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Gas hydrate

Gas hydrate, also known as clatherate, are ice like crystalline molecular complexes
composed of water and natural gas that form when gases, (mainly methane
produced by microbial break down of organic matter) combine with water at low
temperature and high pressure. Although Gas hydrate looks very much like ordinary
ice but it burns with a soft orange flame like the pilot light on a gas stove.

Gas hydrate was first produced in 1810 by Sir Humphrey Davy by bubbling
chlorine gas through water under elevated pressure. In 1930s presence of gas
hydrate was observed in oil & gas pipe lines. In 1970s Russian scientist postulated
the occurrence of natural deposits of gas hydrate. This theory was confirmed in
1980s by recovery of sea sample in black sea. In 1990s it was estimated that
amount of organic carbon recoverable from hydrate are more that all other known
fossil full sources combined. The world wide amount of methane gas hydrate is
estimated to be at least 1x 104 giga tons of carbon from 80 possible fields. This is
twice the amount of carbon held in all fossil fuels on earth. By the end of 20th century
many countries such Japan, Canada, USA, Germany and India has started research
programs for investigation of gas hydrate.

There are three primary conditions that must be satisfied in order that
methane hydrates are naturally able to form and be preserved. These are:

1. Sediment porewaters (or rarely water column) is saturated with CH4 (free gas)
2. Sufficient pressure is available (hydrostatic pressure, P)
3. The temperature (T) of the water and sediment is suitably cold.

The first condition, i.e., that the waters are saturated with respect to methane is
frequently met in shallow coastal waters. There are numerous sources for this
methane, but most commonly in this setting the gas is of bacterial or thermogenic
origin. The combination of temperature and pressure (water depth) necessary for
methane hydrate formation and stability are shown in Figure 1. In the unshaded
region, the pressure is either too low (too shallow) or the temperature too high for
hydrate to exist. The shaded region in Figure 1 shows the depth-temperature (P, T)
region in which gas hydrate is stable.

The gas hydrate stability zone (HSZ) in sediments can be delineated on a

temperature versus depth profile with respect to the hydrothermal gradient (for
subsea gas hydrates), geothermal gradient and clathrate phase boundary, as
shown in Figure (for subsea sediments). The position of the hydrate phase
boundary is primarily a function of gas composition, but may also be controlled by
pore fluid composition (e.g. presence of salts), pore size, and possibly sediment
mineralogy. Hydrothermal and geothermal gradients are locality dependent, and can
differ markedly with geographical location and tectonic setting. The predominant
hydrate-forming gas is methane, with lesser CO2 and hydrogen sulfide (H2S), all of
which are generally produced in-situ by microbial breakdown of sedimentary organic
matter. In hydrocarbon-rich provinces, clathrates may contain a more deep-seated
thermogenic gas component, generally in the form of ethane and propane, which,
due to increased thermodynamic stability, can shift the HSZ to considerably
shallower depths.
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Gas Hydrate Stability Gas Hydrate Stability in Ocean Sediments

Methane hydrates have been found in the subsurface in permafrost regions, but
most occur in oceanic sediments hundreds of meters below the sea floor where
water depths are greater than about 500 meters. Most occurrences of gas hydrate
are inferred from geophysical logs in the permafrost regions and from anomalous
seismic reflectors within ocean sediments called bottom-simulating reflectors, or
BSR’s, which are thought to indicate the base of the gas hydrate stability zone.
Examination of 90 gas hydrate samples recovered from 15 different geologic
regions indicates that most samples consist of individual hydrate grains or particles
in pores of sedimentary rocks. In general, the gas-hydrate-bearing zones in
sedimentary sections range from tens of centimeters to tens of meters in thickness.
Gas hydrate also occurs as nodules, laminae, and veins within sediment and, in one
case, as a pure gas hydrate layer as much as 4 meters thick

EVIDENCE FOR GAS HYDRATES

Although gas hydrate has been recognized in drilled cores, its presence over large
areas can be detected much more efficiently by acoustical methods, using
seismic-reflection profiles.

