Abstract
Gas hydrates are crystalline solids that form from mixtures of water and light natural gases such as methane, carbon dioxide, ethane, propane and butane. Methane was the dominant component among other hydrocarbon gases in the sediments. Gas hydrates are ice-like crystalline solids formed from a mixtures of water and natural gas, usually methane. They occur where pressure, temperature, gas saturation, and local chemical conditions combine to make them stable.
Gas hydrates were discovered in 1810 by Sir Humphrey Davy, and were considered to be a laboratory curiosity. In the 1930s clathrate formation turned out to be a major problem, clogging pipelines during transportation of gas under cold conditions.
Sub-seabed methane within the continental margin sediments is produced primarily by microbial or thermogenic processes. In the microbial process organic debris are decomposed by a complex sequence (methanogenesis) into methane, by bacteria in an anoxic environment. Organic matter is composed of carbon, hydrogen and phosphorus in the ratio of 106:16:1, and decomposition results in production of methane.
Gas hydrate consists of three general structure types. Depending on the size of the guest molecule, natural gas hydrates can consist of any combination of three crystal structures: (1) Structure I or sI, (2) Structure II or sII, and (3) Structure H or sH. When pure liquid water freezes it crystallizes with hexagonal symmetry, but when it “freezes” as a hydrocarbon hydrate it does so with cubic symmetry for sI and sII, reverting to hexagonal symmetry for sH.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Achenbach E, Riensche E (1994) Methane/steam reforming kinetics for solid oxide fuel cells. J Power Sources 52:283
Andersland OB, Ladanyi B (1994) Frozen ground engineering. Chapman and Hall, New York
Bradford MCJ, Vannice MA (1999) CO2 reforming of CH4. Catal Rev Sci Eng 41:1–42
Brewer PG, Orr FM, Friederich G, Kvenvolden KA, Orange DL, McFarlane J, Kirkwood W (1997) Deep ocean field test of methane hydrate formation from a remotely operated vehicle. Geology 25:407–410
Buchanan P, Soper AK, Thompson H, Westacott RE, Creek JL, Hobson G, Koh CA (2005) Search for memory effects in methane hydrate: structure of water before hydrate formation and after hydrate decomposition. J Chem Phys 123:164507
Buffett B, Archer D (2004) Global inventory of methane clathrate: sensitivity to changes in the deep ocean. Earth Planet Sci Lett 227:185–199
Buffett BA, Zatsepina OY (2000) Formation of gas hydrate from dissolved gas in natural porous media. Mar Geol164:69–77
Choudhary TV, Goodman DW (2000) Methane activation on Ni and Ru model catalysts. J Mol Catal A 163:9–18
Collett TS (2002) Energy resource potential of natural gas hydrates. AAPG Bull 86:1971–1992
Dallimore SR, Collett TS (1999) Regional gas hydrate occurrences, permafrost conditions, and Cenozoic geology, Mackenzie Delta area. In: Collett TS (ed) Scientific results from JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, Mackenzie Delta, Northwest Territories, Canada. Geological Survey of Canada, Ottawa, pp 31–43
Desa E (2001) Submarine methane hydrates potential fuel resource of the 21st century. Proc AP Akad Sci 5:101–114
Dickens GR (2003) Rethinking the global carbon cycle with a large, dynamic and microbially mediated gas hydrate capacitor. Earth Planet Sci Lett 213:169–183
Dickens GR, Castillo MM, Walker JCG (1997) A blast of gas in the latest Paleocene: simulating first order effects of massive dissociation of oceanic methane hydrates. Geology 25:259–262
