Fluid Phase Equilibria 185 (2001) 101–109

Hydrate phase equilibria of the guest mixtures

containing CO2 , N2 and tetrahydrofuran
S.-P. Kang a , H. Lee a,∗ , C.-S. Lee b , W.-M. Sung c
a
Department of Chemical Engineering, Korea Advanced Institute of Science and Technology,
373-1 Kusong-dong, Yusong-gu, Taejon 305-701, South Korea
b
Department of Chemical Engineering, Korea University, 5-1 Anam-dong, Songbuk-gu, Seoul 131-071, South Korea
c
Department of Resources Engineering, Hanyang University, Songdong-gu, Seoul, South Korea

Abstract
The three-phase, hydrate-water-rich liquid–vapor (HLV), equilibria of the binary guest mixtures containing CO2
and N2 were determined at the temperature range of 272–275 K and different compositions of vapor phase. In
addition, two phase equilibria of hydrate and vapor were also measured at three isothermal conditions of 274, 277
and 278 K. The resulting P–x diagram indicates that CO2 can be more contained than N2 in the hydrate phase. More
than 96 mol% CO2 in the mixed hydrate phase was obtained from a gas mixture of 17 mol% CO2 and 83 mol%
of N2 at 274 K. The addition of tetrahydrofuran (THF) as a hydrate promoter extended hydrate stability region by
elevating equilibrium dissociation temperature and lowering pressure. The overall hydrate equilibrium results were
found to agree well with the calculated ones. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Solid–liquid–vapor equilibria; Gas hydrate; Carbon dioxide; Nitrogen; Tetrahydrofuran; Model

1. Introduction

Gas hydrates are non-stoichiometric inclusion compounds formed by a lattice of water molecules,
“host”, strongly hydrogen bonded, which encage low molecular weight gases or volatile liquids, “guest”,
in different cavities under appropriate conditions where the low temperatures and high pressures favor
hydrate formation. Although guest molecules are physically enclosed within the lattice, no actual chemical
union exists between the guest and host molecules. In general, several types of polyhedral cavity structures
can be formed depending on the size and chemical properties of guest molecules. These structures are
further arranged into the well-defined three-dimensional crystalline solids.
The hydrates of the various gases may have structures corresponding to the fundamental types of
structure I (SI ), structure II (SII ), and structure H (SH ) [1]. Mixtures containing more than one gas
∗
Corresponding author. Tel.: +82-42-869-3917; fax: +82-42-869-3910.
E-mail address: [email protected] (H. Lee).

0378-3812/01/$20.00 © 2001 Elsevier Science B.V. All rights reserved.

PII: S 0 3 7 8 - 3 8 1 2 ( 0 1 ) 0 0 4 6 0 - 5
102 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109

component can similarly form a hydrate structure of one kind, but it is possible that the hydrates of
the individual constituents are characterized by different structures. If a system containing only one
type of hydrate is formed, the phenomenon corresponding to complete mixing of the solid solution is
manifested, and thus, a mixed hydrate is formed. In this study, the CO2 + N2 mixed hydrate system would
be investigated in detail. The pressure and temperature ranges of hydrate stability region were carefully
determined through phase equilibrium measurements of the ternary CO2 + N2 + water system that is
considered a simplified flue gas because the main components of flue gas become CO2 , N2 and O2 after a
suitable pretreatment method. General characteristics of N2 and O2 for gas hydrates are nearly similar [2].
A conceptual CO2 separation process from flue gas will be organized on the basis of these equilibrium data.
In the patents of Spencer [3,4], he suggested the methods of separating CO2 from gaseous stream using
the hydrate-nucleated solution. However, in the present work, THF was additionally used as a hydrate
promoter that can greatly reduce the required hydrate formation pressure and enhance the corresponding
kinetic rate. Cyclic ethers have been generally known to form simple hydrates with water or mixed hydrates
with low-molecular weight gases such as CO2 , CH4 and N2 [1]. In particular, THF forms SII hydrate in
which THF molecules occupy only the larger cages in the hydrate lattice. The hydrate phase behavior of
the binary THF and water system can be found from Callanan and Sloan [5]. The HLV equilibria can be
predicted by the statistical thermodynamic model calculation. The Soave–Redlich–Kwong equation of
state (SRK-EOS) incorporated with the modified Huron–Vidal second-order mixing rule (MHV2) was
adopted in this study. Details about this model calculation can be found in our previous work [6].

