THE BASIC KNOWLEDGE

ABOUT GAS HYDRATE

Hailong Lu
Steacie Institute for Molecular Sciences
National Research Council Canada

Gas hydrate (GH)

P, T

Gas + Water

The occurrence of natural gas hydrate around the world (Updated

from Collett, 2002)

Natural gas hydrate: the largest organic carbon reserve on the Earth

Slope failure caused by mass dissociation of gas

hydrate (Kvenvolden, 1993)

Pingo on the shelf of Beaufort Sea,

N.W.T.

Gas hydrate is taken as a reason for the

formation of Pingo (Paull et al., 2007)

Pipeline blockage caused by the formation of gas hydrate (AGAR Corporation)

Source: CBC TV

5 2/3 H2O

5 3/4 H2O

7 2/3 H2O
17 H2O
cyclopentane

C6: cyclohexane, methyl-cyclopentane

C7: methyl-cyclohexane

Gas hydrate formers

(Updated from Sloan &
Koh, 2007)

sI
+
tetrakaidecahedron

+
dodecahedron

sII

+
hexakaidecahedron

+
dodecahedron

sH
icosahedron

Water molecules

Fig. 1 The most stable (lowest energy) hydrogen-bond arrangement

for the cluster geometries with eight, ten and twelve water molecules
as obtained from B3LYP/cc-pVDZ computations. (Lenz and Ojamae,
2005

Fig. 4 The structures with the

most stable hydrogen-bond
arrangements for the
different shapes and cluster
sizes from B3LYP/cc-pVDZ
optimizations. (Lenz and
Ojamae, 2005)

FIG. 6. Density distribution of the orientations of a water molecules dipole moment

vector in the hydration shell around methane in aqueous solution. (Koh et al. 2000)

The formation of methane hydrate

Methane gas + water

Methane dissolving in water

Cage constructed with 161 water molecules surrounding

methane molecule

Aggregation of these cages into methane hydrate (20 water

molecules in small cage24 water molecules in large cage
Koh et al. (2000), Dec and Gill (1985), Bridgeman et al. (1996)

Cubic structure I
Pm3n
a=12.0

51262

512

Cubic structure II
Fd3m

a=17.0

51264

512

Structure H
P6/mmm
a=12.0
c=10.0

51268

512

435663

Schicks &
Ripmeester, 2004

Chou et al. 2000

At superhigh pressure0.8 GPa)

THF hydrate appearing with a new
strcuture, orthorhombic system
Pnma a=12.54, b=11.44, c= 6.60 A.

Figure 2. Packing and

schematic view of the new
space-filling polyhedron.
(Kurnosov, 2004)

At super-high pressure crystalline gas hydrate can be

converted to amorphous materialTanaka & Amano, 2002)

At certain ratio mixed CH4-C2H6 hydrate can be changed

from sI to sII (Subramanian et al. 2000)

The unit-cell parameters of methane hydrate changing with

pressureKlapproth et al. 2003)

CO2 occupancy rates in cages changing with pressure

(Klapproth et al. 2003)

Occupancy rates of methane hydrate changing with

pressure (Klapproth et al. 2003)

Table 1-2 Ratios of molecular diameters to cavity diameters for natural gas
Molecules including natural gas hydrate formers ( Cited from
Sloan, 1990)

Molecular diameter/Cavity diameter

Molecule

Guest
Size(A)

Structure I

Structure II

(2)*512

(6)*51262

(16)*512

(8)*51264

CH4

4.36

0.886

0.757

0.889

0.675

H2S

4.58

0.931

0.795

0.934

0.708

CO2

5.12

1.041

0.889

1.044

0.792

C2H6

5.5

1.118

0.955

1.122

0.851

C3H8

6.28

1.276

1.090

1.280

0.971

c-C3H6

5.8

1.178

1.007

1.182

0.897

i-C H

6.5

1.321

1.128

1.325

1.005

70

1. CH (sI)
4

60

2. CH -methylcyclopentane (sH)
4
3. natural gas hydrates (sII-sH)

4. 95.2% CH -propane (sII)

4

5. CH -6% isobutane (sII)

4
6. CH -cyclopentane (sII)
50

3
40

30
4

20
6

10

0
250

260

270

280

290

300

310

T (K)
Figure 3 The dissociate conditions of gas hydrates from Barkley Canyon, offshore
Vancouver Island.

Lu and
Matsumoto
(2001)

Gas hydrate (GH) Gas + Water

2 Phases (gas + liquid)

Gas hydrate
1 Phase

Gas phase gas + water

vapor
Liquid gas dissolved in
water

In natural environment gas hydrate can form either from 2

phases or 1 phase

Sea surface

3 Phases GH+G+L)
Seafloor
2 phases GH+L) or
3 phases GH+G+L)
BSR

3 phases GH+G+L)

The occurrence of gas hydrate in natural

environment

Materials
Stability (P-T)

Gas Hydrate

Time

Space

Conditions to be met for the formation of gas hydrate

 Materials: gas, water

Time: experienced for pore water to
be saturated with hydrocarbon
Space: sediment type, sediment
structure
Stability condition: gas composition,
sediment, pore water composition, and
mineral composition.

Materials
Water: always available in marine environment

Gas: biogenic, thermogenic. It seems most of the recovered gas

hydrates are composed of biogenic gas as indicated by gas
composition and isotope composition, however it doesnt mean
hydrate is formed with the in situ gas.
Most of the gas hydrate is formed with the gas transported from
deeper sediments, either biogenic or thermogenic.

