Fluid Phase Equilibria, 19 (1985) 21-32 21

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THE PHASE BEHAVIOR OF TWO MIXTURES OF METHANE,

CARBON DIOXIDE, HYDROGEN SULFIDE, AND WATER

SAM S.-S. HUANG *, A.-D. LEU **, H.-J. NG *** and DONALD B. ROBINSQN
Department of Chemical Engineering, University of Alberta, Edmonton, Alberta, T6G 2G6
(Canada)
(Received November 7, 1983; accepted in final form July 23, 1984)

ABSTRACT

Huang, S.S.-S., Leu, A.-D., Ng, H.-J. and Robinson, D.B., 1985. The phase behavior of two
mixtures of methane, carbon dioxide, hydrogen sulfide, and water. Fluid Phase Equilibria,
19: 21-32.

The behavior of two mixtures of CH,, CO,, H,S and H,O was studied over a temperature
range from - 37.8O to 204OC at pressures in the 0.4-18.5 MPa range. The work was carried
out to determine the composition of the equilibrium phases over a range of experimental
conditions within the two- or three-phase envelope for each mixture, and to determine the
two- and three-phase boundaries for each mixture within the temperature and pressure range
of the study.
A variable volume equilibrium cell consisting of a transparent sapphire cylinder was used
for the experimental measurements and observations.

INTRODUCTION

Natural gas handling and processing operations are frequently carried out
under conditions where an aqueous liquid phase appears. This phase may be
in equilibrium with either a hydrocarbon gas phase or a hydrocarbon-rich
liquid phase or both. Interest in the composition and behavior of these
systems in the presence of relatively large concentrations of carbon dioxide
and/or hydrogen sulfide has been prompted in part by the trend toward
processing sour mixtures from reservoirs that had hitherto been considered
economically unattractive.
Although some reliable data exist on the behavior of the methane-water
(Olds et al., 1942; Culberson and McKetta, 1951), carbon dioxide-water
(Wiebe and Gaddy, 1941; Todheide and Franck, 1963; Takenouchi and

* Present address: Gulf Canada Ltd., Sheridan Park, Ontario, Canada.

** Present address: Shell Canada Ltd., Calgary, Alberta, Canada.
*** Present address: DB Robinson and Assoc. Ltd., Edmonton, Alberta, Canada.

037%3812/85/$03.30 Q 1985 Elsevier Science Publishers B.V.

22

Kennedy, 1964) and hydrogen sulfide-water (Selleck et al., 1952) systems,

reliable information on the behavior of ternary and quaternary mixtures of
these compounds is essentially non-existent. Such data are considered to be
useful as they provide a severe test of the capability of fluid property
predictive correlations.
In the work presented in this paper, the behavior of two mixtures of CH,,
CO,, H,S and H,O was studied over a temperature range from -37.8 to
204 OC at pressures in the 0.4-18.5 MPa range. The primary objectives of the
work were:
(1) to determine the composition of the equilibrium phases over a range of
experimental conditions within the two- or three-phase envelope for each
mixture.
(2) To determine the two- and three-phase boundaries for each mixture
within the temperature and pressure range of the study.
The composition of the two mixtures chosen for the study had the
following nominal compositions on a mol% basis:
Component Mixture Mixture
1 2
CHd 1s S
co2 30 S
H,S 5 40
Hz0 so 50

The composition of Mixture 2 assured the existence of 3 phase

liquid-liquid-vapor equilibrium within the study conditions.

EXPERIMENTAL METHOD

Figure 1 schematically shows the experimental measurements and ob-

servations were made in a variable volume equilibrium cell consisting of a
transparent sapphire cylinder mounted between steel headers. The top
header contained the necessary openings and valves for charging the compo-
nents to the cell, for measuring the cell pressure, and for removing samples
for analysis. The bottom header accommodated a movable stainless steel
piston which was driven manually by an externally mounted hand wheel.
The body of the cell was - 2.5 cm inside diameter with a length of 15.2 cm.
The working volume of the cell was - 45 cm3. The main cell and all the
necessary auxiliary lead lines and valves. were mounted inside a controlled
temperature air bath. Equilibrium was obtained by mechanically rocking the
entire assembly.
After charging the cell with the required amount of each component as
required to achieve the composition of Mixture 1 or 2, the temperature was
set to the required value, and the pressure was controlled by movement of
 23

