depth of 945 m over an 88-day period, from November 1999 to February 2000. This was a national project led by the Ministry of International Trade and Industry (MITI) to seek a new energy source. It was organized by Japan National Oil Corporation (JNOC) in collaboration with Japan Petroleum Exploration Co., Ltd. as the drilling operator. The Nankai-Trough wells were drilled with a deepwater semisubmersible rig. The location was selected where BSR (Bottom Simulating Reflector) is the clearest on the seismic section. Six wells were drilled through the BSR horizon and the hydrate rich formation was confirmed between 1135 m to 1213 m BMSL (below mean sea level) by LWD data, core samples and electric logging data. [hydrate, deepwater, offshore, exploration, Nankai-Trough] |
| *2001年5月1日，高橋がOffshore Technology Conferenceにて同題目で講演，邦訳した物を若月が高圧討論会用に補足再編集した。Wakatsuki revised this paper for RHPST. This was originally prepared by Takahashi for presentation at the OTC annual conference held in Houston TX., May 1, 2001. **〒261-0025 千葉県千葉市美浜区浜田1丁目2-2 石油公団石油開発技術センター wakatk-m@jnoc.go.jp Technology Research Center, Japan National Oil Corp. 2-2, Hamada 1-Chome, Mihama-ku, Chiba-shi, Chiba 261-0025 ***〒140-0002 東京都品川区東品川2丁目2番20号天王洲郵船ビル 石油資源開発?? Japan Petroleum Exploration Co., LTD. 2-2-20, Higashi-Shinagawa, Shinagawa-ku, Tokyo 140-0002 ****〒100-8931 東京都千代田区霞ヶ関1丁目3番1号 経済産業省 Ministry of Economy, Trade and Industry, 3-1, Kasumigaseki 1-Chome, Chiyoda-ku, Tokyo 100-8931 |
| 特集−ガスハイドレート− Rev. High Pressure Sci. Technol. 12-1,56-61(2002) |
| CO2によるメタンハイドレート中のメタンの置換速度 Recovery Rate of Methane by CO2 in Clathrate Hydrate |
| 乗京 逸夫* 川村 和茂** 村椿 良司*** Itsuo NORIKYO Kazushige KAWAMURA Ryoji MURATSUBAKI |
| Injection of liquid CO2 in hydrate layers of natural gas is a promising technique to recover methane simultaneously segregating CO2 from the biosphere. This work examined the rate of the conversion of CH4-hydrate immersed in liquid CO2 to CO2-hydrate in a temperature range of 274-281 K and a pressure range of 4-10 MPa . About 17％ of the methane, utilizing CO2, was recovered after 300 hours at 10 MPa and 281 K, and the conversion was on going even at the end of every experiment. The solute mobility rose as the temperature increased; it decreased as the total pressure increased The solute mobility of methane and CO2 in hydrate solid was determined for future feasibility studies. The configuration of the system should be investigated in a feasibility study, including the recovery system for CH4. [disposal of CO2, methane hydrate, CO2 hydrate,displacement] |
| * 〒930‐0848 富山市久方町2-54 北陸電力?葛Z術開発研究所 Engineering Research & Development Center, Hokuriku Electric Power Co., 2-54, Hisakata-machi, Toyama 930-0848 za50078@pi.rikuden.co.jp **〒210‐0855 川崎市川崎区南渡田町1-1 千代田化工建設(株)研究開発センター Research & Development Center, CHIYODA Co., 1-1, Minamiwatarida-cho, Kawasaki-ku, Kawasaki 210-0855 ***〒937‐8511 魚津市本江2410番地 (株)スギノマシン Sugino Mashine Ltd., 2410, Hongo, Uozu, 937-8511 |
| 技術シリーズ「圧力スケール」 1 Rev. High Pressure Sci. Technol. 12-1,63-68(2002) |
| メガバール領域でのPtとAu圧力スケールのクロスチェックとBiの状態方程式 Crosscheck of Pt and Au Pressure Scales and EOS of Bi to Megabar Pressures |
| 赤浜 裕一 川村 春樹 Anil K. Singh* Yuichi AKAHAMA Haruki KAWAMURA Anil K. SINGH |
| The volume compression of Bi, Pt and Au has been measured to megabar pressures by x-ray powder-diffraction experiments using a synchrotron radiation source. The EOS's of Pt and Au as the pressure scale have been crosschecked up to 145 GPa, and a considerable inconsistency between them is revealed in the megabar pressure region. The EOS of Au has been determined up to the megabar pressure range by the Pt scale. Stability of the high-pressure bcc phase of Bi is confirmed up to 222 GPa. The equation of state (EOS) of bcc-Bi is determined in a megabar pressure range with the bulk modulus, B0 = 35.45(26) GPa , its pressure derivative, B0' = 6.294(32) and the relative atomic volume, V/V0 = 0.8927(8) at atmospheric pressure, respectively. [bismuth, gold, platinum, equation of state, x-ray diffraction, high pressure, pressure scale, synchrotron radiation] |
| 〒678-1297 兵庫県赤穂郡上郡町光都3-2-1 姫路工業大学理学部 Faculty of Science, Himeji Institute of Technology, 3-2-1 Koto, Kamigohri-cho, Akou-gun, Hyogo 678-1297, akahama@sci.himeji-tech.ac.jp *Material Science Division, National Aerospace Laboratories, Bangalore 560 017, India |
〒606-0805
京都市左京区下鴨森本町 15 (財)生産開発科学研究所内
日本高圧力学会事務局
Tel (075)721-0376 Fax (075)723-9629
koatsu@mbox.kyoto-inet.or.jp