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Methane Hydrate:
 A Burning Ice

                  By
             Priyaranjan
               2nd Year
       Petroleum Engineering
What is a Gas Hydrate?




•Gas Hydrates are solid mixture of natural gas and water

•Gas molecules are encaged between ice lattices.
 (85 : 15 :: water : gas molecules)

•Contains 160-180 times the natural gas by volume at
standard conditions.
Hydrate samples




      Gas hydrates in sea-floor mounds Here methane gas is
      actively dissociating from a hydrate mound.




Gas hydrate can occur as nodules, laminae, or veins within sediment
Ice That Doesn’t Melt !

•Formed at low temperatures and high pressure.

•Known to occur at temp. below 295K and pressure
greater than 3000KPa.

•Water molecules attach themselves through hydrogen
bonding and form cavities which are occupied by a
single gas or volatile liquid molecule.

•Gas or volatile liquid inside the water cage stabilizes the
structure through physical bonding via weak van der
Waals forces.
Gas Hydrate Potential

Worldwide Estimate of Gas Hydrates
•700,000 Tcf (20,000 trillion cubic meters)

•Conventionally recoverable methane 8,800 Tcf ( 250
trillion cubic meters)

•Two times the total energy in coal oil and conventional
gas.
If 1% of gas –in-place in gas hydrate is recoverable : 2000 Tcf
Stability Zone In Sea




Found inside sea at depths greater than 500m and at
temperatures even higher than those for ice stability.
Stable in association with permafrost in the polar
regions, both in offshore and onshore sediments.
Why is it urgent to be studied ?


•A future energy source


•Climate change


•It can affect sediment strength, which can
initiate landslides on the slope and rise.
A Future Energy Source


•When hydrate fills the pore space of sediment, it can
reduce permeability and create a gas trap, The gas can
continually migrate upwards to fill any open pore
spaces.


•This process, in turn, causes the trap to become more
effective, producing highly concentrated methane and
methane hydrate reservoirs.
A Future Energy Source … Continued

•Hydrate is a gas concentrator; the breakdown of a
unit volume of methane hydrate at a pressure of one
atmosphere produces about 160 unit volumes of
gas.(The worldwide amount of methane
in gas hydrates is considered to contain at least
1x104 gigatons of carbon in a very conservative estimate).


•This is about twice the amount of carbon held in
all fossil fuels on earth.
Climate Change
•Methane from the hydrate reservoir might
significantly modify the global greenhouse, because
methane is ~20 times as effective a greenhouse gas
as carbon dioxide, and gas hydrate may contain
three orders of magnitude more methane than exists
in the present-day
atmosphere.


•Because hydrate breakdown, causing release of
methane to the atmosphere, can be related to
pressure changes caused by glacial sea-level
fluctuations, gas hydrate may play a role in
controlling long-term global climate change.
Climate Change           … continued



•Methane is an environmentally cleaner fuel than
 oil, coal, or oil shale which all have an immense
 environmental impact during production and
 combustion.


•We can find a way to trap carbon dioxide at the
 seafloor where it would eventually be buried by
 sediment.
Affects sediment strength


•Gas hydrate apparently cements sediment, and,
therefore, it can have a significant effect on sediment
strength; its formation and breakdown may influence
the occurrence and location of submarine landslides.


•Such landslides may release methane into the
atmosphere, which may affect global climate.
Affects sediment strength              … continued



•Changes in water pressure due to sea level changes
may generate landslides by converting the hydrate to
gas plus water, causing significant weakening of the
sediment, and generating a rise of pore pressure.
Conversely, sea-floor landslides can cause breakdown
of hydrate by reducing the pressure in sediments.


•These interacting processes may cause cascading
slides, which would result in breakdown of hydrate
and release of methane to the atmosphere.
Present Day Techniques
1. THERMAL INJECTION
2. INHIBHITORS
3. DEPRESSURISATION




                             Courtesy :slb
Production of Gas Hydrates
Problems with present day
           techniques
   Thermal injection – Unavoidable heat losses due to host
    rock, economical infeasibility.

