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水合物研制、结构与性能及其在能源环境中的应用

朱金龙 赵予生 靳常青

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水合物研制、结构与性能及其在能源环境中的应用

朱金龙, 赵予生, 靳常青

Structure and properties of nature clathrate and its application in energy and enviromental science

Zhu Jin-Long, Zhao Yu-Sheng, Jin Chang-Qing
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  • 天然气水合物是与能源和环境相关的物质,可以进行甲烷等能源气体的存储和提取,也可以用于对二氧化碳等废气的封存.天然气水合物主要分为三种结构:sI,sⅡ和sH,在本文中对其稳定性、水笼类型和大小以及可俘获气体进行了论述.中子衍射技术是研究水合物的重要手段之一,有着独特的优势.如中子的穿透性可以研究在高压状态下压力腔体内的大块样品;中子对于轻元素的敏感性可以很好地确定水合物当中的碳、氢、氧元素.通过中子衍射和非弹散射可以得到水合物中H/D原子的位置、各向异性振动因子、不同温度压力下的客体分子的水笼占据率、客体分子在水笼中的无序分布、原子核密度分布(通过最大熵方法);通过时间分辨中子,可以检测水合物形成及分解过程的热力学和动力学过程.而利用非弹中子可以得到气体分子平移和旋转振动模式以及分子的量子态转变.通过二氧化碳气体注入对天然气水合物的开采可以实现能源气体甲烷的开采和废气二氧化碳的水合物封存,在减小地质灾害和开采成本上有着独特的优势.
    Clathrate hydrates are energy and environmental related materials for energy storage and extraction, as well as for waste gas sequestration. The three general structures of natural clathrates, structure I, structure Ⅱ and structure H are reviewed in the aspects of stability, cage size, and preferred guest molecule encapsulation. Neutron scattering technique has its unique advantage of clathrate hydrates characterization, such as large bulk property determination, penetration of high pressure vessel and the clathrate sample inside, sensitive to light elements (clathrate hydrates mainly containing C, H, and O atoms). Neutron diffraction and inelastic neutron scattering of clathrate hydrates are covered on the abilities of H/D atoms positions and anisotropic thermal parameters, pressure-temperature-dependent guest molecule occupancy, the disordered distributions of guest molecules and the nuclear density distributions, the thermodynamic and kinetic process of formation and decomposition, the translational and rotational vibration models of guest molecules and their quantum state transitions. Using CO2 to gently replace CH4 in methane hydrate is one of the most attractive exploiting schemes for its benefits to both geologic hazard consideration and cost efficiency (energy extraction and CO2 sequestration).
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    Walsh M R, Rainey J D, Lafond P G, Park D H, Beckham G T, Jones M D, Lee K H, Koh C A, Sloan E D, Wu D T, Sum A K 2011 Phys. Chem. Chem. Phys. 13 19951

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  • [1]

    Sloan E D, Ann K C 2007 Clathrate Hydrates of Natural Gases (3rd Ed.) (Chemical Industries Series: CRC Press)

    [2]

    Keith C H, Peter G B 2009 Annu. Rev. Mar. Sci. 1 303

    [3]

    Paull C K, Dillon W P 2001 Natural Gas Hydrates: Occurrence, Distribution, and Detection. Geophys. Monogr. Ser. (Vol 124) (Washington: Am. Geophys. Union) pp3-18

    [4]

    Milkov A V 2005 Org. Geochem. 36 681

    [5]

    Kvenvolden K A 2000 Ann. NY Acad. Sci. 912 17

    [6]

    Sloan Jr E D 2003 Nature 426 353

    [7]

    Berecz E, Balla-Achs M 1983 Gas Hydrates (New York: Elsevier Science Publishing Company Inc.)

