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Methane clathrate

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"Burning ice". Methane, released by heating, burns; water drips.
Inset: clathrate structure (University of Göttingen, GZG. Abt. Kristallographie).
Source: United States Geological Survey

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Methane clathrate, also called methane hydrate, hydromethane, methane ice or "fire ice" is a solid clathrate compound (more specifically, a clathrate hydrate) in which a large amount of methane is trapped within a crystal structure of water, forming a solid similar to ice.[1] Originally thought to occur only in the outer regions of the Solar System where temperatures are low and water ice is common, significant deposits of methane clathrate have been found under sediments on the ocean floors of Earth.[2] The worldwide amounts of methane bound in gas hydrates is conservatively estimated to total twice the amount of carbon to be found in all known fossil fuels on Earth. [3]

Methane clathrates are common constituents of the shallow marine geosphere, and they occur both in deep sedimentary structures, and as outcrops on the ocean floor. Methane hydrates are believed to form by migration of gas from depth along geological faults, followed by precipitation, or crystallization, on contact of the rising gas stream with cold sea water. Methane clathrates are also present in deep Antarctic ice cores, and record a history of atmospheric methane concentrations, dating to 800,000 years ago.[4] The ice-core methane clathrate record is a primary source of data for global warming research, along with oxygen and carbon dioxide.

The average methane clathrate hydrate composition is 1 mole of methane for every 5.75 moles of water, though this is dependent on how many methane molecules "fit" into the various cage structures of the water lattice. The observed density is around 0.9 g/cm3.[5] One litre of methane clathrate solid would therefore contain, on average, 168 litres of methane gas (at STP).[nb 1]

Methane forms a structure I hydrate with two dodecahedral (12 vertices, thus 12 water molecules) and six tetradecahedral (14 water molecules) water cages per unit cell. This compares with a hydration number of 20 for methane in aqueous solution.[6] A methane clathrate MAS NMR spectrum recorded at 275 K and 3.1 MPa shows a peak for each cage type and a separate peak for gas phase methane. Recently, a clay-methane hydrate intercalate was synthesized in which a methane hydrate complex was introduced at the interlayer of a sodium-rich montmorillonite clay. The upper temperature stability of this phase is similar to that of structure I hydrate.[7]

Methane hydrate phase diagram. The horizontal axis shows temperature from -15 to 33 Celsius, the vertical axis shows pressure from 0 to 120,000 kilopascals (0 to 1,184 atmospheres). For example, at 4 Celsius hydrate forms above a pressure of about 50 atmospheres.

Natural deposits[edit]

Worldwide distribution of confirmed or inferred offshore gas hydrate-bearing sediments, 1996.
Source: USGS
Gas hydrate-bearing sediment, from the subduction zone off Oregon
Specific structure of a gas hydrate piece, from the subduction zone off Oregon

Methane clathrates are restricted to the shallow lithosphere (i.e. < 2000 m depth). Furthermore, necessary conditions are found only either in polar continental sedimentary rocks where surface temperatures are less than 0 Â°C; or in oceanic sediment at water depths greater than 300 m where the bottom water temperature is around 2 Â°C. In addition, deep lakes may host gas hydrates as well, e.g. the freshwater Lake Baikal, Siberia.[8] Continental deposits have been located in Siberia and Alaska in sandstone and siltstone beds at less than 800 m depth. Oceanic deposits seem to be widespread in the continental shelf (see Fig.) and can occur within the sediments at depth or close to the sediment-water interface. They may cap even larger deposits of gaseous methane.[9]

Oceanic[edit]

There are two distinct types of oceanic deposit. The most common is dominated (> 99%) by methane contained in a structure I clathrate and generally found at depth in the sediment. Here, the methane is isotopically light (δ13C < -60‰) which indicates that it is derived from the microbial reduction of CO2. The clathrates in these deep deposits are thought to have formed in situ from the microbially produced methane, as the δ13C values of clathrate and surrounding dissolved methane are similar.[9]

These deposits are located within a mid-depth zone around 300–500 m thick in the sediments (the Gas Hydrate Stability Zone, or GHSZ) where they coexist with methane dissolved in the pore-waters. Above this zone methane is only present in its dissolved form at concentrations that decrease towards the sediment surface. Below it, methane is gaseous. At Blake Ridge on the Atlantic continental rise, the GHSZ started at 190 m depth and continued to 450 m, where it reached equilibrium with the gaseous phase. Measurements indicated that methane occupied 0-9% by volume in the GHSZ, and ~12% in the gaseous zone.[10]

In the less common second type found near the sediment surface some samples have a higher proportion of longer-chain hydrocarbons (<99% methane) contained in a structure II clathrate. Carbon from this type of clathrate is isotopically heavier (δ13C is -29 to -57 ‰) and is thought to have migrated upwards from deep sediments, where methane was formed by thermal decomposition of organic matter. Examples of this type of deposit have been found in the Gulf of Mexico and the Caspian Sea.[9]

Some deposits have characteristics intermediate between the microbially and thermally sourced types and are considered to be formed from a mixture of the two.

