Fluid Phase Equilibria 175 (2000) 53–61

Solubility of H2 S and CO2 in diethylene glycol at

elevated pressures
F.-Y. Jou, F.D. Otto, A.E. Mather∗
a
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alta., Canada T6G 2G6
Received 23 February 2000; accepted 18 August 2000

Abstract
The solubility of hydrogen sulfide (H2 S) and carbon dioxide (CO2 ) in diethylene glycol (DEG) has been de-
termined at temperatures in the range 298–398 K at pressures up to 7.5 MPa (for H2 S) or 20 MPa (for CO2 ). The
experimental results were correlated by the Peng–Robinson equation of state, and interaction parameters have been
obtained for these systems. The parameters in the Krichevsky–Ilinskaya equation were calculated from these in-
teraction parameters. The vapor-phase compositions predicted by the equation of state have been compared with
published data. © 2000 Elsevier Science B.V. All rights reserved.
Keywords: Hydrogen sulfide; Diethylene glycol; Carbon dioxide

1. Introduction

Diethylene glycol (DEG) has long been used for the removal of water from natural gas. Recently, it has
been applied to the dehydration of CO2 for the purpose of enhanced oil recovery. Substantial amounts of
CO2 dissolve in the glycol at the conditions in the contactor and high losses of the glycol occur compared
with typical natural gas dehydration. Absorption of H2 S and CO2 in the glycol causes the solution to be
corrosive, especially in the regenerator where the aqueous solution is at elevated temperatures.
Some studies of the vapor–liquid equilibria in the acid gas-DEG systems have been reported. Dow
Chemical [1] presented smoothed values for the solubility of CO2 in DEG for temperatures in the range
298–423 K at pressures up to 2 MPa. Smoothed values for the solubility of H2 S in DEG for temperatures
in the range 298–470 K at pressures up to 5.1 MPa were also given. Union Carbide [2] presented a
few values of the solubility of CO2 in DEG at 298 K at pressures up to 1.4 MPa. Khoroshilov et al.
[3] determined the solubility of H2 S-containing natural gas in DEG solutions at 278, 288 and 298 K at
pressures from 3 to 13.2 MPa. Takahashi et al. [4] measured the solubility of CO2 in DEG at 297, 311
∗
Corresponding author. Tel.: +1-780-492-3957; fax: +1-780-492-2881.
E-mail address: alan.mather@ualberta.ca (A.E. Mather).

0378-3812/00/$20.00 © 2000 Elsevier Science B.V. All rights reserved.

PII: S 0 3 7 8 - 3 8 1 2 ( 0 0 ) 0 0 4 4 0 - 4
54 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61

and 322 K at pressures from 2.5 to 8.0 MPa. Wallace [5] reported the concentration of DEG in CO2 vapor
at 8.3 MPa at three temperatures between 296 and 319 K. Kaminishi et al. [6] also reported values of the
vapor-phase concentration of DEG in CO2 at 313 and 333 K at pressures up to 15.6 MPa. Diaz et al. [7]
presented experimental data for the solubility of CO2 in DEG as well as the vapor-phase concentration
at temperatures in the range 275–325 K at pressures from 3.8 to 11.3 MPa.
The present work was undertaken to provide data on the solubilities of the acid gases in DEG over a
wide range of temperatures and pressures to correlate the results for use in phase equilibria calculations
in these systems and to compare the experimental vapor-phase compositions with calculated values.

2. Experimental details

The apparatus and experimental technique that were used are similar to those described by Jou et al. [8].
The equilibrium cell is mounted in an air bath. The temperature of the contents of the cell was measured
by a calibrated iron–constantan thermocouple and the pressure in the cell was measured by digital Heise
gauges. These gauges had an accuracy of ±0.1% of full scale by comparison with a dead-weight gauge.
The thermocouple had an accuracy of ±0.1◦ C by comparison with a platinum resistance thermometer.
The apparatus was checked by determination of the critical point and vapor pressure of propane, carbon
dioxide, and hydrogen sulfide. Differences of ±0.1◦ C and 0.1% in vapor pressure were found.
The DEG was introduced into the cell and was heated to 110◦ C and a vacuum applied to remove
traces of water. Chromatographic analysis indicated that the water content of the DEG was 0.1 mol%.
The H2 S or CO2 were added in amounts of determined by observation of the pressure. The vapor phase
was circulated using a magnetic pump and was bubbled through the liquid phase until equilibrium was
reached. Samples of the liquid phase were withdrawn from the equilibrium cell into a solution of 2 M
NaOH which converted the H2 S or CO2 into involatile species. Aliquots of the solution were titrated to
determine the concentration of H2 S or CO2 in the liquid solution. Replicate analysis indicated that the
concentration of solute in the liquid phase is accurate to about 2–3%. Attempts were made to analyze the
vapor using a gas chromatograph. The analysis was found to be inaccurate because of the small amount
of DEG present and the insensitivity of the thermal conductivity detector in the chromatograph.

