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Computation of equilibrium hydrate

formation temperature for CO2 and
hydrocarbon gases containing CO2 in the
presence of an alcohol, electrolytes and
their mixtures
Article in Journal of Petroleum Science and Engineering May 2000
DOI: 10.1016/S0920-4105(00)00028-0

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Khashayar Nasrifar

M. Moshfeghian

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Journal of Petroleum Science and Engineering 26 2000. 143150

www.elsevier.nlrlocaterjpetscieng

Computation of equilibrium hydrate formation temperature for

CO 2 and hydrocarbon gases containing CO 2 in the presence
of an alcohol, electrolytes and their mixtures
Kh. Nasrifar, M. Moshfeghian)
Department of Chemical Engineering, School of Engineering, Shiraz Uniersity, Shiraz, Iran
Received 12 December 1998; accepted 15 December 1999

Abstract
This work presents the applicability of a unified model to predict the CO 2-rich gas and pure CO 2 hydrate formation
conditions in aqueous solutions containing glycerol, methanol, ethylene glycol, electrolytes and their mixtures. A water
activity model is introduced that combines the effect of the soluble gases, an alcohol and electrolytes. Then this model is
used together with the model of Holder et al. wHolder, G.D., Corbin, G., Papadopoulos, K.D., 1980. Thermodynamic and
molecular properties of gas hydrates from mixtures containing methane, argon and krypton. Ind. Eng. Chem. Fundam. 19 3.
282x to predict CO 2-rich gas and CO 2 hydrate formation conditions. The predictions are in excellent agreement with
experimental data. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: gas hydrate; carbon dioxide; inhibition; electrolytes; alcohol

1. Introduction
Gas hydrates are clathrate compounds, inclusions
which obtain their stability through occupation of
suitable size gas molecules into cavities of water
crystalline lattice. Depending on the conditions and
relative size of the gas molecule and cavity, one of
the two structures I or II is being formed. Small gas
molecules like CH 4 , C 2 H 6 or CO 2 form structure I.
However, larger gas molecules such as C 3 H 8 or
i-C 4 H 10 form structure II. Some small gas molecules
like Ar or Kr form both structures. Ripmeester et al.
)

Corresponding author. Tel.: q98-71-67-2060; fax: q98-7130-3071.

E-mail address: moshfeg@succ.shirazu.ac.ir
M. Moshfeghian..

1987. discovered another structure, viz., structure

H. It is a double hydrate and needs two kinds of gas
molecule, one small and one large, to form. Small
gas molecules like Xe or H 2 S, together with a larger
molecule like methyl cyclohexane, can form structure H.
Calculating the conditions of CO 2-forming hydrate can be used in enhanced oil recovery during oil
production, in studying deep oceans where CO 2 can
be stored as a means for reduction of CO 2 in the
atmosphere, or in the calculations of seawater desalination by forming CO 2 hydrate. As a result, developing accurate methods for the prediction of CO 2
hydrate forming conditions is essential for many
industries.
van der Waals and Platteeuw 1959. were the first
who developed the basic statistical theory for compu-

0920-4105r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 4 1 0 5 0 0 . 0 0 0 2 8 - 0

144

Kh. Nasrifar, M. Moshfeghianr Journal of Petroleum Science and Engineering 26 (2000) 143150