    [8]

    Sloan E D 1998 Clathrate Hydrates of Natural Gases Marcel Dekker (Inc.: New York)

    [9]

    Khokhar A A, Gudmundsson J S, Sloan E D 1998 Fluide Phase Equilibria 150/151 383

    [10]

    Strobel T A, Koh C A, Sloan E D 2008 J. Phys. Chem. B 112 1885

    [11]

    Krawitz A D 2001 Introduction to Diffraction in Materials Science and Engineering (New York: John Wiley and Sons, Inc.)

    [12]

    Zhao Y, Xu H, Daemen L L, Lokshin K, Tait K T, Mao W L, Luo H, Currier R P, Hickmott D D 2007 Proc. Natl. Acad. Sci. USA 104 5727

    [13]

    Lokshin K A, Zhao Y 2005 Rev. Sci. Inst. 76 063909

    [14]

    Lokshin K A, Zhao Y, He D, Mao W L, Mao H K, Hemley R J, Lobanov M V, Greenblatt M 2004 Phys. Rev. Lett. 93 125503

    [15]

    Tait K T 2007 Dissertation for Doctoral Degree (Phoenix: Department of Geosciences, the University of Arizona)

    [16]

    Kirichek O, Done R, Goodway C M, Kibble M G, Evans B, Bowden Z A 2012 JPCS 340 012008

    [17]

    Zhao Y, Zhang J, Xu H, Lokshin K A, He D, Qian J, Pantea C, Daemen L L, Vogel S C, Ding Y, Xu J 2010 Appl. Phys. A 99 585

    [18]

    Mao W L, Mao H K, Goncharov A F, Struzhkin V V, Guo Q, Hu J, Shu J, Hemley R J, Somayazulu M, Zhao Y 2002 Science 297 2247

    [19]

    Klapproth A, Goreshnik E, Staykova D, Klein H, Kuhs W F 2003 Can. J. Phys. 81 503

    [20]

    Kuhs W F, Chazallon B, Radaelli P G, Pauer F 1997 J. Inclusion Phenom. Mol. Recognit. Chem. 29 65

    [21]

    Struzhkin V V, Militzer B, Mao W L, Mao H K, Hemley R J 2007 Chem. Rev. 107 4133

    [22]

    Mulder F M, Wagemaker M, van Eijck L, Kearley G J 2008 Chem. Phys. Chem. 9 1331

    [23]

    Chazallon B, Kuhs W F 2002 J. Chem. Phys. 117 308

    [24]

    McMullan R K, Kvick A 1990 Acta Cryst. B 46 390

    [25]

    Tse J S, Handa Y P, Ratcliffe C I, Powell B M 1986 J. Inclusion Phenom. Mol. Recognit. Chem. 4 235

    [26]

    Fortes A D, Brodholt J P, Wood I G, Vocadlo L, Jenkins H D B 2003 J. Chem. Phys. 119 10806

    [27]

    Henning R W, Schultz A J, Thieu V, Halpern Y 2000 J. Phys. Chem. A 104 5066

    [28]

    Rondinone A J, Chakoumakos B C, Rawn C J, Ishii Yoshinobu 2003 J. Phys. Chem. B 107 6046

    [29]

    Klapproth A, Chazallon B, Kuhs W F 1999 Monte-Carlo sorption and neutron diffraction study of the filling isotherm in clathrate hydrates. AIP Conference Proceedings 479 70-73

    [30]

    Chazallon B, Klapproth A, Kuhs W F 1999 Molecular-dynamics modeling and neutron powder diffraction study of the site disorder in air clathrate hydrates. AIP Conference Proceedings 479 74-77

    [31]

    Ikeda T, Yamamuro O, Matsuo T, Mori K, Torii S, Kamiyama T, Izumi F, Ikeda S, Mae S 1999 J. Phys. Chem. Sol. 60 1527

    [32]

    Izumi F, Kawamura Y 2006 Bunseki Kagaku 55 391

    [33]

    Izumi F, Momma K 2011 IOP Conf. Ser.: Mater. Sci. Eng. 18 022001

    [34]