3. Results

The solubility of CO2 and H2 S in DEG was determined at 298.15, 323.15, 348.15, 373.15 and 398.15 K
at pressures up to about 20 and 7.5 MPa, respectively. The data are presented in Table 1 for CO2 and in
Table 2 for H2 S. The present data are in good agreement with the data of Dow and Union Carbide at
low temperatures and pressures but deviate at higher pressures and temperatures with differences of up
to 20% noted. The data of Takahashi et al. [4] agree within 3–7%. The few points of Diaz et al. [7] agree
within 4%.

4. Data reduction and correlation

The equilibrium data were correlated in the manner described by Jou et al. [8]. The method requires
that an equation of state valid for the solvent and dilute solutions of the solute in the solvent be available.
 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61 55

Table 1
Experimental T–P–x data for the system DEG (1), CO2 (2)
P (MPa) x2

T = 298.15 K
0.0421 0.00291
0.187 0.0117
0.377 0.0238
0.719 0.0440
2.08 0.120
3.36 0.185
5.38 0.285
6.38 0.331
8.81 0.361
10.0 0.353
12.3 0.378
14.5 0.371
16.7 0.382
19.0 0.390
21.10 0.395
T = 323.15 K
0.0405 0.00179
0.159 0.00647
0.442 0.0174
0.997 0.0414
1.990 0.0760
3.480 0.129
6.520 0.223
7.83 0.254
9.16 0.290
11.52 0.311
14.20 0.329
15.26 0.327
17.57 0.341
19.81 0.346
20.61 0.353
T = 348.15 K
0.0367 0.00117
0.161 0.00476
0.447 0.0130
1.10 0.0312
2.64 0.0759
3.94 0.102
5.87 0.147
8.38 0.209
10.59 0.241
12.80 0.249
15.07 0.281
17.45 0.296
19.89 0.299
56 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61

Table 1 (Continued)
P (MPa) x2

T = 373.15 K
0.0482 0.00115
0.127 0.00298
0.343 0.00769
0.929 0.0204
2.68 0.0592
4.52 0.0942
6.18 0.128
8.21 0.159
9.89 0.173
12.4 0.219
14.6 0.233
16.9 0.253
19.1 0.265
T = 398.15 K
0.0377 0.000828
0.0945 0.00191
0.363 0.00694
0.842 0.0157
1.85 0.0347
3.80 0.0677
5.49 0.0978
7.13 0.125
8.34 0.143
10.49 0.162
12.58 0.189
14.41 0.206
16.66 0.232
18.89 0.249

The Peng–Robinson [9] equation of state was used in the calculations. The parameters a22 and b2 of the
solutes were obtained from the critical constants. The parameters a11 and b1 for DEG were obtained from
the vapor pressure and liquid density. The critical constants and acentric factors of the solutes and the
equations for the vapor pressure and density of DEG were taken from the compilation of Daubert and
Danner [10]. The resulting values of a11 and b1 for DEG, and a22 and b2 for the solutes are given in
Table 3. The experimental solubility data were used to obtain the binary interaction parameter δ 12 which
appears in the mixing rule of the equation of state
a12 = (a12 a22 )1/2 (1 − δ12 ) (1)
Values of δ 12 were found to be dependent on the temperature and can be fit by a linear relationship
δ12 = a0 + a1 T (2)
The parameters a0 and a1 are presented in Table 4 for the H2 S and CO2 Using the values of δ 12
calculations of the vapor-liquid equilibria were made using the Peng–Robinson equation. The results of
 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61 57

Table 2
Experimental T–P–x data for the system DEG (1), H2 S (2)
P (MPa) x2

T = 298.15 K
0.00193 0.00112
0.00644 0.00325
0.0409 0.0182
0.0951 0.0414
0.219 0.0895
0.506 0.199
1.035 0.383
1.570 0.588
1.840 0.726
1.900 0.835
1.980 0.953
T=323.15 K
0.00342 0.001023
0.0222 0.00573
0.142 0.0327
0.370 0.0825
0.967 0.206
1.810 0.369
2.600 0.556
3.200 0.716
3.500 0.942
T = 348.15 K
0.00491 0.000883
0.0294 0.00491
0.192 0.0282
0.519 0.0735
1.18 0.163
2.34 0.310
3.16 0.412
4.64 0.613
5.52 0.884
5.61 0.933
T = 373.15 K
0.00607 0.00075
0.0428 0.00480
0.225 0.0234
0.659 0.0669
1.130 0.112
3.010 0.277
5.150 0.470
7.480 0.678
T = 398.15 K
0.0074 0.00070
0.0732 0.00580
58 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61

