MSc – Petroleum and Gas

Engineering

Unconventional Resources (M24607)

Gas Hydrates
Dr. Jeb Gholinezhad
Jebraeel.Gholinezhad@port.ac.uk
Contact Detail:

Email: Jebraeel.Gholinezhad@port.ac.uk

Office: Room A2.05b

Tel: 023 92 84 2341

 Gas Hydrates - Outline

1. Introduction
2. Fundamentals
3. Opportunities and Challenges
4. Gas Hydrate Reservoirs
Introduction
 Natural Gas

• Natural gas: mixture of gases

➢ More than half is CH4
• Natural Gas: a Useful and Clean-Burning Fossil Fuel
• Natural Gas: can be used as Conventional natural gas
➢ Conventional natural gas
➢ Liquefied petroleum gas (LPG)
➢ Liquefied natural gas (LNG)
➢ Compressed natural gas (CNG)
➢ Gas to liquids (GTL)
Natural Gas – Trade-offs
 Natural Gas

Natural Gas Has More Advantages

Than Disadvantages

Will natural gas be the bridge fuel

helping us make the transition to a
more sustainable energy future?
 Natural Gas – Energy Scenario

Assessing energy sources:

1. Demand
2. Availability
3. Technology
4. Efficiency
5. Environmental impact
6. Cost
Natural Gas – Energy Scenario

The 21st century imbalance

• Annual population increases at 2%.

• Energy use per capita increases at
2% per year.
• As a result, energy consumption
increases at 4% per year.
– Doubles every 36 years!
World fossil consumption (1950-2003)

4000
3500
Coal
3000
2500 Oil
2000
1500
Natural
1000
Gas
500
0
1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52

Source: World Watch Institute, 2003

Projected world energy supply
 Electrical Efficiency (%) .

10
20
30
40
50
60
70
80

0
1
Biomass 80

8
Geothermal

10
Solar-PV

15
Solar Thermal

25
Wind
33

Nuclear
38

Gas Turbine cycle

43

Coal
58

Gas-Combined cycle
80

Hydro
Efficiencies of power technologies
 CO2 emissions [includes
Construction/Operation/Fuel Preparation]

1.4
1.18
CO2 Emissions (kg CO2/kWh)

Natural Gas
1.2
1.04
1

Biomass/ Steam
0.8
Geothermal 0.79
0.58

Solar-PV
0.6
Nuclear

Coal
0.47
0.4
W ind
Hydro

0.38
0.2 0.1
0.004 0.02 0.025
0.025 0.06
0
 Cost of electricity

Source: PB Power (2006). Generation costs include capital and equipment cost, fuel costs,
and O&M costs
Natural Gas – Energy Scenario

• Using every yardstick: availability,

efficiency, environment, and cost,
the 21st century will see an
irrevocable shift towards gas-based
energy generation
Methane Hydrate Discoveries
Methane Hydrate Discoveries
 Methane Hydrates

Natural Gas (135) Oil (142)

Coal (498)

Gas Hydrates (2171 for 15% recovery factor)

Carbon Balance Future Energy Sources (109 TOE)

Y. Makogon SPE 77334
 In-Situ Methane Hydrates
The existing estimates of the quantity of
gas captured in submarine hydrates
varies between 1015 and 7.6x1018 m3.

This is equivalent to 535 to 4,000,000

Gigaton carbon compared to 5,000
Gigaton carbon in fossil fuel deposits.
Conventional NG vs NGH
Fundamentals
What are Gas Hydrates ?
▪ Ice-like crystalline solids wherein guest or “former”
(generally gas) molecules are trapped in cages formed
from hydrogen bonded water molecules (host)

▪ Formed as a result of physical combination of water and

gas molecules – Stabilization caused by van der Waals
forces

▪ No bonding exists between the guest and host molecules

▪ Guest molecules are free to rotate inside the cages

▪ Unlike inorganic hydrates (e.g., CuSO4.5H2O) the ratio

between water and gas is not constant
Gas Hydrate Formation
Necessary conditions :

✓ Presence of water or ice

✓ Suitably sized gas/liquid

molecules (such as C1, C2, C3, C4,
CO2, N2, etc.)

