Water Content of CO, in Equilibrium

With Liquid Water andlor Hydrates —

Kyoo Y. Song, Rice U.
Riki Kobayashi, SPE, Rice U.

SUMMWy. Experimentally measured water content in C02-rich fluid in the g&eous or liquid stme in =e@ibrium with liquid
water or hydrate is presented for pressures ranting from l@l to ,2,C832psia [0.69 to 13.79 MPa] and temperatures from – 19 to
77°F [–28.33 to 25. O”C]. The water content of the CCi2-rich phase along @ three-phase equilibria, i.e., liquid water/liquid
C02/gas to the rhre~phase critical endpoint, is also reported. Tbe experimental restdts from this study on the water content in the
C02mich phases have been combined with earlier research results of the C02/water bimry system in tie hydrate-free region from
77 to 200eF [25.0 to 93.33”C] and pressures to 3,(CO psia [20.69 MPa] to prcduce a comprehensive plot.
The high degree of complexity in me phase behavior of a C02/wmer binary system, which exhibis SeverAl,pairs Of .+quilibkm
phases for the cckdhions, is show”. To make the dab more imelligible drm they are in their raw form, the &ta ark presented in
terms of the pre3sure enhancement of the water mntent along isotherms. Fdy, tie activity coefficients of water in the C02-ricii
phases am summarized,

Introduction
Information on the equilibrium water content, of C02-rich fluids
is mcessaty over a broad range of pressures and temperatures to
complete specifications for the ptcceisirig and transpmmion of the
fluids associated with C02 EOR projects.
Fig. 1 presents the pressureltemperature projection for C021
water binary system along its univariint thre&phase loci and in tw6-
phase regions, obviously showing the extent and varie~ of ,phase
equilibria most relevant to EOR technologists. As Fig. 1 shows,
the phase behavior of the C02/water system k “muchmore COrn-
plicated over the namral gaslwater system because of the occur-
rence of multiple condensed phases-e.g., the existence of two $qbid
phases,, one compad: of liquid water, I@id C02, anda”g%eous
C02 phase at high, temperamres, and one composed of sotid hy-
drabdliquid C02 and solid. hydrate/gas C02 at low temperatures.
Consequently, establishing the water-ctmtent specifications was
difficult and challenging.
The water content of compressed C02 was first measured by
Wkbe and Gaddy!,, who flowed expanded C02-rich samples
through a train of absorbents and determined the weight gained by
the train. In this study, a special experimental apparatus used by
Galloway et al. 2 and a water analysis scheme devised by Bloch
and LiOand3 were used to measure the water content in the
C02-rich phases. The data reported by Wieke and Gaddy hive re-
cently “been supplemented in the fluid C02/water regjon by
Kobayashi et al. ~ and by Gillespie and Wikon. 5 CaICU1atiOn
methcds for the prediction of hydrate formation conditions have
I&n developed by van der Wads and Platkeuw, 6 Saito >r al.,7
and -y ~~er$. 8-!0 Dmn,s11 correlation yields a good &timate
of ihe water content from the phase density and other thermodynamic
parameters in the fluid C02 /water region.
Equations of state (EOS ‘s), such as those formulated by Peng
And R.5binson12 and Soave, 13 are frequently usd, however, we
used, available tabulations of thermodynamic properties of C02
provided by Angus et .21.14to reduce the errors resulting from the
use of in EOS.
Exp&rim&rtal Apparatus and Procadure
The experimental apparaius iriitially used by Galloway et al. 2 to
measure hydrate numbers has been mcdified by Sloan et al, 15
Kotayashi et al.,4 and Song and Kobayzshi 16to measure the water
content of gases in equilibrium with hydrate. A line diagrain of the
apparatus is shown in Fig. 2.
CoPWQhl1987Scdetyof Petroleum
Engineers
Equilibrium in the fluid C02/water sys~em was eshblished by
misting the cylindrical autoclave containing cdrefulfy selected and
aligned ball biarings. Tbe equilibration prncess in,the fluid C02/.
hydrate region is considerably more complicated than that of the
fluid C02/water region. It was necessary first to establish ga.sfiy-
drate equilibrium by converting + the metastible water imo hy-
drate crystals by an extended rotation of the autoclave. A tandem
pump (shown in Fig. 2) wai us~d to cixcidate ffie fluid piiase
throughout the system and to store C02-rich fluid Ofthe s?@ com-
position, but not at the same temperamre as the equilibrium fluid
phase in the cell. A second hWd pump was used to charge or to
add pure C02 to the cell. The elimination of metastable liquid
water was confined by many successive analyses of samples (up
to 30) mken from the @liirium gas phase. The sampling and anal-
yses are ,difficult to wrform becaitse of the low water concentra-
tion, the long sample line, and ihe tedious mdified chromatogmphic
mi.alytictechnique developed by Bkh imd Lifland. 3
Tle dekndnation of water content in the C02-rich phase in the
liquid C02iIiydrme region was mdertaken after all the smdies of
the gas C02/hydmte region were completed. Tore-establish equi-
librium i“ the liquid COzihydrate region, pure COZ was SIOWIY
added to the autoclave to the desired prsssure. Owing to the greater
Water-carrying .capacily of liquid C02 than gaseous C02 m the
same tempramq, a small amount of the hydrate phase decomposes
in the re-equilibrmion process at a new pressure.
-use the demiiy difference between C02 in the hydrate phase
and C02 in the liquid phase was estimated to be sm~l (Fig. 3),
it is necessary to stir the contents of tie autoclave gently. fn this
mtdy, all the water~nte?t meamt’emen~ were made at states where
the density of C02 in hydrate, Phyd, was greater tk+t the density
of fluid C02, PC02. However, PC02 could be greatir than Phyd
at high pressures, as shown in Fig. 3.
The subsequent experimental condition was always chosen in the
direction of inct’eaiing water concentrations in the C02-rich phaie
because the elimination of m:tastable water from the system con- -
taining dense C02 was almost impossible.
Experimental Results
EWerimentaUy measured water contents in the C02-rich phases
are presented in Table 1, and the phases in equilibrium are identified.
fn general, a series of phase tqui!iirium rim was taken along isobars
(liKwof cOmtampress@), although a f~ expwimentaf F9ims were
obtained along tie th-phase, H20(l)/C02(l)/C02@, locus. lM-
perimental && from this and earlier studies are plotted along k
bars in Fig. 4 and plotted isothermally in Fig. 5. The complexity
resulting from intersecting lines made interpolation and interprets-

