J. Chem. Eng.

Data 1994, 39, 191-194 191

Hydrate Equilibrium Conditions in Aqueous Electrolyte Solutions:

Mixtures of Methane and Carbon Dioxide
Pankaj D. Dholabhai and P. Raj Bishnoi*
Department of Chemical and Petroleum Engineering, The University of Calgary,
2500 University Drive Northwest, Calgary, Alberta, Canada T2N 1N4

Three-phase equilibrium conditions (aqueous solution-vapor-hydrate) of methane + carbon dioxide mixtures

in electrolyte solutions containing NaCl, KC1, CaCl2, and their mixtures were measured in the temperature
range of 262-285 K and in the pressure range of 1.5-10.6 MPa using a “pressure search” method. The ionic
strengths of the solutions ranged from 0.7 to 6.76 m.
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Introduction
Gas hydrates play an important role in the exploitation,
transportation, and processing of natural gas. There is a risk
of hydrate formation at all the stages of natural gas handling
due to the operating conditions of pressure and temperature
that favor hydrate formation. Large reserves of natural gas
also exist as hydrates. In addition, natural gas may have to
be drilled through a zone of hydrates. Carbon dioxide is
normally present along with these hydrocarbons. CO2 emis-
sion from the various combustion processes is identified to
be the major reason for the greenhouse effect, and it is
suggested that it be extracted and stored in deep sea waters
as hydrates. Hydrate phase equilibrium data on CO2 and its
mixtures with hydrocarbons are, therefore, essential.
Hydrate equilibrium data on CO2 and its mixtures in pure
water are available in the literature (1-7). The gas industry
Figure 1. Schematic of the experimental apparatus: DP,
uses methanol to inhibit hydrate formation. Ng and Robinson
(4, 8) reported equilibrium data for CO2 and a mixture of
pressure transmitter; R, nitrogen reservoir; S, sampling bomb;
methane and CO2 in the presence of methanol. Electrolytes, F, filter; PG, pressure gauge; SV, solenoid valve; CV, control
valve.
which are present in natural waters, also inhibit hydrate
formation. As a part of a systematic research program,
hydrate equilibrium data on CO2 hydrates in aqueous system. A computer receives the pressure and temperature
solutions of electrolytes were obtained at the University of values from the data acquisition system and saves them at
Calgary (9). In the present work, experimental data on the preset sampling intervals. The cell is immersed in a cooling
equilibrium conditions of two mixtures of methane and carbon bath; a mixture of glycol and water is circulated from a
dioxide in pure water and electrolyte solutions are reported. refrigerated/heated bath. The set point of the temperature
controller on this bath can be changed by multiples of 0.1 K.
The temperature in the cell generally oscillates within 0.1 K
Experimental Setup during a period of 24 h.
The span of the DP was adjusted to 0-12 MPa. The low-
The apparatus and the pressure search procedure employed
pressure side of the DP was left open to the atmosphere. The
were the same as those used by Dholabhai et al. (9) and Bishnoi stated accuracy of the DP was ±30 kPa (±0.25 % of its span).
and Dholabhai (11). The presence of hydrates in the solution The DP was calibrated against a dead weight tester. The
was detected visually through the windows in the equilibrium
standard deviation of the linear least-squares fit was 11.7
cell. For easy reference a schematic of the apparatus is given kPa. The accuracy of the RTDs was ±0.06 K.
in Figure 1. The experimental apparatus and procedure are Materials and Preparation of Electrolyte Solutions.
briefly described below. The electrolytes used were certified ACS-grade supplied by
Experimental Apparatus. The main component of the Fisher Scientific Co. Deionized water was distilled in the
apparatus consists of a stainless steel equilibrium cell laboratory before use. Gas mixtures having nominal com-
equipped with two marine-type Plexiglass windows for visual positions of 80 mol % methane + 20 mol % C02 and 50 mol
observation, a magnetic stirrer, and suitable connections for % methane + 50 mol % CO2 supplied by Union Carbide
charging/discharging of materials. The temperature of the Canada Limited and Liquid Carbonic Inc. were used.
cell contents is measured with two platinum resistance
Appropriate quantities of the electrolyte were weighed on
thermometers (RTDs). A 0-15-MPa Heise gauge is used to a top-loading Mettler balance with a readability of 0.01 g and
display the pressure. The pressure in the cell is measured added to a weighed quantity of the water. The mixture was
with a differential pressure transmitter (DP). The signals stirred at room temperature to dissolve the electrolyte.
from the RTDs and the DP are taken up by a data acquisition Analysis of the Vapor Phase. Samples from the vapor
phase from the cell were analyzed on an HP 5840A gas
• To whom correspondence should be addressed. chromatograph (GC) using a DC200 column. Pure-compo-
0021-9568/94/1739-0191$04.50/0 © 1994 American Chemical Society
192 Journal of Chemical and Engineering Data, Vol. 39, No. 1,1994
Table 1. Compositions of the Aqueous Solutions Table 3. Experimental Data on Hydrate Equilibrium
Conditions of 80 mol % Methane + 20 mol % Carbon
composition/ (mass % on wet basis) ionic Dioxide
solution NaCl KC1 CaCU strength/m
solution T/K P/MPa % C02« T/K P/MPa % C02"
Na5 5.02 0.9044
NalO 9.99 1.8992 CalO 268.59 1.96 18.7 272.00 2.80 19.4
Nal5 15.00 3.0197 276.04 4.32 19.7 279.13 6.08 19.7
Na20-1 20.00 4.2779 Cal5 273.11 4.61 19.0 266.65 1.88 19.6
Na20-2 20.01 4.2806 269.13 3.00 19.7 276.88 7.09 19.7
K5 5.00 0.7060 Ca20 263.78 2.89 19.8 267.60 4.30 19.8
K10 10.00 1.4904 271.34 7.24 19.9 273.69 9.46 19.9
K15 15.01 2.3690 NaSCalO 273.67 5.04 19.4 265.54 2.06 19.7
CalO 9.91 2.9733 269.35 3.12 19.8 276.71 7.14 19.9
Cal5 15.00 4.7699 KlOCaS 265.07 1.65 19.8 269.36 2.46 19.8
Ca20 20.00 6.7574 274.76 4.60 19.9 281.57 10.61 19.9
Na5K10 5.00 10.00 2.5847 Na5K10 269.28 2.59 19.2 275.21 4.99 19.7
NalOKS 10.00 5.00 2.8022 281.27 10.41 19.8 265.09 1.66 20.3
K10Ca5 10.00 5.00 3.1681 NalOCaS 275.13 6.07 19.5 269.18 3.10 20.0
NaSCalO 5.01 10.00 4.1890 265.52 2.11 20.1 278.74 9.71 19.4
NalOCalO 10.00 10.00 5.5176 Na6K5Ca4-l 275.11 5.23 19.9 268.99 2.67 19.9
NalOCaS 10.17 5.08 3.6736 278.25 7.65 19.7 265.48 1.85 20.3
Na6K5Ca4-l 6.01 5.00 3.99 3.2677
Na6K5Ca4-2 6.00 5.00 4.00 3.2689
0
Mole percent carbon dioxide in the vapor phase at equilibrium.

