Energy Geotechnics – Wuttke, Bauer & Sánchez (Eds)

© 2016 Taylor & Francis Group, London, ISBN 978-1-138-03299-6

A small pore size effect on dissociation behavior of gas hydrates

in fine-grained sediments

Taehyung Park, Hak-Sung Kim & Tae-Hyuk Kwon

Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology (KAIST),
South Korea

ABSTRACT: As capillarity in small pores is known to affect dissociation of gas hydrates, the dissociation
behavior of gas hydrates in fine-grained sediments need to be clearly understood for successful practices of
resource recovery. Therefore, this study investigated the dissociation behavior of gas hydrates in different sized
pores of host sediments. Gas hydrates were synthesized from a partially water-saturated conditions in a sand
sample and a natural fine-grained sediment sample cored from Ulleung Basin (UB), offshore Korea, and these
hydrates were thermally dissociated under a constant volume condition while monitoring the pressure and
temperature. The dissociation of gas hydrate in the fine-grained sediments occurred at the lower temperature
than the bulk equilibrium by ∼1.5◦ C. When compared with the pore size distribution obtained by the mercury
intrusion porosimetry, gas hydrate was preferentially formed in small pores for a given range due to the initial
water locations in partially water-saturated conditions.

1 INTRODUCTION effect on hydrate equilibrium conditions (Handa and

Gas hydrates are ice-like crystalline structure com-
prised of hydrogen bonded water cages with gas
molecules inside (Sloan, 1998). These are naturally
formed under high pressure and low temperature con-
ditions (Sloan, 1998). In deep ocean sediments where
those conditions are satisfied, abundant amount of
natural gas hydrates exist in continental margins and
permafrost regions (Sloan and Koh, 2008). As energy
use and fossil fuel consumption increase from decade
to decade, gas hydrate deposits in oceanic sediments
have been spotlighted as prospective energy resource
for the large amount of methane (Lee et al., 2003).
Potential reserves of natural gas hydrates are over
1.5 × 1016 m3 all over the offshore earth areas (Mak-
ago et al., 2007). Additionally, gas hydrates have been
considered as one of the possible solutions for car-
bon dioxide (CO2 ) mitigation. By the formation of
a CO2 hydrate layer in subsurface, CO2 hydrate can
also function as a cap-rock structure which provides
the secondary shield to prevent the leakage of CO2
(Tohidi et al., 2010).
For successful practices of methane recovery from
hydrate deposits or CO2 storage using hydrates, bet-
ter understanding of the dissociation behavior and the
phase equilibrium of gas hydrates in natural sediments
is required (Lee et al., 2007, Uchida et al., 2004). For
these reasons, there have been numerous studies to
understand the phase equilibrium of gas hydrates in
porous media; previous studies found that dissociation
pressure of gas hydrates were higher in small pores
than that in a bulk phase, which means the inhibition
Stupin, 1992; Uchida et al., 1993; Tohidi et al., 2001;
Anderson et al., 2003; Uchida et al., 2002).
Despite of numerous gas hydrate studies in porous
media, there have been lack of experimental data on
the dissociation behavior of gas hydrates in natural
fine-grained sediments as most of the previous studies
were conducted using porous silica gels. Therefore, in
this study, we investigated the dissociation behavior
and the equilibrium conditions of CO2 hydrate in the
sediments with different pore sizes, including a fine
sand and a natural clayey silt sample cored from the
Ulleung Basin (UB), offshore South Korea.
2 EXPERIMENTAL PROGRAM
2.1 Materials
CO2 gas (commercial-grade with the purity of 99.9%,
Sam-Oh Gas Co., South Korea) was used for CO2
hydrate formation in this study. Fine sand (Ottawa
F110) was selected as representative coarse-grained
sediments, as shown in Figure 1a. A natural fine-
grained sediment sample retrieved from Ulleung
Basin, located in the southwestern part of the East Sea
of South Korea was used for the experiment, as shown
in Figure 1b. Detailed descriptions of the sediment
samples are available in previous references (Kwon
et al., 2011; Kim et al., 2013). The basic properties of
the tested samples, including mean particle diameter
(D50 ), specific gravity (Gs ), specific surface area (Sa ),
porosity, and water saturation (Sw ), are described in
Table 1.