SW SPE FormationEvacuation,December 1987

 “c -40-34.44 “- -23.33
-17,78 -6,67 4,44 15,56 26,S7 5000
I I I I 1

5000 34,48 ““\

~
4000 –
.s-
< 2000 Y 13!79
: : H@(ll - cod!] K
1000 H-CO*(!) : ~*L,.co4; 6090 PC02(Hyd) ‘~CO,(L)
L!#- :
*=0(1)- <
: ; 3000 – – 20>69
~ 500 3,45 ~
<t).Got@ -
u *.co2 #
~ 0
# HzO[l)- C+(g)
200 H -COz[gl 1,38 $ 2
n
**% 0’+”*+$’$:0($).H4(,) -co,,,, = 0!69 $ 2000 —’ – 13.79 ..
100
. [k; 1
+o[s)-cO.Jqll
50 0.34
0 20 40 60 80
TEMPERATURE , OF
1000 – – 6.90
Fig. 1—Pressure/temperature projection of wtivariant loci for
CO Jwater system.

1 I ! I 1 0,00
o’
-40 -30 -20 -lo 0
PRESSURE TEMPERATURE, “F
TRANSDUCER
F@. 3—Densities of CO, hydrate and fluid CO..

pressure, and the thefnmdynamic properties of C02 by Angus et

CONSTANT
TEMPERATURE
AIR BATH
Fig. 2-Line sketch of experimental
tion of the data extremely difficult. Therefore, the water-content
&@ are presenkd in Fig. 6 in a reduced form, the enhancement
of the vapor pressure of water in which the vapor pressure is s!a-
ble above 32-F [O”C] and is metastable below 32°F [O”C].
Table 2 gives the enhancement factors of water vapor pressure
as a result of the total pressure of C02/water (defined by Eq.
A-IO). Table 3 shows the water vapor pressures used in calculating
the water vapor pressure enhancement at various temperatures.
Fig, 5 obscures .tbe breaksalong isotherms that accompany phase
tm”~itions; thus, w suggest that Fig. 1 be used in.conjunction with,
Fig. 5 to identify the phases in equilibrium.
Hydrate Calculations
The experimental water-content data in the hydrate region reprted
in Table 1 were etined in te~s of the statistkzd mwhanical solid-
solutiim theory of clathrates by van der wads and Plat@mw. 6 In
their compufatiom, a set of parameters obtained by SIoan9 and
Erickson 10,for the Kihara potential were used. Several investi-
gators9.10. 17cdc”latid the metastable empty hydrate vaPor Pr=-
sures with the experimental data at the conditions of hydrate
formation for various sets of gashin.ter systems around the ice
point.* With the recommended parayetem, the empty hydrate vapor
. Personalcommunication
WohE.D. Gl@an,
Cilor% school,
01Mln!s.SePC14. 1978.
~l. 14the panial vapor pr6sures of water in equilibrium with the
PROPORTIONAL hvdrate were calculated for various conditions of pressures and tem-
p_eramresa“d are tabulated in Table 4. Fig. 7 pr~sems an example
of the water partial vapor pressure calculated at 260 K [8‘F]. Fig.
7 shows(1) the precipitous drop in the water partial pressure from
its metastable value, Pwm, until the partial pressure becomes stable,
which is indica.md by a solid line in the C02(g) /hydrate region,
(2) the fo~ation of liquid ,cOI to produce the three-phase,
C02(g)/C02(l) /hydrate, invariant point at a constant temperamre,
apparatus. and (3) the dkqxarance of the gas phase td prcduce a C02(l)/hy-
drati branch of the diagram. The composition trace in Fig. 7 is
not constant, but varies over a very small but significant concen-
tration range. For other temperature and composition conditions,
other phase transitions may be encountered, as shown in Fig. 1.
It is apparent from Fig. 7 that the effect of pressure on tbe water
content of the C02-rich fluid will be small in the C02(l) /hydrate
region. At supercritical temperatures of COZ, the water content
varies much mo?e sensitively to pressure, as shown in Fig. 4.
The activity coefficients of water in the C02-rich phase in equi-
librium with hydrate as defined by Eq. A-11 are given in Table
5 and plotted in Fig. 8. In general, the calculated activity coefficient
of water are shown [P vary by almost three orders of magnitude.
The experimental data, van der Waals and Platteeuw’s solid so-
Iution “theory, and the thermodynamic properties of C02 provide
a sound basis for the prediction of the water-content data at much
higher pressures.
Conclusions
The water content of COz-rich fluids in equilibrium with liquid
water andlor hydrate was measu~d over a broad range of condi-
tions. Liquid C02 shows greater water-cariying capacity than
gaseous C02. Tbe water content varies vety sensitively to pres.
sure as a result of hydrate formation and tbe supercritical behavior
of fluid C02.
The water content is presented tabularly and graphically in terms
of the eohancemertt of the va~r pressure of water over its metastable