Dicks AL, Pointon KD, Siddle A (2000) Intrinsic reaction kinetics of methane steam reforming on a nickel/zirconia anode. J Power Sources 86:523
Durham WB, Kirby SH, Stern LA, Zhang W (2003) The strength and rheology of methane clathrate hydrate. J Geophys Res 108(B4):2182
Edmonds B, Moorwood R, Szczepanski R (1996) A practical model for the effect of salinity on gas hydrate formation. SPE paper 35569. Paper presented at the Society of Petroleum Engineers European production operations conference and exhibition, Stavanger, 16–17 April 1996
European Renewable Energy Council (2006) Renewable energy scenario by 2040. European Renewable Energy Council, Brussels
Farkhondeh M, Gheisi AR (2002) An introduction to natural gas hydrate. Transportation. Methane gas hydrate report. Tehran University
Gao S, House W, Chapman WG (2005) NMR/MRI study of clathrate hydrate mechanisms. J Phys Chem B 109:19090–19093
Goldberg D, Saito S (1998) Detection of gas hydrates using downhole logs. In: Henriet J.-P, Mienert J (eds) Gas hydrates – relevance to world margin stability and climate change. Geological Society, London, pp 129–132
Grassi G (1999) Modern bioenergy in the European Union. Renew Energy 16:985–990
Guerin G, Goldberg D, Meltse A (1999) Characterization of in situ elastic properties of gas hydrate-bearing sediments on the Blake Ridge. J Geophys Res 104:1778–17795
Gupta AK (2004) Marine gas hydrates: their economic and environmental importance. Curr Sci 86:1198–1199
Hacisalihoglu B, Demirbas AH, Hacisalihoglu S (2008) Hydrogen from gas hydrate and hydrogen sulfide in the Black Sea. Energy Educ Sci Technol 21:109–115
Handa YP, Stupin D (1992) Thermodynamic properties and dissociation characteristics of methane and propane hydrates in 70A radius silica gel pores. J Phys Chem 96:8599–8603
Handy MR (1994) Flow laws for rocks containing two non-linear viscous phases: a phenomenological approach. J Struct Geol 16:287–301
Helgerud MB (2001) Wave speeds in gas hydrate and sediments containing gas hydrate: a laboratory and modeling study. PhD thesis, Stanford University Press, Stanford
Hiraia H, Tanaka T, Kawamura T, Yamamoto Y, Yagi T (2004) Structural changes in gas hydrates and existence of a filled ice structure of methane hydrate above 40 GPa. J Phys Chem Solids 65:1555–1559
Holbrook WS, Hoskins H, Wood WT, Stephen RA, Lizarralde D (1996) Methane hydrate and free gas on the Blake Ridge from vertical seismic profiling. Science 273:1840–1843
Hornbach MJ, Holbrook WS, Gorman AR, Hackwith KL, Lizarralde D, Pecher I (2003) Direct seismic detection of methane hydrate on the Blake Ridge: Geophysics 68:92–100
Hovland M, Judd AG (eds) (1998) Seabed pockmarks and seepages: impact on geology, biology and the marine environment. Graham and Trotman, London
Hu YH, Ruckenstein E (2006) Clathrate hydrogen hydrate – a promising material for hydrogen storage. Angew Chem 45:2011–2013
Iwasa N, Kudo S, Takahashi H, Masuda S, Takezawa N (1993) Highly selective supported Pd catalysts for steam reforming of methanol. Catal Lett 19:211–216
Jenkins BM, Baxter LL, Miles TR Jr, Miles TR (1998) Combustion properties of biomass. Fuel Process Technol 54:17–46
Katsumasa K, Koga K, Tanaka H (2007) On the thermodynamic stability of hydrogen clathrate hydrates. J Chem. Phys 127:044509
Koh CA (2002) Towards a fundamental understanding of natural gas hydrates. Chem Soc Rev 31:157–167
Koo KY, Roh H-S, Seo YT, Seo DJ, Yoon WL, Park SB (2008a) Coke study on MgO-promoted Ni/Al2O3 catalyst in combined H2O and CO2 reforming of methane for gas to liquid (GTL) process. Appl Catal A Gen 340:183–190