2. Experimental

2.1. Apparatus and materials

A schematic diagram of the experimental apparatus used in this work is illustrated in Fig. 1. The
apparatus was constructed to measure the gas hydrate dissociation pressures and analyze the equilibrium
compositions of all the coexisting phases via an on-line gas chromatograph. An equilibrium cell was
made of stainless steel and has an internal volume of about 70 cm3 . Two sapphire sight glasses were at the
front and back of the cylindrically shaped cell, and allowed visual observation of phase transitions. The
cell contents were agitated by a magnetic spin bar that was coupled with an immersion magnet placed
under the cell in the bath that contained about 30 l of ethylene glycol and water mixture. Its temperature
was controlled by an externally circulating refrigerator/heater. The actual temperature in the cell was
measured by a K-type thermocouple probe with a digital thermometer (Barnant Co.) of which resolution
was ±0.1 K. A Heise high pressure gauge (Dresser Industries, CMM 104957) was used to measure the cell
pressure within a maximum error of ±0.1 bar. For measurements of vapor and liquid phase compositions
at a given equilibrium condition two sampling valves (Reodyne Inc., Model 7410 and 7413) having loop
volumes of 5 and 0.5 ␮l were installed and connected to a on-line gas chromatograph (Hewlett-Packard,
HP5890) through a high pressure metering pump (Milton Roy, 2396-31). In particular, a careful procedure
was made to analyze the compositions of solid hydrates existing with other phases at equilibrium. At a
specific temperature and pressure, a hydrate sampling tube directly connected to the equilibrium cell was
completely evacuated by a vacuum pump. When the connection valve equipped between the tube and
cell was open, a desired amount of hydrates was placed and dissociated in the tube. The dissociated gas
constituents were then introduced into a gas chromatograph by a syringe injection.
 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109 103

Fig. 1. Experimental apparatus for measuring hydrate phase equilibria.

Gaseous mixtures composed of the high-purity CO2 and N2 (over 99.99 mol%) were prepared by using
two microsyringe pumps (ISCO, 260 D) having an isometric function of constant flow rate. CO2 was
initially charged to a reservoir with a predetermined amount of moles using one syringe pump and then N2
using another syringe pump. The prepared gaseous mixtures were analyzed using a gas chromatograph
for confirmation.

2.2. Procedure

After the equilibrium cell was well cleaned, the overall inner parts were evacuated with vacuum
pump. An amount of approximately 50 cm3 of water or aqueous solution containing THF was initially
charged into the cell. At first, the cell was pressurized to the desired pressure with the predetermined
gaseous mixture. Once the cell temperature was kept constant, hydrate nucleation was then induced by
agitation of the magnetic spin bar. When gas hydrates formed and the system pressure reached a steady
state, the external heater was used to increase the temperature at a rate of 1–2 K/h to a condition where
the hydrate phase was dissociated and in coexistence with liquid and vapor phases. The nucleation and
dissociation steps were repeated at least twice in order to remove the possibility of hysteresis effect. When
the amount of minute crystals and system pressure were kept constant at least for 8–10 h, the pressure was
considered to be the hydrate equilibrium dissociation pressure at the specific temperature. In measuring
the equilibrium compositions, the experiments need to be more carefully carried out. When the system
temperature and pressure was in equilibrium, the vapor phase was analyzed at least five times through
104 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109

gas chromatograph. The average value was then taken as an equilibrium vapor-phase composition. On
the other hand, the corresponding hydrate phase compositions were measured when the hydrate phase
was in coexistence with the vapor phase. Two phases of solid hydrate and vapor can only appear either
below the equilibrium temperature or above the equilibrium pressure of the HLV phases.

3. Results and discussion

The three phases HLV equilibria of the ternary CO2 + N2 + water system were determined at several
different ratios of CO2 and N2 . The mixed hydrates formed over the wide temperature and pressure
ranges of 272–282 K and 15–300 bar largely depending on the gas-phase compositions. The measured
equilibrium data were listed in Table 1 and also demonstrated in Fig. 2. As simple hydrates, CO2 and N2

Table 1
HLV equilibria of the CO2 + N2 + H2 O system
Loading composition (CO2 ) Temperature (K) Pressure (bar)
0.9659 274.95 15.65
277.45 20.60
280.25 29.00
282.55 40.00
283.55 51.15
0.7780 274.00 20.00
276.15 26.00
280.65 42.25
283.45 64.50
284.25 74.45
0.4815 273.75 31.95
276.00 42.57
279.00 58.67
281.00 74.49
282.00 89.75
0.1761 272.85 72.40
274.05 81.20
277.45 106.50
278.65 117.48
280.55 142.20
0.1159 274.25 110.20
275.65 138.70
277.60 181.00
278.95 222.30
0.0663 273.95 140.85
274.55 154.00
277.00 206.80
278.25 241.20
 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109 105

Fig. 2. Hydrate phase equilibria for the CO2 + N2 + water mixture measured at several composition ratios of CO2 and N2 .