SPE Formation Evaluation,December 1967 501

 TABLE 1—EXPERiMENTAL WATER CONTENT IN CO ,-RICH PHASE

Pressure Temperature Equilibrium Fraotion, -

psia MPa ‘F Oc Phases fLxlo3
100 0.69 – 6.52 -21.4 C02(g)/H ,0(H) 0.1800
-2.20 -19.0 C02(g)/H20(H) 0.2190
17.60 -8.0 CO ~(g)iice 0.5570
69.96 21.1 CO, (g)/H ~0([) 4,3276
200 1.38 -0.40 - i 8.0. CO ,(g)/H , O(H) 0.1142
4.67 -15.2 CO,(g)/H , O(H) 0.1471
12,20 -11.0 C02(g)/H20(H) 0“2201
28.4 -.2.0 C02(g)/H20(H) 0.4S65
35.6 2.0 C02(g)/H 20(l) 0.6336
300 2.07 32.0 0.0 C02(g)/H ,O(H) 0.2775”
36.5 2.5 C02(g)/H ,O(H) 0.4368 .-
60.0 15.56 CO, (g)/H ,0(1) 1.0656..
24,25 -4.31 CO,(g)/H,O(H) 0,2321
9.5 -12.50 CO ,(g)/H , O(H) 0.1194
3.2 -16.0 CO ,(g)/H , O(H) 0.0890
-4.9 -20,50 C02(l)/H ,0(H) 0.2013
-18.4 -28.0 CO,(l)/H 20(H) 0,1361
500 3.45 0 -17.78 CO,(l)/H,O(H) 0.2616
3.6 -13,0 C0,(l)/H20(H) 0.3222
25.7 -3.5 C02(l)/H 20(H) 0.4585
33.6 1.0 C02(g)/H20(H) 0.2410
41.9 5.5 C02(g)/H20(H) 0.3794
53.6 12.0 C02(g)/H,0(l) 0.6030
68.0 “20.0 CO *(g)/H * O(1) 1.0010
700 4.83 0,04 -17.76 C02(l)/H ,O(H) 0.2313
14.00 -10.0 C02(l)/H ,0(H) 0.4705
25.70 -3,5 C02([)/H20(H) 0.5402
37.40 3.0 C02(l)/H20(H] 0.71S2
62.50 17.0 CO, (g)/H ,0(1) 0.8229
77.00 25.0 CO, (g)/H ~0(1) 1.2737
760 5.24 60.00 15.56 CO Jg)/H ,0(1) 0,6400
CO, (1)/H, O(1) 1.1200
840 5.79 68.36 20.20 C02(g)/H , O(1) 0.8999
CO, (1)/H, O(l) 1.5000
900 6.21 3.20 -16,0 C02(l)/H * O(H) 0.5170
15.0 -9,44 C02(l)/H 20(H) 0.6647
44.6 7.0 COJl)/H , O(H) 1.096
970 6.69 80.00 26.67 CO, (g)/H ,0(1) 1.2700
C02(l)/H 20(l) 1.9541
1,040 7.17 85.1 29.5 CO, (g)/H ,0([) 1,4981
C02(l)/H20 (l) 2.1940
1,07T 7.39 87.9 31.06 3-.+ critical endpoint 2.1079
1,200 8.28 1.40 -17,0 C02(l)/H 20(H) 1.0890
19.0 -7,22 C02(l)/H ,O(H) 1.5741
26.6 -3.0 C02(l)/H 20(H) 1.8895
56.8 13.78 CO, (1)/H, O(1) 2.7852
77.0 25.0 C02 (1)/H20(1) 3,0152
1 ,s00 10.34 1.40 -17.0 C0,(l)/H20(H) 1.2738
15,80 -9.0 C02(l)/H20(H) 1.6509
37.40 3.0 C02(i)/H20(H) 2,4687
77.0 25.0 C02(l)/H 20(1) 3.3739
2,000 13.79 -0.04 -17.8 C02(l)/H ,0(H) 1.5091
8.50 -13,06 CO, (1)/H, O(H) 1.8057
22.20 -5.44 CO,([)/H 20(H) 2.2042
36.90 2.72 C02(l)/H 20(H) 2.7441
55.70 13.17 CO,(l)/HzO(l) 3.3627

.?0’ x mtilfla,tionfa,, -lb n!/MMcfat , ahnand60aF.