   Depressurization – Endothermic nature causing
    decrease in reservoir temperature.

   Inhibitors – methanol and ethylene glycol are expensive
    chemicals.
New concept
             diagram of reservoir.
Production well                        Injection well




                                              Antenna
                                            (micro waves)


                    Gas hydrate reservoir
Steps involved
Release of microwaves (@2450Mhz).
Melting of gas hydrate or ice .(Temp. > 273 k )
Injection of Fluorine.
Reaction between methyl radical and injected fluorine gas
(halogenation).
   .
 CH 3 + F2 = CH3F( -431KJ/mole)
(Solubility of methyl fluoride(166cc in 100ml of water))
Recovery of liquefied gas hydrate   solution.
Step 1: Wurtz Reaction
2 CH3F + Na ----- 2 NaF + CH3-CH3
Step 2 :Electrolysis
 NaF ----- Na + 1/2 F2 ↑
Step 3 :Cracking
CH3-CH3 ------ 2 CH4 ↑
Advantages with respect to normal
                  techniques

•Cost effective ,instantaneous and selective heating,
catalyze chemical reaction.

•Methyl fluoride is not an class 1 or 2 ozone depleting
chemical and stable compound.

•Huge reduction in disaster on rig floor or drill floor
related issues.

•Increase in the permeability and porosity of rock.
Challenges

•Fluorine is highly electronegative and
 reactive in nature e.g. injection problems.


•Transportation of methyl fluoride solution.
Conclusion
•Huge amount of natural gas trapped in hydrates : too
enormous to ignore.

•It’s a threat to climate as well so there is an urgent
need that we use it for positive purpose.

•Technology and scientific understanding for exploitation
of gas hydrate is to be developed .

•Much to be learned before gas hydrates can be
considered a resource.

•The integration of various sciences and using the
fluorine in this technique will definitely play a vital role
in the methane extraction.
References