Table 2 (Continued)
P (MPa) x2

0.235 0.0179
0.503 0.0402
0.984 0.0752
2.210 0.163
3.780 0.270
6.880 0.459

Table 3
Equation of state constants of DEG, H2 S and CO2 for the Peng–Robinson equation
Temperature (K) DEG H2 S CO2

a11 a b1 b a22 b2 a22 b2

298.15 6.9917 88.766 0.5473 27.04 0.4019 26.66

323.15 6.7467 89.260 0.5285 27.04 0.3791 26.66
348.15 6.5089 89.742 0.5106 27.04 0.3578 26.66
373.15 6.2766 90.208 0.4937 27.04 0.3379 26.66
398.15 6.0477 90.652 0.4777 27.04 0.3191 26.66
a
Units of a are Pa m6 mo1−2 .
b
Units of b are cm3 mol−1 .

the calculations for CO2 are shown in Fig. 1. The correlation is in good agreement with the experimental
data. At 298.15 K, there is a cusp at 6.9 MPa which is the three-phase pressure where vapor, DEG-rich
liquid, and CO2 -rich liquid are present. At higher pressures, the two liquid phases are in equilibrium. The
equation of state is seen to represent both vapor–liquid and liquid–liquid equilibria well.
Prausnitz et al. [11] have discussed the application of the Krichevsky–Ilinskaya [12] equation
( )
fˆ2
RT ln = RT ln H21 + v̄2∞ (P − P1S ) + A[x12 − 1] (3)
x2

The use of the Krichevsky–Ilinskaya equation requires the evaluation of three parameters, H21 , v̄2∞
and A. Bender et al. [13] have shown the connection between the Krichevsky–Ilinskaya equation and the
Peng–Robinson equation of state and their corrected equations (Deshmukh and Mather [14]) have been
used to obtain the three parameters of the Krichevsky–Ilinskaya equation from the equation of state.

Table 4
Correlation parameters for δ ij

H2 S CO2

a0 −0.0519 −0.0487
a1 × 103 0.2131 0.3431
 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61 59

Fig. 1. Experimental data for DEG (1), CO2 (2) compared with correlated values using the Peng–Robinson equation.

The Henry’s constant H21 , the Margules parameter A and the partial molar volume of the solute at infinite
dilution were calculated from the pure component parameters and the binary interaction parameter. The
results are presented in Table 5 for the two solutes. The Henry’s constants are presented in Fig. 2 as a
function of temperature for comparison with those of Takahashi et al. [4]. The Henry’s constants for CO2

Table 5
Parameters for the Krichevsky–Ilinskaya equation
Temperature (K) H21 (MPa) v̄2∞ (cm3 mo1−1 ) A/RT

H2 S 298.15 2.72 34.5 0.132

323.15 4.36 35.8 0.129
348.15 6.98 37.4 0.158
373.15 9.87 39.1 0.170
398.15 10.5 39.4 0.173
CO2 298.15 16.1 34.8 0.380
323.15 24.3 36.3 0.389
348.15 33.5 38.1 0.398
373.15 42.5 40.1 0.408
398.15 52.2 42.5 0.419
60 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61

Fig. 2. The dependence of the Henry’s constants on temperature for the solutes in DEG: (䊏) this work (CO2 ); (䉱) this work
(H2 S); (䊉) Takahashi et al. [4] (CO2 ).

are about 15% lower than those of Takahashi et al.; this is different from the case of triethylene glycol, for
which the Henry’s constants were in good agreement [8]. The parameters of the equation of state were
used to predict the glycol concentration in the vapor phase. The predictions at 40◦ C are compared with
the experimental data of Kaminishi et al. [6] and Diaz et al. [7] in Fig. 3. It is seen that the equation of
state gives results in good agreement with the experimental data.

Fig. 3. Comparison of calculated and experimental vapor compositions at 40◦ C: (—) Peng–Robinson equation of state; (䊉)
Kaminishi et al. [6]; (䊏) Diaz et al. [7].
 F.-Y. Jou et al. / Fluid Phase Equilibria 175 (2000) 53–61 61

List of symbols
A Margules parameter (J mol−1 )
a parameter in the Peng–Robinson equation (Pa m6 mol−2 )
b parameter in the Peng–Robinson equation (cm3 mo1−1 )
fˆi fugacity of component i in a mixture (MPa)
H21 Henry’s constant of solute 2 in solvent 1 at P1S (MPa)
P total pressure (MPa)
P1S vapor pressure of the solvent (MPa)
R gas constant (J mol−1 K−1 )
T absolute temperature (K)
v̄2∞ partial molar volume at infinite dilution (cm3 mol−1 )
xi mole fraction in the liquid phase
yi mole fraction in the vapor phase

Greek letter
δ 12 binary interaction parameter in the Peng–Robinson equation

Acknowledgements

The authors are grateful to the Natural Sciences and Engineering Research Council of Canada and the
Canadian Gas Processors Association for financial support of this research. Thanks are due to Mr. R.D.
Deshmukh who performed the calculations.

References

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[5] C.B. Wallace, Oil Gas J. 83 (25) (1985) 98–104.
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[14] R.D. Deshmukh, A.E. Mather, Fluid Phase Equil. 35 (1987) 313–314.