S*

SL76qI

Sulfur-Bearing Capacity of Hydrogen Sulfide Gas

S. C, SWIFT

I U.CITIES SERVICE
TULSA, OKLA.
OIL CO.

I
F. S. MANNING OF TULSA
R. E. THOMPSON TULSA, OKLA.
MEMBERS SPE-AIME

ABSTRACT equilibrium cell shown in Fig. 1. This cell is a

special design developed with Autoclave Engineers
Recent deep drilling has generated a need for
of Erie, Pa. It is constructed o{ A-286 Armco
data on the physical and chemical properties o{
stainless steel and uses pressure-tightening,
reservoir fluids at high pressures and temperatures.
metal-to-metal seals on the closures at each end.
Here, experimental data are presented on the total
This provides 12.25 in. of 2-in. -ID volume with a
quanti:y o~ sul/ur that can be associated with sour
working pressure of 25,500 psia.
gas up to 20,000 psi and 350 “F. A mode) is /i/ted
The cell is fitred with a MoneI piston with Viton
arJ the data, thus permitting rational interpolation
O-rings that allow a noncorrosive working fluid to
and extrapolation and prediction o{ the effect of
apply pressure on the sample across the piston.
udding inert materia Is.
Constant pressure was maintained on the working
fluid with a .Murphy switch-gauge that activated a
INTRODUCTION
Ruska mercury pump when the pressure fell below a
Lack of knowledge of the physical and chemical set value. Pressure was measured with a ?JO,OOO-
behavior of reservoir fluids at pressures as high as psia, 16-in. Heise pressure gauge accurate to + 0.1
20,000 psi a and temperatures up to 400 “F is a percent. Pressure control during equilibration was
problem associated with production of deep, high- very good. However, because of piston friction,
-pressure reservoirs. Some reservoir compounds, such fluctuations of 3 5 percent sometimes occurred
as CH4 and H20, appear to be quite stable momentarily during sampling.
chemically, while others such as H2S and S undergo The cell was mounted on a pivot inside an
marked chemical and physical changes. insulated cabinet and could be agitated externally
Experience in attempting to produce deep wells to accelerate equilibration. The air-bath temperature
in the Smackover lime of Mississippi indicates that was regulated by a thermostatically controlled,
deposition of elemental sulfur in production channels electrical heating element. The temperature was
of these wells could completely shut off production. measured with an iron- ;onstanton thermocouple
The ability to predict the amount of sulfur deposition attached to the outer surface of the equilibrium
to be expected at a given pressure and temperature cell. The cell temperature would drop slightly while
would be very beneficial. For example, this might taking a sample, but never dropped more than 2 ‘F.
permit operation of a particular reservoir so that
C+Z 8 NZ SUWLY
the fluid in that reservoir is produced into the well
with no sulfur precipitation in the reservoir rock.
Or, this knowledge could be used to design solvent
circulation systems within the welIbore to dissolve 10
any sulfur that otherwise might be precipitated.
16)
This study theoretically and experimentally
examines the equilibrium behavior of H2S and S at FILTER
conditions of pressure and temperature up to 20,000
psia and 400 ‘F, respectively. CCW)ENSER
T

The heart
DESCRIPTION

of the
OF EQUIPMENT

experimental apparatus is the

—
D
{
FILTER

htEA&&MENT
Original manuscript received in Society of Petroleum Engineers
office July 15, 1975. Paper accepted for publication Sept. 8, CSZ COLLECTOR
1975. Revised manuscript (SPE 5669) received Dec. 29, 1975.
g) CopyrSght 1976 American Institute of Mining, MetaM.wgic~, 4
snd Petroleum Engineers, Inc. CONSTA:Tw~SURE
preferences given at end of PWer.

This paper will be incIuded in the 1976 Transactions volume. FIG. 1 — EXPERIMENTAL APPARATUS.

