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VAPOR-LIQUID EQUILIBRIA OF H2S AND C02 AND

ETHYLENE GLYCOL AT ELEVATED PRESSURES
a a a a
F.-Y. JOU , R.D. DESHMUKH , F.D. OTTO & A.E. MATHER
a
Department of Chemical Engineering, University of Alberta Edmonton, Alberta, T6G 2G6,
Canada

Version of record first published: 06 Apr 2007.

To cite this article: F.-Y. JOU, R.D. DESHMUKH, F.D. OTTO & A.E. MATHER (1990): VAPOR-LIQUID EQUILIBRIA OF H2S AND C02
AND ETHYLENE GLYCOL AT ELEVATED PRESSURES, Chemical Engineering Communications, 87:1, 223-231

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 Chem. Eng. Comm. 1990, Vol. 87, pp. 223-231
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VAPOR-LIQUID EQUILIBRIA OF HzS AND

COz AND ETHYLENE GLYCOL AT
ELEVATED PRESSURES
F.-Y. JOU, R.D. DESHMUKH, F.D. OlTO and A.E. MATHERt
Downloaded by [Stanford University Libraries] at 02:38 26 September 2012

Department of Chemical Engineering

University of Alberta
Edmonton, Alberta, Canada T6G 2G6
(Received July 31, 1989; in final form July 31, 1989)

The solubility of HzS and COz in ethylene glycol has been measured at temperatures in the range 25
to 125C at pressures up to 6.7 and 20 MPa respectively. The data have been correlated using the
Peng-Robinson equation of state. Henry's coefficients have also been obtained from the experimental
data. Values oJ the vapor phase composition predicted by the equation of state have been compared
with some experimental data and with published data.
KEYWORDS Solubility Hydrogen sulfide Carbon dioxide Gas treating.

INTRODUCTION

Ethylene glycol is used for the dehydration of gas streams containing the acid
gases, H 2S and CO 2 , CO 2 must be dehydrated before it can be transported for use
in enhanced oil recovery processes. The phase behavior of ethylene glycol (EG)
and the CO 2 is important because of the loss of EG in the high pressure gas
stream which results when large volumes of CO 2 are processed. The absorption of
H 2S and CO 2 in the glycol causes the solution to become corrosive and
modification.s to the standard dehydration process are required. Few data are
available for the phase compositions in systems containing EG and the acid gases,
especially at elevated pressures. Union Carbide (1969) presented a few values for
the solubility of CO 2 in EG at 25C at pressures up to 1.14 MPa. Hayduk and
Malik (1971) reported the solubility of CO 2 in EG and aqueous solutions of EG
at 25C and 1 atm. Wallace (1985) reported three values of the vapor-phase
concentration of EG in CO 2 at 8.27 MPa. Adachi et al. (1986) also reported
values of the vapor-phase concentration of EG in CO 2 at pressures from
2.76 MPa to 22.1 MPa over the range of temperatures from 35 to 60C.
Kaminishi es al. (1989) presented values of the vapor-phase concentration of EG
in CO 2 at 40 and 60C at pressures up to 15 MPa. The solubility of H 2S in EG
has been determined at 1 atm over the range of temperatures from -8 to 20C by
Gerrard (1972) and at 1 atm over the temperature range -10 to 60C by Short et

[Author to whom all correspondence should be addressed.

223
 224 F.-Y. JOU et al.
al. (1983). The present work was undertaken to provide data on the solubilities of
the acid gases in EG over a wide range of temperatures and pressures, to
correlate the results for ease in calculations of the phase equilibria in these
systems and to compare the vapor-phase compositions with the calculated
values.

EXPERIMENTAL DETAILS

The apparatus and experimental technique that were used are similar to those
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described by Jou et al. (1987). The EG was introduced into a windowed

equilibrium cell which was mounted in a constant temperature air bath. The cell
was heated to 100C and a vacuum applied to remove traces of water.
Chromatographic analysis indicated that the water content of the EG was 0.5
mole per cent. The HzS or CO z were added in amounts determined by
observation of the pressure. The vapor phase was cirulated by means of a

TABLE [

Experimental T-P-x data for the system EG(I)-C02(2)

P/MPa X2 P/MPa x2
T = 298.15 K T = 373.15 K
20.29 0.1388 18.31 0.1206
15.89 0.1342 14.7 0.1029
11.04 0.1307 11.69 0.08721
6.45 0.1215 7.51 0.06252
2.94 0.0645 3.95 0.03664
0.84 0.02057 0.802 0.00742
0.145 0.00321 0.129 0.001273
0.0293 0.000693 0.076 0.0007231