459
Table 1. Properties of the sediments

Fine sand (Ottawa F110) Natural UB sediment

(Kwon et al., 2008) (Kim et al., 2013)

Mean diameter, Mean diameter,

D50 = 120 μm
Specific gravity, Gs = 2.65
Specific surface area,
Sa = 0.019 m2 /g
Porosity = 0.41
Water saturation, Sw 0.46
D50 = 4.83 μm
Specific gravity, Gs = 2.52
Specific surface area,
Sa = 32.09 m2 /g (dry method)
Porosity = 0.61
Water saturation, Sw = 0.52

Figure 3. Temperature and pressure conditions of CO2

hydrate in sand sample during 1st heating, 2nd cooling and
3rd heating procedures.

Figure 1. (a) Microscopic image of the fine sand (Ottawa
F110) sample and (b) scanning electron microscope (SEM)
image of the natural UB sediment.
Figure 2. Schematic diagram of experimental setup.
A proper amount of deionized water (DIW, 18 M-
cm) was prepared to partially saturate the sediments
and form CO2 hydrates.
2.2 Experimental Apparatus
The experimental setup was designed to measure the
dissociation temperature and pressure of CO2 hydrate
in the sediments. These experimental setup is graphi-
cally described in Figure 2.A cylindrical, transparent
high pressure cell made of polycarbonate with a
volume of 3.18 cm3 was used for this study.
During whole experimental procedures, the cell
was submerged in the temperature-controlled bath
(RW-2025G; Lab Companion, South Korea) to con-
trol the temperature of the cell. A platinum resistance
thermometer (Pt100; Hankook Electric Heater, South
Korea) was placed at the center of the sediment inside
the cell and two pressure transducers (PX302; Omega,
United States) were connected to the cell. For real
time monitoring of the temperature and pressure con-
ditions, the data acquisition unit (34970A; Agilent,
United States) was used.
2.3 Experimental Procedures
Each sample was mixed with DIW and the mixture was
hand-tamped in the cell to achieve a partially saturated
condition. The porosity of 0.41 and 0.61 was achieved
for the fine sand and natural UB sediment, respec-
tively (Table 1).The cell was flushed with pure CO2 gas
several times to remove the residual air inside the reac-
tion cell. CO2 gas was then injected and pressurized
to 3 MPa. The temperature of the cell was lowered to
274.15 K. CO2 hydrate nucleation took place, and the
pressure and temperature was maintained for 24 h until
forming a sufficient amount of CO2 hydrate. Hydrate
nucleation was confirmed by appearance of a temper-
ature peak where an exothermal reaction takes place.
After 24 h, the temperature of the reaction cell was
increased in steps of 0.5◦ C every 6 h under a con-
stant volume condition (i.e., isochoric heating). When
the temperature exceeded the equilibrium temperature,
hydrates started to melt due to the increased temper-
ature. The pressure also increased as the dissociation
of CO2 hydrate released free CO2 gas. Thereby, the
pressure and temperature were tracked to obtain the
hydrate phase equilibrium. Such step-wise heating was
continued until complete dissociation of CO2 hydrate
(i.e., 1st heating cycle). Then, the reaction cell was
cooled again to 0◦ C for CO2 hydrate formation (i.e.,
2nd cooling cycle). The aforementioned dissociation
procedure was repeated to make sure the experiment
results shows the repeatability (i.e., 3rd heating cycle).
3 RESULTS AND DISCUSSION
3.1 Dissociation behaviors of CO2 hydrate in fine
sand and fine grained sediment
Figure 3 and Figure shows the pressure-temperature
trances during the experiments with the fine sand and
UB sediment samples, respectively. CO2 hydrate in
the fine sand sample started to dissociate at 5◦ C, 2.25