. ‘FromRef.4.

or stable values, respectively, by compressed C02 over a broad T = .ternperature, “F [“C]

range of equilibrium conditions. Tab, =temperature absolute, K [“R]
P = densi~
Nomenclature 4$= activity coefficient
C = Langmuir inteniction constant + = chemical potential
E = enhancement
@ [MPa]
f = figacity, Subscripts
f~ = frzctiori of water
mole abs = absolute
n = ““mbcr of hyd~te cavities L = water
P = pressure, psia or atm [MP.] m = type
R = gas constant o = pr~~flre for &ree.ph%e equilibrium

502 SPE Fcmmticm Evaluation, Dmanter 1987

 I
MPo
1,30 4.14 6,90 9.66 12,4! 15,17 17.93
,.-,
. . 4RCQRwr,4 (!979] ~,----- -’20 ~~. .
200 Ut?u w’etta G.@ OW ..- -----

100 .

.
;
20 - ,,
5

?
25
z

~ I
2,3 2,2 2,1 2,0 1,9 0 400 800 1203 1600 20C0 2403 EBOO
INVERSE TEMPERATuRE 103/T , ‘R-‘ PRESSURE , PSIA

Fig. 4—Experimental water content isobars of CO,lwater Fig. 6–Enhancement oi water content (partial vapor pressure)
svstem. as a result of total pressure of CO ./water.

12. Peng, D.Y. and Robinson, D. B.: “A New Two-Constant Equation of

State,” Ind, E.g. Chem. F.”d. (1976) 1S, 59-64.
13. SOave, G.: SEquilibrium Constants fmm a Modified Re61ichKwong
Superscripts Equation of Ssate,” Chem. Eng. Sci. (1972) 27, 1197-1203.
- = partial molar property 14. Angus, S., Armstrong, B., and def+$uck,K. M.: Carbon Dioxide-,In-
wmxionol Thermodynamic Tahks of the Fluid .Wre, Vol. 3, Perga-
hyd = filled hydrate nwn Press, New York City (1976).
MT = empty hydrate 15. Sloan, E.D., Khoury, F., and Kobayashi, R.: ‘.Water Content of
o = m~ra$ion Methane h in Equilibriumwith Hydrates,” Ind. Eng. Chem. Fu~.
(1976) 15, No. 4, 318-22.
Acknowledgments
We acknowledge the support and leadership of Arco Oil and Gas
Co. and Amoco Oil and Gas Co. during the earlier wages of fhis
work. Substantial subsequent suppon was provided by the Gas MPa
processors As6n. and the Natl. Science Foundation. 0,14 0,28 0,69 1,3S 2,76 6.9013.7927,59 6S,9’
b , I ,,2,
f ,
References ❑ W;eb,
araddyl094,,
100
““’...+~ e w!,< RR-48, [1982)
1.Wiebe, R. and Gad<y, V,L.: “Vapor Phase Composition of Carbon ... . +F[93.3.C1 . VA. T~;, ~.,,
DioxideWafer Mixtures at Various Temperatures and pressures to X0 50 ~ ‘... \ \ @ 0.04, P,,
Atmospheres,” J. Am. Chem. Sot. (1941) 63, 475-77. 167.F(7?C1-+ lies CO,(, I a CO.(QI 1
2. Grdloway,T.J,.! cd.: .. ExFrimemal Mess.remem of Hydrate N.mk’s
for )@thme and Ethane and Compadsoo with Theoretical Values;’
lnd. E.g. Cht-m. Fundam. (IP70) 9, No. 2, 237-43.
3. B1.ch, M.G. and Liflmd, P.P.: “Calalyti. ReformingImprovedby
Moisture Metering,,, Chem. E.g. Prog. (1973) 69, No. 9, 49-52.
4, Kabayash,, R. a of.: ,<Final Revised Rep’! on the Water Content of
Carbon Dioxide Gas and Liquid in Equilibrium with Liquid Water and
wifi Gas Hydrates;’ r+mrl to Arco Oil a“d Gas Co., Dallas(June 1979).
S. Gillespie, P.C, and Wilson, G.M.: .’Vapor-Liqtiidand Liq.id-Liquid
Equilibria Water-Methane,Water-CarbonDioxide, water.Hy@ge”
Sulfide, Water-”Pentane, Water-Methane-nPenrane, ” RR-$8, Gas
Processors Ass.., Tulsa, OK (April 1982).
6. van der Wads, J.H. andPlatteeuw,J.C.: “Clatbrate Solutions,” Ad..
Chem. Phys, (1959) 2S, 1-57,
7, Saito, S., Marshall, D. R., and Kobayasbi, R.: ‘<Hydratesat High Pres-
sures: Part 11.Application of Statistical Mechanics to the Study of Hy-
drates of Methane. ArEon. and Nitrogen,” A1ChE3. (SePt. 1964) 10.
No. .5,734-40. -
8. Parrish, W.R. and Pra.sniiz, J.M.: “Dissociation Pressures of Gas HY-
drates Formed by Gas Mixtures,” lnd. E.g. Chem. Process Des. De-
V,[Op. (1972) 11, No. 1, 26-35.
9. Sloan, E. D.: .’Phase Equilibria of Natural Gas Hydrates.” Paper 67F
presented at the 1983 AfChE Summer Natl. Meeting, Drover, Aug.
28-31,
10. Erickson, D. D.: . .D.velopment of a Natural Gas Hydrate Prediction
Computer Program,” MS thesis, Colorado School of Mines, Golden
T-YIL_J 102
PRESSURE , PSI A
103 104