✓ Suitable thermodynamic
conditions: low temperatures and
elevated pressures
P
✓ Temperature and pressure
conditions is a function of Hydrates
gas/liquid and water No Hydrates
compositions.
T
✓ Can be stable well above the
freezing point of water Hydrate phase boundary
Gas Hydrate Formation

• Not necessary:

– Presence of a gas phase

– Presence of a free water phase
– Very low temperature conditions
– Very high pressure conditions
Gas Hydrate Formation Apparatus

GC
T
Temperature Recorder Stirrer

P
Pressure Gauge

Data
Acquisition

Cooling Jacket

Pump

Gas Cylinder

Equilibrium Cell
Gas Hydrate Formation
Gas Hydrate Burning
Gas Hydrate Phase Boundary

stable

unstable
Gas Hydrate Structures

– Structure-I
• Forms from small molecules, C1, C2, CO2, etc.
• The main structure in natural hydrates
– Structure-II
• When intermediate size molecules exist, C3, C4
• Forms in most oil and gas systems
– Structure-H
• Discovered in 1987
• Need very large molecules, C6H12, C7H14
• Unlikely to form in real systems
Gas Hydrate Structures

Methane, ethane,
carbon dioxide….
6
Water molecule ‘cage’

2
5 126 2 Structure I 46 H2O

Propane, iso-butane,
16 8 natural gas….

512 5 126 4
3 Structure II 136 H2O
Gas molecule
(e.g. methane) Methane + neohexane,
2 1 methane +
cycloheptane….
4 35 66 3
5 126 8 Structure H 34 H2O
Hydrate Formers and Structures

H2 C2H6
C-C3H6
6Å
Ar (CH2)3O
4Å Kr N C3H8
2
O2 i-C4H10
CH4
Xe; H2S
7Å
n-C4H10
5Å
CO2 No Hydrates
Hydrate Formers and Structures

Ar Hydrogen Hydrates
6Å
(CH2)3O
4Å Kr
N2 sII C3H8
O2
CH4 i-C4H10 sII
Xe; H2S

7Å
n-C4H10
5Å
sII (double)
CO2 Benzene

Adamantane
C2H6
sH (double)
sI 8Å Cyclo octane
C-C3H6
Methyl Cyclopentane
 Interesting Properties
– Capture large amounts of gas (up to 15 mole%)
– Remove light components from oil and gas
– Form at temperatures well above 0 ºC
– Generally lighter than water
– Need relatively large latent heat to decompose
– Non-stochiometric
– More than 85 mole% water in their structure
– Exclude salts and other impurities
– Result from physical combination of water and gas
– Hydrate composition is different from the HC phase
 Interesting Properties
– Whether a gas is a hydrate former or not depends on
its molecular diameter. For example, iso-pentane can
form hydrate while n-pentane cannot.
– In general, gases with larger molecular diameter
have higher tendency to form hydrate. For example,
CO2 has higher tendency to form gas hydrate than
methane due to its larger molecular diameter
– Gas hydrate formation is an exothermic process, i.e.
releases heat.
– Large amounts of methane hydrates exist in nature
 Where Can They Form?

• They can form anywhere, such as:

– Pipelines (offshore and onshore)

– Processing facilities (separators, valves, etc)
– Heat exchangers
– Sediments (permafrost regions and subsea
sediments)
– Offshore drilling operations
– Etc
Gas Hydrates: Friend or Foe
Gas Hydrates Applications
History of Gas Hydrates
History of Gas Hydrates
Opportunities
and Challenges
 Flow Assurance
• Gas Hydrates can block oil and gas pipelines in
subsea and deep water operations and long tie-
backs
• Some of the options to prevent hydrate problems
– Subsea separation
– Thermodynamic Inhibitors
– Low dosage kinetic inhibitors
– Anti-depositional internal coating
– Electrical heating or tube bundles
– Anti-agglomerants
– Cold Flow/HYDRAFLOW
Gas hydrate formation in pipeline can result in
pipeline blockage!!
 Hydrate Formation during Drilling

• Gas Hydrates can form during offshore

drilling.
• Some of the options for preventing gas
hydrate problems
– Design of drilling fluids
– Improved drilling practices
– Better monitoring
– Low dosage hydrate inhibitors
 Gas and Water Purification

• Gas Hydrates can be used in separation

processes, such as desalination, waste
water purification, gas purification, as they:
– Exclude any impurity
– Concentrate some compounds
– Produce water and gas
– Form at temperatures well above 0 °C
 Source of Energy