APRIL. 1976 57”

The temperature at the beginning of a run was 12. Displace C% with N2, still accumulating
normally reported. CS2.
The cell was connected to the mercury pump and 13. Place preweighed beakers on low heat (about
the sampling manifold by several coils of I/S-in. 100 W) to boil off CS2.
316 SS tubing. The manifold arrangement is shown 14. Weigh beakers and dried sulfur to determine
schemati tally in Fig. 1. The actual design minimized weight of sulfur precipitated.
holdup volume between Valves 1 and 2. All three
valves were 60,000 -psia, l/4-in. Autoclave valves. EXPERIMENTAL RESULTS
Sulfur precipitated immediately on the low-pressure
side of Valve 3. A condenser coil (steel tube in Data taken from H2S/S systems are presented in
water bath) was used to assure ccmplete sulfur ;igs. 2 through 4. Fig. 2 shows all data taken
precipitation. Sulfur was collected in fiber glass at 250 ‘F. A curve represenung the upper envelope
filters. of the data points is also included (see clscussion
Gas volume was measured directly by displacing of equilibration below). Fig. 3 contains the same
hydrogen- sulfide-saturated water from a graduated information for a sample temperature of 350 ‘F.
cylinder. Sulfur was measured by dissolving all Data are included in both figures if the temperature
precipitated sulfur in carbon di sulfide (CS2), was within 10 ‘F of the specified value. Since most
accumulating the liquid CS2, boiling off the CS2, discrepancies in temperature were low, use of the
and precisely weighing the residual sulfur. This upper envelope should prevent any significant errors
method of sulfur measurement was shown by Roofl resulting from the temperature spread. ‘
to be the most effective way to recover the Fig. 4 is a composite showing the envelope lines
precipitated sulfur. from Figs. 2 and 3, as well as two other data points
at intermediate temperatures, The above data were
SAMPLING PROCEDURE used to interpolate the intermediate lines shown in
Fig. 4.
Each data point was taken in the following Because of sulfur-ring scission, the time required
manner. for equilibration varied drastically with temperature.
1. Bring air bath, equilibrium cell, and manifold To help define the equilibrium time, a series of
up to desired temperature.
2. Pressurize cell to desired pressure.
3. Allow for equilibration of mixture in cell,
agitating as required.
4. Close Valves 1 and 3.
5. Open Valve 2.
6. Withdraw sample by manually operating Valve
3. AH the pressure drop occurs across this valve.
7. Close Valve 2.
8. Bleed down pressure on manifold through

Valve 3.
9. Record total volume of gas withdrawn.
10. Disconnect gas measurement device at outlet
of second filter.
11. Dissolve sulfur in lines and filters by dis-
placing with CS2, accumulating C% and S in at
.! ‘=& ~~
! , 000 ,0 m.
.,,,, ”,, ,.$!.1
1east four different 100-ml beakers.
FIG. 3 — WEIGHT FRACTION OF SULFUR VS
PRESSURE AT 350 ‘F.
OJ

0.

o oar,,. w!,,> — (0,,,,.,,0. Iioe O*IS 8, -’l,,’

0$
— [nm.rco,oual, *l.* * ml.
,,,0
w *00*
., .,A! A,*OM
‘
01 l., .s ,!

.,
04

J
0,

02,

03

*8 H-
0 ~ 10 C@ ,,C+O 10 ac

Ut,,u+l [w.,

FIG. 2 — WEIGHT FRACTION OF SULFUR VS FIG. 4 — WEIGHT FRACTION OF SULFUR VS

PRESSURE AT 250 ‘F. PRESSURE (250 TO 350 ‘F).

a SOCIETY OF PETROLEUM ENGINEERS JOURNAL

samples were made at various time intervals at the chain that breaks will react immediately with an
two different temperatures. The weight fraction of H2S molecule to form H2S9. Based on this premise,
SU1fur leveled out at about 30 hours for 250 ‘F and it can be shown (see Swi ft3 or Appendix A) that
at 3 hours for 350 ‘F.
Because of the safety hazards involved,
continuous attendance by at least two people was ‘V/s=
required whenever the pressure was above 2,000
- -1
psia. Therefore, it was not practical to equilibrate
all tests
approached
completely.
exponentially,
Since
a system
equilibrium
was devised
was
1+
MD, (1- 2s8) (1 + Z~8K)
1
J
(1 + K)
where the cell was mechanically
minutes of additional agitation
agitated
resulted
until 5
in no
‘s8
apparent volume decrease (the con stant-pressure [
pump would come on when the volume decreased). . . . . . . . . . . . . . . . . . . . . .(1)
Following this. a soak period of 15 to 60 minutes
where
was allowed, depending on temperature. Agitation
was applied every 15 minutes during the soak period. ~H2 S9

Samples were then withdrawn as discussed above. K=- .