(1982).
11. Dewan, A. K.R.: .’Water Saturation Pndiction for CO,-Rich Mixmres
Co”tiini”g Traces of CH. and N,,, Spaper 27B presented al the 19S5 ‘[g. 5—isothermal water content in C02 @or I)-rich phase.
AICbE Natl. Meeting, Houtcm, March 24-2S.”
SPE Fomtion Evrdwio% December 1987 503
 TASLE 2—SMOOTHED WATER CONTENT AND ENHANCEMENT VALUES FOR FIG. 6

Water Content Enhancement Factor

Temperature Pressure lbm/MMcf at
‘F Oc psia MPa 1 atm and 600F Eq. A-10
— —
= -28.89 300 2.07 6.21 4.8
500 3.45 7.58 9,8
700 4.63 9.62 17.4
900 6.21 14.36 33.3
1,200 8.28 33,41 103.4
1,500 70.34 39.34 152.1
?,000 13.79 49.2s 254.2
0 -17.78 300 2.07 3.46 1.1
500 3.45 12.40 6.4
700 4.83 15.69 11.3
900 6.21 22.75 21.0
1.200 8.28 50.24 61.9
1;500 10.24 57.82 89.1
2,000 13.79 72.04 147.9
15 -9.4 300 2.07 7.16 1.04
50D 3.45 17.49 4.24
700 4.83 22.28 7.5
900 6.21 31.33 13.7
1,200 8.28 67.77 39.43
1,500 10.24 78.20 56.87
2,000 13.79 95.26 92.37
30 -1.1 300 2.07 14.41 ‘1.12
500 3,45 23.93 3.1
700 4.63 30,81 5.6
900 6.21 42.65 9.9
1,200 8.28 81,0 2s.2
1,500 10.34 102.37 39.7
2,000 13.79 120.36 62.2
45 7.2 300 2.07 27.01 1.15
500 3.45 21.0 1.5
700 4,83 41.71 4.14
800 6.21 56,87 7.3,6.6.
1,200 8.28 119.43 20.24
1,500 10.34 133.65 28,45
2,000 13.79 154.03 43.71
85 18.3 300 2,07 62.56 1.28
500 3.45 43.1 1.5 ,. —...
700 4.83 37.92 1.7
900 6.21 72,51 4.5
1,200 S.28 137.92 11.3
1,500 10.34 151.66 15.5
2,000 13.79 168.25 22.9
77 25.0 300 2.07 85,31 1.16
367.5 2.53 82.20 1.3,
500 3.45 68.70 1.5
700 4.63 64.7 1.8
735 5.07 60.20 2.1..,7
792 5.46 60.50 2.3,
900 6,21 54.03 2,2
1,200 8.28 148.9, 130.4 8.0,7.2-
1,448 9.99 176.0/185.8 [11.6/12.$]S
1,470 10.14 163.8 ll.O,.,t 10-6. <
1,500 10.34 161.1 11,0
1,800 12.41 183.0 16.7.
2,000 13.79 177.7 16,2
2.205 15.21 170.6 11.2*
2;940 20.28 184.0 24.7t
87.9 31,0
100.0, 0.69 338.2 1.1+
300 2.07 120.4 1.16
367.5 2.53 106.5 1.3,--1.47
735 5,07 74.10 1,8,”’ 1.9t
1,470 10.14 173.6 8.3,. - 9.4t
2,94o 20.26 188.7 19.1,”” 20,8t

504 3PE Fminatim Evaluation, December 1987

 I TABLE 2-SMOOTHED WATER CONTENT AND ENHANCEMENT
VALUES FOR FIG. 6 (continued)

Water Content Enhancement Factor

Temperature lbm/MMcfat
OF .C 1 atm and 600F Eq. A-10
122 50.0.. 183.7 1.6
172.2 1.8
168.4 2.2
.218.2 3,7
289.8 7.6
315.8 11.2
167 75.0
100 0.69 2,941.0 1.1?
367.5 2.53 873.1 0.7,”” 1.2*
735 5.07 509.4 1:2,’” 1.4*
1,470 10.14 400.1 ; 2.2,.. 1.9t
1.617 11.15 403.4 2.4”’
1;237 12.67 421.9 2.6..
2,205 15.21 443.6 3.6. - . .
2,940 20.28 545.8 6.0,’ ‘ 5.07
200 93.3t 5,717.0
100 0.69 1.05
3$7.5 2.52 1,644,0 1.1
735 5.07 940.6 1.3
1.470 10.14 655.7 1.8
2;940 20.28 664.9 3,7
met 4,
.-Ref. <
Vm?. 5