the piston. When equilibrium had been achieved by rocking the cell and bath
assembly, the final pressure and temperature were read, and the phases were
analyzed by sequentially removing them isobarically and isothermally to the
chromatographic system.
During the sampling procedure, the total amount of each phase was
removed slowly from the cell and expanded into the heated line leading to
the chromatographic sampling valve. Thus the lines became thoroughly
purged with the gaseous sample and the surfaces had ample time to reach
equilibrium with the materials in the sample. This was important particularly
for the water. Samples could be taken for analysis at any time during the
phase-removal procedure.
For phase boundary determinations, the lower dew points along the
two-phase boundary for Mixtures 1 and 2 were determined by visual
observation. The system was controlled at the desired temperature with the
contents of the cell in the single phase. The pressure of the system was then
increased or decreased alternately by the movement of the piston in the cell.
The formation or disappearance of an opaque cloud or a droplet on the
sapphire cell wall due to a slight change in pressure was observed repeatedly.
The dew point was considered to be the condition where the appearance and
disappearance of the cloud or droplet occurred within c 3.5 kPa.

Fig. 1. Schematic illustration of equilibrium cell and auxiliary equipment.

24

The dew points and bubble points along the three-phase boundary were
determined by graphical analysis. After the system reached the desired
pressure and temperature, a series of equilibrium pressures and volumes
(measured in terms of the height of the piston with respect to a fixed point)
of the system were measured. Figure 2 shows the values were then plotted to
determine the intersection of the two straight lines. The point of intersection
was considered to be the dew point or bubble point.

MATERIALS USED AND MIXTURE MAKE-UP

In view of the high water content of both experimental mixtures and the
high hydrogen sulfide content of Mixture 2, it was not possible to prepare
mixtures having these overall compositions, store them, and charge them to
the equilibrium system without entering the two-phase region. Consequently,
two synthetic gas mixtures A and B having the compositions given below

Ah (cm)
0 I 2 3 4 5 6 7 6 P
I I I I I I I I
I
20
4.A
t Ah = h, - ho
ho : Reference height of piston
h, : Final height of piston I8
4.2

16

0 Dew Point observation

* Bubble Point observation

Ah (cm)
Fig. 2. Isothermal plot of pressure versus volume for determining the phase boundary in the 3
phase region.
 25

were prepared for use in making up the final test Mixtures 1 and 2:
Component Composition Mol %
Mixture A Mixture B

CH4 29.91 + 0.02 50.07 + 0.02

CO, 60.03 * 0.02 49.93 + 0.02
H,S 9.95 f 0.02 0
N,, C,, C, 0.107 Trace

To obtain Mixture 1, a known amount of Mixture A was added to the

equilibrium cell. After this, the predetermined amount of liquid water
required to match the required overall mixture composition was injected into
the cell using a small high pressure stainless steel plunger pump calibrated
and readable to the nearest 0.005 cm3.
The same procedures were followed to prepare Mixture 2 except that the
cell was first charged with a known amount of Mixture B, followed by the
injection of pure water and pure liquid hydrogen sulfide from separate
plunger pumps to make up the required composition for the mixture.

EXPERIMENTAL MEASUREMENTS

The pressure of the equilibrium cell contents was measured using a

Statham pressure transducer having a range of O-34.5 MPa. The transducer
was calibrated against a Ruska dead weight gauge at room temperature. The
pressure of the system was known to within 0.25% of the reading. To protect
the transducer diaphragm from corrosion by the wet hydrogen sulfide, a 2.54
cm diameter, 0.005 cm thick gold plated stainless steel plate was placed
between the cell contents and the transducer.
The temperatures of the cell and the air bath were measured using
iron-constantan thermocouples which had been calibrated against a certified
platinum resistance thermometer. The temperature of the cell contents was
known to within + 0.05 OC.
The output from both the transducer and the thermocouple was read on a
Hewlett-Packard Model 3490A digital voltmeter.
The volume of the equilibrium cell and the dead volume resulting from
the pressure connections and the sampling valves and lead lines was de-
termined by expanding nitrogen from a high pressure container at known
volume, temperature and pressure into the total evacuated equilibrium cell.
From the new pressure, temperature, and known properties of nitrogen, the
volume of the cell and the dead volume could be determined. The dead
volume represented < 5% of the total cell volume. The volume of the visible
portion of the cell above the piston was determined from the known
dimensions.
26