The methane in gas hydrates is dominantly generated by microbial consortia degrading organic matter in low oxygen environments, with the methane itself produced by methanogenic Archaea. Organic matter in the uppermost few centimetres of sediments is first attacked by aerobic bacteria, generating CO2, which escapes from the sediments into the water column. Below this region of aerobic activity, anaerobic processes take over, including, successively with depth, the microbial reduction of nitrite/nitrate, metal oxides, and then sulfates are reduced to sulfides. Finally, once sulfate is used up, methanogenesis becomes a dominant pathway for organic carbon remineralization.

If the sedimentation rate is low (about 1 cm/kyr), the organic carbon content is low (about 1% ), and oxygen is abundant, aerobic bacteria can use up all the organic matter in the sediments faster than oxygen is depleted, so lower-energy electron acceptors are not used. But where sedimentation rates and the organic carbon content are high, which is typically the case on continental shelves and beneath western boundary current upwelling zones, the pore waters in the sediments become anoxic at depths of only a few cm or less. In such organic-rich marine sediments, sulfate then becomes the most important terminal electron acceptor due to its high concentration in seawater, although it too is depleted by a depth of centimeters to meters. Below this, methane is produced. This production of methane is a rather complicated process, requiring a highly reducing environment (Eh -350 to -450 mV) and a pH between 6 and 8, as well as a complex syntrophic consortia of different varieties of Archaea and Bacteria, although it is only Archaea that actually emit methane.

In some regions (e.g., Gulf of Mexico) methane in clathrates may be at least partially derived from thermal degradation of organic matter, dominantly in petroleum.[11] The methane in clathrates typically has a biogenic isotopic signature and highly variable δ13C (-40 to -100‰), with an approximate average of about -65 ‰ .[12][13][14] Below the zone of solid clathrates, large volumes of methane may occur as bubbles of free gas in the sediments.[15][16][17]

The presence of clathrates at a given site can often be determined by observation of a "Bottom Simulating Reflector" (BSR), which is a seismic reflection at the sediment to clathrate stability zone interface caused by the unequal densities of normal sediments and those laced with clathrates.

Reservoir size[edit]

The size of the oceanic methane clathrate reservoir is poorly known, and estimates of its size decreased by roughly an order of magnitude per decade since it was first recognized that clathrates could exist in the oceans during the 1960s and '70s.[18] The highest estimates (e.g. 3Template:e m³)[19] were based on the assumption that fully dense clathrates could litter the entire floor of the deep ocean. Improvements in our understanding of clathrate chemistry and sedimentology have revealed that hydrates only form in a narrow range of depths (continental shelves), only at some locations in the range of depths where they could occur (10-30% of the GHSZ), and typically are found at low concentrations (0.9-1.5% by volume) at sites where they do occur. Recent estimates constrained by direct sampling suggest the global inventory occupies between one and five million cubic kilometres (0.24 to 1.2 million cubic miles).[18] This estimate, corresponding to 500-2500 gigatonnes carbon (Gt C), is smaller than the 5000 Gt C estimated for all other fossil fuel reserves but substantially larger than the ~230 Gt C estimated for other natural gas sources.[18][20] The permafrost reservoir has been estimated at about 400 Gt C in the Arctic,[21] but no estimates have been made of possible Antarctic reservoirs. These are large amounts. For comparison the total carbon in the atmosphere is around 700 gigatons.[22]

These modern estimates are notably smaller than the 10,000 to 11,000 Gt C (2Template:e m³) proposed[23] by previous workers as a motivation considering clathrates as a fossil fuel resource (MacDonald 1990, Kvenvolden 1998). Lower abundances of clathrates do not rule out their economic potential, but a lower total volume and apparently low concentration at most sites[18] does suggest that only a limited percentage of clathrates deposits may provide an economically viable resource.