form snow-liie hydrate cfystals, causing ffequent plugging along

TABLE 3–VAPOR PRESSURES OF WATER the pipelines even above the ice point.
Gas hydrate forms when a gas molecule enters or isenclathrated
Reference Water Vapor’ Pressure for
(trapped) in the cavities formed by a number of water molecules.
Fig. 6 and Table 2
The degree of filing of fbe cavhies is known to be governed by
p“H,O system pressure and temperature and by the ty~ of guest molecule.
(.2) , psi kPa The van der Wads and p1atteeuw6 sofid-solution theory related
the equilibria of the empty hydrate to the tilled hydrate as
o. 0.02215 0.15276’
15 0.04352 0.30014.
30 0.08162 0.56290 -- .@w–@wm=–RT=b, 1“ Zmm ln(l+C~-co,), (A-1) -.. —
45 0.1487 1.02552 t m
65 0.3098 2.13655t
77 0.4641 3.20069t where ‘3Wznd .3Wwere the chemical potential of water in the filled
87.9 0.6538 4.50897..
and emp~ hydrates, resp&dvely, and ??=is the number of cavities
122 1.769 12.33793..
of type m per water molecule in a unit hydrate cell. Cm, the Lang-
167 5.592 38.56552..
200 11.525 79.43276.. muir interaction consrmt between the guest molecule and tie host
water molecules, cm be determined from smtistical mechanics by
.Wrwahw M Tower Wweraw. fromMm-:enwrawn integrating fhe radial Kibara potentiaf function. In the integration
da!., R.Is. i 8 and 1% the,. are rneta,teble VW., $.res-
SUres of waler,
procedure of the Kibara potentiat function in this study, a set of
.. Tablm 2-48. 62-5 of Ref.18. ~r~gem evahmd by s10a119 and Erickson 10 was adopted. Fi-
t Table9-9/, OfRef.19, mlfy, f ~02 and T,b, aro the partial fugaciv of CO* andSystem
temperamre (in K), respectively.
The dfierence in fhe chemical potentials in Eq. A- 1 can be re-
16. Song, K.Y. and Kobayashi, R.: “Measurement and Interprecuion of written as
the Water Content of a Methane-Propane Mixmrein the GaseousState
i“ Equilibriumwith Hydrate,,, Ind. Enz, Chem, Fund. (1982) 21, No. @w–cZwm=RTab$ h(P$’d/P#T), . .(A-Z)
4, 391-95.
17. Dharmawardbana, P.8.: “Experimental Thermodynamic Parameters where p~yd and p .M are the pressures of water in the filed and
for the Predictim of Natursl Gas Hydrate Dissociation Conditions,., empty hydrates, respectively. Note that pressures replace the fu-
PhD dksertatio”, Colorado School of Mines, Golden (1980). gacities in Eq. A-2 because of their ve~ small values.
18. Perry, R.H. and Cldlton,C.H.: Chemical EngineeringHandbook, fifth
Combining Eqs. A-1 and A-2 and rearranging, one obtsins
edition, McGraw-HillBcok Co. Inc., New York City (1973) Tables
34, 3-5.
19. C.Tableof Thermal Properties of Gases, ” U.3. Dept. of Commerce, ]np~d=in pwm Xnm ln(l+C~–cG2)
[/ (A-3)
NSS circular (1955) Table 9-9/a. m 1.
20. Schroeder, W.: ‘<A Review and Disamion of Gas Hydrates.,, Ahren >
S&g chend.cher und chemisch-rech.iscfw Vorwflge ( 1926-28)
Tbe hypothetical vapor pressure of water in the empty hydrate was
21-71.
calculated by Dbannawardbana, 17 wbo used Otefttme-phase equi-
librium dab for iceihydratdgas and ice pmperdss. The vapor pres-
Append’ix-Solid-Solution Theory sures were expreked in fhe inverse absolute temperature by Sloan*
and Other Correlations and used in the cafcufation to predict the water content of a
Since chlorine hydrate was discovered by Davyzo in 1810, it has methane/propane mixture by Song and Kobayasbi. 16The hypofhet-
been proved that water molecules enclatbrme various types of gas
molecules, such as C02; CH4, and natural gas constiment?., to .Pmonel ccmm.nication with E.D. S1..., Colmdo Schcd 0! Mines. sew 14, 1972.

SPE Formation Evaluation, December 1987 505

 TASLE 4—VAPOR PRESSURE OF WATER IN HYORATE PHASE IN EQUILIBRIUM WITH C02 (g or 1) PHASE”

Temperature Pressure p~TX103, Eq. A-1 Deviation

(K/OR) (MPa) (MPa) (%)
240/432.3 0.4184 0.05192 2.0
0.5512 i .7
0.6690 1.6
0,8613 1.8
1.0335 0.02S96 0.02954 1.4
2.0265 0.02893 0.02893 0.00
3.0398 0.02834 0.02883 0.04
4.0530 0.02674 0.02674 0.00
5,0663 0.02663 0.02864 -0.04
6.0795 0.02854 0.02854 0.0
7.0928 0.02845 0.02645 0.0
8.1060 0.02635 0.02636 -0.04
9.1193 0.02826 0.02827 -0.04
10,1325 0.02817 0.02817 0.0
15.1988 0.02770 0.02771 -0.04 .-.
20,2650 0.02725 0.02726 -0.04
25.3313 0,026S5 0.02662 0.11
30.0003 0.02644 0.02642 0.08
34.4606 0,02605 0.02603 0.06
34.99n 0.02601 0.02599 0.08
Average absolute deviation 0.46
250/450.3 0.6690 0.14123 0.09260 0.09308 -0.30
1.0335 0.06736 0.06762 -0.28
1.3790 0.08382 0.06393 -0.13
1,5857 0.08295 0.08291 0.05
1.6546 0.06169 0.06180 -0.26
2.0265 0,06069 0.06076 -0.09
3.0398 0.08041 0.06049 -0.10
4.0530 0.06015 0.08023 -0.10
5.0663 0.07987 0.07997 -0.11
6.0795 0.07961 0.07970 -0.11
7.0923 0.07935 0.07944 -0.11
8.1060 0,07908 0.07918 –0.12
9.1193 0.07882 0.07891 -0.12
10.1325 0.07856 0.07866 -0.13
15.1988 0,07726 0.07737 -0.12
20.2650 0.07603 0.07611 -0.01
25.3313 0.07493 0.07487 0.08
20.0003 0.07381 0.07374 0.08
34.4606 0.07275 0,07268 0.10
34.9977 0.07255 0.07263 0.11
Averaae absolute deviation 0.13
260/468,3 0.62.90 0.35569 0.24840 0.24639 0.0
1.0385 0.23419 0.23633 -0.91
1.3790 0,22474 0.22614 -0,62
1.7235 0.21779 0.21852 -0.24
2.0265 0.21302 0.21392 -0.42
3.0398 0.20746 0.20774 -0.13
4.0530 0.20676 0.20706 -0.14
5.0683 0,20607 0.20638 -0.15
6.0795 0.20539 0.20570 -0.15
7.0928 0.20470 0.20502 -0.16
8.1060 0.20402 0.20435 -0.16
9.1193 0.20335 0.20367 -0.16
10.1325 0.20266 0.20300 -0.16
15.1986 0.19941 0.19969 -0.14
20.2650 0.19623 0.19644 -0.11
25.3313 0.19340 0.19323 0.09
30.0003 0.19049 0.19032 0,09
34.4606 0.16781 0.18756 0.12
34.9977 0.18758 0.18726 0.17
Average absolute deviation 0,23

