ARMA 10-291

Effects of Self-Preservation of Natural Gas-Hydrates

Makogon, Y.F, and Ghassemi, A.
Harold Vance Department of Petroleum Engineering, Texas A&M University, College Station, TX, U.S.A

Copyright 2010 ARMA, American Rock Mechanics Association

th th
This paper was prepared for presentation at the 44 US Rock Mechanics Symposium and 5 U.S.-Canada Rock Mechanics Symposium, held in
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ABSTRACT: Exploration and economic development of natural gas-hydrate (NGH) deposits as an unconventional energy source
requires understanding their conditions of formation and stability in porous media, both on land and offshore, and the fundamental
properties of a hydrate-saturated rock. Despite significant investigations within the past forty years, some of the most important in-
situ properties of hydrates are not well known. This work presents the results of a study of the process of gas hydrate self-
preservation in porous media and its effects on NGH formation and production. The study shows that the self-preservation effect
increases the hydrate dissociation temperature by several degrees oC, with the consequence of increasing the energy requirements
for hydrate dissociation during gas production from a hydrate deposit by 7-15%.

obtained during the decomposition of hydrates by

1. INTRODUCTION lowering the pressure below equilibrium when T <0 oC.
Study of natural gas hydrates is important in In this paper, we show the effect of self-conservation of
understanding the dynamics of earth’s interior as well as gas hydrates in temperatures above 0 oC.
those of the hydro- and atmosphere. It has been
suggested that methane hydrates (MH) have had a
significant effect on contemporary geotectonic [1].
Natural gas hydrates influence earth’s climate through
gas balance of the hydrosphere and the atmosphere.
They also impact the dynamics and composition of
reservoir water and influence the stability of the sea-
floor sediments in the oceans. The volume of natural gas
in the hydrate state in the subsurface has been estimated
to be on the order of 1.5x1016 m3 [2] and 1.6x1016 m3
[3]. This is a huge source of unconventional energy. A
majority of gas-hydrate deposits are in the supercooled
state (Fig. 1) and nearly 97 % of the known hydrated gas
resources are concentrated beneath the ocean floor.
As a potential unconventional energy source, natural
gas-hydrates have been studied for over 45 years. Over
230 hydrate deposits have been explored and various
methods have been proposed to estimate their gas
reserves in the hydrate state [5,6]. Several studies have
been carried out to determine a number of parameters of Fig. 1. Pressure-Temperature of some Gas Hydrate Deposits in
natural hydrates including parameters that characterize offshore conditions (Makogon at. al. [10]).
the conditions of their formation and their stability in
porous media [4,8,9]. In addition, some experience has The hydrate group at the Texas A&M University has
been gained in commercially producing gas from hydrate extensively studied the kinetics of hydrate formation and
deposits [10]. dissociation in porous media including experiments
involving real core samples. These experiments have
The self-conservation of gas hydrates was first observed been performed in visual cells at pressures of up to 35
in studies of the hydrate decomposition under sub-zero MPa. The studies have shown that the phase transitions
temperatures [7]. However, “self-conservation” was the of the water–natural gas system are strongly affected by
result of the formation of cellular ice from the water
the morphology, composition, and properties of the was controlled by the binary system of internal and
porous media. However, some important properties of external thermostats with an accuracy of 0.1 oC. The
hydrates and their self-conservative nature in geological porous materials used were fractionated quartz sand
settings are still unknown, hindering development of consisting of 40 to 120 mesh particles sizes, and real
economically effective techniques for using gas hydrate cores saturated with water at 20 to 75 %. The fluids used
deposits. were methane of high purity (99.99%), natural gas,
freshwater condensate, and sea water (U.S. Standard,
Production from gas-hydrate deposits by traditional
41.95 g/liter). The natural gas and sea water
means requires they be dissociated from a solid state to a
compositions are shown in Table 1 (The density of the
free state within the porous formation. As the conditions
sea water = 1.025 g/cm3 at T = 15 oC, PH = 8.2.).
of hydrate formation and dissociation and self-
conservation depend on the pore size and structure, it is