• www.spe.org

•http://en.wikipedia.org

•http://www.cbc.ca
Gas Hydrate

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Gas Hydrate

  • 1. Methane Hydrate: A Burning Ice By Priyaranjan 2nd Year Petroleum Engineering
  • 2. What is a Gas Hydrate? •Gas Hydrates are solid mixture of natural gas and water •Gas molecules are encaged between ice lattices. (85 : 15 :: water : gas molecules) •Contains 160-180 times the natural gas by volume at standard conditions.
  • 3. Hydrate samples Gas hydrates in sea-floor mounds Here methane gas is actively dissociating from a hydrate mound. Gas hydrate can occur as nodules, laminae, or veins within sediment
  • 4. Ice That Doesn’t Melt ! •Formed at low temperatures and high pressure. •Known to occur at temp. below 295K and pressure greater than 3000KPa. •Water molecules attach themselves through hydrogen bonding and form cavities which are occupied by a single gas or volatile liquid molecule. •Gas or volatile liquid inside the water cage stabilizes the structure through physical bonding via weak van der Waals forces.
  • 5. Gas Hydrate Potential Worldwide Estimate of Gas Hydrates •700,000 Tcf (20,000 trillion cubic meters) •Conventionally recoverable methane 8,800 Tcf ( 250 trillion cubic meters) •Two times the total energy in coal oil and conventional gas. If 1% of gas –in-place in gas hydrate is recoverable : 2000 Tcf
  • 6. Stability Zone In Sea Found inside sea at depths greater than 500m and at temperatures even higher than those for ice stability. Stable in association with permafrost in the polar regions, both in offshore and onshore sediments.
  • 7. Why is it urgent to be studied ? •A future energy source •Climate change •It can affect sediment strength, which can initiate landslides on the slope and rise.
  • 8. A Future Energy Source •When hydrate fills the pore space of sediment, it can reduce permeability and create a gas trap, The gas can continually migrate upwards to fill any open pore spaces. •This process, in turn, causes the trap to become more effective, producing highly concentrated methane and methane hydrate reservoirs.
  • 9. A Future Energy Source … Continued •Hydrate is a gas concentrator; the breakdown of a unit volume of methane hydrate at a pressure of one atmosphere produces about 160 unit volumes of gas.(The worldwide amount of methane in gas hydrates is considered to contain at least 1x104 gigatons of carbon in a very conservative estimate). •This is about twice the amount of carbon held in all fossil fuels on earth.
  • 10. Climate Change •Methane from the hydrate reservoir might significantly modify the global greenhouse, because methane is ~20 times as effective a greenhouse gas as carbon dioxide, and gas hydrate may contain three orders of magnitude more methane than exists in the present-day atmosphere. •Because hydrate breakdown, causing release of methane to the atmosphere, can be related to pressure changes caused by glacial sea-level fluctuations, gas hydrate may play a role in controlling long-term global climate change.
  • 11. Climate Change … continued •Methane is an environmentally cleaner fuel than oil, coal, or oil shale which all have an immense environmental impact during production and combustion. •We can find a way to trap carbon dioxide at the seafloor where it would eventually be buried by sediment.
  • 12. Affects sediment strength •Gas hydrate apparently cements sediment, and, therefore, it can have a significant effect on sediment strength; its formation and breakdown may influence the occurrence and location of submarine landslides. •Such landslides may release methane into the atmosphere, which may affect global climate.
  • 13. Affects sediment strength … continued •Changes in water pressure due to sea level changes may generate landslides by converting the hydrate to gas plus water, causing significant weakening of the sediment, and generating a rise of pore pressure. Conversely, sea-floor landslides can cause breakdown of hydrate by reducing the pressure in sediments. •These interacting processes may cause cascading slides, which would result in breakdown of hydrate and release of methane to the atmosphere.
  • 14. Present Day Techniques 1. THERMAL INJECTION 2. INHIBHITORS 3. DEPRESSURISATION Courtesy :slb
  • 15. Production of Gas Hydrates
  • 16. Problems with present day techniques  Thermal injection – Unavoidable heat losses due to host rock, economical infeasibility.  Depressurization – Endothermic nature causing decrease in reservoir temperature.  Inhibitors – methanol and ethylene glycol are expensive chemicals.
  • 17. New concept diagram of reservoir. Production well Injection well Antenna (micro waves) Gas hydrate reservoir
  • 18. Steps involved Release of microwaves (@2450Mhz). Melting of gas hydrate or ice .(Temp. > 273 k ) Injection of Fluorine. Reaction between methyl radical and injected fluorine gas (halogenation). . CH 3 + F2 = CH3F( -431KJ/mole) (Solubility of methyl fluoride(166cc in 100ml of water)) Recovery of liquefied gas hydrate solution. Step 1: Wurtz Reaction 2 CH3F + Na ----- 2 NaF + CH3-CH3 Step 2 :Electrolysis NaF ----- Na + 1/2 F2 ↑ Step 3 :Cracking CH3-CH3 ------ 2 CH4 ↑
  • 19. Advantages with respect to normal techniques •Cost effective ,instantaneous and selective heating, catalyze chemical reaction. •Methyl fluoride is not an class 1 or 2 ozone depleting chemical and stable compound. •Huge reduction in disaster on rig floor or drill floor related issues. •Increase in the permeability and porosity of rock.
  • 20. Challenges •Fluorine is highly electronegative and reactive in nature e.g. injection problems. •Transportation of methyl fluoride solution.
  • 21. Conclusion •Huge amount of natural gas trapped in hydrates : too enormous to ignore. •It’s a threat to climate as well so there is an urgent need that we use it for positive purpose. •Technology and scientific understanding for exploitation of gas hydrate is to be developed . •Much to be learned before gas hydrates can be considered a resource. •The integration of various sciences and using the fluorine in this technique will definitely play a vital role in the methane extraction.