ical vapor pressure of water in the empty hydrate of Structure 1 been developed through a least-square procedure with the values
is given by of pwm and the values of piyd X 103 calculated from the solid so-
Iution theory for various sets of temperakwe and pressure. They
P#T=(0.101325)E+ (17.44 -6,W3.93/T,bs). . . (A-i) are given by Eqs. A-5 and A-3 as
The values in Col. 3 of Table 4 were calculated from E@ A-4.
(P:yd X103) =(0.101325)E
The water vapor pressures in the fdted hydrate were calculated from
Eqs. A-3 and A-4 and are presented in Col. 4 of Table 4. 6,150.93
Empirical relatiom for the vapor pressures of water in the ffled
hydrate phme for any condition of pressure and temperature haVe
+
[
z4.3773—––
Td,
3.291 XlO-4(p–PO)
“1, (A-5)

506 3PE Formation Evaluation,December 1987

 TABLE 4—VAPOR PRESSURE OF WATER IN HYDRATE PHASE IN ECWNLISRIUM WITH CO, (g Or 1) PHASE’ (continued)

p~yd (103 MPa)

Temperature Pressure p~’xi03, Eq. A-4 Solid-Solution Theory From Empirical Deviation
(lV”R) (MPa) (MPa) (Eq. A-3) Eqs. A-$ and A-S (%)
270/486.8 >.0335 0.s3658 0.56332 0.58843 -0.88
4 .37s0 0.56023 0.56685 -1.1s
1.7235 0.54300 0.54797 -0.91
2,0265 0.53103 0.52410 - 0,5s
2.4115 o.5i8s.3 0.52071 -0.36
2.7702 0.51026 0.51180 -0,30
4.0530 0.498’60 0.49642 0.06
5.0663 0.49713 0.49678 0.07
6.0795 0.49547 0.49514 0.07
7.092S 0.49362 0.49351 0.06
8.1060 0.49217 0.49169 0.06
9.1193 0.46052 0,49028 0,05
10.1325 0.4S892 .0.43867 0.05
15.i988 0.46103 0.43070 0.07
20.2650 0.47338 0.472S4 0.11
25.3313 0.46661 0.46523 0.30
30.0003 0.45976 0.45623 0.34
30.3975 0.45927 0.46255 -0.71
24.9977 0.45275 0.45088 0.42
Average absolute deviation 0.35
280/504.3 3.039s 1.85103 1.17431 1.17901 -0.40
3.4451 1.15639 1.15998 -0.31
3.7906 1.14346 1.14538 -0.17
3.9963 1.13765 1.13535 0.20
4.0530 1.13495 i .13209 0,25
5.0663 1.12727 1.12370 0.32
6.0795 1.12339 1.12001 0.80
7.0926 1.11957 1.11623 0.29
S.106O 1.11576 1.11266 0.28
9.1193 1.11204 1.10900 0.27
10.1325 1.10835 - 1.10536 0.27
15.198S 1.09036 1.08732 0.26
20.2650 1.07307 1.06956 0.33
25.3313 i .05796 1.062S0 0.49
30,0003 1.04236 ,1.03895 0.52
30,3975 1.04137 1.03554 0.55
34.4606 1.02802 1.02024 0.77
34.9977 1.02665 1.02203 0.45 -.. ..
,Average absolute deviation 0.36

abs(Col. 4-Cal. 5) ~ ,00 Total avetage absolute deviation 0.31

Average absolute deviation = ~ z
Col. 4
.S.. theAF.F.mdlx
1.x,xPI.”,M”.

- 0,304
“Q
.

- 0,253 ~
?..-
I (
0,00] 4,3 4.2 4.( 4,0 3,9 3,8 3,7 3,6 3,5
INVERSE 7EMPER&Tu* IOVT. K-[

- 0.203
Fig. 3-Estimah?d activity coefficients of water in the C02 (g
x I)-rich ohase in eauilibnkiin with hvdrate.
~
o 568o
PRESSURE , PSIA

i9. 7—W2tet vaPOr PreSSIJre$ of empty and filled hydrate.