    Hoshikawa A, Igawa N, Yamauchi H, Ishii Y 2005 J. Phys. Chem. Sol. 66 1810

    [35]

    Igawa N, Taguchi T, Hoshikawa A, Fukazawa H, Yamauchi H, Ustumi W, Ishii Y 2010 J. Phys. Chem. Sol. 71 899

    [36]

    Tulk C A, Klug D D, Chakoumakos B C, Yang L 2009 Phys. Rev. B 80 052101

    [37]

    Igawa N, Taguchi T, Hoshikawa A, Yamauchi H, Birumachi A, Ishii Y 2011 IOP Conf. Series: Materials Science and Engineering 18 022021

    [38]

    Murshed M M, Schmidt B C, Kuhs W F 2010 J. Phys. Chem. A 114 247

    [39]

    Klapproth A, Piltz R O, Peterson V K, Kennedy S J 2011 Proceedings of the 7th International Conference on Gas Hydrates Edinburgh, Scotland, United Kingdom, July 17-21, 2011 pp17-21

    [40]

    Halpern Y, Thieu V, Henning W R, Wang X, Schultz A J 2001 J. Am. Chem. Soc. 123 12826

    [41]

    Staykova D K, Hansen T, Salamatin A N, et al. 2002 Proceeding of the Fourth International Conference on Gas hydrates Yokohama, Japan, May 19-23, 2002

    [42]

    Staykova D K, Kuhs W F, Salamatin A N, Hansen T 2003 Model. J. Phys. Chem. B 107 10299

    [43]

    Kuhs W F, Genov G, Staykova D K, Hansen T 2004 Phys. Chem. Chem. Phys. 6 4917

    [44]

    Pauling L 1935 J. Am. Chem. Soc. 57 2680

    [45]

    Wernet P, Nordlund D, Bergmann U, Cavalleri M, Odelius M, Ogasawara H, Naslund L A, Hirsch T K, Ojamae L, Glatzel P, Pettersson L G M, Nilsoon A 2004 Science 304 995

    [46]

    van der Waals J H, Platteeuw J C 1959 Adv. Chem. Phys. 2 1

    [47]

    Parrish W R, Prausnitz J M 1972 Ind. Eng. Chem. Process Des. Dev. 11 26

    [48]

    Munck J, Skjold-Jorgensen S, Rasmussen P 1988 Chem. Eng. Sci. 43 2661

    [49]

    Berendsen H J C, Postma J P M, van Gunsteren W F, Dinola A, Haak J R 1981 Proceedings of the Fourteenth Jerusalem Symposium on Quantum Chemistry and Biochemistry (Vol 4) Israel, Jerusalem, April 13-16, 1981 pp331-342

    [50]

    Grim R G, Kerkar P B, Shebowich M, Arias M, Sloan E D, Koh C A, Sum A K 2012 J. Phys. Chem. C 116 18557

    [51]

    Walsh M R, Koh C A, Sloan E D, Sum A K, Wu D T 2009 Science 326 1095

    [52]

    Walsh M R, Rainey J D, Lafond P G, Park D H, Beckham G T, Jones M D, Lee K H, Koh C A, Sloan E D, Wu D T, Sum A K 2011 Phys. Chem. Chem. Phys. 13 19951

    [53]

    Udachin K A, Ratcliffe C I, Ripmeester J A 2007 J. Phys. Chem. B 111 11366

    [54]

    Manesh H M, Alavi S, Woo T K, Ashrafizaadeh M, Najafi B 2009 Phys. Chem. Chem. Phys. 11 8821

    [55]

    Takeya S, Udachin K A, Moudrakovski I L, Susilo R, Ripmeester J A 2010 J. Am. Chem. Soc. 132 524

    [56]

    Harris K D M, Cheung E Y 2004 Chem. Soc. Rev. 33 526

    [57]

    Favre-Nicolin V, Cerny R F O X 2002 J. Appl. Crystallogr. 35 734

    [58]

    Cerny R, Favre-Nicolin V 2007 Z. Kristallogr. 222 105-113

    [59]