460
Figure 4. Temperature and pressure conditions of CO2
hydrate in UB natural sediment sample during 1st heating,
2nd cooling and 3rd heating procedures.
MPa during 1st heating process, in which the pressure-
temperature trance (or PT trace) followed the phase
boundary of pure CO2 hydrate in a bulk condition
(or bulk phase boundary). As expected, CO2 hydrates
formed in find sand sample did not experience any
capillarity effect due to the large enough pore sizes
larger than 1 μm. This is consistent with with an ear-
lier work (Kwon et al., 2008), confirming the validity
of our experimental procedures and measurements.
While the dissociation conditions of CO2 hydrate
in fine sand sample was indistinguishable to those
of pure CO2 hydrate, the dissociation of CO2 hydrate
in the natural UB sediment started at 5.6◦ C, 2.8 MPa
which was at a lower temperature than the bulk phase
boundary. Natural UB sediment showed a pronounced
capillary effect depressing the melting point of CO2
hydrate in fine-grained sediments.
3.2 Capillary effect of fine-grained sediments
on dissociation behavior of CO2 hydrate
Association of water molecules with mineral surfaces
in the fine-grained sediments becomes dominant in
small pore sizes, which lowers the water activity and
leads to the depression of melting temperature of
ice crystals. Such melting temperature depression has
been widely observed in ice melting or water freez-
ing in fine-grained sediments. Likewise, due to the
decreased water activity by capillarity in small pores,
CO2 hydrate equilibrium condition was inhibited in
fine-grained sediments with the melting temperature
depression, as shown in Figure 4. The depression of
melting temperature (Tdep ) in porous media from
bulk conditions (Tbulk ) can be estimated by Gibbs-
Thomson equation (e.g., Anderson et al., 2003; Kwon
et al., 2008):
where γhw is the surface tension between CO2 hydrate
and water, mh is the molar mass of the CO2 hydrate,
461
Figure 5. Shift of phase boundaries of CO2 hydrate in small
pore sizes (calculated from Gibbs-Thomson equation) and
dissociation behavior of CO2 hydrate in natural UB sediment.
Figure 6. Pore size distribution of natural UB sediment
analyzed by mercury intrusion porosimetry.
ρh0 is the density of CO2 hydrate, and Lf is the latent
heat of dissociation of CO2 hydrate. In this study,
Tdep were calculated using previously reported data:
γhw = 0.030 N/m, mh = 174 g/mol, ρh0 = 1065 kg/m3 ,
and Lf = 65.2 kJ/mol (Anderson et al., 2003; Kwon
et al., 2008).
The phase boundaries considering the melting point
depression (Tdep ) by different pore sizes were super-
imposed with the bulk phase boundary in Figure 5. It
appeared that the hydrate-containing pore size of the
natural UB sediment was in the range of ∼50–70 nm.
This implies that CO2 hydrate formation and dissocia-
tion in fine-grained sediments is affected by capillarity
while those in coarse-grained sediments may not be
affected.
Figure 6 shows the pore size distribution of the
natural UB sediment measured by the mercury intru-
sion porosimetry (MIP). The MIP results showed that
the pore size of the natural UB sediment ranged from
10 nm to 10 μm. Whereas, our experimental data (Fig-
ure 5) indicated that the hydrate-containing pores sized
∼50–70 nm. This implies the preferential formation of
CO2 hydrate in small pores of fine-grained sediments.
This was possibly attributed to the initial location of
water when hydrates were nucleated, as water favors
small pores in partially water-saturated conditions due
to the capillarity.
ACKNOWLEDGMENTS
This work was partially supported by This work was
supported by the Korea Institute of Energy Technology
Evaluation and Planning (KETEP) and the Ministry of
Trade, Industry & Energy (MOTIE) of the Republic of
Korea (No.20152520100760).
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