T = 323.15 K T = 398.15 K
19.51 0.1327 18.31 0.1098
14.78 0.1226 14.49 0.09925
10.74 0.1 [22 10.11 0.07409
6.2 0.08309 6.31 0.04978
3.38 0.0533 2.84 0.02428
1.35 0.02144 0.826 0.006998
0.343 0.005397 0.13 0.001162
0.044 0.0007943

T=348.15K
[9.4[ 0.1288
15.01 O. J 138
11.01 0.09587
7.32 0.07322
2.95 0.03455
0.546 0.006262
0.114 0.001431
0.076 0.0009218
 VAPOR-LIQUID EQUILIBRIA 225
magnetic pump and bubbled through the liquid phase until equilibrium was
reached. The vapor phase was analysed using a gas chromatograph. Liquid samples
were withdrawn from the equilibrium cell into a solution of NaOH which
converted the H 2S or CO 2 into involatile species. Aliquots of the solution were
titrated to dletermine the concentration of H 2S and CO 2 in the liquid solution.
The analysis of the vapor phase was found to be inaccurate because of the small
quantity of EG present and the insensitivity of the thermal conductivity detector
of the chromatograph. To obtain vapor-phase compositions, CO 2 was bubbled
through the EG in the cell and passed through a metering valve to reduce the
pressure to atmospheric. The gas was passed through a coil immersed in a dry ice
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bath to trap the EG and then through a dry test meter to determine the volume of
CO 2 , After a period of time which depended on the temperature of the
experiment, the coil was weighed to determine the mass of EG collected. From
the total volume of CO 2 and the mass of EG, the concentration of EG in the
vapor phase was calculated.

TABLE II

Experimental T-P-x data for the system EG(I)-H 2S(2)

P/MPa P!MPa
T = 298.15 K T = 373.15 K
2.03 0.4055 6.75 0.3174
1.56 0.2532 2.82 0.117
1.03 0.1535 1.28 0.05446
0.677 0.09558 0.536 0.02285
0.153 0.02165 0.119 0.005161
0.054 0.007649 0.0144 0.000664
0.0055 0.000901 0.00961 0.00044
0.00324 0.000511 0.00364 0.000152

T = 323.15 K T=398.15 K
3.52 0.4494 6.46 0.2347
3.04 0.3104 2.78 0.09681
1.89 0.1676 0.854 0.02863
0.621 0.05057 0.134 0.00451
0.186 0.01468 0.0262 0.000821
0.0356 0.00316 0.0153 0.000432
0.00497 0.000499 0.00646 0.00011
0.0032 0.000335

T = 348.15 K
5.66 0.482
4.73 0.3287
3.49 0.2057
2.39 0.1412
0.629 0.03558
0.148 0.00848
0.0564 0.00335
0.0049 0.000337
 226 F.-Y. JOU et at.

15

0

0
298.15K
3B. IS K
0-
::;: ~ 3A8.\5 K

0 373.15 K
~
::J
Vl
Vl
10
398.15 K

~
e
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0-

0.00 0.05 0.10 0.15

Mole fraction. CO
2
FIGURE! Solubility of carbon dioxide in ethylene glycol.

298.15 K
o 32.1.15 K
6 'V J'-lU5 K
o 373.15 K

398.15 K

o ,!"=--~--~~-~--~--
0.0 0.1 0.2 0.3 0.4 0.5
Mole trocfion, H
2S

FIGURE 2 Solubility of hydrogen sulfide in ethylene glycol.

 VAPORLIQUID EQUILIBRIA 227
RESULTS AND DISCUSSION

The solubility of H 2S and CO 2 in ethylene glycol was determined at 25, 50, 75,
100 and 125C at partial pressures of the acid gases up to 6.7 and 20 MPa
respectively. The experimental data are presented in Tables I and II for CO 2 and
H 2S respectively. The data for CO 2 are shown in Figure 1. At 25C a three-phase
(L1L, V) condition is reached at 6.4 MPa. At higher pressures the data points
represent liquid-liquid equilibria. The data for H2S are presented in Figure 2.
The solubility of H 2S in EG decreases markedly with increasing temperature. The
vapor-phase concentration of EG in CO2 was measured at pressures of 3.000 and
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5.707 MPa at temperatures in the range 0.1 to 150C. The results are presented in
Table III. The experimental solubility data were correlated using the Peng-
Robinson equation of state. The procedure followed was analogous to that
described by Jou et al. (1987). The parameters for the pure solvent (EG) were

TABLE III

Experimental P-T-y data for the system EG(I)-C02 (2)