Errors introduced by nonequilibrium should be ‘S8 ‘H2S
consistently low. It was concluded that it was
possible to draw a meaningful upper envelope for It is necessary to know Z58 to obtain K from
the data in Figs. 2 and 3, /WS (see Appendix B). Wiewiorowski and Touro4
Phase-rule considerations indicate that tempera- suggest the approach used here. They show that
ture and pressure uniquely define a two-phase, the volubility of the unreacted H2S species is a
two-component system. Since these data were taken Iinear function of T-l, even though reaction is
from a blind cell, the two-phase condition was causing the apparent volubility to be much higher.
checked by material balance. The weight fraction of From this reasoning, it is logical to assume that
sulfur (/wS) was calculated from the mnounts of the volubility of S8 sulfur rings in H2S might lx
sulfur and H2S introduced into the cell. If the well behaved, even though the rings that break
measured fws was even close to the calculated react to form H2S9, thus causing the apparent
uniform-mixture value, the run was aborted and the volubility to rise more rapidly with temperature
cell was cleaned and recharged. than would be expected. Eq. 2 (from Ref. 2)
Further details, including the extensive laboratory expresses the sulfu-r volubility in the nonreactive
safety procedures, are presented by Swift.3 range as

ANALYSIS OF DATA 9
-1
814

1
To obtain meaningful extrapolations of the data (~+s)
presented in Fig. 4, and to develop a model of
1+
10 . . . (2)
ex~ected behavior,
theory was used.
the following semiempirical
‘s8 = ‘H9S
&
A theory for sulfur “volubility” was developed k. d

from the general methods used by Wiewiorowski

and Touro.4 Because of the abundance of H2S The assumption that Eq. 2 is valid e~ en into the
molecules in the light phase of a two-phase H2S/S reactive range aJlow.= the equilibrium constant, K,
mixture, it is reasonable to expect that any sulfir :0 be calculated from the data on the weight fraction
of sulfur. These data are tabulated in Table 1 and
are plotted in Fig, 5. Fig, 5 shows that log K is a
TABLE 1 — EQUILIBI%IUM CONSTANT
linear function of T-t, as is expected. The effect
Pressure log K
of pressure is to vary the slope (m) and the intercept
(psia) 250°F
—— 275°F 300”F
..— S25°F 350” F
— m b
5,000 0.629 0.607 0.600 0,594 0s578 266 ix (b) of this linear relationship.
are plotted vs pressure in Fig. 6.
Values of m and h
6,000 0.745 0.720 0.718 0.712 0.721 134 0.547
7,000 0.831 0.819 0.824 0.822 0.832 -8.92 0,837
8,000 0.910 0.903 0.914 0.915 0.930 -117 1.C89 CORRELATION OF DATA
9,000 0.973 0,977 0.990 1.000 1.018 -259 f ,333
10,000 1,030 1.037 1.059 1,079 1.101 -422 1.616 Values of fws were calculated from a least-squares
11,000 1.082 1.095 1.124 1.143 1.174 -533 1.827 fit of the slope and intercept for K as a function of
12,000 1,131 1.150 1.182 1.208 1,249 -675 2.075
temperature and pressure and from Eq. 2 for Zs8.
13,000 1.175 1,198 1.237 1.274 1.321 -645 2.358
14,000 1.213 1.248 1.289 1.337 1.391 -1,028 2.650 Table 2 and Fig. 7 summarize the results. Fig. 7
15,000 1.247 1.293 1.346 1.403 1.465 -1,2s7 3.008 compares very well with the measured data.
16,000 1.275 1.335 1,407 1.476 1.544 -1,585 3,471 The final form of the correlation used for H2S/S
17,000 1.8(JO 1.375 1,472 1.551 1.632 -1,938 4,022
1,319 1.417 1.542 1.642 1.735
systems is, then,
18,000 -2,441 4.750
19,000 1,S34 1.458 1.620 1.749 1.887 -3.133 5.738
20,000 1.34S 1.497 1,714 1.697 2.072 -4,285 7.358

