Ind. Eng. Chem. Res.

2006, 45, 4441-4446

4441

CORRELATIONS
Estimating the Hydrate Safety Margin in the Presence of Salt and/or Organic
Inhibitor Using Freezing Point Depression Data of Aqueous Solutions
Hesam Najibi,*, Amir H. Mohammadi, and Bahman Tohidi
Faculty of Petroleum Engineering, Petroleum UniVersity of Technology (PTU), Ahwaz, Iran, and Centre for
Gas Hydrate Research, Institute of Petroleum Engineering, Heriot-Watt UniVersity,
Edinburgh EH14 4AS, Scotland, U.K.

Developing systematic methods for controlling and monitoring gas hydrate risks along the pipeline and/or
downstream conditions could provide the solution for future challenges. In this paper, the possibility of
predicting the hydrate suppression temperatures of fluids from freezing point depression data of aqueous
solutions containing different concentrations of salt and/or non-hydrate-forming organic inhibitor is investigated
by developing a general correlation. The developed correlation considers only the changes in the freezing
point of the aqueous solution, and there is no need for the analytical composition of the aqueous solution.
Since measurement of the freezing point for the aqueous phase is much easier than measuring the hydrate
dissociation point, such a relation can reduce the experimental costs. A well-proven thermodynamic model
is used for generating pseudoexperimental data of hydrate suppression and freezing point depression for 160
different aqueous solutions containing various salts and/or organic inhibitors over a wide range of concentrations
in order to develop this correlation. To examine the reliability of this model in predicting the freezing point
depression, some experimental freezing point depression data are measured and compared with literature
data and the predictions of the model. Independent data are used to examine the reliability of this method.
The predictions of this approach are in acceptable agreement with the independent experimental data,
demonstrating the reliability of this predictive method.
1. Introduction
Application of extended subsea tiebacks and transportation
of unprocessed well streams are among favorable options for
reducing field development and operational costs. These pipelines normally convey a cocktail of multiphase fluids, including
formation water and liquid and gaseous hydrocarbons, and may
therefore be prone to hydrate formation, which potentially can
block the pipeline and lead to serious operational and safety
problems. The conventional method to prevent or reduce hydrate
risks in transfer lines and process facilities is to use the socalled thermodynamic inhibitors. These are water-soluble
chemicals that reduce the water activity, hence shifting the
hydrate phase boundary to higher pressure and/or lower temperature conditions. The common industry practice is to use
methanol or glycols. However, due to uncertainties in the
inhibitor losses to other phases, changes in the system variables
(e.g., water cut, hydrocarbon rates, seasonal temperature changes)
hydrate could form.1
Downstream monitoring could significantly reduce the risks
associated with gas hydrate formation. However, systematic
ways of controlling and monitoring along the pipeline to examine the degree of inhibition are very limited. Hydrate monitoring
systems can be produced based on simple techniques such as
freezing point depression measurement of aqueous phase.
* To whom correspondence should be addressed. E-mail:
najibi@put.ac.ir or najibih@yahoo.com.
PTU.
Heriot-Watt University.

In the 1930s Hammerschmidt2 presented an equation for

predicting hydrate supression of typical natural gases in contact
with dilute aqueous solutions of antifreeze agents such as
methanol. The equation is

T )

1,297W
M(100 - W)

(1)

where M is the molecular weight of the antifreeze agent, W is

the weight percent of the antifreeze agent in the solution, and
T is the hydrate supression in kelvin. This correlation is
independent of pressure, hydrocarbon composition, and hydrate
structure, but it is dependent on the type and amount of inhibitor
present in the aqueous solution. Other investigators after
Hammerschmidt2 have correlated the degree of hydrate inhibition in terms of the amount and nature of the inhibitor present
in the system.3-9 Recently, a review article explained the
existing correlations in detail.9
In this paper, we report the results of our study into using
the freezing point of aqueous solutions for estimating the hydrate
inhibition characteristics. A successful outcome could significantly simplify the hydrate management strategy using sampling
or online measurements. We correlate the degree of hydrate
inhibition directly to the freezing point depression due to the
presence of salt and/or organic inhibitor in the aqueous phase,
regardless of the type and amount of salt and/or inhibitor present
in the system, eliminating the need for compositional analysis
of the aqueous phase. The hydrate stability zone in the presence
of the salt and/or organic inhibitor could be determined by
combining the results of the above correlation with the