The composition of the gas mixtures and the equilibrium phases was
determined using a Hewlett-Packard Model 5880A gas chromatograph with
a thermal conductivity detector. The samples were eluted through a 3.2 mm
OD by 1 m long Porapak QS column with temperature programming from
30 to 60 OC. Methane, carbon dioxide, and hydrogen sulfide were calibrated
using a gravimetrically prepared sample of known composition containing
0.2991+ 0.0002 CH,, 0.6003 + 0.002 CO,, and 0.0995 f 0.0002 H,S. The
calibrations with water were done using a mixture of carbon dioxide and
water sampled at equilibrium with liquid water over a range of temperatures
and pressures. The repeatability of the analyses was generally within kO.2
mol%.
RESULTS

The experimental test conditions were chosen to cover a range in tempera-

ture from 37.8 to 176.7 “C. At each temperature, two to four pressure

l- I I I I I , I I I
20 , - MIXTURE COMPOSITION. MOLE %

=t-b 14.05 f 0.02 l-q 4.97 f 0.01

CO, 30.07 f 0.04 Hz0 50.00 f 0.08
18

16

I-

A Experimental Two-phase Dew Points

0 Experimental Two-phase Conditions

TEMPERATURE, “C
Fig. 3. Experimental phase boundary and experimental pressure- temperature conditions for
Mixture 1.
 27

conditions were chosen so that the amount of liquid present at the equi-
librium..conditions would be large. enough to make visual observation and
chromatographic analysis of each phase possible.
A total of nine experimental runs were made on Mixture 1, covering three

TABLE 1
Equilibrium phase compositions and relative liquid volumes in the 2 phase region for Mixture
1

Pressure Temperature Component Composition, Mole fraction Liquid Vol. %I

MPa OC Feed Liquid Vapor
4.82 37.8 CH, 0.1494 2.76~10-~ 0.3040 4.08
co2 0.3005 9.30 x10-s 0.5945
H2S 0.0497 5.03 x1o-3 0.0998
H2O 0.5004 0.9854 1.91 x 10-3
7.60 37.8 CH, 0.1488 4.66~10-~ 0.3031 7.30
co2 0.2991 0.0121 0.5970
H2S 0.0494 5.4Ox1o-3 0.0982
H2O 0.5027 0.9816 1.71 x 1o-3
12.52 37.8 CH, 0.1497 7.96 x 1O-4 0.3029 14.5
co2 0.3010 0.0151 0.5967
H2S 0.0498 5.95 x10-a 0.0985
H2O 0.4996 0.9781 1.87~10-~
16.93 37.8 CH, 0.1495 9.9Ox1o-4 0.3021 19.9
co2 0.3006 0.0154 0.5963
H2S 0.0497 6.08 x10-3 0.0996
H2O 0.5002 0.9777 1.99x 10-s
8.36 107.2 CH, 0.1496 3.79x1o-4 0.2907 5.38
co2 0.3009 6.98~10-~ 0.5919
H2S 0.0498 3.42x10-’ 0.0967
H2O 0.4997 0.9894 0.0225
12.93 107.2 CH, 0.1496 5.78 x 1O-4 0.2929 8.66
co2 0.3009 9.59 x lo-’ 0.5920
H2S 0.0498 4.47 x 10-3 0.0963
H2O 0.4997 0.9854 0.0196
17.17 107.2 CH, 0.1496 7.79x1o-4 0.2935 11.8
co2 0.3009 0.0113 0.5916
H2S 0.0498 4.73 x 10-3 0.0970
H2O 0.4997 0.9834 0.0179
11.80 176.7 CH., 0.1495 7.17 x 10-4 0.2641 5.82
co2 0.3006 7.95x10-3 0.5575
H2S 0.0497 3.74x 10-3 0.0848
H2O 0.5001 0.9877 0.0950
17.31 176.7 CH, 0.1500 1.10 x 10-3 0.2762 8.65
co2 0.3015 0.0114 0.5520
H2S 0.0499 4.78 x lo- 3 0.0870
H2O 0.4986 0.9827 0.0848
28

temperatures of 37.8, 107.2, and 176.7 OC at pressures from 4.8 to 17.3 MPa.
Table 1 presents the results and Fig. 3 shows graphically the conditions. All
of these experimental conditions were in the vapor-aqueous liquid equi-
librium region.
For Mixture 2, five experimental runs in the vapor-aqueous liquid equi-
librium region were made. These covered two temperatures at 107.2 and
176.7 “C at pressures from 7.6-18.2 MPa. Table 2 presents the results and
Fig. 4 shows graphically the conditions. Two experimental runs in the

