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Calculation of Phase Diagrams


of Gas Hydrates

Article in Fluid Phase Equilibria August 1992


DOI: 10.1016/0378-3812(92)85083-K

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Fluid Phase Equilibria, 76 (1992) 141-149 141
Elsevier Science Publishers B.V.. Amsterdam

Calculation of Phase Diagrams of Gas-Hydrates.

Lars Lundgaard and Jorgen Mollerup*

Department of Chemical Engineering, Building 229, DTH, 2800 Lyngby, Denmark

ABSTRACT

The phase diagrams of gas-hydrates are calculated using van der Waals and
Platteeuws model with a Kihara spherical-core potential for the interaction
between water and the guest molecule. The Kihara parameters are obtained
independent of the mutual solubility of gas and water by constraining the model
to the experimental dissociation pressures along the hydrate-ice-gas equilibrium
line. Further, the fugacity coefficients in that region are close to unity wherefor
the Kihara parameters are rather insensitive to the choice of equation of state.
We use the Redlich-Kwong-Soave equation of state to calculate the fugacity the
guest molecule. The gas solubility in the water rich phase is likewise calculated
from the Redlich-Kwong-Soave equation of state combined with the DDLC
(Density Dependent tical composition ) mixture model.
The calculated phase diagrams comprise the hydrate - ice - gas, the hydrate -
water -gas/condensate, the hydrate-gas-condensate, and the hydrate structure I -
structure II - gas/condensate lines. Further we have investigated the influence of
the uncertainty of the lattice cavity size on the location of the hydrate structure
I - structure II - gas/ condensate equilibrium curve which turns out to be very
sensitive to even minor changes in the cavity size. The thermodynamically stable
phase is determined by a total Gibbs energy minimization of the system.

INTRODUCTION

Correlation of the dissociation pressure of inclusion compounds like hydrates


are made with three initial assumptions. First, the host lattice behaves as if it
were inert, second, there is no correlation between the behavior of guest
molecules even when they are in adjacent guest sites, and third there is
orientational disorder of guest molecules. Using the van der Waals and
Platteeuws model and a Kihara spherical-core potential (McKay and Sinanoglu,
1963) these assumptions lead to a model for the dissociation pressure of the
hydrate which apart from the properties of the empty clathrate hydrate lattice
requires the potential parameters for the interaction between water and the guest

0378-3812/92/$05.00 0 1992 Elsevier Science Publishers B:V. All rights reserved


142

molecule, the fugacity of the guest molecule, and the chemical potential of water
in the water rich phase. Gas-hydrates of natural gas compounds are known to
form two structures, a structure I and a structure II. All the experimental data
used in this work is form the book Clathrate Hydrates of Natural Gases by E.
D. Sloan (Sloan, 1990).

THE HYDRATE MODEL

The van der Waals and Platteeuws model (van der Waals and Platteeuw, 1959)
with a Kihara spherical-core potential leads to a model for the dissociation
pressure of the hydrate which in summary can be written as

Ak = kT &ln(l + cCtifj) (14


i j

Where Ap is the difference in the chemical potential between empty hydrate


and water or ice. The chemical potential of water is calculated from equation
(lb).

(lb)

We have used the same model for the chemical potential and the structure
parameters of the empty hydrate lattice as Parrish and Prausnitz did (Parish and
Prausnitz, 1972) because application of their chemical potential model gives a
very good agreement between experimental and correlated hydrate dissociation
pressures. The Langemuir constants C, are calculated from the van der Waals-
Platteeuw model. The fugacities 4 of the guest molecule is calculated from the
Redlich-Kwong-Soave (RKS) equation of state (Soave, 1072) and the activity of
water a, is likewise calculated with the RKS equation of state combined with the
DDLC mixture rule (Mollerup and Clark, 1989). The DDLC model is a local
composition model which corrects the classical equation of state model with the
van der Waals mixing rule by adding a one parameter density dependent local
composition mixture correction term to the conventional model.

The Kihara parameters are obtained by constraining the model to experimental


dissociation pressures. We determine the Kihara parameters by fitting the model
to data along the hydrate - ice - gas - line where the pressures are low and the
fugacity coefficients are close to unity wherefore an error in the calculated
fugacity coefficients only have a minor influence on the estimated parameters.
Since there is no gas solubility in the ice-phase the estimated parameters depend
mainly on the van der Waals-Platteeuw model, the model for the chemical
potential of the empty hydrate lattice, and only slightly on the equation of state
for fugacities. The thermodynamically stable phase is at any point determined by
143

a total Gibbs energy minimization of the system (Lundgaard and Mollerup, 1991).