• There are massive quantities of gas hydrates

in permafrost and ocean sediments. They
can:
– Cement sediments
– Reduce porosity and permeability
– Change fluid saturations
– They alter rock’s mechanical properties
– Consist of mainly methane hydrates
– Act as a cap rock for the gas below
Hydrate veins within sediment Gas hydrates in sea-floor mounds
Gas Hydrates in Sediments
Requirements Permafrost Subsea
Sediments
H2O Ice/Water Water
Gas Molecule Mainly Biogenic Mainly Biogenic
Methane* Methane*
Temperature Low Permafrost Low Seabed
Temperature Temperature
due to the high
density of 4 C
water
Pressure Overburden Column of Water
* In some cases gases from thermogenic sources.
Dangers to Deepwater Production

The consequences of an
uncontrolled gas blowout
Gas Hydrates and Seafloor Stability

Subsea landslides
can generate
tsunamis
 Gas Hydrates and Climate Change

• Huge volumes of methane trapped as relatively

unstable hydrates in shallow geosphere
• Methane is a very potent greenhouse gas (20x as
powerful as CO2)
• Changes in pressure or temperature can result in
hydrate dissociation, e.g.:
• Sea level fall (reduces pressure)
• Increase in ocean temperatures
• Response to change (e.g. glaciation) depends on
whether hydrates are continental or oceanic
 Global Climate Change

100

Present
Sea Level

-100

-200

-300

-400
0 100 200 300 400 500 600 700 800 900
Time, Thousands of Years Before Present
Global Climate Change
 Gas Storage and Transportation

• Two important encouraging

factors:
– Very high gas to solid ratio
– Self preservation effects

• Prohibiting factors:
– Subzero temperatures
– Unfavourable formation kinetics
– Lack of an economical means
for the mass-production of solid
hydrates
 CO2 Sequestration

CO2 separation, and storage

CO2 could be trapped in the

form of gas hydrates,
reducing the emission of
greenhouse gases to the
atmosphere.

CO2 hydrates may act as a

secondary seal for
subsurface storage of CO2
Gas Hydrate
Reservoirs
 Natural Gas Hydrates

➢ Naturally occurring gas hydrates are a form of water

ice which contains a large amount of methane
within its crystal structure.

➢ They are restricted to the shallow lithosphere

▪ In Permafrost regions: depths about 150 - 2000 m below
the surface.
▪ In oceanic sediment: ocean is at least 300 m deep, depths
of 0 - 1,100 m below the seafloor.

➢ With pressurization, they remain stable at

temperatures up to 18°C.
 Natural Gas Hydrates (Cont.)

➢ The average hydrate composition is 1 mole of

methane for every 5.75 moles of water.
➢ The observed density is around 0.9 g/cm3.
➢ One liter of methane clathrate solid would contain
164 liters of methane gas (at STP).
 Natural Gas Hydrates (Cont.)
➢ The gas is held in a crystal structure, therefore gas
molecules are more densely packed than in
conventional or other unconventional gas traps.
➢ Hydrate forms as cement in the pore spaces of
sediment and has the capacity to fill sediment pore
space and reduce permeability. CH4-hydrate-cemented
strata thereby act as seals for trapped free gas.
➢ Production of gas from hydrate-sealed traps may be an
easy way to extract hydrate gas because the reduction
of pressure caused by production can initiate a
breakdown of hydrates and a recharging of the trap
with gas.
 Where are gas hydrates located?

It is present in oceanic sediments along continental margins and in polar

continental settings.
 Gas Hydrate Zone
T/K
• Pipelines 275 285 295 305 315 325 335 345 355
0
• Processing facilities
35
• Offshore drilling 5 30

operations 10
25
hydrates

P/MPa
20

• Porous media 15

Depth 15 10 no hydrates

P/MPa
– Permafrost 5

regions 20 0
275 285 295 305
T/K
– Subsea 25
sediments hydrates no hydrates
30

35
Zone of Hydrates in Subsea Sediments
273 283 293
0 Temperature / K
Hydrothermal
Gradient

Depth/Metre
500
Hydrate Phase
Boundary

Sea Floor 1000

Geothermal
Zone of
Gradient
Gas Hydrates
in Sediments
1500

The Sediments are saturated with water

Zone of Hydrates in Subsea Sediments
Zone of Hydrates in Permafrost
263 273 283 293
0 Temperature / K

