Ramin Khodafarin,RIPI,NIOC
8/9/2006
Learning Objectives:
What are Gas Hydrates?
The necessary conditions for Gas Hydrate formation
Different Gas Hydrate structures
Interesting properties of Gas Hydrates
How can we benefit from gas hydrate technology?
How can we avoid hydrate problems?
Ramin Khodafarin,RIPI,NIOC
8/9/2006
Hydrates:
In general sense:
Hydrate is a compound containing water
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8/9/2006
What are Gas Hydrates?
Crystalline solids wherein guest (generally gas)
molecules are trapped in cages formed from hydrogen
bonded water molecules (host)
They are formed as a result of physical combination
of Water and Gas molecules
Unlike inorganic hydrates (e.g., CuSO4.5H2O) the
ratio between water and gas is not constant
Ramin Khodafarin,RIPI,NIOC
8/9/2006
Hydrates Definition
Natural gas hydrates are ice-like structures composed
of water and natural gas molecules. Under favorable
conditions of high pressure and low temperature,
water molecules form cages which encapsulate gas
molecules inside a hydrogen-bonded solid lattice
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8/9/2006
Methane Hydrate Molecular
Structure
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WATER
and Periodic Table
6A
O
S
Se
Te
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H2X
Water
Hydrogen Sulfide
Hydrogen Selenide
Hydrogen Telluride
8/9/2006
Water
and Unusual Properties
Boiling Point
Enthalpy of Vaporization
Expanding upon freezing
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8/9/2006
Hydrogen Bond
Essentially an electrostatic attraction between the
molecules
Only 5-10% as strong as a covalent bond, but this is
still strong enough to explain the properties
Ramin Khodafarin,RIPI,NIOC
8/9/2006
Hydrates
It is a result of the hydrogen bond that water can
form hydrates
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Historical Perspective
1810
Sir Humphrey Davy discovers chlorine hydrate.
1888
Villard measured hydrates of CH4, C2H6, C2H4,C2H2, and N2O
1930's Hammerschmidt determines hydrates are blocking gas lines, and
investigates inhibitor gases.
1940's Soviets hypothesize the existence of natural methane hydrates in cold
northern climates
1960's Molecular structure of hydrate is determined. Soviets recognize
methane hydrate as a possible energy source, discover and
produce the first major hydrate deposit in permafrost.
1970's A bottom simulating reflector is drilled and is found to be associated
with the base of hydrate stability.
1990's Initial characterization and quantification of methane hydrate
deposits in deep water.
2000
Efforts to quantify location and abundance of hydrates begin. Largescale efforts to exploit hydrates as fuel begin.
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Gas Hydrate formation
The necessary conditions:
Sufficient amount of water (not too much and not
too little)
Hydrate former (N2, H2S, CO2, C1, C2, C3, iC4)
Right combination of Temperature and Pressure
(Low T and High P)
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Gas Hydrate formation
Improvement by:
Turbulence
High Velocity
Agitation
Nucleation Sites
Free Water
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Elements Necessary for Hydrate
Formation
Hydrate
Natural
Gas
Water
High
Press.
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Low
Temp.
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Crystal Structure
Guest (gas molecules)
Houst (water molecules)
Cavities
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Known Structures
Structure I
Forms from small molecules, C1, C2, CO2, etc.
The main structure in natural gas 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
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Structure I
Cubic unit cell (a=12 A)
2 small cages and 6 large cages
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Structure II
Cubic unit cell (a=17.3 A)
16 small cages and 8 large cages
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Structure I
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Structure I & II
The three types of cavities present in Structure I and II
methane hydrates.
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Hydrate Structures
512 62
512 64
512
Structure I
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Structure II
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Structure H
Hexagonal (a=12.26 A, c=10.17A)
3 small cages and 2 medium cages 1 large cages
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Structure H
The two types of cavities unique to Structure H
methane hydrates.
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Double gas hydrates (SH)
Very Large molecules (such as C7H14) with small
molecules (such as C1, C2, CO2, and N2) may form
structure H hydrates.
Large cages are mainly filled with very large
molecules, while small molecules will occupy small
and medium size cages.
When structure II hydrate formers are present (e.g.
C3, i-C4, c-C5, and benzene), structure II is
generally more stable than structure H
For some binary systems (e.g. C1/ i-C5) structure H,
in particular at higher temperatures.
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Geometry of Hydrate Cavities
I
II
II
Cavity size
small
medium
small
large
small
huge
huge
Cavity shape
round
oblate
round
round
round
oblate
oblate
Cavity description
512
51262
512
51264
512
51268
51268
Number/unit cell
16
Average radius (A)
3.91
4.33
3.902
4.683
3.91
5.71
5.71
Real size of CH4
88.6%
75.7%
88.9%
67.5%
88.6%
Coordination No.
20
24
20
28
20
36
36
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Types of Hydrates
Structure
Structure
II
Compound
Small
cavities
Large
cavities
Small
cavities
Large
cavities
C1
C2
C3
iC4
nC4
CO2
N2
H2S
O2
Ar
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Structures of gas hydrates
Structure I(a) and II(b) form with relatively small guests, e.q.,
methane, ethane, nitrogene, etc.
Structure I and II contains 48 and 136 water molecules,
respectively.
Structure H(c) is only known to form with at least one small guest
(i.e., methane) and one large guest, e.q., cyclooctane,
methylcylcohexane, etc.
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Where can they form?
Hydrates
Pressure
No Hydrates
Temperature
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Gas Hydrate auto clave
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Please press a key.
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Where Gas Hydrate is found?
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Natural Gas Hydrate on the
Sea Floor
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Storage Capacity of Hydrates
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Gas Hydrates; friend or foe?
Can cause Problems
Source of Energy
CO2 Sequestration
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Gas Hydrates
is one of the problems in
Production(Offshore drilling operations))
Processing facilities (separators, Valves, Heat
exchangers , etc.)
Transportation (offshore and onshore Pipeline)
Sediments (permafrost regions and subsea sediments)
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Natural Gas Transportation
CNG
Compressed Natural Gas
GTL
Gas-to-Liquid
GTW
Gas-to-Wire (DC and AC)
LNG
Liqufied Natural Gas
NGH
Natural Gas Hydrate
ANG
Absorbed Natural Gas
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Which one is the BEST way?
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10.0
LNG
Capacity (BCM/year)
PIPE
1.0
ALL
CNG, GTW, NGH
0.1
100
1000
GTL
10000
Distance (km)
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Alternative Methods for
Storing
Solid(Crystal)
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Slurry
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CO2 Deep-sea Storage
Technology
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Hydrate Prevention
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Natural Gas Hydrates Problem
(P, T)
Water + Hydrocarbon
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NGH
8/9/2006
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Formation of a hydrate plugs in
a Pipeline and its hazards
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Remove one of the components
needed for hydrates to form
Hydrate
Natural
Gas
Water
High
Press.
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Low
Temp.
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Thermodynamic Hydrate
Inhibitors
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Thermodynamic Inhibitors
Salts
Alcohols
Glycols
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Low-Dosage Inhibitors
Kinetic Inhibitors (KIs)
Crystal Growth Inhibitors
Anti-Agglomerants (Aas)
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Kinetic Inhibitors
Kinetic Inhibitors X
KIs delay the nucleation and growth of hydrate
crystals for substantial periods of time.
XX
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Kinetic Inhibition
Hydrate
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Hydrate
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Anti-Agglomerants
Anti-Agglomerants X
AAs prevent agglomeration of hydrate crystals.
Crystal reach critical radius and are transported as a
slurry.
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NGH
as a future source of energy
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