Figure 1 shows the phase diagram calculated for ethane hydrate. The properties
of the fluid phases are calculated by the Redlich-Kwong-Soave equation of state
combined with the DDLC mixture model. This model enables calculation of the
mutual solubility of gas-condensate-water. No Henrys constant correlation is used
for the gas solubility. The two quadruple points are calculated directly specifying
the equilibrium conditions and the three phase lines gas-water-condensate and
gas-condensate-hydrate are also calculated from the RKS-DDLC model. This and
the fact that the thermodynamically stable hydrate structure is determined by a
total Gibbs energy minimization of the system means that the model can be used
as an integrated part of a flash calculation.

Hydrae + Liqnid

kU+ChS
I I I I I I I

260 265 270 275 260 265 290 295 300

T (K)
Figure 1. The Figure shows experimental and calculated dissociation pressures for ethane
hydrate and the calculated hydrate-gas-liquid equilibrium line. - calculated; A
Experimental.

The importance of calculating the lower quadruple point temperature is


indirectly shown in Figure 2. The Figure show the dissociation pressure for
carbon dioxide hydrate calculated with the program CMSHYD.EXE distributed
with the book Clathrate Hydrates of Natural Gases by E. D. Sloan (Sloan 1990).
The fact that they have a fiied quadruple point temperature at 273.15 causes a
jump on the calculated dissociation pressure curve.
144

I I I

250 260 270 260 290

J. (K)

Figure 2. Dissociation pressure for carbon dioxide hydrate calculated with the program
CMSHYD.EXE (Sloan, 1990). - Calculated; A Experimental.

PHASE DIAGRAMS OF METHANE AND NITROGEN HYDRATES

The size of the lattice cavities greatly influences the phase diagrams of hydrates
and the predicted thermodynamically stable structure. Methane and nitrogen is
normally known to form hydrate structure I but recently Davidson et al. (1986)
have reported that nitrogen forms structure II. They prepared a sample at
ambient temperature and cooled to 100 K to determine the structure.

Various cavity sizes have been reported in the literature. Table 1 summarizes
the cavity sizes used. To resolve the question of the structure of nitrogen hydrate
and investigate the influence of the cavity size on the calculated thermodynami-
cally stable structure we have calculated the complete phase diagrams of methane
and nitrogen hydrates including the ice - gas - hydrate, the water - gas - hydrate,
the ice - water - gas and the hydrate - gas - condensate lines. The latter line ends
close to the critical point of methane or nitrogen contrary to Figure 1 where it
cuts the gas - water - hydrate equilibrium line and gives rise to a quadruple point.
145

Figures 3 and 4 show the phase diagrams calculated with the cavity sixes of van
der Waals and Platteeuw. The dashed line in Figure 3 which lies below and runs
parallel to the ice-gas-hydrate equilibrium line is the projection in the PT-plane
of the intersection between the Gibbs surfaces of hydrate structures I and II.
Below the dashed line hydrate structure II has a lower Gibbs energy than
structure I and above the dashed line structure I has the lower Gibbs energy.
However, below the equilibrium lines the hydrate is unstable and the calculations
therefore shows that hydrate structure I is stable throughout the entire region.
In Figure 4 we have calculated a similar phase diagram for nitrogen hydrate but
extended the calculations to temperatures well below that of the experimental
data. The phase diagrams look very similar, there is however one important
difference.The equilibrium line between hydrate structures I and II, the dashed
line in Figure 3, cuts for nitrogen the ice-gas-hydrate equilibrium line at 130 K
and goes right into the region where hydrate is stable compared to ice. The line
is dashed in the unstable region and solid in the stable region. This means that
our model predicts that hydrate structure I is only stable at temperatures and
pressures to the right of the solid line. At 100 K the stable structure is structure
II what is in agreement with the investigation of Davidson.

Table 1

Published lattice cavity size


Author Structure I cavities Structure II cavities di-
diameter A ameter A
Small Large Small I-=ge
van der Waals and 7.90 8.60 7.82 9.46
Platteeuw, 1959 a
E. D. Sloan, 1990 7.82 8.66 7.80 9.37
Holder and Hand, 1982 7.88 8.60 7.82 9.46

aAl~~ used by Parrish and Prausnitz (Parrish and Prausnitz, 1972)


146

t, I I I I #,:I, I I, I, I I ,, I I I I

11oo 140 180 220 260 300 340

T (K)

Figure 3. Calculated phase diagram for methane hydrate. The dashed line represents a hypo-
thetical equilibrium line between hydrates structure I and II and gas in a region
where hydrates are thermodynamically unstable compared to water or ice. Cavity
sizes from van der Waals and Platteeuw. - Calculated; A Experimental.