necessary to study the nature of this dependency.
The first experimental studies of gas/water systems
phase transitions in porous media under hydrate-
formation conditions were conducted in Moscow’s I.M.
Gubkin Institute of Oil and Gas [5]. The results
compellingly showed the possibility of formation and
stable existence of naturally occurring gas hydrates in
rock layers, and were recorded as the scientific discovery
of natural gas hydrates. After a comprehensive
international examination, the discovery of natural
hydrates was recorded in the USSR State Register of
scientific discoveries (Moscow, 1969) as № 75 with [11]
the following formulation: “Experimentally established
was the previously unknown property of natural gases to
form deposit in the solid gas-hydrate state in earth's crust
at specific thermodynamic conditions.”
In this paper, we present a study of the self-conservation
character of gas hydrates and describe its role in
formation and production of gas hydrates.
Fig. 2 General scheme of cell for study hydrate
formation-dissociation gas hydrates in porous media
2. EXPERIMENTAL PROCEDURES
In this work, we have used contemporary control
All controlled parameters were recorded and processed
methods and technology to perform the complex study
using a computer every 20 to 60 seconds.
of phase transitions for a gas/water system in porous
Simultaneously, we recorded the change in the
media under hydrate-forming conditions. We used a
electrical resistance of the porous medium which made
reactor with variable working volume from 320 to 1200
it possible to not only determine the phase transitions,
cm3 and pressure up to 35 MPa. This is a stainless steel
but also to study the dynamics of hydrate saturation at
high pressure cell (Fig. 2) with transparent windows.
any point in the process. For measuring the electrical
Experience has shown that uniform and full water
resistance, we used 10 fixed electrodes in the reactor.
saturation of the pore space is important when studying
phase transition during the formation and dissociation of
hydrates in porous media. A special procedure has been
3. EXPERIMENTAL RESULTS
developed and used to guarantee optimal saturation
(Makogon, 1974). In this section, we describe the conditions for formation
and decomposition of methane hydrates in a porous
Phase transitions were recorded using a Nikon, high-
medium saturated by fresh water. Fig. 3 shows the
resolution microscope while controlling and recording
characteristic variation of pressure (A-B-C-H-D-E), and
the pressure and temperature. Pressure was monitored
temperature (a-b-c-d-e-f-g) over time. The curve of the
using an Omega transducer system with an accuracy of
change in temperature has two rapid changes, namely
0.05 atm; temperature was monitored at five fixed points
(B-C) and (D-E). The first change (B-C) reflects the heat
of the test chamber using an Omega thermistors system
of formation of hydrates at the irregular gas/water
with an accuracy of 0.05 oC. The pressure in the reactor
contact surface in the pore space. The second change (D-
was maintained using a Ruska pump. The temperature
E) corresponds to the active adsorption of water vapor
(by capillary condensation) at the surface of the formed considerably reduced after the hydrate layer forms a
hydrate when it completely covers the free-gas/water complete film at the gas/water contact. The equilibrium
contact. In this case, the size of the pores decreases and pressure of water vapor above the hydrate layer can be
the pore structure changes and thus, capillary pressure defined as:
sharply increases. The presence of a hydrophilic medium
shifts the starting point of hydrate formation to the right 2V σ s
ρr = ρw e e .
(3)
i.e., it reduces the degree of supercooling and increases rRT
the temperature of at which hydrate begins to form.
in which ρw is the saturation vapor pressure of water in
Table 1. Composition of the Natural Gas and Sea water. the porous medium at the beginning of the hydrate-
formation process, V is the molar volume of hydrate
NG mol. % SW Component Mass. % (M/d), σs is the interfacial tension (surface energy on
Component
NaCl
the interface hydrate-gas), r is a radius of the micro-
CH4 - 87.2 58.49
C2H6 -7.6 MgCl2 × 6H2O 24.46
crystals of formed hydrate, R is the universal gas
C3H8 - 3.1 Na2SO4 9.75 constant, and T is the temperature. The surface energy
i-C4 -0.5 CaCl2 2.765 on the interface of hydrate with the gas that is saturated
n-C4 -0.8 KCl 1.645 by water vapor can be defined as:
N2 - 0.4 NaHCO3 0.477 x
ρc
CO2 -0.1 KBr 0.238 σ s = ∫ RT ln( )dx (4)
C5H12 - 0.3 SrCl2 × 6H2O 0.095 o
ρA
H3BO3 0.071
NaF 0.007