tation of gas hydrate dissociation pressure. Later,

Parrish and Prausnitz 1972. developed a generalized
method based on van der Waals and Platteeuw theory for calculating gas hydrate conditions in the
presence of pure water. In order to improve its range
of applicability, this method is modified later by Ng
and Robinson 1976., Holder et al. 1980. and John
et al. 1985.. To include the effects of inhibitors on
the hydrate formation conditions, Anderson and
Prausnitz 1986. developed a method based on the
identity of fugacities to calculate hydrate formation
conditions in the presence of methanol. Englezos et
al. 1991. developed another method for calculation
of natural gas hydrate in the presence of methanol.
Englezos and Bishnoi 1988., Tohidi et al. 1993.
and Zuo and Stenby 1997. developed other methods
and calculated the hydrate formation conditions in
the presence of electrolytes. Moshfeghian and Maddox 1993. developed an alternative method based
on the pioneer work of Pieroen 1955.. They included the effect of hydrate number on the enthalpy
of hydrate formation. Consequently, they calculated
accurately the hydrate formation conditions of natural gas streams in solutions containing methanol and
ethylene glycol. Nasrifar et al. 1999. extended the
method of Moshfeghian and Maddox 1993. to glycerol and triethylene glycol.
Formation of CO 2 hydrate is different from the
other hydrate formers. This is due to the high solubility of CO 2 in the aqueous phase during the hydrate
formation. This fact makes it difficult to model the
aqueous phase for computation of CO 2 hydrate formation conditions. The method of Englezos and
Bishnoi 1988. does not give good results for CO 2
hydrate formation conditions in the presence of electrolytes. Therefore, Englezos 1992. used a method
similar to that of Anderson and Prausnitz 1986. for
the calculation of CO 2 hydrate formation conditions.
He used the model of Aasberg-Petersen et al. 1991.
for characterizing aqueous phase in contact with
CO 2 . Later, Tse and Bishnoi et al. 1994. showed
that the Aasberg-Petersen et al. 1991. model gives
poor results for prediction of CO 2 hydrate formation
conditions in aqueous CaCl 2 electrolyte solutions. So
they examined the methods of Chen and Evans
1986. and Zuo and Guo 1991..
Although all the above methods are quite accurate
for their range of applicability, none of them can be

used out of their range. For instance, the method of

Anderson and Prausnitz 1986. is only applicable for
calculating hydrate formation conditions in solutions
containing methanol. The method of Moshfeghian
and Maddox 1993. is applicable for calculating
hydrate formation conditions in natural gas streams
and the method of Englezos 1992. is applicable for
calculating CO 2 hydrate formation conditions in solutions containing electrolytes, and is not extended to
alcohols. None of them is applicable for calculating
hydrate formation conditions in solutions containing
both alcohol and electrolytes. Therefore, the need for
developing a method that extends the calculation of
CO 2 hydrate forming conditions in solutions containing electrolytes, alcohol or both, is justified. Moreover, CO 2 is normally produced in a substantial
amount with hydrocarbons. So the method must also
be applied to rich CO 2 hydrocarbon gases. These
systems show great deviations from predictions due
to structural change during the hydrate formation.
Recently, Nasrifar et al. 1998a,b. developed two
combining rules that combine water activities and
enthalpy of hydrate formations. They can be used
along with the method of Moshfeghian and Maddox
1993. for calculating hydrate formation conditions
in solutions containing an alcohol and electrolytes.
This method requires the enthalpies of hydrate formation in the presence of each inhibitor and an
activity model for calculating water activity in solutions containing that inhibitor and water. In this
work, the water activity model combining rule given
by Nasrifar et al. 1998a,b. is extended and used
together with the Holder et al. 1980. model. The
extension considers the effect of CO 2 solubility on
the water activity. The resulting method, while
avoiding the use of enthalpy of hydrate formation,
calculates accurately the CO 2 and CO 2 rich gas
hydrate formation conditions in the presence of glycerol, methanol, ethylene glycol, electrolytes and their
mixtures.

2. Methodology
For a system in which gas, hydrate and liquid
water phase are in equilibrium,

mlw s mHw

1.

Kh. Nasrifar, M. Moshfeghianr Journal of Petroleum Science and Engineering 26 (2000) 143150

where mlw and mHw are the chemical potential of

water in liquid and hydrate phase, respectively. If the
chemical potential of hypothetical empty hydrate
phase is denoted by m wb , the equilibrium criteria
could be restated as:
D mlw s D mHw

2.