10.1021/ie051265v CCC: $33.50 2006 American Chemical Society

Published on Web 05/12/2006

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Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006

Table 1. Measured Freezing Point Temperatures for Different

Aqueous Solutions
wt %
NaCl ( 0.1

wt %
EG ( 0.1

wt %
methanol ( 0.1

freezing
point ( 0.2, K

1.0
3.0
5.0
7.0
10.0
0.0
0.0
0.0
0.0
0.0
3.2
4.2
7.0
8.2
7.1
6.3
10.2
12.8
12.4

0.0
0.0
0.0
0.0
0.0
10.0
20.0
30.0
40.0
50.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.8
4.2
6.4
7.8
11.5
12.9
10.1
10.8
12.9

272.7
271.4
270.0
268.5
266.4
269.6
264.8
258.3
249.2
236.2
269.0
267.1
263.0
260.4
258.0
257.5
255.9
252.1
250.1

Figure 1. Comparison of freezing point data for aqueous solutions of NaCl.

*, measured value; 9, CRC handbook data; solid curve, thermodynamic
model1,12,13,20,21 prediction.

measured/predicted hydrate stability zone for hydrocarbon

systems in the presence of distilled water.10 Clearly, this equation
cannot provide reliable results for thermodynamic inhibitors that
take part in hydrate formation (e.g., 2-propanol11).
2. Thermodynamic Model and Data Generation
The required freezing point depression and hydrate suppression data have been generated using a well-proven thermodynamic model,1,12,13 for 160 different aqueous solutions containing
various salts and/or organic inhibitors over a wide range of
concentrations.
The data generated from thermodynamic model was preferred
to real experimental data for the following reasons:
(1) The amount of experimental hydrate dissociation data and
freezing point data, especially in the presence of salts and/or
organic inhibitors, is very limited.14,15
(2) Because of the limited experimental data, any error could
easily result in unreliable correlation.
A detailed description of the model is given elsewhere.1,12,13
Briefly, the comprehensive thermodynamic model uses the
Valderrama modification of the Patel and Teja equation of state
(VPT-EOS)16 for fugacity calculations in all fluid phases. Nondensity-dependent (NDD) mixing rules17 are applied to model
polar-nonpolar and polar-polar interactions. The hydrate phase
is modeled using the solid solution theory of van der Waals
and Platteeuw.18 The Kihara model for spherical molecules19
is applied to calculate the potential functions for compounds
forming the hydrate phase. The presence of salt(s) in aqueous
solution is taken into account by coupling the equation of state
(short-range interactions) with a Debye-Huckel (D-H) electrostatic term (long-range interactions).1,20,21
3. Results and Discussion
The reliability of the thermodynamic model in predicting the
hydrate stability zones of reservoir fluids in the presence of
aqueous solutions of various salts and/or organic inhibitors has
been demonstrated in previous publications.1,12,13,20,21 To demonstrate the reliability of this model in predicting the freezing
point depression of aqueous solutions containing salts and/or
organic inhibitors, data on some systems have been measured.
The experimental method is explained in detail elsewhere.22
Briefly, the freezing points were measured using a simple and
reliable method based on the difference between the bath and

Figure 2. Comparison of freezing point data for aqueous solutions of EG.