form SI and SII , respectively. The mixed hydrate structure is considered to be either SI or SII depending
on the relative ratio of these two different gas molecules occupied in the small and large cavities. As
generally expected, all the hydrate formation lines were located between two pure CO2 and N2 HLV
lines, and the overall experimental data were well predicted by the statistical thermodynamic model
proposed in our previous work [6]. According to the literature [7], 85 mol% of CO2 gaseous mixture was
known as the boundary of coexisting SI and SII hydrate. In the present work, the coexistence boundary
was found to be 83.7 mol% of CO2 . While the relative amount of N2 to CO2 increases in the gas mixture,
the HLV equilibrium lines were shifted to higher pressure and lower temperature domain. As clearly seen
in Fig. 2, the slopes of the HLV equilibrium lines for both 6.63 and 11.59 mol% CO2 in gaseous mixture
appeared to be almost same to that of pure N2 , which confirms that SII hydrates formed. However, the
HLV results of 96.59 mol% CO2 showed a small promotion effect on the HLV equilibria of pure CO2 .
This phenomenon might be caused from the fact that smaller N2 molecules occupied empty cages that
could not be filled with larger CO2 molecules. But, when the relative mol% N2 in the binary gas mixture
increases, two species might compete with each other for cage occupancy resulting in no promotion.
After close examination of equilibrium temperature and pressure behavior shown in Fig. 2, three
isotherms of 274, 277 and 280 K were particularly chosen. Two phase equilibria of hydrate and vapor for
the ternary CO2 + N2 + water system were determined at these temperatures in order to produce the P–x
diagram and the complete data were listed in Table 2 and presented in Fig. 3 along with the calculated
results. The proposed model was successfully applied to the P–x as well as P–T equilibrium relationships.
The relative CO2 amount in the hydrate phase increased when that in the vapor phase increased. At a fixed
vapor composition of 15 mol% CO2 the corresponding CO2 composition in the hydrate phase at 274, 277
and 280 K appeared to be about 56, 47 and 36 mol%, respectively. It might be worthy to note from this result
that the CO2 selectivity in the hydrate phase increases at lower hydrate formation temperature. Another
sample of 17 mol% CO2 in the vapor phase shows a similar trend resulting to a little higher selectivity
106 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109

Table 2
HV equilibria of the CO2 + N2 + H2 O system measured at 274, 277 and 280 K
Temperature (K) Pressure (bar) Vapor phase (CO2 ) Hydrate phase (CO2 )
274 13.94 1.0000 1.0000
17.69 0.8205 0.9850
23.54 0.5999 0.9517
28.35 0.5048 0.9301
35.60 0.3994 0.9001
72.35 0.2057 0.5836
112.00 0.1159 0.3426
149.28 0.0498 0.1793
179.26 0.0000 0.0000
277 19.53 1.0000 1.0000
26.00 0.8491 0.9782
33.77 0.5867 0.9455
52.33 0.3899 0.8867
119.80 0.1761 0.5400
155.00 0.1159 0.3526
191.74 0.0663 0.1928
240.41 0.0000 0.0000
280 28.01 1.0000 1.0000
36.00 0.8250 0.9765
42.33 0.6999 0.9612
50.68 0.5917 0.9432
82.75 0.3924 0.8641
149.74 0.2510 0.6400
207.53 0.1709 0.4500
266.90 0.0905 0.2217
323.08 0.0000 0.0000

of 58 mol% CO2 in the hydrate phase at 274 K. Fig. 2 also suggests the possibility of CO2 separation
process using hydrate formation. The total amount of gas components captured in the hydrate phase can
be dissociated and easily recovered simply by either elevating temperature or decreasing pressure. Only
two consecutive steps are expected to achieve the recovery of >95 mol% CO2 according to Fig. 3.
According to Fig. 2, the mixed gas having concentrations of 17 mol% CO2 and 83 mol% N2 can
form hydrates with water slightly above 70 bar in the case that the hydrate-dissociation temperature is
maintained at 273 K. However, such a high pressure requirement might be regarded as a fatal disadvantage
when adopted to the actual CO2 separation process. Therefore, the more favorable condition is to lower
pressure and raise the temperature much higher than 273 K for hydrate formation. But, as shown in Fig. 2,
when the hydrate formation temperature increases, the corresponding equilibrium pressure also increases.
To solve this inherent problem, a hydrate promoter can be used to enable the operating conditions to
shift to the milder one. In this study, we used THF as a potential hydrate promoter and the promotion
effect of THF on the mixed hydrate formation temperature and pressure was closely examined and the
overall results were given in Table 3 and Fig. 4. Aqueous solutions containing 1 and 3 mol% of THF
 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109 107

Fig. 3. P–x diagram of the CO2 + N2 + water mixture measured at three temperatures of 274, 277 and 280 K.