Hydrate has a very strong effect on acoustic reflections because it has a high
acoustic velocity (approximately 3.3 km/s - about twice that of sea-floor
sediments), and thus grains cemented with hydrate produce a high-velocity
deposit due to the mixing of hydrate with the sediment. The existence of
free gas below the BSR causes a drastic decrease of seismic velocity,
sometimes to levels lower than the seismic velocity of sea water (1500
m/sec). If there is no free gas below a deposit of gas hydrate, there will not
be a BSR and thus it will be impossible to detect the deposit
by conventional seismic methods. The fact these geophysical methods
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sometimes fail to detect gas hydrate may indicate that the total volume of
gas hydrate worldwide is still underestimated.

The BSR

BSRs (Bottom Simulating Reflectors) are seismic reflectors with a negative

reflection co-efficient. They occur at the interface between sediment containing
methane hydrate and sediment containing free methane. BSR structure and roughly
parallel to the seafloor morphology along isotherms. The reflector occurs in depths
of several hundred meters below the sea floor indicating the lower boundary of gas
hydrate stabilityconsequently, gas hydrate exists above the BSR, whereas below
the BSR there is free gas.

Hydrates in offshore Hydrocarbon production operation

Water based drilling fluids are used more often due to environmental concerns
especially in offshore exploration. A well hazard in deep water offshore drilling is
formation of gas hydrates on the event of a gas kick. In deep water drilling the
hydrostatic pressure of drill fluid column and low sea bed temperature could provide
a suitable thermodynamic condition for formation of hydrate in event of a gas kick.
This can cause a serious well safety and control problem during containment of kick.

Gas Hydrates formation in drill string, BOP stack,choke sand kill line can result
hazardous condition i.e. flow blockage, hindrance to drill string movement, loss of
circulation. Formation of hydrates could remove significant amount of water from
drilling fluids changing the properties of fluid which could result in salt precipitation
increase in fluid weight of the formation of solid plug.

Production

High pressure multi phase transfer lines from well head to the production platform
where sea bed temperature is low are prone to risk of blockage due gas hydrate
formation. Other facilities such as well and process equipment can also be prone to
hydrate formation.

Huge volume of gas hydrate entrapped within Earth’s surface and its wide
geographical distribution makes it attractive energy resource for coming years. But
there are two major issues related to hydrate exploration.

i. Production and use of gas hydrate will also release the

green house gas carbon dioxide and
ii. A production technology that is cost effective and
environmentally safe in yet to be developed.
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Indian Scenario

India has resources to produce 202, 552 MSCMD (Million Standard Cubic Meter of
Gas per day), around 1360 time the current demand of 150 MSCMD. Even if a part
of it is utilized, gas requirements will be full filled for a long time to come.

In 1984 the presence of gas hydrate in Indian offshore was first identified in
Andaman offshore. Realizing the potential of gas hydrates Natural Gas Hydrate
Programme (NGHD) was instituted on 1997 by Govt. of India (NGHP) was
reconstituted in the year 2000 to achieve maximum self sufficiency in hydrocarbon
through taping this unconventional source of energy.

The presence of gas hydrates along the Indian subcontinent margins has been
confirmed mainly from BSR.

Presence of large deposits in Krishna Godavari Basin in east coast, Andaman

offshore and Kerla Konkan basin in west coast is indicated based on analysis and
interpretation of various data.

Production of oceanic gas hydrate may seem most attractive because of the large
quantities available, but it is in fact less likely to be achieved in a short-term
perspective for several reasons Safe Exploitation of Gas hydrate reserve is
important from environmental point of view. Methane is a green house gas which is
23 lines more effective than carbon dioxide. If appropriate recovery technologies are
developed gas hydrate could become a new clean energy source.

The conditions for production of hydrocarbon are complicated and the geohazards
involved as well as the impact on the environment are difficult to assess. Only a
little is known for certain about the ultimate resource potential of gas hydrates
ongoing hydrate research programs throughout the world, will significantly
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contribute to our understanding of the technical challenges that must be overcome

to turn this potentially enormous storehouse of gas into a producible energy
resource.