*, measured value; 9, CRC handbook data; solid curve, thermodynamic
model1,12,13,20,21 prediction.

sample temperature relying on detection of the latent heat

required to melt ice within a sample. The measured freezing
point data are given in Table 1. The freezing point data measured
for NaCl aqueous solution and aqueous solution of ethylene
glycol (EG) are compared with the data reported in the CRC
handbook23 and the prediction of the thermodynamic model1,12,13
in Figures 1 and 2, respectively. The data measured for aqueous
solutions of methanol and NaCl are compared with the prediction of the thermodynamic model1,12,13 in Figure 3. It should
be mentioned that none of the freezing points measured and
reported in this work have been used in developing the
thermodynamic model. As can be seen in Figures 1-3, the
agreement between experimental data and the predictions of the
thermodynamic model1,12,13 is good, demonstrating the reliability
of the model.
As mentioned earlier, freezing point depression and hydrate
suppression data for 160 different aqueous solutions with a large
number of salts and/or organic inhibitors over a wide range of
concentrations (as shown in Table 2) were used in developing
the correlation. The hydrate suppression temperatures of methane at 20 MPa were used for developing the correlation, and
the effect of the hydrocarbon composition as well as the system
pressure was ignored as previously mentioned by Nielsen and
Bucklin,3 Carroll,7 and Mohammadi and Tohidi.9
The predicted hydrate suppression temperatures were plotted
versus the freezing point depressions for the systems shown in
Table 2. Figure 4 shows the collapse of all the data onto a

Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006 4443

Figure 3. Comparison of measured freezing point data and predictions of

thermodynamic model1,12,13,20,21 for aqueous solutions of methanol + NaCl.

Figure 5. Experimental25 and predicted (correlation and thermodynamic

model1,12,13,20,21) hydrate stability zones in the presence of NaCl aqueous
solutions. Gas composition: C1 (80 mol %) + CO2 (20 mol %). 9, 5%
NaCl; 2, 10% NaCl; b, 15% NaCl; [, 20% NaCl; solid curve, correlation
predictions; dashed curve, thermodynamic model1,12,13,20,21 predictions.

Table 2. Concentrations of Salt and/or Organic Inhibitor Used in

Developing the Correlationa
inhibitor
NaCl
KCl
CaCl2
KBr
NaBr
HCOONa
HCOOK
methanol
ethanol
EG
diethylene glycol
triethylene glycol
methanol + NaCl
methanol + KCl
a

organic inhibitor, wt % salt, wt % no. of data points

0
0
0
0
0
0
0
2.8-50
4.2-31.1
5.8-23.1
7-49
7.9-59.5
3.1-14.2
2.9-11

2-23
2-13
2-32
2-32
2-40
2-30
2-30
0
0
0
0
0
3.2-12.5
3-9.7

12
7
16
16
20
15
15
18
8
4
7
8
9
5

Concentrations are relative to aqueous solutions.

Figure 6. Experimental25 and predicted (correlation and thermodynamic

model1,12,13,20,21) hydrate stability zones in the presence of KCl aqueous
solutions. Gas composition: C1 (80 mol %) + CO2 (20 mol %). 9, 5%
KCl; 2, 10% KCl; b, 15% KCl; solid curve, correlation predictions; dashed
curve, thermodynamic model1,12,13,20,21 predictions.

solutions containing salts and/or organic inhibitors to the

aqueous phase freezing point depression, is given by the
following expression:

T ) T0 - 0.6825TF

Figure 4. Hydrate suppression temperature for methane hydrates vs freezing

point depression temperature in the presence of aqueous solutions containing
salt and/or organic inhibitor.

straight line, suggesting a linear relationship between hydrate

suppression temperatures and freezing point depressions with
a slope of 0.6825. As can be seen, the hydrate suppression
temperature is always less than the corresponding freezing point
depression, which is in good agreement with that mentioned
by Nielsen and Bucklin,3 Sloan,24 Carroll,7 and Mohammadi
and Tohidi.9 Nielsen and Bucklin3 derived an equation indicating
that the hydrate suppression temperature will always be less
than the freezing point depression by a factor of [1 - (heat of
fusion of ice)/(heat of hydrate dissociation)].
The correlation, which relates the hydrate dissociation temperature of the reservoir fluid in the presence of aqueous