Continental[edit]

Methane clathrates in continental rocks are trapped in beds of sandstone or siltstone at depths of less than 800 m. Sampling indicates they are formed from a mix of thermally and microbially derived gas from which the heavier hydrocarbons were later selectively removed. These occur in a Alaska, Siberia as well as Northern Canada.

In 2008, Canadian and Japanese researchers extracted a constant stream of natural gas from a test project at the Mallik gas hydrate field in the Mackenzie River delta. This was the second such drilling at Mallik: the first took place in 2002 and used heat to release methane. In the 2008 experiment, researchers were able to extract gas by lowering the pressure, without heating, requiring significantly less energy.[24] The Mallik gas hydrate field was first discovered by Imperial Oil in 1971-1972.[25]

Commercial use[edit]

The sedimentary methane hydrate reservoir probably contains 2–10 times the currently known reserves of conventional natural gas. This represents a potentially important future source of hydrocarbon fuel. However, in the majority of sites deposits are likely to be too dispersed for economic extraction.[18] Other problems facing commercial exploitation are detection of viable reserves; and development of the technology for extracting methane gas from the hydrate deposits. To date, there has only been one field commercially produced where some of the gas is thought to have been from methane clathrates, Messoyakha Gas Field, supplying the nearby Russian city of Norilsk.

A research and development project in Japan is aiming for commercial-scale extraction by 2016.[26] In August 2006, China announced plans to spend 800 million yuan (US$100 million) over the next 10 years to study natural gas hydrates.[27] A potentially economic reserve in the Gulf of Mexico may contain ~1010 m3 of gas.[18] Bjørn Kvamme and Arne Graue at the Institute for Physics and technology at the University of Bergen have developed a method for injecting CO2 into hydrates and reversing the process; thereby extracting CH4 by direct exchange.[28]

Hydrates in natural gas processing[edit]

Routine operations[edit]

Methane clathrates (hydrates) are also commonly formed during natural gas production operations, when liquid water is condensed in the presence of methane at high pressure. It is known that larger hydrocarbon molecules such as ethane and propane can also form hydrates, although as the molecule length increases (butanes, pentanes), they cannot fit into the water cage structure and tend to destabilise the formation of hydrates.

Once formed, hydrates can block pipeline and processing equipment. They are generally then removed by reducing the pressure, heating them, or dissolving them by chemical means (methanol is commonly used). Care must be taken to ensure that the removal of the hydrates is carefully controlled, because of the potential for the hydrate to undergo a phase transition from the solid hydrate to release water and gaseous methane at a high rate as the pressure is reduced. The rapid release of methane gas in a closed system can result in a rapid increases in pressure.[5]

It is generally preferable to prevent hydrates from forming or blocking equipment. This is commonly achieved by removing water, or by the addition of ethylene glycol (MEG) or methanol, which act to depress the temperature at which hydrates will form (i.e. common antifreeze). In recent years, development of other forms of hydrate inhibitors have been developed, such as Kinetic Hydrate Inhibitors (which dramatically slow the rate of hydrate formation) and anti-agglomerates, which do not prevent hydrates forming, but do prevent them sticking together to block equipment.

Effect of hydrate phase transition during deep water drilling[edit]

When drilling in oil- and gas-bearing formations submerged in deep water, the reservoir gas may flow into the well bore and form gas hydrates owing to the low temperatures and high pressures found during deep water drilling. The gas hydrates may then flow upward with drilling mud or other discharged fluids. As they rise, the pressure in the annulus decreases and the hydrates dissociate into gas and water. The rapid gas expansion ejects fluid from the well, reducing the pressure further, which leads to more hydrate dissociation and further fluid ejection. The resulting violent expulsion of fluid from the annulus is one potential cause or contributor to what is referred to as a "kick".[29] (Kicks, which can cause blowouts, typically do not involve hydrates: see Blowout: formation kick).

Measures which reduce the risk of hydrate formation include:

  • High flow-rates, which limit the time for hydrate formation in a volume of fluid, thereby reducing the kick potential.[29]
  • Careful measuring of line flow to detect incipient hydrate plugging.[29]
  • Additional care in measuring when gas production rates are low and the possibility of hydrate formation is higher than at relatively high gas flow rates.[29]
  • Monitoring of well casing after it is "shut in" (isolated) may indicate hydrate formation. Following "shut in", the pressure rises as gas diffuses through the reservoir to the bore hole; the rate of pressure rise will exhibit a reduced rate of increase when hydrates are forming.[29]
  • Additions of energy (e.g., the energy released by setting cement used in well completion) can raise the temperature and convert hydrates to gas, producing a "kick".