D mlw s m wb y mlw

D mHw s m wb y mHw .

where
and
In
this work the expression for the difference in chemical potential of water between the empty hydrate
lattice and liquid water derived by Holder et al.
1980. is used:
D m lw
RT

D m0w

D hw

RT 2

/
H /
y

RT0
q

HT

Dw
RT

ln a w ,alrx w . s 1 y x w .

B q 2 A y B . x w

d P y ln a w

A s a1 q a 2 = 10y3 T
y3

3.

where
is the reference chemical potential difference between water in empty hydrate lattice and
ice phase. T0 is the reference temperature, 273.1 K,
and the reference pressure is 0 MPa. The temperature
dependency of D h w , the difference in chemical potential of water between ice and empty hydrate lattice, is given by:

HT DC

sure. However, a w,al and a w,el are taken as pressure

independent. In fact, the water activity model of
Nasrifar et al. 1998a. is extended such that it includes the effect of soluble gases on the activity of
water. Eq. 6. is derived based on the assumption
that the alcohol, electrolytes and each of soluble
gases separately affect the water but they do not
have any effect on each other.
In this work a w,al is calculated from the Margules
1895. equation,

7.

where
dT

D m0w

D h w s D h ow q

145

P w dT

B s b 1 q b 2 = 10

ln a ow ,el ,i s y

5.

The reference property differences for structures I

and II, D h0w , D m0w , D yw and constants a and b were
provided by Parrish and Prausnitz 1972..
For a system in which the water phase is altered
by alcohol, electrolytes and soluble gas components,
the activity of water in the aqueous phase is evaluated by:
a w s a w ,al a w ,el a w ,gas1 a w ,gas 2 . . . a w ,gasnc

9.

where a ow,el ,i is calculated from the equation given

by Pitzer and Mayorga 1973.:

and the temperature dependency of DCP w is given

by:
DCP w s a q b T y T0 .

The parameters a1 , a 2 , b 1 and b 2 are given for

methanol, glycerol and ethylene glycol in Table 1.
The parameter a w,el is calculated from the expression given by Patwardhan and Kumar 1986.:
ns m
i
ln a w ,el s o ln aow ,el ,i
10 .
m
i
i

4.

8.

18mq
1000

1 q Zq Zy Q 1 q mQ 2 q m2b 2 .
11 .

where Zq and Zy are the charge of positive and

negative ions, m is molality, Q 1 and Q 2 are some
functions of ionic strength and q is the stoichiometric number in the salt.
For calculating a w,gas i , the water activity that is
altered by the ith dissolved gas, it is supposed that
Henrys law is applicable to the soluble gas and
hence LewisRandall rule to the water. This can be

6.

where a w, j is the activity of water in a solution

containing only the water and species j j could be
alcohol, electrolytes or ith dissolved gas.. Eq. 6. is
an extension to the derived equation by Nasrifar et
al. 1998a.. This equation is evaluated at hydrate
formation temperature. For calculating a w,gas i , the
activity of water in the presence of ith dissolved gas,
the required pressure is gas component partial pres-

Table 1
Parameters of Eqs. 8. and 9. for methanol and ethylene glycol
and glycerol
Aqueous system a1
Methanol
Ethylene glycol
Glycerol

a2

b1

b2

y5.8466 27.0884 y2.8226

19.6439
y2.3245 y3.9237
0.6660 y49.3572
y11.7361 27.5212 y3.0106
3.8468

Kh. Nasrifar, M. Moshfeghianr Journal of Petroleum Science and Engineering 26 (2000) 143150

146

supposed to be due to low aqueous solubility of gas

components, which causes x w to be very close to
unity. It is to be noted that for a hydrocarbon dissolved gas containing CO 2 there may be other gas
components that participate in the hydrate formation.
However, this work supposes that only CO 2 dissolves in water in an appreciable amount and so
a w,gas i / CO 2 is unity. Therefore, whether the hydrate
gas is CO 2 or a hydrocarbon gas containing CO 2 ,
only the solubility of CO 2 in water is considered.
Hence,
a w ,CO 3 ( x w

12 .