Figure 4. Calculated Phase diagram for nitrogen hydrate. The dashed line represents an
unstable equilibrium line between hydrate structures I and II and gas, where it cuts
the ice-gas-hydrate equilibrium line there is a change in the stable hydrate structure.
Its solid extension represents the equilibrium between stable hydrate structure I and
structure II at pressures above the dissociation pressures. Cavity sizes from van der
Waals and Platteeuw. - Calculated; A Experimental.
147

The next question we address is what influence will it have on the phase
diagrams of methane and nitrogen hydrate if we make the size of the cavities a
little smaller than the numbers published by van der Waals and Platteeuw. The
numbers used by Sloan, and Holder and Hand, see Table 1, are either the same
numbers as van der Waals and Platteeuw used or smaller. We subtract only 0.02
8, from the cavity sizes of van der Waals and Platteeuw and repeat the calcula-
tions. The results are shown in Figures 5 and 6. Figure 5 looks very much like
Figure 3 with one exception. The dashed line in Figure 5 at one point cuts the
equilibrium line between ice-gas-hydrate and extends into the stable hydrate
region. This extension, which is drawn as a solid line, represents the line where
the Gibbs energy of the gas, hydrate structure I and hydrate structure II are
equal. This means that if we reduce all cavity sizes of van der Waals and
Platteeuw by 0.02 8, the model predicts that the thermodynamically stable
hydrate structure changes from I to II at a temperature of 170 K on the
dissociation pressure line. In Figure 6 we repeat the calculations for nitrogen
hydrate with the same reduced cavity sizes. By comparing Figures 4 and 6 we
observe that the equilibrium line between hydrate structure I and structure II now
has moved to the top of the diagram. With the reduced cavity sizes our model
now predicts that the hydrate structure II is stable at dissociation pressures to
5000 kPa.

I
400 140 180 220 260 300 340
T W)

Figure 5. Calculated phase diagram for methane hydrate. The dashed line represent an
unstable equilibrium line between hydrate structures I and II and gas, where it cuts
the ice-gas-hydrate equilibrium line there is a change in the stable hydrate structure.
Its solid extension represents the equilibrium between stable hydrate structure I and
structure II at pressures above the dissociation pressures.
- Calculated; A Experimental.
148

I I 0 I, I I

lo-k
I I, I I, I I, I I I I I I, I

100 140 180 220 280 300 340

'I-(K)

Figure 6. Calculated phase diagram for nitrogen hydrate. The solid line at the top of the
diagram represents the equilibrium line between hydrate structures I and II and gas.
The dashed extension represents an unstable equilibrium line between hydrate
structure I and structure II. - Calculated; A Experimental.

DISCUSSION AND CONCLUSION.

We have calculated complete phase diagrams of the gas hydrates of nitrogen,


methane, and ethane. The phase diagrams include the equilibrium line between
hydrate structure I and structure II whether stable or not. If the states are stable
it is drawn as a full line if unstable it is drawn as a dashed line. In Figure 2 this
line is not shown because it represents an unstable state which lies well below the
pressures shown in the diagram. We have demonstrated that the calculated
thermodynamically stable structures corresponds to the experimentally deter-
mined structures. Our calculations show that nitrogen hydrate is structure II at
temperatures below 130 K in agreement with what Davidson et al. have
determined. We have also demonstrated that even a very small reduction in the
cavity sizes of van der Waals and Platteeuw causes dramatically changes in the
location of the equilibrium line between hydrate structure I and structure II. The
reduction in the cavity size is less than the experimental uncertainty and the
reduced cavity sizes are in most cases larger than the sizes used by other authors.
149

REFERENCES

Davidson, D. W., et. all., 1986. Crystallographic Studies of Clathrate Hydrates Part 1. Mol.
tryst. Liq. qvst., 141: 141-149.
Holder, G. D.; Hand, J. H., 1982. Multiple-Phase Equilibria in Hydrates from Methane,
Ethane, Propane and Water Mixtures. AIChE Journal, 28: 440-447.
Lundgaard, L.; Mollerup, J. M., 1991. The infhtence of gas phase fugacity and solubility on
correlation of gas-hydrate formation pressures. Fluid Phase Equilibria, 70: 199-213.
McKay, V.; Sinanogul, O., 1963. Theory of Dissociation Pressures of some Gas Hydrates. .I.
Chem. Phys., 38: 2946-2956.
Mollerup, J. M.; Clark, W. M., 1989. Correlation of Solubilities of Gasses and Hydrocarbons
in Water. Fluid Phase Equilibria, 51: 257-268.
Parrish, W. R.; Prausnitz, J. M., 1972. Dissociation Pressures of Gas Hydrates Formed by Gas
Mixtures. I&. Eng. Chem. Process Dess. Develop., 11: 26-35.
Sloan, E. D., 1990. Clathrate Hydrates of Natural Gases. Marcel Dekker, inc., 641 pp.
Soave, G., 1972. Equilibrium Constants from a Modified Redlich Kwong Equation of State.
Chem. Eng. Sci., 27: 1197-1203.
van der Waals, J. H.; Platteeuw, J. C., 1959. Clathrate Solutions. Adv. Chem. Phys 2,21: l-55.

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