APRIL, 1976 59
 TABLE 2 — CALCULATED fws (INCLUDING
‘m= EXTRAPOLATION TO 375 AND 400 “F)

Pressure fws
r 1-1
—(psia) 250”F
—— 275° F .3000F 3250F
—— 350”F 375° F
—— 400”F
5,000 0.087 0.092 0.097 0.102 0.107 0.112 0.117
6,000 0.104 0,112 0.119 0.126 0.133 0.140 0.147
7,000 0,122 0.131 0.141 0.151 0,161 0.170 0.179
8,000 0.140 0.152 0.164 0.176 0.188 0.200 0.212
9,000 0.156 0.171 0.187 0.202 0.217 0.232 0.247
10,000 0.171 0,190 0.209 0.229 0.246 0.266 0.285
where 11,000 0.167 0.209 0.232 0.254 0.276 0.298 0.319
12,000 0.203 0,229 0,255 0.281 0.307 0.332 0.356
. 13,000 0.217 0.247 0.278 0.308 0,338 0.368 0.396
-1
(~
814
+3) 1 14,000
15,000
0.230
0.243
0.265
0.284
0.300
0.326
0,336
0.387
0.370
0.407
0.404
0.445
0.436
0.481
16,000 0.255 0.303 0.352 0.401 0.447 0.491 0.531

and
‘s8 =
[
,+ 10
‘H2S
1 9
17,000
18,000
19,000
20,000
0.2~5
0.273
0.279
0.277
0,323
0.343
0.364
0.389
0.381
0.413
0.452
0.502
0.438
0.481
0.533
0.602
0.492
0.544
0.604
0.682
0.541
0.599
0.664
0.741
0.536
0.646
0.711
0.783
-.

Referring to Fig. 4, we see that the measured

(+- +b) data, as well as the data from the semiempirical
correlation, appear to be direct extensions of the
K=1O . . . . . . . . . . (3)
data measured by Roof.1 This lends credence to
The parameters 71[ and b are functions oi pressure, the data and to the correlation. However, assuming
as given in Fig. 6. that (1) all sulfur chains terminate at the unit
This correlation allows logical extension of the length and (2) the volubility of S8 rings in the
data to higher temperatures. Extension of the data
to higher pressures is not as certain because of the
asymptotic behavior of m and b as pressure rises
above 20,000 psia. It is likely that miscibility in
all proportions is achieved at higher pressures. If
this is the case, a single-phase fluid is present.
This implies that temperature and pressure alone
no longer speci$ the system.

400 ‘1

It!!i=ix+ - — LEAS1 SWARM SIRAlOH1 LINf

4 w. 17
0 , w. ,0 m ,,OM 20 ma
,,,,s”1, (,,,,,

FIG. 6 — LINEAR PARAMETERS FOR LOG K VS

PRESSURE.

10G 01

.6 -

— _ 0$ -

mo
0. -
ii
10 - j

03 -

08 -
0,

0$
06 - 5.C40

0 I
o ,- ,. Oc+ I>w mm
I

041 I II I I I I I I ,, KSUI1 {mm

0m12 00013 000!4
, l,.t.l,
FIG. 7 — CALCULATED WEIGHT FRACTION OF
FIG. 5 — EQUILIBRIUM CONSTANT VS T-l. SULFUR VS PRESSURE.

60 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

reacted mixture is identical with the volubility of theoretical or experimental basis for this extension;
S8 rings in nonreactive H2S, is obviousIy physical thus, it should be used only with its empirical
oversimplification. Therefore, the correlation must origin in mind. Obviously, experimental data would
be considered as semiempirical. be preferred.