In this work, x w is calculated by using a modified

form of the Krichevsky and Kasarnovsky 1935.
expression,
x w s 1 y x CO 2
fCO 2

s1y
899683.5exp

0.3411
PCO
y 22.33
2

RT

13 .

where fCO 2 and PCO 2 are the fugacity and partial

pressure of CO 2 in the gas phase, respectively and T
is hydrate formation temperature. In Eq. 13., R is
gas constant equal to 8.314 = 10y3 kJ moly1 Ky1 .
Eq. 13. was optimized using pure CO 2 solubility
experimental data in water; however, our evaluation
indicated that the application of theequation in the
form of Eq. 13. is reasonable. In fact, in Eq. 13.,
the partial fugacity and pressure of CO 2 are substituted for pure CO 2 fugacity and pressure.
The expression for D m Hw , the difference in chemical potential of water between the hydratephase and
the hypothetical empty hydrate phase, was given by
van der Waals and Platteeuw 1959.:
2

Fig. 1 shows the experimental data for CO 2 hydrate formation conditions in the presence of pure
water, aqueous 10 wt.% methanol solution, and
aqueous 20 wt.% CaCl 2 solution. It also shows the
predictions for the case in which the CO 2 solubility
in the liquid phase is considered and when it is
ignored x w s 1.. It is seen that this model predicts
accurately the CO 2 hydrate formation conditions in
the presence of pure water. Using the experimental
data of Dholabhai et al. 1993, 1996. for comparison, the average of absolute temperature deviation
AATD. was 0.04 K for six data points. It is also
seen that for the same number of data points, there is
a considerable deviation, AATDs 1.22 K, when
CO 2 solubility is ignored. The same conclusion
would be drawn for predictions with and without
CO 2 solubility for aqueous 10 wt.% methanol and 20
wt.% CaCl 2 solutions. The AATDs for the prediction of CO 2 hydrate formation temperatures in the
presence of 10 wt.% methanol and 20 wt.% CaCl 2
were 0.26 and 0.14 K when CO 2 solubility is considered, and 1.54 and 1.33 K when the CO 2 solubility is
neglected. Consequently, the solubility of CO 2 has a
considerable impact on prediction of hydrate formation conditions in pure water and solutions containing methanol or electrolytes. For 20 wt.% CaCl 2
solution, the predictions in the absence of solubility considerations is the same as the Englezos and
Bishnoi 1988. model. Obviously, the Englezos and
Bishnoi 1988. model gives poor results for the
prediction of CO 2 hydrate formation conditions.

nc

D mHw s RT i ln 1 q
is1

3. Results

fk Ci k
ks1

14 .

where i is the number of type I cavities per water

molecule in the unit hydrate cell. Ci k is Langmuir
constant given by Parrish and Prausnitz 1972. and
fk is the fugacity of gas k that is calculated using the
modified PatelTeja equation of state Valderrama
1990..

Fig. 1. Effect of solubility on the CO 2 hydrate formation conditions experimental data from Dholabhai et al., 1993, 1996.. Ca20
stands for 20 wt.% aqueous solution of CaCl 2 and Me10 stands
for 10 wt.% aqueous solution of Methanol.

Kh. Nasrifar, M. Moshfeghianr Journal of Petroleum Science and Engineering 26 (2000) 143150

Fig. 2. Equilibrium conditions of CO 2 hydrate in aqueous glycerol

solutions experimental data from Breland and Englezos, 1996..
G1 stands for glycerol and the numbers for the weight percent of
the glycerol in water.