Table 2. Experimental Data on Hydrate Equilibrium Table 4. Experimental Data on Hydrate Equilibrium
Conditions of 80 mol % Methane + 20 mol % Carbon Conditions of 50 mol % Methane + 50 mol % Carbon
Dioxide Dioxide
solution T/K P/MPa % C02° T/K P/MPa % C02‘ solution T/K P/MPa % C02« T/K P/MPa S3 Oo

pure water 277.56 3.41 15.3 274.10 2.36 16.4 NalOCalO 268.08 3.53 48.6 270.80 5.16 49.4
281.50 5.14 16.7 284.84 7.53 17.9 264.14 2.15 49.7 268.21 3.52 49.7
Na5 281.99 6.98 17.7 274.98 3.26 16.1 NalOKS 275.48 4.59 46.5 268.04 1.82 49.8
279.23 5.08 17.2 271.59 2.30 15.2 271.57 2.78 49.5 265.76 1.38 50.0
NalO 278.98 6.56 17.4 276.14 4.66 19.4 Na6K5Ca4-2 275.50 4.46 47.5 265.97 1.46 48.1
272.07 3.10 16.1 268.46 2.03 19.3 271.86 2.80 50.0 268.08 1.81 49.6
Nal5 277.17 7.31 18.9 273.14 4.40 19.8
269.12 2.88 19.4 264.78 1.86 17.3
e
Mole percent carbon dioxide in the vapor phase at equilibrium.
276.79 7.37 18.2
Na20-1 270.37 5.42 19.3 267.48 3.85 19.8
261.95 2.12 19.1
Na20-2 274.31 9.15 19.9
K5 271.38 2.04 19.7 274.97 2.96 19.8
278.83 4.46 19.8 281.98 6.43 19.8
K10 275.90 3.94 19.6 272.16 2.59 19.8
269.16 1.83 19.7 278.96 5.56 19.8
K15 266.96 1.89 18.4 272.69 3.45 19.5
270.07 2.62 19.0 277.07 5.63 19.7