TABLE 2
Equilibrium phase compositions and relative liquid volumes in the 2 phase region for Mixture
2

Pressure Temperature Component Composition, Mol % Liquid vol.%

MPa OC Feed Liquid Vapor
Aqueous liquid-vapor
7.56 107.2 CH, 0.0494 1.55 x 1o-4 0.1182 6.43
CO, 0.0493 1.25 x 1o-3 0.1112
Hz8 0.4072 0.0304 0.7485
Hz0 0.4941 0.9682 0.0253
12.27 107.2 CH4 0.0498 3.32 x 1O-4 0.1060 13.0
CO, 0.0496 2.26 x 1O-3 0.1148
H2S 0.4019 0.0361 0.7528
H2O 0.4986 0.9613 0.0264
16.92 107.2 CH4 0.0499 6.06X 1o-4 0.1207 20.3
co2 0.0498 3.34 x lo- 3 0.1176
HzS 0.4009 0.0392 0.7322
H2O 0.4994 0.9568 0.0295
11.00 176.7 CH4 0.0502 3.50x 1o-4 0.1092 6.43
co2 0.0501 1.64x1O-3 0.1078
Hz8 0.4012 0.0286 0.6896
H20 0.4985 0.9694 0.0938
18.17 176.7 CH4 0.0496 7.15 x 1O-4 0.0928 12.3
co2 0.0494 2.92 x 10 - 3 0.0914
H2S 0.4000 0.0517 0.704
Hz0 0.5000 0.9454 0.113
Aqueous liquid-hydrogen sulfide-rich dense fluid
13.00 37.8 CH4 0.0500 8.59 x 1O-4 0.0891 a 27.1
co2 0.0498 3.62x1O-3 0.0994
H2S 0.4006 0.0291 0.8016
I.320 0.4996 0.9666 9.32~10-~
16.46 37.8 CH4 0.0500 8.82 x 1O-4 0.0891 a 28.0
co2 0.0499 3.81 X lo- 3 0.1061
H2S 0.4000 0.0281 0.7958
H2O 0.5001 0.9672 9.o5x1o-3

a Hydrogen sulfide-rich dense fluid phase.

 29

aqueous liquid-hydrogen sulfide-rich dense fluid region were made at a

temperature of 37.8 OC and pressures of 13.0 and 16.5 MPa (Table 2 and Fig.
4). Two experimental runs in the three-phase aqueous liquid-hydrogen
sulfide-rich liquid-vapor equilibrium region were made at 37.8 OC, 6.3 MPa
and 65.6 OC, 8.4 MPa. Table 3 presents the results and Fig. 4 shows
graphically the conditions.
In addition to directly determining the equilibrium phase compositions
and liquid volume fractions in the two- and three-phase regions for these
mixtures, phase boundaries were determined by extensive studies. The stud-
ies included determining experimental dew points along the two-phase
boundary for Mixture 1 and 2 from - 121.4 to 204.4O C at pressures from
0.42 to - 3.7 MPa. The results and presented in Table 4 and shown
graphically in Fig. 3 for Mixture 1, and in Table 5 and Fig. 4 for Mixture 2.
The study also included determining dew points and bubble points and an

24 I I I I I I I I 1

MIXTURE COMPOSITION, MOLE %

22 C”4 5.00 f 0.04
CO, 4.98 * 0.05
kt,s 40.09 f 0.03
20
H,O 49.93 f 0.08

l
I8

.
0

6 A Dew Point (L2v)

0 Dew Point (L, L2V)
0 Bubble Point (L, L2V,
0 Experimental Conditions P

0 50 100 150 2oc

TEMPERATURE, “C
Fig. 4. Experimental phase boundaries and experimental pressure-temperature conditions for
Mixture 2.
TABLE 3
Equilibrium phase compositions and relative volumes in the 3 phase region for Mixture 2