Fig. 2 presents CO 2 hydrate formation conditions

in aqueous solutions containing 0%, 10%, 20% and
30 wt.% glycerol. The experimental data of Breland
and Englezos 1996. are used for the comparison.
Except for 30 wt.% glycerol solution, the agreement
between predictions and experimental data is excellent. The AATDs for predicting the incipient of CO 2
hydrate formation were 0.2, 0.12, 0.18 and 1.13 K in
0%, 10%, 20% and 30% aqueous glycerol solutions,
respectively. The large error for predicting CO 2 hydrate formation in 30 wt.% glycerol solution maybe
due to high concentration of glycerol in aqueous
phase so that the Margules equation was not able to
characterize the solution. However, the average of
AATDs was 0.4 K for the available 20 experimental
data points.
Fig. 3 depicts the predicted and experimental
hydrate formation conditions for 20% CO 2 q 80%
CH 4 in the aqueous solutions of 0, 10 and 20 wt.%
methanol. Using the experimental data of Dholabhai

Fig. 3. Equilibrium conditions for hydrate formation of 20%

CO 2 q80% CH 4 in aqueous methanol solutions experimental
data from Dholabhai et al., 1997.. Me stands for methanol and the
numbers for the weight percent of the methanol in water.

147

Fig. 4. Equilibrium conditions of CO 2 hydrate in aqueous solutions of electrolytes experimental data from Dholabhai et al.,
1993.. Na stands for NaCl and the numbers for the weight percent
of the electrolyte in water.

et al. 1997. for the comparison, it was obtained that

the AATDs are 0.34, 0.66 and 1.47 K and the overall
AATD for these three systems is 0.90 K.
Fig. 4 illustrates CO 2 hydrate formation conditions in aqueous solutions containing 3, 5, 10, 15 and
20 wt.% NaCl 2 . As can be seen, there are good
agreements between the predictions and the experimental data of Dholabhai et al. 1993.. The average
of AATD for these five systems consisting of 20
data points is 0.17 K.
Fig. 5 depicts the predicted and experimental
hydrate formation conditions in the presence of
aqueous NaCl solution; however, the gas hydrate
former is 20% CO 2 q 78% CH 4 q 2% C 3 H 8 . The
experimental data of Bishnoi and Dholabhai 1999.
were used for the comparison. Except for the solution containing 20 wt.% NaCl, the agreement is
good. The average of AATDs for the four systems
consisting of 12 experimental data points is 0.99 K.
In comparison with the case that pure CO 2 is hydrate

Fig. 5. Equilibrium conditions for hydrate formation of 20%

CO 2 q2% C 3 H 8 q78% CH 4 in aqueous electrolyte solutions
experimental data from Bishnoi and Dholabhai, 1999.. Na stands
for NaCl and the numbers for the weight percent of the NaCl in
water.

148

Kh. Nasrifar, M. Moshfeghianr Journal of Petroleum Science and Engineering 26 (2000) 143150

Fig. 6. Equilibrium conditions of CO 2 hydrate in aqueous solutions of mixed electrolytes experimental data from Dholabhai et
al., 1993.. Na, K and Ca stand for NaCl, KCl and CaCl 2 and the
numbers for the weight percent of the electrolyte in water.

formerly, the deviation for this case is much larger.

This is due to the presence of C 3 H 8 in the gas
mixture, which causes the gas mixture to form both
structures I and II depending on the conditions.
These systems exhibit deviations from predictions,
especially in the structural transition region Adlsasmlto and Sloan, 1992..
Fig. 6 demonstrates the predictions of this work
for CO 2 hydrate formation conditions in the presence of aqueous electrolyte mixtures and the experimental data of Dholabhai et al. 1993.. The average
of AATDs for these four systems consisting of 15
experimental data points is 0.28 K. Figs. 4 and 6
indicate that the model of this work uses the CO 2
solubility correctly to modify the model of Englezos
and Bishnoi 1988.. It is recalled that this work in
the absence of an alcohol reduces to the modified
Englezos and Bishnoi 1988. model and in the absence of alcohol and CO 2 reduces to the Englezos
and Bishnoi 1988. model itself.

