Journal of Natural Gas Science and Engineering 21 (2014) 1107e1112

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Journal of Natural Gas Science and Engineering

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Study of methane replacement in hydrates by carbon dioxide in a

cyclic process
V.P. Voronov, E.E. Gorodetskii*, A.R. Muratov
Oil and Gas Research Institute, Russian Academy of Sciences, 119991 Moscow, Gubkina St. 3, Russia

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 31 July 2014
Received in revised form
30 September 2014
Accepted 2 November 2014
Available online 14 November 2014

The process of replacement of methane molecules in hydrate by carbon dioxide was studied by PVT
measurements in a cyclic process. A cycle of the process consisted of the injection of some amount of
carbon dioxide into the gas phase, which contacts with the hydrate, relaxation of the gasehydrate system
and evacuation of a portion of gas coexisting with the hydrate. The hydrate number and concentration of
gas mixture in the hydrate were determined during the replacement process. The dependency of the
extent of methane replacement on the amount of injected carbon dioxide was obtained.
2014 Elsevier B.V. All rights reserved.

Keywords:
Methane hydrate
Replacement
Carbon dioxide

1. Introduction
Recently the study of clathrates of natural gases has attracted
signicant attention. Natural deposits of methane clathrates on
continental margins and in permafrost regions contain huge
amounts of hydrocarbons (Makogon, 1997). One of the possible
ways of developing of such deposits is the replacement of methane
in hydrates by another gas. The utilization of carbon dioxide to
swap methane in hydrates has been considered in several articles
(see review article (Jung et al., 2010)). To analyze the composition of
gas hydrates and the replacement process spectroscopic methods
are often used (Rauh and Mizaikoff, 2012). The most common
techniques are Raman scattering (Ota et al., 2005, 2007; Komai
et al., 2000; Komai et al., 2002) and solid-state nuclear magnetic
resonance spectroscopy (Park et al., 2006). To accelerate the
replacement process, the hydrate is usually formed in some porous
medium or ice powder is used. The extent of methane replacement
by pure carbon dioxide obtained in Lee et al. (2003) was 64%. When
a mixture of carbon dioxide with nitrogen was used (Park et al.,
2006) the extent was 85%. The authors argue that carbon dioxide
replaces methane mainly in large hydrate cages whereas the use of
nitrogen allows to swap effectively the methane in small cages also.
It is known that the stability region of the methane hydrate is
located inside the stability region of the carbon dioxide hydrate
(Sloan, 1998). From the thermodynamic point of view this means

* Corresponding author.
E-mail address: gorod@ogri.ru (E.E. Gorodetskii).
http://dx.doi.org/10.1016/j.jngse.2014.11.003
1875-5100/ 2014 Elsevier B.V. All rights reserved.

that the methane in hydrate can be replaced by the carbon dioxide

completely if the methane concentration in the gas phase is low
enough. In our previous work (Voronov et al., 2010) the replacement extent obtained by a single addition of carbon dioxide was
about 69%. Thus, taking into account that the amount of small cages
is equal to one fourth of the total amount of cages it is unclear
whether the methane molecules in small clathrate cages were
replaced.
Clathrates can be considered like a host lattice of water molecules partially occupied by the guest gas molecules. In the rst
approximation it is supposed that gas molecules interact only with
the lattice. This model allows one to describe hydrates theoretically
in a universal way. The well-known Van der WaalsePlatteeuw
model (Van der Waals and Platteeuw, 1959) was used in our work
(Voronov et al., 2010) for the quantitative interpretation of data.
Unfortunately this model contains a large number of unknown
empirical parameters, which complicates the analysis of the
experimental data. Therefore in our present work we analyze the
data using the equation of state for gas mixture and material balance equations. The replacement process is slow and it is necessary
to be convinced that the obtained data describe the thermodynamically equilibrium state of the system. We study the replacement process and the kinetics of the replacement in a cyclic
process. A cycle consists of the injection of some amount of carbon
dioxide into the gas phase, which contacts with the hydrate, the
relaxation of the gasehydrate system and the successive evacuation of the gas portion. When injecting an amount of carbon dioxide
equal to the doubled amount of methane in the cell we obtained a
replacement extent about 85%.