Geothermal
Permafrost Gradient in
Permafrost
500

Depth/Metre
Depth of Permafrost
Zone of Phase
Gas Hydrates Boundary
in Permafrost
Geothermal
1000 Gradient

1500

The Sediments are saturated with water

Zone of Hydrates in Permafrost
Exploration

Geophysical signature of
gas hydrates: presence
of a “bottom simulating
reflector” in seismic
data, due to velocity
contrast (hydrate / free
gas).

water
sediment

hydrate
free gas
 Bottom Simulating Reflector

The boundary where hydrates cannot form and there is actually gas in the
sediments creates a demarcation called a bottom simulating reflector (BSR).
This line also cuts across the geological layers, indicating that is not due to a
change in geology. The BSR is attributed to the change from the ice-like solid
to gas in water.
 Exploitation Schemes

1. DEPRESSURISATION: Drilling through an overlying hydrate

reservoir into free gas allows normal production of gas to
depressurize the gas reservoir, which is replenished by gas from
dissociating hydrates. (The most economic method)
2. INHIBITOR INJECTION: Injecting methanol or brine into the
wellhead which will result in disturbing gas hydrate stability and
dissociation of gas hydrates.
3. THERMAL INJECTION: Increasing the temperature of the
hydrate reservoir to dissociate the hydrates; this is done through
the injection of a hot fluid or sometimes directly heating the
formation.
Gas Hydrate Production Methods

Depressuriza Thermal Inhibitor

tion Injection Injection
Hot Methanol
Gas Gas Brine Gas
Out Out or Gas Out

Imperm. Rock Imperm. Rock Imperm. Rock

Gas Hydrate
Gas Gas
Dissociate Hydrate Hydrate Hydrate
d
Dissociated Hydrate Dissociated Hydrate
Free-Gas Reservoir
Impermeable Impermeable
Rock Rock
After Collett, 2000
Decomposition of hydrates by depressurization,
thermal, and chemical techniques
Mallik Field 2002
• First Attempt at
Hydrate Production
• Depressurization
• Hot Water Circulation
Mallik Field 2002
Methane Hydrate Production Testing at
Mallik Gas Hydrate Well in Canada
 Mallik Field

❖ One of the most concentrated Gas Hydrate

reservoirs
❖ >200 m gross hydrate thickness
❖ >90 % pore saturation
❖ International Consortium (Japan, Canada,
US, Germany, India)
❖ Mallik $22.5 (US) million project
 Mallik Field

❖ A six-day production test in March 2008

successfully demonstrated proof-of-concept
for gas production from gas hydrate by
depressurization
❖ Sustained gas flows ranging from 2,000 to
4,000 m3/day (70,000 to 140,000 ft3/day)
were maintained throughout the course of
the test, and physical operations proceeded
very smoothly
 Unique difficulties to recover methane

❑ Big volumes but in remote onshore or

deep offshore settings
❑ Low concentration regimes
❑ Solid and dispersed character
❑ Slow dissociation - Low flow rate
expectations
❑ Environmentally sensitive areas
 Hydrate concentration is key
to hydrate exploitation

❑ Blake Ridge formation 300 km off the coast

of South Carolina estimated to contain
1,000 TCF
o NGH is spread over 26,000 km2 (2 %
of sediment volume)
o A petroleum engineer would consider
this a “Dry Hole”
Industry Perspective on Gas Hydrates
 Some Videos on Gas Hydrates

https://www.youtube.com/watch?v=kUaZEWcpA4A
https://www.youtube.com/watch?v=PVyTVtMmp-M
https://www.youtube.com/watch?v=pM0LWKQpgvI
https://www.youtube.com/watch?v=EV38ylrHEMI
https://www.youtube.com/watch?v=U46XOoU0DrM
https://www.youtube.com/watch?v=QEJmhokSmZM
 Concluding Remarks

❑ Depressurization appears to be the most feasible

production option.
❑ Mallik tests provide evidence that flows can be
sustained, at least over short periods, with
conventional oilfield technologies adapted for
Arctic conditions.
❑ Production of gas from GH will be more costly
than for conventional gas.
❑ Gas hydrates in marine and sub permafrost sand
are most readily recovered.
 Reference Books

❑ Sloan Jr, E. D., & Koh, C. (2007). Clathrate

Hydrates of Natural Gases. CRC press

❑ Carroll, J. (2014). Natural Gas Hydrates: A Guide

for Engineers. Gulf Professional Publishing
Namit