Fig. 8. Equilibrium conditions for hydrate formation of 20%

CO 2 q80% CH 4 in mixed solutions of ethylene glycol and
electrolytes experimental data from Dholabhai et al., 1997.. Eg,
Na, and Ca stand for ethylene glycol, NaCl, and CaCl 2 and the
numbers for the weight percent of the inhibitors in water.

Fig. 7 represents the predictions of CO 2 hydrate

formation conditions in aqueous solutions containing
methanol and an electrolyte. Using the experimental
data of Dholabhai et al. 1996., it was obtained that
the AATD for aqueous solutions of 5 wt.% methanol
q 5 wt.% NaCl, 5 wt.% methanolq 15 wt.% KCl
and 15 wt.% methanolq 5 wt.% CaCl 2 are 0.18,
0.64, and 0.69 K, respectively.
Fig. 8 exhibits the experimental data of Dholabhai
et al. 1997. and predicted hydrate formation conditions in the presence of ethylene glycol and mixed
ethylene glycol and electrolytes solutions. The gas
hydrate former contains 20% CO 2 and 80% CH 4 .
Most deviations occur for the aqueous mixture containing 15 wt.% ethylene glycol, 5 wt.% NaCl and 5
wt.% CaCl 2 and the least deviations for the aqueous
mixture containing 5 wt.% ethylene glycol and 15
wt.% CaCl 2 . The average of AATDs for these three
systems is 0.84 K.

4. Conclusion

Fig. 7. Equilibrium conditions of CO 2 hydrate in mixed solutions

of methanol and electrolytes experimental data from Dholabhai et
al., 1996.. Me, Na, K and Ca stand for methanol, NaCl, KCl and
CaCl 2 and the numbers for the weight percent of the inhibitors in
water.

The water activity model introduced by Nasrifar

et al. 1998a. has been extended to consider the gas
solubility effect on the water activity in addition to
the effects of alcohol and electrolytes. The proposed
water activity model has been used together with the
model of Holder et al. 1980. to predict accurately
the hydrate formation temperatures for hydrocarbon
gases containing CO 2 and pure CO 2 in solutions
containing glycerol, methanol, ethyleneglycol, elec-

Kh. Nasrifar, M. Moshfeghianr Journal of Petroleum Science and Engineering 26 (2000) 143150

149

trolytes. and their mixtures. The agreements are

satisfactory.

l
o

5. Nomenclature

Acknowledgements

a
aw
a ow

The authors wish to express their appreciation to

the School of Engineering for use of computer facilities and the financial support of the Vice Chancellor
for Research of Shiraz University.

A
b
B
C
C Pw
f
h
m
mo

nc
ns
P
R
T
To

x
Zq
Zy

Constant of Eq. 5.
Water activity
Water activity in an aqueous single electrolyte solution having the same ionicstrength as the mixture
Constant of Eq. 7.
Constant of Eq. 5.
Constant of Eq. 7.
Langmuir constant MPay1 .
Water heat capacity kJrmol K.
Fugacity of gas component in a gas mixture MPa.
Eenthalpy kJrmol.
Molality molr1000 g.
Molality of an aqueous solution containing
a single electrolyte with the same ionic
strength as the mixed electrolyte solution
Number of gas components
Number of salts
Pressure MPa.
Gas constant, 8.314 = 10y3 kJrmol K
Hydrate formation temperature K.
Reference temperature 273.1 K.
Molar volume of ice m3rkmol.
Mole fraction
Number of charge for a positive ion
Number of charge for a negative ion

Greek letters
b2
Constant of Eq. 11.
D
Difference in properties
m
Chemical potential kJrmol.
q
Stoichiometric number in a salt
yi
Number of type i cavity per water molecule
Q
Some function of ionic strength
Subscript
al
el
i, j, k
w

Alcohol
Electrolyte
Dummy indexes
Water

Superscript
b
Empty hydrate lattice phase
H
Hydrate phase

Liquid phase
Reference state

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