EFFECTS OF INERTS CONCLUSIONS

The effects of a concentration of inert material 1. The ranges of temperature and pressure in
(A) are considered in Appendixes A and B. Inciuding which data on the sulfur-bearing capacity of H2S
this effect, the correlation for the weight fraction gas are available have been greatly extended by
of sulfur is the experimental data included here.

r 2. A simplified model developed

observed data satisfactorily.
3. Using this model, the effects
here fits the

of inert materials

‘w A+ ( MD, [l+zSK]
8
[1-z
‘8
in the system can be approximated,
nature
uncertain.
of the model makes
The empirical
the approximation

4. Extrapolation to temperatures above the range

--A( 1- MD2)]
) ;

\
-1
.
of the experimental
confidence
data can be done with reasonable
using the correlation
not the case for lower temperatures
phase transitions occurring
developed.
because
in the constituents
This is
several
at
temperatures below 250 ‘F materially affect both
( z~
8
[l+ K(l-zA)]
)
‘
. . . .(4) physical and chemical behavior.
5. Anomalous behavior of the equilibrium constant
at the higher pressure indicates the system may be
1 nearing a single-phase region.
Parameters m and i%are functions of pressure, as
given in Fig. 6. Swift3 presents further details. NOMENCLATURE
An important consideration in applying Eq. 4 is
b= intercept of log K vs T-* plot
the extent to which S8 rings are soluble in the
inert material. If S8 is totally insoluble in the inert fws = weight fraction of sulfur in mixture
material, then the value of ZS8 given by Eq. 2 must K= equilibrium constant for S8 + H2S ~ H2S9
be discounted by the dilution effect of the inert m= slope of log K vs T-l plot, %
material. WA = molecular weight of inert
MD1 . molecular weight of H2S divided by
= molecular weight of ~
‘s8
II For Eq. 4
h!D2 = molecular
molecular
weight
weight
of inert
of ~
divided by

(1-2A)
ZS8
II
MHz~ = molecular
MS8 = molecular

T. absolute
weight of H2S
weight of S8

temperature, %
From Eq. 2
.zA = mole fraction of inert in H2S-rich phase
. . . . . . . . . . . . . . . . . . . . .(5)
ZH2S = mole fraction of H2S in H2S-rich phase
On the other hand, some inerts (such as CH4)
~H#9 – mole fraction of H2S9 in HiS-rich phase
might be better approximated by assuming that the
volubility of S8 rings in the inert equals the %8 = mole fraction of S8 in H2S-rich phase
volubility of S8 rings in H2S. This would be
equivalent to ACKNOWLEDGMENTS

= The authors thank Cities Service Oil Co. for

.
‘s8 ‘s8 support of this work, which included providing all
For Eq. 4 From Eq. 2 experimental equipment. Appreciation is also
extended to all Cities Service pelsonnel who
. . . . . . . . . . . . . . . . . . . . . (6) assisted in conducting these difficult experiments.
In both cases, the material A doe not participate This work was submitted by S. C. Swift to the U.
chemically in the reaction. The two inte-~retations of Tulsa in partial fulfillment of the requirements
for ZS~ only reflect the relative ability of the inert for the PhD degree in chemical engineering.

to dissolve S8 rings.
REFERENCES
Eqs. 3 through 6 represent an extension of the
1. Roof, J. G.: {tSolubility of Sulfur in Hydrogen sulfide
ase of the interpolating equations. There is no and in Carbon Dioxide at Elevated Temperature and

APRIL, 1976 61
 Pressure, ” Sot. Pet. Eng. J. (Sept. 1971) 272-276. Ultra-High Pressures, ” PhD dissertation, U. of Tulas
2. Smith, J. J., Jensen, D., and Meyer, B.: “Liquid ( 1975).
Hydrogen Sulfide in Contact With Sulfur, ” ]. Cbem. 4. Wiewiorowski, T, K,, and Touro, F. J.: “The Sulfur.
amfl?ngr. Data (1970) Vol. 15, No. 1, Hydrogen Sulfide System, “]. ~/Jys. ~Lrem. (Jan. 1966)
3. Swift, S. C.: “Sulfur-Bearing Capacity of Sour Gas at vol. 70, No. 1, 234,

APPENDIX A

Calculate the weight fraction of sulfur (other than the single S atom coritained in the H2S units) in the light
phase of an equilibrated mixture of H2S, S, and an inert material, A. As~ume all S8 rings that break in the
H2S-rich phase-immediately react to form H2~.