Koo KY, Roh H-S, Seo YT, Seo DJ, Yoon WL, Park SB (2008b) A highly effective and stable nano-sized Ni/MgO–Al2O3 catalyst for gas to liquids (GTL) process. Int J Hydrogen Energy 33:2036–2043
Kvenvolden K (1993a). Gas hydrates – geological perspective and global change. Rev Geophys 31:173–187
Kvenvolden KA (1993b) Gas hydrates as a potential energy resource – a review of their methane content. In: Howell DG (ed) The future of energy gases – US Geological Survey professional paper 1570. United States Government Printing Office, Washington, pp 555–561
Kvenvolden KA (1998) A primer on the geological occurrence of gas hydrate. Geol Soc Lond Spec Publ 137:9–30
Kvenvolden KA, Lorenson TD (2000) The global occurrence of natural gas hydrate. In: Paull CK, Dillon WP (eds) Natural gas hydrates: occurrence, distribution, and dynamics. Geophysical monograph 124. American Geophysical Union, Washington, pp 3–18
Laosiripojana N, Assabumrungrat S (2007) Catalytic steam reforming of methane, methanol, and ethanol over Ni/YSZ: the possible use of these fuels in internal reforming SOFC. J Power Sources 163:943–951
Lerche I, Bagirov E (1998) Guide to gas hydrate stability in various geological settings. Mar Pet Geol 15:427–438
Mahajan D, Taylor CE, Mansoori GA (2007) An introduction to natural gas hydrate/clathrate: the major organic carbon reserve of the Earth. J Pet Sci Eng 56:1–8
Mao WL, Mao HK, Goncharov AF, Struzhkin VV, Guo Q, Hu J. Shu J, Hemley RJ, Somayazulu M, Zhao Y (2002) Hydrogen clusters in clathrate hydrate. Science 297:2247–2249
Martinson O (1994) Mass movements. In: Maltman A (ed) Geological deformation of sediments. Chapman and Hall, New York, pp 127–165
Matsumoto R, Watanabe Y, Satoh M, Okada H, Hiroki Y, Kawasaki M, ODP Leg 164 Shipboard Scientific Party (1996) Distribution and occurrence of marine gas hydrates – preliminary results of ODP Leg 164: Blake Ridge Drilling. J Geol Soc Jpn 102:932–944
Mazzini A, Ivanov MK, Parnell J, Stadnitskaia A, Cronin BT, Poludetkina E, Mazurenko L, van Weering TCE (2004) Methane-related authigenic carbonates from the Black Sea: geochemical characterization and relation to seeping fluids. Mar Geol 212:153–181
McCarthy VN, Jordan KD (2006) Structure and stability of the (H2O)21 and (H2O)20·(H2S) clusters: relevance of cluster systems to gas hydrate formation. Chem Phys Lett 429:166–168
Minh NQ, Takahashi T (1995) Science and technology of ceramic fuel cells. Elsevier, Amsterdam
Morrison RT, Boyd RN (1983) Organic chemistry, 4th edn. Allyn and Bacon, Singapore
Mulder T, Alexander J (2000) The physical character of subaqueous sedimentary density flows and their deposits. Sedimentology 48:269–299
Ohmura R, Shigetomi T, Mori YH (1999) Formation, growth and dissociation of clathrate hydrate crystals in liquid water in contact with a hydrophobic hydrate-forming liquid. J Cryst Growth 196:164–173
Patchkovskii S, Tse JS (2003) Thermodynamic stability of hydrogen clathrates. Proc Natl Acad Sci USA 100:14645–14650
Peña MA, Gómez JP, Fierro JLG (1996) New catalytic routes for syngas and hydrogen production. Appl Catal A 144:7–57
Popescu I, De Batist M, Lericolais G, Nouzé H, Poort J, Panin N, Versteeg W, Gillet H (2006) Multiple bottom-simulating reflections in the Black Sea: potential proxies of past climate conditions. Mar Geol 227:163–166
Roh H-S, Jun K-W, Baek S-C, Park S-E (2002) Carbon dioxide reforming of methane over Ni/q- Al2O3 catalysts: effect of Ni content. Bull Korean Chem Soc 23:1166–1168
Rostrup-Nielsen JR (1984) Catalytic steam reforming. In: Anderson JR, Boudart M (eds) Catalysis science and technology. Springer, Berlin