“
Mole percent carbon dioxide in the vapor phase at equilibrium.

nent response factors for methane and C02 were obtained on

the GC. Standard mixtures of methane and C02 were
prepared gravimetrically and analyzed on the GC. The
compositions of these mixtures were computed from the actual
masses of the pure gases used as well from the GC analyses
Figure 2. Hydrate equilibrium conditions for methane +
using the pure-component response factors. The two sets of
C02 mixtures in pure water: (A) ref 6; (·) this work. The
compositions matched within 0.001 mole fraction. constant C02 mole percent (in the vapor phase) curves were
Experimental Procedure. About 115 cm3 of the solution obtained using the correlation of ref 6: (—) 15 mol %; (···)
was charged into the cell, and the vapor phase of the cell was 18 mol %; (—) 22 mol %. The numbers indicate the mole
purged with the gas mixture. A sample from the vapor phase percent C02 in the vapor phase at equilibrium.
of the cell was analyzed on the GC to ensure the absence of
air. The solution was then allowed to cool to the required
decrease continuously. In such a case the pressure was
temperature. Once the desired temperature was reached,
the pressure in the cell was increased beyond the expected readjusted to a lower value. On the other hand, if all the
equilibrium value by introducing the gas from the cylinder. hydrates had decomposed, then the hydrates were formed
When the hydrates formed, the pressure was reduced to a again as described above, the pressure was adjusted to a value
value slightly less than the expected equilibrium pressure by slightly higher than that at which all the hydrates had
venting out the excess gas. The system was left to equilibrate. decomposed, and the observations were continued. At the
If the temperature and pressure of the system remained end of the experiment, the vapor phase was analyzed twice
constant for 3-4 h with a negligibly small quantity of the on the chromatograph. The results from the two samples did

hydrates present in the solution, the constant pressure and not differ from each other by more than 0.2 mol % and were
temperature were taken as the equilibrium conditions and averaged. The cell pressure was then lowered by approxi-
the experiment was terminated. If the system pressure were mately 30 kPa to verify that all the hydrates decomposed at
higher than the equilibrium pressure, then the pressure would the lower pressure.
 Journal of Chemical and Engineering Data, Vol. 39, No. 1,1994 193

T/K
Figure 3. Experimental hydrate equilibrium conditions for Figure 5. Experimental hydrate equilibrium conditions for
the 80 mol % methane + 20 mol % CO2 mixture in pure water the 80 mol % methane + 20 mol % CO2 mixture in pure water
and NaCl solutions: (·) pure water (this work); (T) Na5; ( ) and CaCU solutions: (·) pure water (this work); (T) CalO;
NalO; (A) Nal5; ( ) Na20-1 and Na20-2. Each solid curve is ( ) Cal5; (A) Ca20. Each solid curve is a visual fit of the data
a visual fit of the data for an electrolyte solution and is drawn for an electrolyte solution and is drawn to clarify the trend
to clarify the trend for the solution. The numbers indicate for the solution. The numbers indicate the mole percent CO2
the mole percent CO2 in the vapor phase at equilibrium. in the vapor phase at equilibrium.