TIK y,

P=3.000MPa
273.25 1.78 x 10- 6
298.15 I.12 x 10-5
323.15 6.29 x 10- 5
348.15 2.90 x 10-'
373.15 9.59 x 10-'
398.15 2.95 x 10-- 3
423.15 7.95 x 10- 3

P =5.707 MPa
298.15 1.97 x 10- 5 2.03 x 10-'
310.95 4.15xlO-'
323.15 8.12 x 10-' 7.18 x 10-' 6.89 x 10-'
348.15 2.49 x 10-' 2.26 X 10-'
373.15 7.81 x 10-' 6.48~. 10-'
398.15 2.29 x 10- 3 1.58 X 10- 3
423.15 5.27 x 10-3 5.35 x 10- 3

TABLE IV

Equation of state constants for EG for the Peng-Robinson equation

TIK
298.15 3.6517 51.683
323.15 3.4982 51.863
348.15 3.3586 52.037
373.15 3.2293 52.203
398.15 3.1067 52.358

t Units of all are Pam 6mol- 2 .

:I: Units of b l are cnr' mol"".
 228 F.-Y. JOU et at.
TABLE V

Correlation parameters for Ojj

CO z HzS

-0.1026 -0.0559
0.4602 0.2943

obtained from the liquid density and vapor pressure obtained from the compila-
tion of Daubert and Danner (1985). The parameters are given in Table IV. The
experimental solubility data were used to obtain the binary interaction parameter
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which appears in the mixing rule of the equation of state. The values of {jjj were
found to be a function of temperature and were correlated by the linear equation:
(1)
The parameters ao and a1 are presented in Table V for the two solutes. The
results of the correlation are compared with the experimental data in Figures 1
and 2. In general, the correlated values are in good agreement with the
experimental data over the wide ranges of temperature and pressure involved.
Bender et al. (1984) have shown the connection between the binary interaction
parameter and the three parameters in the Krichevsky-Ilinskaya (1945) equation:
the Henry's constant, the partial molar volume of the solute at infinite dilution,
and the Margules parameter. Their equations (corrected) have been used to
obtain these parameters, which are presented in Table VI. The results for the
Henry's constant are shown in Figure 3 for comparison with the data of other
workers. The value for CO 2 at 25C is somewhat smaller than the value of
Hayduk and Malik. Byseda et al. (1985) measured the Ostwald coefficient at
297.1 K. The Henry's constant of 29.6MPa is much smaller than the present
results, as is the value of 26.5 MPa reported by Lenoir et at. (1971). The data for
CO 2 are in good agreement with the three values reported by Union Carbide; the
present data (interpolated) agree within 0.3 mole per cent.
TABLE VI

Parameters for the Kriehevsky-Ilinskaya equation

H2 1 ii;'
MPa em' mo)-l AIRT

CO z 298.15 42.04 33.17 1.073

323.15 60.87 34.44 1.067
348.15 82.69 35.93 1.076
373.15 103.7 37.68 1.080
398.15 112.0 39.67 1.029

HzS 298.15 7.13 33.05 0.698

323.15 12.15 34.20 0.733
348.15 17.81 35.51 0.734
373.15 22.74 36.99 0.697
398.15 27.95 38.73 0.672
 VAPOR-LIQUID EQUILIBRIA 229

'00
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'a

o CO This work
2,
EaCO Hayduk 6: lrdalik
2,
o H This work
2S.
o H S. Short ,I at.
2
D H Gurorcl
2 L- ~
2S,~ __J

250 300 .150 400

Temperature, K
FIGURE 3 Henry's constants for H 2S and CO 2 in ethylene glycol.

0.01 .--------.-----
..\ \ . , -----'------'-,,/71
0.001

8 0\

'0 ~\v ~,/

c v ~.P
o 0
0
This wor1(. 3.0 WPO
nO.OOOl
g o
PA [qn., 3.0 "Po
Kamlnl.hl, 3.0 WPo
11>
'0 ~ Adochl, 3.0 WPo
:::!' This work, 5.7 "'Po