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The transformations in the gasehydrate system were carried out

in the high-pressure cell of an adiabatic calorimeter with the volume Vc 10.966 ml. The experimental setup was described in
detail in Voronov et al. (2007). The mass of substances was
measured on analytical Sartorius and Sartogosm scales with the
accuracy 0.1 and 1 mg. The measurements were carried out in a
scanning regime with the heating rate of 1.5e2 K/h. The temperature, the pressure in the cell and the amount of heat injected into
the cell (enthalpy) were measured directly. The accuracy of the
measurements of these values was equal respectively to 0.0005 K,
0.003 MPa, and 0.1%.
Quartz powder with the mass ms 8.973 g was placed into the
experimental cell to increase the interface surface between the gas
and water or hydrate. Thus the free volume of the cell was
V0 Vc  ms/rs, where rs is the density of the powder. The powder
with a grain size about 5 mm was obtained by the sedimentation of
ground rock crystal in water.
Subsequently, water with the mass mH2 O 1.114 g was injected
into the cell. Afterwards the cell was heated up to evaporate all the
water and cooled slowly to room temperature. As a result the vapor
condenses rst in narrow pores and the water distributes homogeneously over the volume of the porous space. Thereafter, the
experimental cell was cooled to the water crystallization point.
Then the cell was pumped to vacuum and lled by methane with
the mass mCH4 0.259 g. Thereafter the experimental cell was
heated up to 285 K. The measured value of the pressure at the
temperature 282.07 K was 5.32 MPa. Using the standard equation
of state for methane (http://webbook.nist.gov/c) we nd that the
methane density is equal to 0.04087 g/ml. The volume of the cell
available for gas is equal to Vg mCH4 =0:04087 g=mlz6:34 ml.
Thus
the
free
volume
of
the
cell
is
equal
to
V0 Vg mH2 O =1 g=ml z 7.45 ml and the density of the quartz
powder is rs z 2.55 g/ml. At the end of the preliminary procedure
the experimental cell was cooled and the methane hydrate was
formed. At the temperature 262 K almost all the water in the cell
formed a hydrate.
The total measurement procedure consisted of four similar cycles which were done one after another. The measured dependencies of pressure on temperature at the rst cycle are
presented in Fig. 1.
In the gure, open circles are used to represent our data for the
decomposition of carbon dioxide hydrate in the analogous porous

medium. Solid circles represent the data for methane hydrate

decomposition in bulk taken from Sloan (1998). For clarity, the
curve describing the formation of methane hydrate from the
methaneewater mixture was omitted in Fig. 1. The cycle starts at
point A, where the system in the cell is in the two-phase equilibrium state (methane hydrateegas). First, in section AB the cell
was heated up to a temperature close to the methane hydrate
decomposition point to accelerate the transformation in the system. A portion of carbon dioxide was injected into the cell in
section BC during 10 min. Then the cell was sealed and the system
relaxed in adiabatic conditions during 20 h (section CD). After this
relaxation a state of hydrateegas system close to the equilibrium
state was obtained. In section DE the cell was heated up and the
hydrate in the cell was decomposed completely. As it follows from
Fig. 1, the decomposition of the obtained hydrate takes place along
the curve, located between the decomposition lines of the hydrates of pure methane and pure carbon dioxide. Thus, all
methane hydrate in the cell was transformed to the hydrate of gas
mixture.
Next, in the section EF, the cell was cooled and the hydrate of gas
mixture was formed again directly from the wateremethaneecarbon dioxide mixture. Afterwards, the slow heating
and cooling steps were repeated once more and the system turned
out at the point HG1. At this point the mixture is in two-phase state
gasehydrate and all water is contained in hydrate. The second
heating with the rate 1 K/h is necessary to obtain the hydrate
decomposition curve, close to equilibrium. The curve DE measured
at the rst heating of the hydrate, obtained by the replacement of
methane from hydrate by carbon dioxide does not describe equilibrium state, because the replacement process is slow (see below).
Curves EF measured at cooling are not equilibrium since the water
in the cell is always overcooling. Moreover, in the experiment, the
cooling rate was about 9 K/h. At the end of the cycle on the section
HG1-G a sample of the gas phase, coexisting with the hydrate, was
evacuated from the cell during 15 min.
The mass of water and gases used in the experiment was chosen
so that neither ice nor liquid carbon dioxide appeared in the cell.
This fact was always controlled by enthalpy measurements. For
example, the measured dependencies of the enthalpy and the heat
capacity along the line FE in the rst cycle are presented in Fig. 2.
As it is seen from Fig. 2, the hydrate melting takes place at the
temperature interval of about 3 K.
There is no anomaly in heat capacity or enthalpy in Fig. 2 near
ice melting point.