The capillary pressure in the porous rock depends on the

pore size and shape, fluid composition, the value of
surface tension at the gas/water boundary, as well as on
pressure and temperature. Theoretically, the value of the
capillary pressure developed in a rock is determined by
the [12] formula:
−2σ cos θ
Δp = (1)
r
where σ is the surface tension at the gas/water boundary,
θ is the wetting angle in the pore space, and r is the
capillary radius.

The magnitude of the surface tension of the gas/water

system depends on pressure and temperature [9]. The
presence of capillary pressure in the hydrophilic pore
space reduces surface tension on the gas/water boundary
and contributes to the hydrate-formation process. In
general form, the pressure drop (Δps) at the beginning of
the hydrate formation process has the form:
dps
Δps = pc (2)
dpc
That is, the pressure drop (Δps) is equal to the rate of
pressure change with respect to capillary pressure
variation (dps/dpc ) times the value of capillary pressure
(pc). At the beginning of hydrate formation in the porous
medium, the vapor pressure next to the interstitial water
corresponds to the pressure at saturation with gas and
water. Taking into account the capillary pressure and
surface tension, the pressure of the water vapor is
The accumulation of hydrate in the pore space changes
the structure and the size/dimension of the pores,
increasing the value of capillary pressure. Capillary
condensation during the second phase of hydrates
formation causes the adsorption of water vapor and a
significant reduction in vapor pressure. This is when the
effect of self-conservation of hydrate is clearly
manifested. When the chemical potential of the water
molecules in the hydrate lattice and those in the vapor
phase reach equilibrium, hydrate dissociation requires a
significant increase in temperature or a reduction in
pressure. The temperature increase required to
decompose fresh water-methane hydrates ranges from
2.5 to 3.6 oC. The necessary reduction in pressure ranges
from 12-27 atm lower than the equilibrium pressure of
the free-gas/water contact.
Fig. 4 is a characteristic phase diagram for formation
and dissociation of hydrates in a porous medium with
coordinates of pressure and temperature. The black
curve M-N corresponds to the equilibrium conditions for
existence of methane hydrates in free volume. Curve A-
B-C reflects an isochore of a temperature decrease
without phase transitions. Point C shows the pressure
and temperature corresponding to the beginning of
hydrate formation in this porous material at a specific
water saturation and size of pores.
The degree of supercooling that is necessary to initiate
formation of hydrates (Curve B-C) is determined by a
number of factors central to which are the structural state
of water, the pore space geometry, the composition of
gas and water, and the capillary pressure of the porous
medium. The enormously tortuous free-gas/water
contact in porous medium contributes to the active
process of hydrate formation within the pores and the
associated heat of liberation (CD). We can easily
determine the mass of hydrate formed at the free-
gas/water contact from the change in temperature
between the heat of hydrate formation and heat capacity
of the containing medium. Also, from the mass of
hydrate that has formed and the surface of the porous
medium, we can determine the average thickness of the
hydrated film and the change in geometry of the pore
space.
Section CDE of the curve represents the usual process of
lateral accumulation of hydrates in pore volume where
hydrates have completely covered the free-gas/water
contact. In this situation, the irregularly branched
hydrate surface continues to actively adsorb water
vapors. Next, the liberation of the heat of condensation
(curve EF) causes capillary condensation of water vapors
within the pore space of the hydrates.
The second rapid increase in temperature provides
information for determining the mass of the sorbed water
(water that is not passed into hydrate in the first stage)
and the finite quantity of the vapor pressure of water
above the hydrate layer. At point E, the process of
hydrate formation transforms from free gas-water
contact to volume-diffusion by sorbtion through the
hydrate film. From the value of the vapor pressure of the