Blowout recovery[edit]

Concept diagram of oil containment domes, acting as upsidedown funnels to pipe oil to surface ships. The sunken oil rig is nearby.

At sufficient depths, methane complexes directly with water to form methane hydrates, as was observed during the Deepwater Horizon oil spill in 2010. BP engineers developed and deployed a subsea oil recovery system over oil spilling from a deepwater oil well 5000 ft below sea level to capture escaping oil. This involved placing a 125 ton dome over the largest of the well leaks and piping it to a storage vessel on the surface.[30] This option had the potential to collect as much as 85% of the leaking oil but is previously untested at such depths.[30] BP deployed the system on May 7–8, when it failed due to buildup of methane clathrate inside the dome; with its low density of approximately 0.9g/cm3 the methane hydrates accumulated in the dome, adding buoyancy and obstructing flow.[31]

Methane clathrates and climate change[edit]

Main article: Wikipedia:Clathrate gun hypothesis


Methane is a powerful greenhouse gas. Despite its short atmospheric half life of 7 years, methane has a global warming potential of 62 over 20 years and 21 over 100 years (IPCC, 1996; Berner and Berner, 1996; vanLoon and Duffy, 2000). The sudden release of large amounts of natural gas from methane clathrate deposits has been hypothesized as a cause of past and possibly future climate changes. Events possibly linked in this way are the Permian-Triassic extinction event and the Paleocene-Eocene Thermal Maximum.

Climate scientists such as James E. Hansen expect that methane clathrates in the permafrost regions will be released as a result of global warming, unleashing powerful feedback forces which may cause runaway climate change that cannot be controlled.

Recent research carried out in 2008 in the Siberian Arctic has shown millions of tonnes of methane being released[32][33][34][35][36] with concentrations in some regions reaching up to 100 times above normal.[37][38]

Natural gas hydrates (NGH) vs. liquified natural gas (LNG) in transportation[edit]

Since methane clathrates are stable at a higher temperature than liquefied natural gas (LNG) (−20 vs −162 °C), there is some interest in converting natural gas into clathrates rather than liquifying it when transporting it by seagoing vessels. A significant advantage would be that the production of natural gas hydrate (NGH) from natural gas at the terminal would require a smaller refrigeration plant and less energy than LNG would. Offsetting this, for 100 tonnes of methane transported, 750 tonnes of methane hydrate would have to be transported; since this would require a ship of 7.5 times greater displacement, or require more ships, it is unlikely to prove economic.

See also[edit]

Notes[edit]

  1. ↑ The average methane clathrate hydrate composition is 1 mole of methane for every 5.75 moles of water. The observed density is around 0.9 g/cm3.[5] For one mole of methane, which has a molar mass of about 16.04 g (see Methane), we have 5.75 moles of water, with a molar mass of about 18.02 g (see Properties of water), so together for each mole of methane the clathrate complex has a mass of Template:nowrap = 119.65 g. The fractional contribution of methane to the mass is then equal to Template:nowrap = 0.134. The density is around 0.9 g/cm3, so one litre of methane clathrate has a mass of around 0.9 kg, and the mass of the methane contained therein is then about Template:nowrap = 0.1206 kg. At a density as a gas of 0.717 kg/m3 (at 0 Â°C; see the info box at Methane), that means a volume of Template:nowrap = 0.168 m3 = 168 L.

References[edit]