~~.~~!'!::.~:!..!':l.~...
0.00001 o Koml",I.I'II, 5.7 MPo
Q Adachi, 5.7 WPO

o
~.~~"~~~~~~ _~--
WoUac:., 8.3 WPO
..
t::. Kamlnl.hl, 8.3 WPo
'V Adathl, 8.5 MPo
0.000001
250 275 300 325 350 375 400 425
Temperature, K
FIGURE 4 Predicted vapor composition compared with experimental data.
 230 F.-Y. IOU et al.
The results for HzS are in good agreement with the high temperature values of
Short et al. (1983). Fogg and Young (1988) have recommended the data of Short
et al., which are in good agreement with those of Gerrard (1972). Fogg rejects the
solubilities of Byeseda et al. and Lenoir et al. for HzS in EG as being too large
(Henry's constants too small).
The parameters obtained from the present work were used to predict the
composition of the vapor phase for comparison with the experimental values
determined in this work and those of Wallace (1985), Adachi et al. (1986) and
Kaminishi et al. (1989). The calculated results are shown in Figure 4, together
with the data points of this work and those of Wallace. The values of Adachi et
al. and Kaminishi et al. were interpolated from their plots. At 3.0 MPa the
Downloaded by [Stanford University Libraries] at 02:38 26 September 2012

calculated values are in good agreement with the data; at 5.7 MPa the agreement
is not as good, but there is more scatter in the experimental data. At 8.3 MPa the
predictions are higher than the experimental values of Wallace at lower
temperatures, but in better agreement with the data of Adachi et al. and
Kaminishi et al. In general, the predictions of the vapor phase data of Adachi et
al. (1986) are in good agreement at the lower pressures 7 MPa) but
over-estimate the concentration of EG in the vapor phase at the higher pressures
(8-22 MPa). Most of the predictions at the higher exceed the measured values by
a factor of 3 to 4.

ACKNOWLEDGEMENT

The authors are grateful to the Canadian Gas Processors Association for financial
support of this research and to EXXON USA for permission to publish the vapor
phase data.

REFERENCES

Adachi, Y., Malone, P., Yonemoto, T., and Kobayashi, R., "Glycol Vaporization Losses in
Super-Critical CO 2 '' , GPA Research Report No. RR-98, (1986).
Bender, E., Klein. U., Schmitt, W.P., and Prausnitz, J.M., 'Thermodynamics of Gas Solubility:
Relation Between Equation-of State and Activity-Coefficient Models", Fluid Phase Equilibria.
15,241 (1984).
Byeseda, J.J., Deetz, J.A., and Manning, W.P., "New gas-sweetening solvent proves successful in
four field trials", Oil & Gas J., 83(23), 144 (1985).
Daubert, T.E., and Danner, R.P., "Data Compilation: Tables of Properties of Pure Compounds",
A.I.Ch.E. (1985).
Fogg, P.G.T., and Young, C.L., "Hydrogen Sulfide, Deuterium Sulfide and Hydrogen Selenide",
Solubility Data Series No. 32, Pergamon Press (1988).
Gerrard, W., "Solubility of Hydrogen Sulphide, Dimethyl Ether, Methyl Chloride and Sulphur
Dioxide in Liquids. The Prediction of Solubility of All Gases", J. appl. Chern. Biotechnol., n,
623 (1972).
Hayduk, W., and Malik, V.K., "Density, Viscosity, and Carbon Dioxide Solubility and Diffusivity in
Aqueous Ethylene Glycol Solutions", J. Chern. Eng. Data, 16, 143 (1971).
lou, F.-Y., Deshmukh, R.D., Otto, F.D., and Mather, A.E., "Vapor-Liquid Equilibria for Acid
Gases and Lower Alkanes in Triethylene Glycol", Fluid Phase Equilibria, 36, 121 (1987).
Kaminishi, G.-I., Takano, S., Yokoyama, C., Takahashi, S., and Takeuchi, K., "Concentration of
Triethylene Glycol, Diethylene Glycol and Ethylene Glycol in Supercritical Carbon Dioxide up
to 16MPa at 313.15, 333.15 K", paper presented at the Fifth International Conference on Fluid
 VAPOR-LIQUID EQUILIBRIA 231
Properties & Phase Equilibria for Chemical Process Design, Banff, Canada, April 30-May 5,
1989. To appear in Fluid Phase Equilibria.
Kritchevsky, I., and Iliinskaya, A., "Partial Molal Volumes of Gases Dissolved in Liquids. (A
contribution to the thermodynamics of dilute solutions of non-electrolytes)", ACla Physic-
ochim. lJ.R.S.S., 20,327 (1945).
Lenoir, J.-Y., Renault, P., and Renon, H., "Gas Chromatographic Determination of Henry's
Constants of 12 Gases in 19 Solvents", J. Chern. Eng. Data, 16,340 (1971).
Short, I., Sahgal, A., and Hayduk, W., "Solubility of Ammonia and Hydrogen Sulfide in Several
Polar Solvents", J. Chern. Eng. Data, 28, 63 (1983).
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