SPE Formati.m E.ahmtion. Decernker 1987 507 .

 TABLE 5–ESTIMATED VALUES OF IPW OF WATER IN THE C02 (g or 1)-RICH
PHASE IN EQUILIBRIUM WITH HYDRATE

p;ydxlos,
Pre33ure Temperature Eqs. A-5 and A-8 Activity Coefficient Water
psia MPa OF ~c (MPa) (Eq, A-11)
200 1.379 0,0 -17.78 0.144s1 0,9131
15.0 -9,44 0.32093 0,9346
30.0 -1.11 0.59690 0.8924
300 2.069 -4.9 -20.5 0.10457 0.2512
- i 8.4 -28.0 0.04959 0.1762
0.0 -17.78 0.13664 0.9453
15.0 -9.44 0.30177 0.9664
30.0 -1.11 0.59556 0.9290
500 3.44s 0.0 -77.78 0.13473 0.1494
8,6 -13.0 0.21032 0.1694
25.7 -3.5 0.43481 0.3068
700 4.82! 0,04 -17.76 0.13668 0.0855
14.0 -10.0 0.27433 0.1206
25,7 -3.5 0.48284 0,1852
37.4 3.0 0.82741 0.2388
900 6.207 3.2 -16.0 0.15810 0,0493
15.0 -9.44 0.28704 0.0696
44.0 6.67 1.10449 0.1624
1,200 8.276 1.4 -17.0 0.14302 0.0159
19.0 -7.22 0.34658 0.0266
1,500 10.345 i .4 -17.0 0.14206 0.0108
15.8 -9.0 0.29448 0.0173
37.4 3.0 0,81272 0.031 s
2,000 13.793 -0.04 -17.6 0.13028 0.0083
8.5 -13.06 0.20227 0.0081
22.2 -5.44 0.39719 0.0131
36.9 2.72 0.78564 0.0208
2,940 20.276 0.0 -17.78 0.12781 0.0063
15.0 -9,44 0.27423 0.0135
30.0 -1.11 0.56138 0.0277
3,675 25,345 0.0 -17.78 0.12572 0.0050
15.0 -9,44 0.26975 0.0106
30.0 –1.11 0,55222 0.021s
4,410 36.414 0.0 -17.78 0.12367 0.0041
15.0 -9.44 0.26535 0.0067
30.0 -1.11 0.54321 0,0179
5,080 35.034 0.0 -17.78 0.12183 0.0035
15.0 -9.44 0.28139 0.0075 . . ..
30.0 -1.11 0.53512 0,0153

where where

PO‘O. 101325 E+(9.8664– 1,737 .280/T,b,) Pr=(po–p)lpo. . . . . . . . . . . . . . . . . ., . . . . . . . . . . . . . ..(A-9)

The values of p~yd x 103 in Col. 5 of Table 4 were calculated

for Tab,<.265K . . . . . . . . . . . . . . . . . . . . . . . ... . . . ..(A-6)
and
P. =0. 101325 E+(10.6561S– 1,944 .806/T,b,)
for Tab,>270K, . . . . . . ... . . . . . . . . . . . . . . . . . . . .. (A-7)
where PO is the pressure (in MPa) for the three-phase coexistence
at temperature T (in K)—i.e., C02(l)/C02(g)/hydrate equilibrium.
However, for the condition where the system pressure is greater
rhan the pressure for initial hydrate formation, but smaller than the
three-phase equilibrium pressure, the following empirical relation
should be used
from E@. A-5 through A-9 and compared with COL 4 from the
solid solution theory. The agreement is excellent, yielding an ab-
solute average deviation of 0.31%.
The etiancement factor of the water partial vapor pressure re
suiting from the total system pressure is defined by
E=pfL/pw,o . . . . . . . . . . . . . . . ... . . ..- . . . . . . . . . . . .... (A-10)
where p and p; are the total pressure and saturation vapor pressure
of stable or metmtable water, respectively, and~L is the mole frac-
tion of water in the C02-rich phase.
The activity coefficient of water in tbe C02-rich phase in equi-
librium with hydrate phase is defined by
k.=p:ydj(pf~). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..(A-11)

(P:yd X103) =(0.101325) E S1 Metric Conversion Factors

atm X 1.013 250* E+05 = Pa
6,150.93 fr3 X 2.831685 E–02 = m3
+ [ 24.3773 –— +0.23460 (P,) -0.72241 (P,)2 ‘F (aF–32)/l.8 =. c
L Td, lbm X 4.535924 E–01 = kg
psia x 6.894757 E+OO = kpa
+2.45086(Pr)3 –2.78934(P,)4 + 1.133565(P,)5
1 ,
.C.mvamlo”
“R “RII.8
factor IS exacL
=K

Ofiginn! SPE manuscript (SPE 15905) received for review May 5, 798S. Paper acmmd
SPEFE
. . . . . . . . . . . . . . . . ... . . . . . . . . . . ... . . . ..(A-8) for publim! ion 8P% 27, 1987. Retissd rmn.scr!pt mceiwd July 8, 1S37.

508 3PE Fmmwion Evaluation,December 1987