water above the hydrate layer, we can easily determine
the pressure and temperature of decomposition of
hydrate for the equilibrium conditions (function of
composition).
Fig. 5 shows the results of repeated formation and
decomposition of methane hydrates in the same porous
medium. The difference is that contrary to the first
hydrate formation experiment that used fresh water, the
sample is saturated with water obtained after the
decomposition of hydrates and sustained at a
temperature less than 5 to 7 oC above equilibrium. This
water contains stable “clusters” of water molecules with
retained structured. The presence of clusters in the
volume of interstitial water contributes to the initiation
of hydrate formation (point C on CDE) at a higher
temperature, and at a higher rate of accumulation (by
almost three times). The rate of secondary hydrate
formation in porous media is much higher than for free
gas-water contact and totally closes the free-gas/water
contact over the equilibrium curve (E), although the
overall result is the same as before. The temperature for
start of hydrate melting is ~ 3oC higher. This is a
significant phenomenon and has implication for the
energy needed in MH production.
The practical consequence of the effect of self-
preservation during the development of gas-hydrate
deposits is that 10 to 30% more power would be required
to initiate the decomposition of hydrate layers. The
effect of self-preservation must be considered during the
development of the technology that will allow us to
master production from gas-hydrate deposits under
actual conditions.
4. DISCUSSION & CONCLUSIONS
The conditions for formation and accumulation of
hydrates in porous media considerably differ from
formation and dissociation of hydrates in the free
volume. The structure of the pore space, initial fluid
content and its composition determine the value of initial
capillary pressure and the corresponding shift of the
temperature at the beginning of the process of hydrate
formation. With the accumulation of hydrates, the
structure of the pore space also changes causing
capillary pressure to increase. The expanding hydrate
crystals also induce mechanical changes in the rock.
The extent of the translation of the equilibrium curve for
hydrate dissociation (effect of self conservation of
hydrate) is determined by the final condition of the pore
space, the presence of capillary condensation of water
vapor (reduction of vapor pressure), the type of formed
hydrates, and the capillary pressure magnitude.
While conducting this series of experiments, the shift in
temperature caused by the self conservation of hydrate
was from 2.5 to 3.6 oC and the pressure from 12-27 atm.
Under the specific geological conditions, the effect of
self conservation can considerably differ from these
values. The effect of self-conservation of hydrate
contributes to the stability of gas hydrate deposits, and
increases the energy needed in their development.
 Fig. 3 - Pressure and temperature trace for the methane hydate formation in pores
Fig. 6 P-T Secondary Methane Hydrate formation & dissociation in the porous media
100 17
pressure 110 N
A
temperature
95 16
a 100
A
90
b 15 B
I
90 C
85
14 D
80

Temperature, oC
Pressure, kg/cm2

80
13

Pressure, kg/cm2
75

12 70

70
C
11 60
65 E
c F H
B
E 10
60
G
50
F
D d

55 9
e 40
Cooling
50 8 Equilibr
300 420 540 660 780 900 Heating
30 M
Time, min 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Temperature, C

Fig 3. Pressure and temperature methane hydrate formation in

porous media. Fig. 5. P-T for secondary hydrate formation and dissociation
in a porous medium.
Fig. 5 P-T Methane Hydrate formation & dissociation in the porous
media
100 N

90
A
References
B
H
C
80
D
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70
Prevention of Formation and Utilization. Moscow.
Nedra.
Pressure, kg/cm2

60 2. Makogon,Y.F., 1982. Perspectives for the development of

Gas Hydrate deposits. Fourth Canadian Permafrost
50
Conference, Calgary, March 2-6, 1981.
40
3. Kvenvolden K.A., 1988. Methane hydrate – a major
E
F
Cooling reservoir of carbon in the shallow geosphere? Chem.
30 M Heating
Equilibrium
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20
0 2 4 6 8 10 12 14 16 18

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