Fig. 1. The experimental P(T) dependence during the rst measurement cycle. The
cycle starts from the point A and terminates in the point G. Solid and open circles
present the decomposition lines of hydrates of methane and carbon dioxide correspondingly. Open squares present characteristic points, described in text. Solid squares
present points used in calculation.

Fig. 2. The measured enthalpy and heat capacity along curve FE at the rst cycle. The
maximum in the heat capacity describes the hydrate decomposition, there is no any
singular behavior at the ice melting temperature 273.15 K.

2. Experiment

V.P. Voronov et al. / Journal of Natural Gas Science and Engineering 21 (2014) 1107e1112

Section FE, corresponding to the heating of the equilibrium

hydrate of gas mixture for all four cycles is shown in Fig. 3. Points
HG and WG in the gure present the equilibrium state hydrateegas
and wateregas correspondingly. The numbers of these points
correspond to the number of the cycles. The open triangles in the
gure present the P(T) dependence for the hydrateegas system
after sampling, analogous to curve AB in Fig. 1. The sampling was
done so that all four curves were close to each other.
The mass of injected carbon dioxide portions for all cycles is
given in Table 1 as well as the mass of sampled methaneecarbon
dioxide portions.
Any of the four PeT dependencies obtained at heating of the
hydrateegas system, which are presented in Fig. 3, consists of three
parts. The left part presents the PeT dependence at hydrateegas
coexistence and is close to the isochore of the corresponding gas
mixture. The middle part corresponds to the hydrate decomposition stage, which is accompanied by the accelerated growth of the
pressure in the cell. The right part of the curve describes the
coexistence of the gas phase with liquid water and is close to the
isochore of the gas mixture. Note that the sections of the curves
presenting the hydrate decomposition stage are shifted to the
higher temperatures with the increase of its number. For the last
fourth cycle this section touches the decomposition curve of carbon
dioxide hydrate, i.e. for the fourth cycle the methane concentration
in hydrate is low.
3. Analysis of experimental data
We will analyze experimental data using the equation of state of
gas mixture and material balance equations. Note that the accuracy
of a typical cubic equation of state is not better than 3%. It means
that the uncertainty of gas mixture concentration is about 4%,
which restricts the accuracy of our calculation. Using volume shift
correction it is possible to improve the accuracy of the equation of
state in the necessary region. The comparison of the pressure
calculated according to the adapted SoaveeRedlicheKwong equation with the results of experimental study (Arai et al., 1971)
demonstrates that this equation provides the pressure calculation
accuracy about 0.03 MPa.
Further, the appearance of ice in the cell at the process of
methane replacement by carbon dioxide was observed in Komai
et al. (2002). In our experiment the presence of ice in the cell

1109

Table 1
Masses of injected and sampled gas portions.
Cycle
number n

Masses of injected
carbon dioxide mCO2_n , g

Masses of gas mixture

samples msam_n, g

1
2
3
4

0.406
0.677
0.279
0.186

0.205
0.509
0.226
0.154

would result in the appearance of enthalpy singularity near the ice

melting temperature, which was never observed in our measurements, see Fig. 2. Thus, we believe that ice was never formed in our
experiment and all water in the cell was located in the hydrate
lattice in the low temperature region.
Another difculty is that the left and the right sections of the
PeT dependencies obtained by heating of the cell are close to the
isochores of gas mixture but do not coincide with these isochores.
In left sections of the curves the pressure exceeds the pressure
along the corresponding isochore at heating. Our preliminary study
demonstrated that such behavior is specic to the hydrate containing carbon dioxide. Evidently some amount of carbon dioxide is
released from the hydrate at the temperature increase. It is difcult
to state whether the amount of water in hydrate remains constant
during this process. If it is so, the hydrate loses some amount of
carbon dioxide and the hydrate number increases; in the opposite
case some part of the hydrate is decomposed into the water and
gas.
Along the wateregas coexistence sections of the curves, the
pressure is always lower than the pressure at the isochore because
carbon dioxide is dissolved in liquid water. At low pressure the
concentration of the dissolved gas can be calculated in the Henry
approximation (Carroll et al., 1991) as

x P=KH ;