Table 3
HLV equilibria of the CO2 + N2 + THF + water system
Gas and THF concentration Temperature (K) Pressure (bar)
17 mol% CO2 , 1 mol% THF 274.95 4.40
281.45 21.20
287.85 60.70
290.40 93.05
282.15 129.05
17 mol% CO2 , 3 mol% THF 277.55 2.00
281.85 11.40
284.50 18.95
289.65 47.00
293.25 88.60
295.15 128.20
70 mol% CO2 , 1 mol% THF 274.85 3.15
282.45 17.70
286.95 36.60
290.85 75.70
291.85 95.25
70 mol% CO2 , 3 mol% THF 279.55 3.80
284.15 13.20
289.35 32.00
292.15 58.10
295.45 90.86
108 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109

Fig. 4. Hydrate phase equilibria for the CO2 + N2 + THF + water mixture measured at 1 and 3 mol% of THF.

were used to form the mixed CO2 and N2 hydrates. As shown in this figure, a remarkable decrease of
equilibrium dissociation pressure was observed for the entire temperature range. The equilibrium hydrate
formation pressure under the gas compositions of 17 mol% CO2 and 83 mol% N2 was abruptly shifted
from 83.5–4.75 bar at 275 K when 1 mol% of THF is added in the aqueous solution. When aqueous
solution containing THF is used to form the mixed gas hydrate of CO2 and N2 , more favorable condition
can be attained resulting to lowering pressure and elevating temperature. The addition of a small amount
of THF to water expanded hydrate stability region, but it must be carefully noted that the promotion
effect of THF shifts to inhibition effect at a certain composition. Similar results were found by Jager et al.
[8] in the CH4 + 1,4-dioxane + water system. Addition of 1,4-dioxane to water up to 6 mol% showed
promotion effect, which was the stoichiometric ratio of SII 1,4-dioxane hydrate (1/17). THF also forms SII
hydrate and have the same guest/host ratio to 1,4-dioxane hydrate. All lines in Fig. 4 were obtained from
model calculations and well agreed to the experimental data. These mixtures form SII hydrate and THF
molecules occupy only large cavities of the structure. Owing to relatively high vapor pressure of THF, a
rigorous flash calculation was performed by using the modified UNIFAC, SRK-EOS and MHV2. For the
reasonable description of hydrate phase the classical van der Waals and Platteeuw theory was adopted.
The resulting optimized Kihara potential parameters are listed in Table 4. The needed parameters of pure
CO2 and N2 were regressed from the HLV literature [1] data of simple hydrate and those of THF were
obtained from the similar procedure of Jager et al. [8].
 S.-P. Kang et al. / Fluid Phase Equilibria 185 (2001) 101–109 109

Table 4
Optimized Kihara potential parameters of CO2 , N2 and THF

a (Å) σ (Å) ε/κ (Å)

CO2 0.720 2.8870 188.6

N2 0.3526 3.0298 125.07
THF 0.9643 3.2038 243.27

4. Conclusion

Three-phase HLV equilibria for simple and mixed hydrates of CO2 , N2 and THF were determined at the
broad ranges of temperature and pressure. Depending on the compositions of vapor phase, the equilibrium
hydrate dissociation pressures were varied between two HLV curves of pure CO2 and N2 . The dissociation
pressures were largely shifted to higher temperature and lower pressure conditions by adding small amount
of THF. Accordingly, THF was confirmed to act as a hydrate promoter and extend hydrate stability region.
This type of hydrate promoter can play an important role in changing high pressure condition to milder
one, which provides a great advantage when applied to the real hydrate-based processes. In particular, the
P–x diagram implies that the CO2 can be recovered from a power-plant flue gas. The detailed researches
related to this subject are now being carried out in our laboratory.
List of symbols
a radius of the spherical core
P pressure (bar)
T temperature (K)
x mole fraction
Greek Letters
ε/κ depth of the intermolecular potential well
σ distance between the cores at zero potential energy

Acknowledgements

This work was supported by grant No. 98-0502-04-01-3 from the Basic Research program of the
KOSEF and also partially by the Brain Korea 21 Project.

References

[1] E.D. Sloan Jr., Clathrate Hydrates of Natural Gases: Revised and Expanded, 2nd Edition, Marcel Dekker, New York, 1998.
[2] E. Berecz, M. Balla-Achs, Gas Hydrates, Elsevier, Amsterdam, 1983.
[3] D.F. Spencer, US Patent 5700311 (1996).
[4] D.F. Spencer, US Patent 6106595 (2000).
[5] J.E. Callanan, E.D. Sloan Jr., in: Proceedings of the International Gas Research Conference, London, 1983, pp. 1012–1021.
[6] S.-P. Kang, M.-K. Chun, H. Lee, Fluid Phase Equil. 147 (1998) 229–238.
[7] L.W. Diamond, Geochim. et Cosmochim. Acta 58 (1994) 19–41.
[8] M.D. Jager, R.M. de Deugd, C.J. Peters, J.D. Arons, E.D. Sloan, Fluid Phase Equil. 165 (1999) 209–223.