Sanloup C, Mao H, Hemley RJ (2002) High-pressure transformations in xenon hydrates. Proc Natl Acad Sci USA 99:25–28
Satoh M, Maekawa T, Okuda Y (1996) Estimation of amount of methane and resources of gas hydrates in the world and around Japan. J Geol Soc Jpn 102:959–971
Schicks JM, Erzinger J, Ziemann MA (2005) Raman spectra of gas hydrates – differences and analogies to ice Ih and (gas saturated) water. Spectrochim Acta A Mol Biomol Spectrosc 61:2399–2403
Schuth F (2005) Hydrogen and hydrates. Nature 434:712–713
Shipley TH, Houston MH, Buffler RT, Shaub FJ, McMillen KJ, Ladd JW, Worzel JL (1979) Seismic evidence for widespread possible gas hydrate horizons on continental slopes and rises. AAPG Bull 63:2204–2213
Sloan ED (1990) Natural gas hydrate phase equilibria and kinetics; understanding the state-ofthe-art. Rev Inst Fr Pet 45:245-266
Sloan ED Jr (1998) Clathrate hydrates of natural gases, 2nd edn. Dekker, New York
Sloan ED, Koh CA (2008) Clathrate hydrates of natural gases, 3rd edn. CRC, Boca Raton
Sorensen HA (1983) Energy conversion systems. Wiley, New York
Stoll RD, Bryan GM (1979) Physical properties of sediments containing gas hydrate. J Geophys Res 84(B4):1629–1634
Suess E, Bohrmann G, Rickert D, Kuhs WF, Torres ME, Thehu A, Linke P (2002) Properties and fabric or near-surface methane hydrates at Hydrate Ridge, Cassadia Margin. In: Proceedings of the fourth international conference on gas hydrates, Yokohama, 29–23 May
Takezawa N, Shimokawabe M, Hiramatsu H, Sugiura H, Asakawa T, Kobayashi H (1987) Steam reforming of methanol over Cu/ZrO2. Role of ZrO2 support. React Kinet Catal Lett 33:191–196
Tohidi B, Anderson R, Clennell MB, Burgass RW, Biderkab AB (2001) Visual observation of gas-hydrate formation and dissociation in synthetic porous media by means of glass micromodels. Geology 29:867–870
Torres ME, Wallmann K, Trhu AM, Bohrmann G, Borowski WS, Tomaru H (2004) Gas hydrate growth, methane transport, and chloride enrichment at the southern summit of Hydrate Ridge, Cascadia margin off Oregon. Earth Planet Sci Lett 226:225–241
Tucholke BE, Bryan GM, Ewing JI (1977) Gas-hydrate horizons detected in seismic-profiler data from the western North Atlantic. AAPG Bull 61:698–707
Tullis TE, Horowitz FG, Tullis J (1991) Flow laws of polyphase aggregates from end-member flow laws. J Geophys Res 96:8081–8096
UEIC (1989) Hydrogen sulfide. In: Ullmann’s encyclopedia of industrial chemistry, 5th edn, vol A13. VCH, Weinheim, pp 467–485
Waite WF, Winters WJ, Mason DH (2004) Methane hydrate formation in partially watersaturated Ottawa sand. Am Mineral 89:1202–1207
Winters WJ, Pecher IA, Waite FW, Mason DH (2004) Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate. Am Mineral 89:1221–1227
Yentekakis IV, Neophytides SG, Kaloyiannis AC, Vayenas CG (1993) A solid oxide fuel cell using an exothermic reaction as the heat source. Proceeding of the 3rd international symposium on solid oxide fuel cells, vol 4, Honolulu
Zhang W, Durham WB, Stern A, Kirby SH (1999) Experimental deformation of methane hydrate: new results. Eos Trans AGU 80(17):S337
Rights and permissions
Copyright information
© 2010 Springer-Verlag London Limited
About this chapter
Cite this chapter
(2010). Gas Hydrates. In: Methane Gas Hydrate. Green Energy and Technology. Springer, London. https://doi.org/10.1007/978-1-84882-872-8_3
Download citation
DOI: https://doi.org/10.1007/978-1-84882-872-8_3
Publisher Name: Springer, London
Print ISBN: 978-1-84882-871-1
Online ISBN: 978-1-84882-872-8
eBook Packages: EngineeringEngineering (R0)