(1)

where x is the molar concentration of carbon dioxide in water, P is

the partial pressure of carbon dioxide and KH is the Henry's constant. For our purposes it is necessary to determine the amount of
dissolved carbon dioxide up to the pressure values 4e5 MPa. For
such pressures the Henry approximation looks like this

x f =KH ;

(2)

where f is carbon dioxide fugacity, which can be calculated from the

equation of state. The most complete consideration of carbon dioxide solubility known to us is presented in Diamond and Akinev
(2003). Our own experimental data for solubility of carbon dioxide
in water in the PeT range of the present experiment, which were
obtained in the same porous medium, are close to the data presented in Diamond and Akinev (2003). Therefore we tted the
experimental data from Diamond and Akinev (2003) to the
expression, similar to Carroll's expression (Carroll et al., 1991),
which was obtained for the pressure value P 0.1 MPa. As a result
we obtained the following approximation for Henry's constant

KH T; P exp  6:3437 124:28x  365:42x2 288:19x3

.
0:0098P; where x 100 T:
(3)
Fig. 3. The curves HGeWG are sections of curve FE presented in Fig. 1 for four cycles.
The solid and the open circles present the decomposition lines of hydrates of methane
and carbon dioxide correspondingly. The open triangles correspond to the P(T)
dependence obtained after the sampling.

This approximation is presented in Fig. 4 as a function of temperature for different pressures together with Carroll's expression.
For the set of 169 experimental points, given in Diamond and
Akinev (2003), expression (3) provides an average relative

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V.P. Voronov et al. / Journal of Natural Gas Science and Engineering 21 (2014) 1107e1112
Table 3
Hydrate number and compositions of phases at hydrateegas coexistence point.

Fig. 4. The Henry's constant as a function of temperature for different pressures, obtained from the tting of the experimental data presented in Diamond and Akinev
(2003).

deviation in Henry's constant of about 2.5%. We will use this

approximation further.
In our case the hydrate of gas mixture contains three components. We describe this phase by the hydrate number
Nh NH2 O =NCH4 NCO2 and the gas concentration in hydrate
xCH4 NCH4 =NCH4 NCO2 , where NH2 O , NCH4 and NCO2 are the mole
numbers of water, methane and carbon dioxide in the hydrate
respectively. To determine the hydrate number and composition,
the data presented in Table 2 were used. The coordinates of points
HG and WG were taken from the PeT dependencies for four cycles,
presented in Fig. 3.
Taking into account that the density of water in our temperature
range is about rH2 O 0.998 g/ml and the density of empty hydrate
lattice is approximately rh 0.796 g/ml, the volume of the experimental cell available for gas is


Vg V0  mH2 O rH2 O z6:34 ml
at the wateregas coexistence, and is


Vg V0  mH2 O rh z6:05 ml
at the hydrateegas coexistence. In principle, the densities of empty
hydrate lattices of carbon dioxide and methane are slightly
different (Jung et al., 2010), but the difference is small and we will
neglect it.
First, let us estimate the quality of the description of the
experimental data, for example at the line of gasewater coexistence for the rst cycle. At point WG1 the methaneecarbon dioxide
gas mixture of a given composition coexists with a known amount
of water. Calculating the mass of carbon dioxide dissolved in water
(ms) as a small correction, we determine the modied values of the
methane concentration in the gas phase and the gas density. Next,
using these values of the gas concentration and the density it is

Table 2
Coordinates of characteristic points at hydrateegas and wateregas coexistence.
Cycle number#

Hydrateegas (HG#)

Wateregas (WG#)

T, K

P, MPa

T, K

P, MPa

1
2
3
4

270.65
274.00
272.28
272.70

4.794
5.654
3.990
3.533

286.30
286.03
286.96
286.00

7.246
7.282
5.758
5.240

Point

Hydrate
number Nh

xCH4 in the gas,

mol. fr.

xCH4 in the hydrate,

mol. fr.