S8+H2S+
A&_js9+A,
. ... ................ . . . . . . (A-1)

where

z H2 S9
K= . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . (A-2)

z S8= H2S
By material balance,
. . . . . . .(A-3)
1“””””””””””””’”
‘H2S + ‘S8 + ‘H2S9 + ‘A =

Consider 1 mol of equilibrated mixture:

( zs ) MS8
+ z H2S9
8
‘Ws= (=s + ‘Hs ) ‘S8 + ‘z H2S9 + ‘-H2S) ‘H2S + ‘A ‘A
8 29
-1
MD, (ZH s + z H2S ) + ‘~2 (2A)
29 (A-4)
= 1+
9 . . . . . . . .

‘S8 + ‘H2S9
[ 1

where

M H2S 34.08
MD, = —— = = 0.1329
, @54)
8 (32
‘s8

‘A
MD2= —.
%8
From Eq. A-2,
. (A-5)
‘H2S9=ZS8Z HUSK”””””””” ““”””””””””””””””””””

Combine Eqs. A-3 and A-5.

ZH2S (l-iz#)=l-zs
* ‘ZA~
8
or

62 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

*

l-z “Z*
‘8 . . . . . . (A-6)
‘H2S = I+z~ K””””””””””” ““””””””””-””””
8
Similarly, for H2~,

‘~ (1 ‘zs8-zA) K
8 . . . . . . . . . . . . . . . . ...” ““””” “ (A-7)
‘H2S9 = 1 + ZS K
8
Substitute Eqs. A-6 and A-7 into lZq. A-4.
— -1
/’~-z -z
‘8
M’l+z K A (1 + ZS8K) + MD2 ‘A
D1
‘. ‘8 )
1+
‘W=
‘S8 ‘1 - ‘s8 - ‘A) K

‘S8+ l+z K
L
‘8
-1

J
MD, (1- ZS - zA) (~ + zs8K) + MD2 ‘A (1 + ‘s8K) .
8 . . . . .(A-8)
‘r ‘Ws= 1+
‘s8[’ + K “ - ‘A)]
[
For zA = O (no inerts),
-1
MD,(l-Zr)(l+ZSK)-
38 8
=1+ . . . . . . . . . . . . . . . ““””” “ (A-9)
‘w ‘s8 “ + ‘) 1
[ J
APPENDIX B

Solve Eq. A-8 for K = / (ZS8, /ws).

Let w = /ws

‘S8+ZS8K-ZAZS8K =

Wz
S8+ ‘%8K
- ‘ZA ‘s8 K + ‘“D1 ‘1 + ‘s8K - ‘;K - z s8-zA-zAzs8 ‘)

+ WMD2‘A (1+ z W
‘8
2
● ‘K
* zAzs ) - WM ~2ZAZs ‘1
‘s8 - ‘AZS8 - ‘ZS8 + ‘AZS8 - ‘“D1 ‘2$3 - ‘$3 - 8
8

= Wz -z + V/MD, (1-zs - ZA) + WMD2ZA

‘8 ‘8 8
63
APRIL, 1976
 or

‘~ (1 - ‘~~) + ‘~, ‘~~ (z~8+ ‘A- ~)- ‘~2 f ~s z A

— 8
K =
‘s8 [fWs (1 - ‘A) “ 1 + ‘AI + ‘D1 ‘s8 ‘Ws (1-zs8-zA) ‘D2 ‘s8 ‘Ws ‘A

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (B-1)
Or for z~ = O,

ZS (l-fws) + MD, ‘Ws ‘2s8 - 1)

8 . . . . . . . . . . . . . . . . . (B-2)
K=
(fhvs - 1) +M (1- ZS8)
‘s8 D1 ‘S8 ‘WS

***

SOCIETY OF PETROLEUM ENGINEERS JOURNAL