Wallman et al
(2006)

SulfateMethane
Interface

Profiles of CH4 and SO42- along sediment section (Schmidt et al., 2005)

Sea surface
Sea water

GH
Sea floor

Sediments

BSR
(Base of gas
hydrate zone)

The occurrence of gas hydrate in marine environment

Most of the recovered natural gas hydrate were composed

dominantly CH4, however hydrates with other hydrocarbons
of C2+, up to C7, did be recognized existing in natural
environment.
Because C2+ hydrocarbons are thermogenic origin, there are
more opportunities to find gas hydrate in deep sediments.

600

R694
500

400

300

200

100

0
10

20

30
2theta (degree)

40

50

Figure 1. XRD spectra of the gas hydrates from Barkley Canyon, offshore Vancouver
Island (Lu et al., 2007)

Time
In laboratory:
Time is referred to Induction time, needed for hydrate nucleate
since experiment starts, on a scale of minutes, hours, sometimes
days.

In nature:
As compared with the scale of geological time, years, even
million years, the induction time can be negligible. However, 1)
for hydrate formation a condition, pore water to be saturated
with hydrocarbon, has to be met. For this certain time is needed;
2) Time issue will be met upon discussing the kinetics of gas
hydrate growth.

Space
1. Space availability determines the appearance of gas
hydrate in sediments,
2. Sediment, where gas hydrates exist, controls the
saturation level of gas hydrate in sediments.

Visible gas hydrate

Massive gas hydrate occurring

at seafloor, Barkley Canyon,
Cascadia (Chapman et al.,
2004)

Massive gas hydrate

occurring in sediments at
a seepage site, Joetsu
Basin, Japan Sea

Nodular gas hydrate

occurring in
sediments at a cold
vent field, Cascadia

Vein-like gas
hydrate in silty clay,
K-G Basin, offshore
India

Thin film-like gas

hydrate occurring at
the bedding plane in
silty clay, K-G Basin,
offshore India

Invisible gas hydrate In-pore gas hydrate

Gas hydrate in volcanic

ash, offshore Andaman
Island

Gas hydrate in silty clay,

K-G Basin, offshore
India

Gas hydrate in sand,

Mallik, Mackenzie
Delta, N.W.T., Canada

Gas hydrate in sand,

Nankai Trough, offshore
Japan

Gas hydrate in clay silt,

South China Sea

The types of natural gas hydrates

1in pore gas hydrate
2) locally aggregated gas hydrate

In-pore gas hydrate

dispersed
pore-filling
Existing in the pore of sediments, no altering of original sediment
structure. Because the resolution of human eyes is ~150 m and
generally the pore size of sediments is at the scale of m and even
nm, in-pore gas hydrate is not identifiable by naked eyes.

Locally aggregated gas hydrates

Gas hydrates that are identifiable by eyes directly and appear as
certain shape, for example nodular, platy, vein-like, massive, etc.
The size of gas hydrate aggregate is obviously larger than the
normal pore size of sediments, and the original structure of
sediments has been altered, generally related to faults,
fractures, and other sediment structures with large space.

Collet et al. (2000) revised from Malone (1990)

Gas hydrate

?
Sediment particles

Can gas hydrate grow over the confinement of sediment particles?

Due to the density difference between sI gas hydrate (~0.93 g/cm3) and pore
water (~1), the formation of gas hydrate will result in a volume increase. This
volume increase may cause the sediment particles over pressurized
However in most cases, due to the slow growth, the over pressure is so
small that it is not strong enough to push sediment particles away to create
larger space for hydrate growth.

Massive gas hydrate

Pore filling
gas hydrate

Nodular, tabular
gas hydrate
Vein-like gas hydrate

Massive gas hydrate

Hydrocarbon flux
Not to scale

The occurrence of gas hydrate in natural environment

T (degree celsius)
0

10

15

20

25

Water-temperature profile
200

Stability curve of the

sII & sH mixture

400

600

Stability curve of methane

hydrate in seawater

800

Seafloor

1,000
BGHS-1
1,200

1,400

Geothermal gradient
BGHS-2

30

Lu and
Matsumoto
(2005)

Lu and Matsumoto (2002)

100
90

CH hydrate in Nankai Trough sediments (#49)

4

80

P (bar)

70

60

CH hydrate in pure water

4

50

(Sloan, 1998)

40
6

9
T( C)

10

11

100
Methane hydrate stability condition in
water-saturated Na-montmorillonite

90

Methane hydrate stability condition in

water (Sloan, 1998)

80

70

60

50

40

30

20
0

10

12

T (C)
Figure 3. Methane hydrate stability condition in water-saturated Na-montmorillonite.

14

110

105

100
Water-saturated kaolinite
95

90
Pure water
85

80
10

11

12

13

14

15

T (C)
Figure 4. The stability condition of methane hydrate in water saturated kaolinite.

105
Water saturated Ca-montmorillonite
(this research)
Pure water (Sloan, 1998)
100

95

90

85
10

11

12

13

14

15

T (C)
Figure 5. The stability condition of methane hydrate in water-saturated Ca-Montmorillonite.

105
Water saturated Ca-montmorillonite
(this research)
Pure water (Sloan, 1998)
100

95

90

85
10

11

12

13

14

15

T (C)
Figure 5. The stability condition of methane hydrate in water-saturated Ca-Montmorillonite.

Hydrate saturation (%, pore space)

120
100
80
Natural sediments
Silica sands

60
40
20
0
0

2000

4000

6000 8000
T (us)

1 10

1.2 10

The relationship between hydrate saturation and water

relaxation time (T2)

Thanks!