(2)

where T is the hydrate dissociation temperature in kelvin, TF

stands for the freezing point depression of the aqueous solution
in kelvin, and T0 represents the hydrate dissociation temperature
of the same fluid in the presence of distilled water in kelvin.
The developed correlation is simple and enables fast estimation of the hydrate-free zone of various reservoir fluids, in the
presence of salts and/or organic inhibitors regardless of the
system pressure and hydrate structure. The only prerequisite to
use the correlation is the hydrate dissociation temperature of
the same fluid in the presence of distilled water (T0), which
can be calculated using a general correlation10 capable of
predicting hydrate phase boundaries of various reservoir fluids
at temperatures less than 293.15 K.
The results predicted by the newly developed correlation are
compared with independent experimental data reported in the
literature in Figures 5-14. In all comparisons the value of TF
is calculated using the thermodynamic model mentioned in the
previous section.1,12,13 Also, all thermodynamic inhibitor concentrations reported here are relative to the aqueous phase. In
all figures, the predictions of the thermodynamic model are also
reported.

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Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006

Figure 7. Experimental25 and predicted (correlation and thermodynamic

model1,12,13,20,21) hydrate stability zones in the presence of CaCl2 aqueous
solutions. Gas composition: C1 (80 mol %) + CO2 (20 mol %). 9, 9.9%
CaCl2; 2, 15% CaCl2; b, 20% CaCl2; solid curve, correlation predictions;
dashed curve, thermodynamic model1,12,13,20,21 predictions.

Figure 8. Experimental26 and predicted (correlation and thermodynamic

model1,12,13,20,21) methane hydrate stability zones in the presence of methanol
aqueous solutions. 0, 10% methanol; 4, 20% methanol; solid curve,
correlation predictions; dashed curve, thermodynamic model1,12,13,20,21
predictions.

Figure 9. Experimental27 and predicted (correlation and thermodynamic

model1,12,13,20,21) methane hydrate stability zones in the presence of EG
aqueous solutions. 0, 10% EG; 4, 30% EG; O, 50% EG; solid curve,
correlation predictions; dashed curve, thermodynamic model1,12,13,20,21
predictions.

Figures 5-7 show a comparison between predictions of the

correlation developed in this work and the experimental data
reported by Dholabhai and Bishnoi25 for hydrate dissociation
conditions of a gas mixture composed of 80 mol % methane
and 20 mol % carbon dioxide in the presence of various salt
aqueous solutions. As can be seen, the predictions of the newly
developed correlation are in good agreement with the experimental data. It should be mentioned that the wide difference

Figure 10. Experimental28 and predicted (correlation and thermodynamic

model1,12,13,20,21) hydrate stability zones in the presence of methanol aqueous
solutions. Gas composition: methane (95.01 mol %) + propane (4.99 mol
%). 0, 10% methanol; 4, 20% methanol; solid curve, correlation predictions;
dashed curve, thermodynamic model1,12,13,20,21 predictions.

Figure 11. Experimental28 and predicted (correlation and thermodynamic

model1,12,13,20,21) hydrate stability zones in the presence of methanol aqueous
solutions. Gas composition (mol %): C1 ) 84.13%; C2 ) 4.67%; C3 )
2.34%; n-C4 ) 0.93%; n-C5 ) 0.93%; N2 ) 7%. 0, 10% methanol; 4,
20% methanol; solid curve, correlation predictions; dashed curve, thermodynamic model1,12,13,20,21 predictions.

Figure 12. Experimental28 and predicted (correlation and thermodynamic

model1,12,13,20,21) hydrate stability zones in the presence of methanol aqueous
solutions. Gas composition (mol %): C1 ) 71.6%; C2 ) 4.73%; C3 )
1.94%; n-C4 ) 0.79%; n-C5 ) 0.79%; N2 ) 5.69%; CO2 ) 14.19. 0, 10%
methanol; 4, 20% methanol; solid curve, correlation predictions; dashed
curve, thermodynamic model1,12,13,20,21 predictions.

between the solubility of methane and that of carbon dioxide

in the aqueous phase does not seem to have any important effect
on the accuracy of the results. However, this effect may be
important in sour fluids with very high concentrations of acid
gases.1

Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006 4445

Figure 13. Experimental29 and predicted (correlation and thermodynamic

model1,12,13,20,21) methane hydrate stability zones in the presence of NaCl
+ methanol aqueous solutions. 9, 6.2% NaCl + 10% methanol; 2, 6.2%
NaCl + 20% methanol; b, 6.2% NaCl + 30% methanol; [, 6.2% NaCl +
40% methanol; solid curve, correlation predictions; dashed curve, thermodynamic model1,12,13,20,21 predictions. Solid points measured by technique
using Cailletet equipment, and open points measured by Raman spectroscopy
technique.

the prediction of the developed correlation in Figures 13 and

14. As shown in the figures, the predicted data are in acceptable
agreement with the experimental data. However, the method
presented in this work shows some deviations at very high
concentrations of methanol. These deviations may be attributed
to the uncertainties in the experimental data at high concentrations of inhibitors.21 Jager et al.29 used two different techniques
for measuring methane hydrate phase boundaries in the presence
of aqueous solutions containing methanol and NaCl. In the first
technique they used Cailletet apparatus, and the second technique involves Raman spectroscopy. Their reported data show
some deviations at high concentrations of salts and organic
inhibitors for the same conditions, indicating a need for
generating accurate hydrate dissociation data at high concentrations of salts and organic inhibitors. The expression could be
further developed with the availability of new data, in particular
at high concentrations of salts and/or organic inhibitors.
4. Conclusions
The possibility of using freezing point depression of aqueous
solutions to predict the hydrate suppression temperatures of
reservoir fluids in the presence of salts and/or organic inhibitors
was investigated by developing a simple equation. Good
agreement was achieved between the predictions of this equation
and experimental data from the literature, demonstrating the
reliability of the method developed in this work.
Acknowledgment

Figure 14. Experimental29 and predicted (correlation and thermodynamic

model1,12,13,20,21) methane hydrate stability zones in the presence of NaCl
+ methanol aqueous solutions. 9, 11.9% NaCl + 10% methanol; 2, 11.9%
NaCl + 20% methanol; b, 11.9% NaCl + 30% methanol; [, 11.9% NaCl
+ 40% methanol; Solid curve, correlation predictions; dashed curve,
thermodynamic model1,12,13,20,21 predictions. Solid points measured by
technique using Cailletet equipment, and open points measured by Raman
spectroscopy technique.

Figures 8 and 9 show a comparison between the predictions

of this method and the experimental data reported by Ng and
Robinson26 and Robinson and Ng27 for hydrate dissociation
conditions of methane in the presence of methanol aqueous
solutions and aqueous solutions of EG. As can be observed,
the predictions are in good agreement with the experimental
data.
To examine the capability of this correlation for predicting
the hydrate inhibition characteristics in structure II hydrate
forming systems, the predictions of the developed correlation
are compared with the experimental data reported by Ng and
Robinson28 for hydrate dissociation conditions of different gas
mixtures in the presence of methanol. The results are presented
in Figures 10-12. Acceptable agreement between the predictions and the experimental data shows that the effect of gas
composition and hydrate structure can be ignored for engineering
purposes.
Limited experimental data for hydrate dissociation conditions
of gases in the presence of salts and organic inhibitors have
been reported in the literature. Hydrate dissociation conditions
of methane in the presence of different concentrations of
methanol and NaCl reported by Jager et al.29 are compared with

This work was part of a Joint Industrial Project funded by a

consortium consisting of Total, National Iranian Gas Company
(NIGC), Hydro, British Petroleum (BP), Chevron, Statoil, and
Petronas, whose support is gratefully acknowledged. H.N.
wishes to thank the Petroleum University of Technology (PUT)
for financial support during his sabbatical leave.
List of Symbols
D-H ) Debye-Huckel electrostatic term
M ) molecular weight of antifreeze agent (g/g-mol)
NDD ) non-density-dependent mixing rules
T ) hydrate dissociation temperature (K)
T0 ) hydrate dissociation temperature in the presence of distilled
water (K)
VPT-EOS ) Valderrama modification of the Patel and Teja
equation of state
W ) weight percent of antifreeze agent in aqueous solution
T ) hydrate suppression temperature (K)
TF ) freezing point depression (K)
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Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006

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ReceiVed for reView November 15, 2005

ReVised manuscript receiVed February 24, 2006
Accepted April 10, 2006
IE051265V