  1. ↑ US Geological Survey, Gas hydrate: What is it?, accessed 27 February 2010.
  2. ↑ Roald Hoffmann, (2006). "Old Gas, New Gas," American Scientist, 94, 16–18.
  3. ↑ Gas (Methane) Hydrates -- A New Frontier , USGS fact sheet
  4. ↑ D, (2008). "High resolution carbon dioxide concentration record 650,000–800,000 years before present," Nature, 453, 379–382.
  5. ↑ 5.0 5.1 5.2 Michael D. Max (2003 url = http://books.google.com/?id=fd8QFKwcSskC&printsec=frontcover#v=onepage&q). Natural Gas Hydrate in Oceanic and Permafrost Environments, Kluwer Academic Publishers.
  6. ↑ Steven F., (2006). "Direct Measure of the Hydration Number of Aqueous Methane," J. Am. Chem. Soc., 128, 414–415. Note: the number 20 is called a magic number equal to the number found for the amount of water molecules surrounding a hydronium ion.
  7. ↑ S, (2003). "New gas-hydrate phase: Synthesis and stability of clay-methane hydrate intercalate," Geology, 31, 653–656.
  8. ↑ M. et al., (2001). "Multi-frequency seismic study of gas hydrate-bearing sediments in Lake Baikal, Siberia," Marine Geology, 172, 1–21.
  9. ↑ 9.0 9.1 9.2 K., (1995). "A review of the geochemistry of methane in natural gas hydrate," Organic Geochemistry, 23, 997–1008.
  10. ↑ GR, (1997). "Direct measurement of in situ methane quantities in a large gas-hydrate reservoir," Nature, 385, 426–428.
  11. ↑ Kvenvolden, 1998
  12. ↑ Kvenvolden, 1993
  13. ↑ Dickens et al., 1995
  14. ↑ R., (1995). "Causes of the δ13C anomalies of carbonates and a new paradigm 'Gas Hydrate Hypothesis'," Jour. Geol. Soc. Japan, 101, 902–924.
  15. ↑ Dickens et al., 1997
  16. ↑ R., (1996). "Distribution and occurrence of marine gas hydrates - preliminary results of ODP Leg 164: Blake Ridge Drilling," J. Geol. Soc. Japan, 102, 932–944.
  17. ↑ Clathrates - little known components of the global carbon cycle
  18. ↑ 18.0 18.1 18.2 18.3 18.4 18.5 AV, (2004). "Global estimates of hydrate-bound gas in marine sediments: how much is really out there?," Earth-Sci Rev, 66, 183–197.
  19. ↑ A. A., (1973). "{{{title}}}," Doklady Akademii Nauk SSSR, 212, 931–934.
  20. ↑ USGS World Energy Assessment Team, 2000. US Geological Survey world petroleum assessment 2000––description and results. USGS Digital Data Series DDS-60.
  21. ↑ MacDonald, 1990
  22. ↑ Geotimes — November 2004 — Methane Hydrate and Abrupt Climate Change
  23. ↑ Bruce, ({{{year}}}). "Global inventory of methane clathrate: sensitivity to changes in the deep ocean," Earth and Planetary Science Letters, 227, 185.
  24. ↑ Thomas, Brodie Researchers extract methane gas from under permafrost. Northern News Services. URL accessed on 2008-06-16.
  25. ↑ Geological Survey of Canada, Mallik 2002. Natural Resources Canada. URL accessed on 2008-06-16.
  26. ↑ Background and organization
  27. ↑ Agreements to boost bilateral ties
  28. ↑ Norske forskere bak energirevolusjon, VB nett, in Norwegian
  29. ↑ 29.0 29.1 29.2 29.3 29.4 Zhiyuan Wang, Sun Baojiang, ({{{year}}}). "Annular multiphase flow behavior during deep water drilling and the effect of hydrate phase transition," Petroleum Science, 6, 57–63.
  30. ↑ 30.0 30.1 Winning, David US Oil Spill Response Team: Plan To Deploy Dome In 6–8 Days. Wall Street Journal. Dow Jones & Company. URL accessed on 2010-05-05. Dead link?
  31. ↑ Giant dome fails to fix Deepwater Horizon oil disaster. Nature.com. URL accessed on 10 May 2010.
  32. ↑ Compare: Methane bubbling through seafloor creates undersea hills, Monterey Bay Aquarium Research Institute, 5 February 2007
  33. ↑ Translation of a blog entry by Örjan Gustafsson, expedition research leader, 2 September 2008
  34. ↑ N. Shakhova, I. Semiletov, A. Salyuk, D. Kosmach, and N. Bel’cheva (2007), Methane release on the Arctic East Siberian shelf, Geophysical Research Abstracts, 9, 01071
  35. ↑ N. Shakhova, I. Semiletov, A. Salyuk, D. Kosmach (2008), Anomalies of methane in the atmosphere over the East Siberian shelf: Is there any sign of methane leakage from shallow shelf hydrates?, EGU General Assembly 2008, Geophysical Research Abstracts, 10, EGU2008-A-01526
  36. ↑ Volker Mrasek, A Storehouse of Greenhouse Gases Is Opening in Siberia, Spiegel International Online, 17 April 2008
  37. ↑ Connor, Steve Exclusive: The methane time bomb. The Independent. URL accessed on 2008-10-03.
  38. ↑ Connor, Steve Hundreds of methane 'plumes' discovered. The Independent. URL accessed on 2008-10-03.

External links[edit]

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