Pressure Temperature Component Composition, Mole fraction

MPa “C
Feed H,S liquid H ,O liquid Vapor
L, L* V L, L* V
6.26 37.8 CH, 0.0504 0.0653 4.90x 1o-4 0.3213 31.3 17.7 51.0
CO, 0.0503 0.1049 3.50x 1o-3 0.1739
H,S 0.3986 0.8197 0.0284 0.5028
H*O 0.5008 0.0101 0.9677 2.14~10~~
8.43 65.6 CH4 0.0501 0.0580 3.85x 1O-4 0.1872 19.6 15.0 65.4
CO, 0.0499 0.0904 2.72~10-~ 0.1484
H*S 0.4016 0.8287 0.0321 0.6557
H2O 0.4984 0.0212 0.9684 8.66x1o-3
 31

TABLE 4
Phase boundary data along the lower dew point boundary for Mixture 1

Feed composition Temperature pressure

Mol 8 OC MPa
CH, 0.1497 198.8 3.25
CO, 0.3010 190.6 2.70
H2S 0.0498 176.7 1.94
Hz0 0.4995 169.8 1.67

CL-L, 0.1495 163.1 1.39

CO* 0.3005 148.8 0.95
H2S 0.0497 135.0 0.64
H2O 0.5003 121.1 0.42

TABLE 5
Phase boundary data along the lower dew point boundary for mixture 2

Feed composition Temperature Pressure

Mol W OC MPa
CL% 0.0502 120.8 0.42
CO, 0.0501 148.6 0.97
Hz8 0.3996
Hz0 0.5001

CL-L, 0.0500 176.7 1.95

CO* 0.0499 190.7 2.70
H2S 0.3999 204.7 3.70
H2O 0.5002

TABLE 6
Three-phase dew point and bubble point data for Mixture 2

Mixture Composition Dew -points Pressure

Mole fraction Temperature MPA
“C

CH, 0.0504 38.7 3.59

co2 0.0502 49.0 4.50
H,S 0.3980 59.9 5.72
H20 0.5014

CH, 0.0498 71.0 7.23

co2 0.0496 82.1 9.41
H*S 0.4040
Hz0 0.4966
Bubble points
CH, 0.0501 37.7 7.81
co2 0.0499 48.8 8.65
H*S 0.3998 59.9 9.47
HP 0.5002 71.1 10.21
76.0 10.52
32

examination of the critical region for the three-phase region for Mixture 2.
Dew points were determined at temperatures from - 38.9 to 82.2O C and at
pressures from 3.6 to - 9.4 MPa. Bubble points were determined at tempera-
tures from 38.9 to 76.7 “C and at pressures from 7.8 to - 10.5 MPa. The
results are presented in Table 6 and shown graphically in Fig. 4.
It will be noted from the tables that there are minor changes in overall
composition for each experimental point. These result from the fact that a
new charge of material was required after each analysis. The slight dif-
ferences in overall composition represent the ability of the system and
procedures to reproduce a desired composition.

ACKNOWLEDGMENTS

The financial support received for this work from the Gas Processors
Association and the National Research Council of Canada is gratefully
acknowledged.

REFERENCES

Culberson, O.L. and McKetta, Jr., J.J., 1951. Phase equilibria in hydrocarbon-water systems.
Trans. AIME, 192: 223-226, 297-300.
Olds, R-H., Sage, B.H. and Lacey, W.N., 1942. Phase equilibria in hydrocarbon systems.
Composition of the dew-point gas of the methane-water system. Ind. Eng. Chem., 34:
1223-1227.
Selleck, F.T., Carmichael, L.T. and Sage, B-H., 1952. Phase behavior in the hydrogen
sulfide-water system. Ind. Eng. Chem., 44: 2219-2226.
Takenouchi, S. and Kennedy, G.C., 1964. The binary system H,O-CO, at high temperatures
and pressures. Am. J. Sci., 262: 1055-1074.
Tedheide, K. and Franck, E.U., 1963. Das Zweiphasengebiet und die Kritische Kurve im
System Kohlendioxid-Wasser bis zu Drucken von 3500 bar. Z. Phys. Chem. (Frankfurt am
Main) 37: 387-401.
Wiebe, R. and Gaddy, V-L., 1941. Vapor phase composition of carbon dioxide-water
mixtures at various temperatures and pressures to 700 atmospheres. J. Am. Chem. Sot.,
63: 475-477.