T/K

Figure 4. Experimental hydrate equilibrium conditions for Figure 6. Experimental hydrate equilibrium conditions for
the 80 mol % methane + 20 mol % CO2 mixture in pure water the 80 mol % methane + 20 mol % CO2 mixture in pure water
and KC1 solutions: (·) pure water (this work); ( ) K5; ( ) and mixed electrolyte solutions: (·) pure water (this work);
K10; (A) K15. Each solid curve is a visual fit of the data for ( ) NaSCalO; ( ) K10Ca5; ( ) NaSKIO; (A) NalOCaS; (O)
an electrolyte solution and is drawn to clarify the trend for
Na6K5Ca4-l. Each solid curve is a visual fit of the data for
an electrolyte solution and is drawn to clarify the trend for
the solution. The numbers indicate the mole percent C02 in
the vapor phase at equilibrium. the solution. The numbers indicate the mole percent CO2 in
the vapor phase at equilibrium.
Experimental Results and Discussion
trend for a given electrolyte solution. They are not obtained
Experimental three-phase equilibrium data of aqueous from any model or correlation. The inhibiting effect of the
electrolyte solutions, methane + C02 hydrate, and vapor are electrolytes can be seen clearly in these figures: at a given
tabulated in Tables 2-4. The compositions of the electrolyte
pressure, the equilibrium temperature is lower for higher ionic
solutions are given in Table 1.
strengths. In Figure 6 the data for 5 mass % NaCl +10 mass
Pure water. In Figure 2 the experimental hydrate data % CaCl2 solution and those for 10 mass % NaCl and 5 mass
of the 80 mol % methane + 20 mol % CO2 mixture in pure % CaCl2 solution are very close to each other. As has been
water from this work are plotted. Adisasmito et al. (6) fit a observed with pure methane, propane, and CO2 hydrates (9-
polynomial to their data for methane + CO2 binaries in pure 11), this suggests that the inhibiting strengths of NaCl and
water. Using this polynomial, constant concentration lines
CaCl2 on a mass basis are close. Similar behavior can also be
for CO2 concentrations of 15,18, and 22 mol % were computed. observed for 10 mass % KC1 + 5 mass % NaCl and 10 mass
These lines, along with the applicable data from Adisasmito % KC1 + 5 mass % CaCl2 solutions in Figure 6 and for 5 mass
et al., are also plotted in Figure 2. The maximum absolute % KC1 + 10 mass % NaCl and 5 mass % KC1 + 6 mass %
relative difference between the experimental and computed NaCl + 4 mass % CaCl2 solutions in Figure 7.
pressures was 1.74% for data from this work and 1.7% for
data from Adisasmito et al. Conclusions
Electrolyte Solutions. The experimental data with the
electrolyte solutions are plotted in Figures 3-7. The solid Experimental three-phase equilibrium conditions of aque-
curves in these figures are “visually” drawn to clarify the oussolution, methane + C02 hydrate, and vapor in pure water
194 Journal of Chemical and Engineering Data, Vol. 39, No. 1,1994

Acknowledgment
The authors acknowledge the assistance provided by
Ranjan De Silva in obtaining the data in the laboratory.
Literature Cited
(1) Chen, H.-S. The Growth Rate of Ice Crystals: The Properties of
Carbon Dioxide hydrate. A Review of Properties of 61 Gas Hydrates.
Research and Development Progress Report No. 830; Office of Saline
Water, U. S. Department of Interior: Washington, DC, 1972; p 1.
(2) Larson, S. D. Phase Studies of the Two-Component Carbon Dioxide-
Water Systems Involving the Carbon Dioxide Hydrate. Ph.D. Thesis,
University of Illinois at Urbana-Champaign, IL, 1955.
(3) Robinson, D. B.; Mehta, B. R. J. Can. Pet. Technol. 1971,10, 33.
(4) Ng, H.-J.; Robinson, D. B. Fluid Phase Equilib. 1985, 21,145.
(5) Deaton, W. M.; Frost, E. M., Jr. U.S. Bur. Mines Monogr. 1946, 8.
(6) Adisasmito, S.; Frank, R. J., Ill; Sloan, E. D., Jr. J. Chem. Eng. Data
1991, 36, 68.
(7) Adisasmito, S.; Sloan, E. D., Jr. J. Chem. Eng. Data 1992,37, 343.
(8) Ng, H.-J.; Robinson, D. B. Research Report RR-74; Gas Processors
Association: Tulsa, OK, 1984.
Figure 7. Experimental hydrate equilibrium conditions for (9) Dholabhai, P. D.; Kalogerakis, N.; Bishnoi, P. R. Equilibrium
the 50 mol % methane + 50 mol % C02 mixture in pure water Conditions for Carbon Dioxide Hydrate Formation in Aqueous
and mixed electrolyte solutions: ( ) NalOCalO; ( ) Nal0K5; Electrolyte Solutions. J. Chem. Eng. Data 1993, 38, 650.
(10) Dholabhai, P. D.; Englezos, P.; Kalogerakis, N.; Bishnoi, P. R. Can.
( ) Na6K5Ca4-2. Each solid curve is a visual fit of the data J. Chem. Eng. 1991, 69, 800.
for an electrolyte solution and is drawn to clarify the trend (11) Bishnoi, P. R.; Dholabhai, P. D. Fluid Phase Equilib. 1993,83,455.
for the solution. The numbers indicate the mole percent C02
in the vapor phase at equilibrium. Received for review May 18, 1993. Revised September 29, 1993.
Accepted October 24, 1993.· This work was carried out as a part of
and electrolyte solutions containing NaCl, KC1, and CaCl2 the “Solid Deposition in Hydrocarbon Systems” Project, Contract No.
5091-260-2138, funded by the Gas Research Institute, Chicago, IL,
and their mixtures were obtained in the temperature range and the Gas Processors Association, Tulsa, OK.
of 262-285 K and the pressure range of 1.5-10.6 MPa. The
data for pure water agreed with the literature values. • Abstract published in Advance ACS Abstracts, December 1, 1993.