    Schober H, Itoh H, Klapproth A, Chihaia V, Kuhs W F 2003 Eur. Phys. J. E 12 41

    [60]

    Tse J S, Klug D D, Zhao J Y, Sturhahn W, Alp E E, Baumert J, Gutt C, Johnson M R, Press W 2005 Nat. Mat. 4 917

    [61]

    Itoh H, Chazallon B, Schober H, Kawamura K, Kuhs W F 2003 Can. J. Phys. 81 493-501

    [62]

    Ulivi L, Celli M, Giannasi A, Ramirez-Cuesta A J 2008 J. Phys.: Condens. Matter 20 104242

    [63]

    Tait K T, Trouw F, Zhao Y 2007 J. Chem. Phys. 127 134505

    [64]

    Ikeda-Fukazawa T, Yamaguchi Y, Nagashima K, Kawamura K 2008 J. Chem. Phys. 129 224506

    [65]

    Celli M, Colognesi D, Ulivi L, Zoppi M, Ramirez-Cuesta A J 2012 J PCS 340 012051

    [66]

    Chazallon B, Itoh H, Koza M, Kuhs W F, Schober H 2002 Phys. Chem. Chem. Phys. 4 4809

    [67]

    Jones C Y, Peral I 2004 Am. Mineral. 89 1176

    [68]

    Baumert J 2003 Ph. D. Dissertaion (Kiel, German: Christian-Albrechts-Universitat)

    [69]

    Koh D Y, Kang H, Lee J W, Park Y J, Kin S J, Lee J Y, Lee J Y, Lee H 2016 Appl. Energy 162 114

    [70]

    Ohgaki K, Takano K, Sangawa H, Matsubara T, Nakano S 1996 J. Chem. Eng. Jpn. 29 478

    [71]

    Smith D H, Seshadri K, Wilder J W 2001 J. Energy Environ. Res. 1 101

    [72]

    Ersland G, Husebo J, Graue A, Kvamme B 2009 Energy Procedia 1 3477

    [73]

    Jung J W, Santamarina J C 2010 Geochem. Geophys. Geosy. 11 Q0AA13

    [74]

    Ota M, Saito T, Aida T, Watanabe M, Sato Y, Smith Jr R L, Inomata H 2007 AICHE J. 53 2715

    [75]

    Stevens J C, Howard J J, Baldwin B A, Ersland G, Husebo J, Graue A 2008 The 6th International Conference on Gas Hydrates Vancouver, British Columbia, July 6-20, 2008

    [76]

    Bai D, Zhang X, Chen G, Wang W 2012 Energy Environ. Sci. 5 7033

    [77]

    Geng C Y, Wen H, Zhou H 2009 J. Phys. Chem. A 113 5463

    [78]

    Schicks J M, Spangenberg E, Giese R, Steinhauer B, Klump J, Luzi M 2011 Energies 4 151

    [79]

    Ota M, Abe Y, Watanabe M, Smith Jr R L, Inomata H 2005 Fluid Phase Equilibr. 228/229 553

    [80]

    Qi Y X, Ota M, Zhang H 2011 Energy Convers. Manage. 52 2682

    [81]

    Tung Y T, Chen L J, Chen Y P, Lin S T 2011 J. Phys. Chem. B 115 15295

    [82]

    Park Y, Kim D Y, Lee J W, Huh D G, Park K P, Lee J, Lee H 2006 Proc. Nat. Acad. Sci. USA 103 12690

    [83]

    Liu B, Pan H, Wang X H, Li F G, Sun C Y, Chen G G 2013 Energies 6 6242

    [84]

    Zhao J F, Zhang L X, Chen X Q, Zhang Y, Liu Y, Song Y C 2016 Energ. Explor. Exploit. 34 129

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出版历程
  • 收稿日期:  2018-09-03
  • 修回日期:  2018-11-20
  • 刊出日期:  2019-01-05

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