HG1
HG2
HG3
HG4

6.44
6.30
6.17
6.49

0.69
0.34
0.28
0.16

0.55
0.28
0.15
0.177

possible to calculate the pressure at WG1 from the equation of

state. As a result we obtain P 7.247 MPa, which practically coincides with the measured value presented in Table 2. Thus our
approximation is reasonably accurate.
At the beginning of the rst cycle the hydrate in the cell is a
pure methane hydrate. To determine the hydrate number and the
composition of hydrate at the end of the rst cycle it is necessary
to consider points HG1 and WG2. The mass of the gas at these
points
is
expressed
as
mHG1 mCH4 mCO2_1
and
mWG2 mCH4 mCO2_1  msam_1 . The concentration of methane at
point WG2 can be determined from the experimental value of
pressure. It is necessary to take into account the solubility of
carbon dioxide in water. The amount of dissolved carbon dioxide
can be found in the Henry approximation as a small correction.
Then, from material balance equations it is easy to calculate the
methane concentration in the rst gas sample xsam_1

xsam_1 z0:69:
Let us consider point HG1 now. We suggest that the state of
hydrate did not change during the sampling that is the determined
concentration xsam_1 of the gas sample, coexisting with the hydrate,
coincides with the concentration of the gas phase at point HG1.
Having the concentration of the gas phase and pressure at point
HG1 we nd that the gas density is equal to 0.065 g/ml. Eventually
using material balance equations we calculate the hydrate number
Nh 6.44 and the methane concentration in hydrate xCH4 0.55.
Thus, we determine the parameters of the hydrate and the coexisting gas phase at the point HG1, i.e. at the end of the rst cycle of
replacement.
It is possible to consider other cycles in a similar way. These
results are presented in Table 3.
Note that, for the last cycle, the obtained methane concentration
in the hydrate is larger than in the gas phase. Our calculation in
simplied Van der WaalsePlatteeuw model (Voronov et al., 2010)
takes into account only one type of cage. In such approximation the
concentration of carbon dioxide in the gas phase was always larger
than in the hydrate. The behavior observed here may be a result of
the lling of small cages by carbon dioxide.
There are several ways to estimate the accuracy of the calculation. It is possible to study the gas mixture samples evacuated in
section HG1-G in Fig. 1. The known mass of these gas portions
sampled in cycles 1e3 was injected to the experimental cell and the
isochoric PeT dependencies were measured. The measurement
results for these gas samples are presented in Table 4 as well as the
corresponding calculated values. For all samples, the differences
between the measured and calculated values of pressure are less
than the measurement inaccuracy.
Table 4
Measured and calculated parameters of gas mixture samples.
Number
of cycle

Density of gas in the

sample, g/ml

T, K

Measured
P, MPa

Calculated
P, MPa

Calculated
xCH4 , mol. fr.

1
2
3

0.00415
0.00885
0.00348

295.07
287.98
295.02

0.410
0.618
0.249

0.408
0.598
0.234

0.69
0.34
0.28

V.P. Voronov et al. / Journal of Natural Gas Science and Engineering 21 (2014) 1107e1112

1111

Table 5
Measured and calculated parameters of the system after sampling.
Number
of cycle

Mass of
gas after
sampling, g

Methane
concentration
in gas, mol. fr.

Temperature
T, K

Calculated
P, MPa

Measured
P, MPa

1
2
3
4

0.185
0.273
0.282
0.341

0.69
0.34
0.28
0.16

272.00
272.00
272.45
272.45

2.575
2.575
2.48
2.64

2.575
2.575
2.61
2.61

Also it is possible to use the pressure values in the cell after

sampling to estimate the calculation accuracy. The sampling was
done so that the P(T) dependencies for all cycles were close, one
such curve is presented in Fig. 3 by the open triangles. We know the
mass of gas phase after sampling and the composition of the gas
phase coexisting with the hydrate, which are presented in Table 3.
Thus it is easy to determine the pressure using the equation of state.
The calculation results are presented in Table 5. The values of the
pressure for the rst and second cycles coincide with the results of
measurement. For the third cycle the calculation gives a pressure
value lower than the measured value, whereas for the fourth cycle
the calculation gives a greater value than the measurement. Note
that the state of the hydrateegas system after sampling is not
equilibrium, it can be a reason of the large difference between the
calculated and measured values for the third cycle.
The calculated concentration of carbon dioxide in the hydrate as
a function of the carbon dioxide concentration in the gas phase is
presented in Fig. 5. Qualitatively the dependence is similar to the
results, obtained earlier in Voronov et al. (2010). In Fig. 5 the solid
circles correspond to the results of the calculation according to the
equation of state and the material balance equations, whereas the
open circles present the calculation results from Van der WaalsePlatteeuw theory with the parameter values determined in
Voronov et al. (2010). Note that the simplied Van der WaalsePlatteeuw model in Voronov et al. (2010) took into account only
one type of cages. We suggest that this is a reason for the signicant
difference between the result of this model and the recent calculation for the fourth cycle.
Fig. 6 presents the dependence of the relative amount of
methane in hydrate on the amount of carbon dioxide used for the
replacement. As it follows from the Figure the injection of the

Fig. 5. The dependence of the carbon dioxide concentration in the hydrate as a

function of the CO2 concentration in the gas phase. The solid circles present the values,
calculated from the experimental data with the use of equation of state. The open
circles show the values, determined from the simplied Van der WaalsePlatteeuw
model.

Fig. 6. The relative amount of methane as a function of the carbon dioxide amount
used for the replacement.

amount of carbon dioxide equal to the doubled amount of methane

allows to replace 85% of methane in the hydrate.
4. Replacement kinetics
In every measurement cycle the hydrateegas system relaxed in
adiabatic conditions for tens of hours after the injection of carbon
dioxide into the cell. For the rst cycle this step is presented by the
line CD in Fig. 1. At point C the cell was sealed but the pressure in
the cell increased during the subsequent 20 h. This increase is a
result of the replacement of methane from the hydrate by carbon
dioxide, because for the same molar density the pressure of
methane gas is larger than the pressure of carbon dioxide. At the
end of the relaxation process the pressure in the cell must have a
value equal to the pressure of gas mixture coexisting with the hydrate formed directly from the gas mixture with the same
composition. For example, at the rst cycle point D has to be located
on the line FE when the relaxation process has been completed.
In our experiment, the kinetics of the replacement process
depended on the number of the cycle or on the concentration of
carbon dioxide in the cell. The temporal dependencies of the
pressure at the relaxation process are presented in Fig. 7, where P(t)
is the value of the pressure during the relaxation process and P0 is
its limiting value, determined from the tting. These dependencies

Fig. 7. Pressure relaxation curves after the injection of carbon dioxide for four
experimental cycles.

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V.P. Voronov et al. / Journal of Natural Gas Science and Engineering 21 (2014) 1107e1112

Table 6
Characteristic times of relaxation for all cycles.
Number of cycle, n

t1, h

t2, h

1
2
3
4

1.4
e
1.5
e

23
17
12.66
5.46

can be approximated by a sum of two exponentially decaying

functions P(t) P0  A1 exp(t/t1)  A2 exp(t/t2). The values of
characteristic times t1 and t2, obtained by the tting of the data to
this dependency are presented in Table 6. For the second and fourth
cycles the experimental data can be tted by a single mode.
It seems natural to suggest that the faster process is the relaxation of the hydrate to the composition corresponding to the concentration of gas phase in the cell immediately after the injection of
carbon dioxide portion. The slower mode describes the relaxation
of the hydrate to the equilibrium composition, which would appear
at the formation of hydrate from the corresponding gas mixture. It
is controlled by the diffusion of gas molecules throw the hydrate
crystal.
5. Conclusion
We studied the methane replacement from hydrate by carbon
dioxide in a cyclic process. To make the analysis more reliable, the
Van der WaalsePlatteeuw model was not used; we employed only
the equation of state of the gas mixture. Methane in hydrate can be
replaced by carbon dioxide completely. The methane replacement
extent depends on the amount of carbon dioxide used for
replacement. For example, using the amount of carbon dioxide
equal to doubled amount of methane it is possible to replace about
85% of methane. Our results for hydrate compositions during the
replacement process are in reasonable agreement with the calculations according to Van der WaalsePlatteeuw theory but generally

it is necessary to take into account the existence of large and small

cages in the hydrate lattice. We suppose that the accuracy of our
calculation is about 3e4%, the inaccuracy results mainly from the
using of the equation of state for the gas mixture. The characteristic
time of the replacement process decreases with the increase of the
carbon dioxide concentration in hydrate. In our experimental
conditions, the larger relaxation time changes from 23 h for hydrate
of methane to 5.5 h for the hydrate with a methane concentration
of 15%. The formation of ice crystals at the replacement process,
which has been reported in Komai et al. (2002), was never observed
in our experiments.
Acknowledgment
The research was supported by the Russian Fund for Fundamental Investigations (RFFI Grant no. 09-08 00788-a).
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