r

,
f..
r
,,
~Generalized Correlations for Predicting Volubility,swelling
and ~Viscosity Behavior of CO~-Crude Oil Systems
R. SIMON
D, J, GilAUE*
,,
ABSTRACT
f
This paper prmwts correlations for predicting the soh-
bility, s}{,ellitzg ~il(ii~iscosity beItavior,of CO,-cruc[qoiIsys-
mm! TIIe correlations were developed from experimental
data rtbtained by file aulhors, 7hese data are also pre-
wntecl. 7lw data were detctminecf by measuring the p~op-
,erties of mhures of CO, and nine riiflerent oils. Experi-
inen(cil condi[imts cotwed u range of 100. to 250QF and
pre.wwes up to 2,300 psia. Properties predicted by rite
correlations have uverage deviations, expressed as per
rent of experimental value, of 2 per cent for sohbility,
0.5 per cent ;Orsweliing and 12 per ceirt for viscosity.
,
INTRODUCTION -
Interest in CO, i~jection as an oil recovery .process has
led to the development of performance prediction methods
which can bd applied to specific reservoirs, To use these
performance Rrecliction methods, it is necessary to know
the volubility, swelling and. viscosity properties of CO,-
crude oil mixtures iit reservoir conditions. some infopna-
tion onthese properties has appeared in the literature;
howiwer,t his inforrnationdid ngt cover the$arigeof dif-
fererrt oils and concfi[ions need&d to prepare generalized
correlations for reservoir engineering purpose.so Conse-
qllently, an cxperisnental program was undertaken to
collect ~he data needed. The data obtained rind the cor-
relations developed from the data are described in the
following sections of this paper.
VOLUBILITY OF CO, IN CRUDE OILS
CO, volubility data iri the literature come from six
principal sources,- The sohrbility prediction method of
,Welker and DunlopZ is limited to 80F.
The information in Ref. 4 is of two types: the first
includes binary and ternary mixtures of CO, and light
hydrocarbons (C, to C,), and the second gives data for
CO, and heavy hydrocarbons for a temperature range of
40 to 90F.
- Ref. 5 contains a K,,,,, chart for systems whose conver-
gence pressure is 4,000 psia. The &s are based rrminly
on CO,-natural gas mixtures. .Ppeftmanns work covered
CC), soldzility, in, one condensate and one crude .oiI$~_Ja-
co~y and Rzasa meaitiredCO, solti~lities as i function of
(Sri@nal manuscript received at Sodety of Petroleum Engineers office
July 6. 1964. Ravised nmnuscrint received Nov. 26.1964. PaDer present.
MI ut sPE 39th Annual Fal[ Meeting, held in Houston, L_Ict.11-14. 1964.
.;CurrmtIy ~L Cali fro.ia Institut@ of T~hn+w:, .
I(eferences given at end of tmtmr,
.< :* . .: ..-.. .:. . . . . . . .
.
. . . . I ,.
,
CALIFORNIA RESEARCHCORP.
1A HABRA, CAHF. ,
pressu~e and temperature for twq natural gas-absorber oil
mixtures and two natural gas-crude oil Snixtures.a G02 con-
centration in these four systems was fixed at 5 mol per cent.
The work reported in this paper extends CO, volubility
data to a variety of different crude oil types in a tempera-
ture range from 110 to 250F and pressures up to 2,300
psia, The experimental procedure used !IYthe authors to
obtain the volubility data consisted of combining known
amounts of pure CO, and crude oil in a visual cell at a.
fixed temperature and measuring the bubble point of the
mixture. Measurements were made for a total of 40 ditTer-
ent CO,-oil mixtures and the results arc shown in Table 2.
The mixtures included nine different oils (seven crude oils
and two refined oils) whose properties are listed in Table 1,
All nine oils had vapor pressures less than 1 at m at the
experimental temperatures. Consequently, analysis of the
bubble-point vapor showed a CO, concentration over 99
mol per cent. At no time during these experiments WIISa
second, more dense, liquid phase observed.
The volubility correhilion which was developed from the
data in Table 2 is presented in Figs. 1, 2 and 3, In these I
figures, volubility is expressed as -w,,,, the nloI. fraction of
CO, in the CO,-oil mixture,. Fig. 1 shows volubility as a
function of CO, fugacity and temperature. Pig. 2 shows
the same volubility data expressed as. a function of saturrt- .
tie-n pressure and temperature. The volubility shown in
Figs. 1 and 2 is for an oil whose UOP chara@erization
factor is 11.7, UOP characterization factors of crude oils
can be determined from Ref. 10 if the viscosity and API
gravity of the oil are known. Fig. 3 gives the sohsbility
correction factor for oils whose UOP characterization fac-
tors differ from 11.7.
The solubiiity correlation in Figs, 1, 2 and 3 predicted
L. - .
TABLE l-OIL PROPERTIES*
viscosity
Dasig-
-
P,, MOI
natiQn** API (C*) F Weight UOP K
- .
A
.
1?.3 87 110 > 350 .11.4
10,6 200
.B 33.3 4.4 I 2@ 236 I 2.0
!2.65 160
c 33,3 13,0 120 t 345 12,4
3.57 200
.,
D 18,3 74.0 I 20 35s 11.5
5.0 250
E 13,5 1300 120 463 11.5
70 ~ 200. . .
F. 12. I 105 . I 20 330 11.0 - -
G 25.8 23.2 130 373 12.2
,,
,
H 11.9 499 I 30 .44: , 11.3
1s,2 53.6 145 11.6.
..
15.7 200
GCXIS A Ihr.xmh 1 trod, vaoor prenvrm l~ss lh. n one atmosphere al
ihe femperafure shown.
. .
~ls A. B. D, E. G, H, I arc crude oils. C and F are refined oils
/
.
,.
,-
. . . .
-.
,.
. . . . . . .
,. ?
. .
solubiliti~ which differed from experimental measurements
with an average deviation of 2.3 per cent. This deviation
was established by comparing experimental and predieted
values for 33 C09-crude oil nd%tures. me com~i~~ am
shown in Table 2, Maximum deviation for the pointa was
6.8 per cent.
Kmz values calculated with Figs, 1, 2 and 3 were mm-
pared with selested points from Poettmann~ The values
agreed within 1 per cent. ,.
SWELLING OF CO,-CRUDE OIL MfXTURES ,
When CO, dissolves in oil, an increase in liquid volume
occurs. The volume of the oil and dissolved CO, divided by
the volume of the oil without CO, is detlned as,the swell-
ing factor. Some swulling factor data are presented in the
literature, but these data are not extensive enough to ,serve
as the basis for a generalized swelling factor correlation
for CO,-crude oil systems.<
The authors have extended the availnble swelling data as
part of their experimental work, The method used was to
mearaire the volume of oil before CO, was added and then
measure the volume of the CO,-oil mixture at bubble-point
conditions. This work was done at the same time as the
volubility determinations described previously. The re=sults
of the measurements are summarized in Table 2.
An analysis of the data in Table 2 and Ref. 12 indicated
that swelling factor is not only a function of the arnoimt
of dissolved CO,, but also of the size of the oil molecules
,(&f/p cc/gm-mol, see Ref. 10 for mol weights). The rela-
tionship between swelling factor, mol fraction of @, dis-
solved, and molecular size is correlated in Fig. 4.
Fig. 4 was used to cafculate ,wveltig factofi which dif-
fered from experimental values tith an average deviation
( F
XC02
IN .OIL Wllti UOP K= II .7
.
FIG. lCOZ%LUBILITY IN- OIL. ~
-..... .. ...
of (L5 per cent. This deviation is based on a comparison of
calculated and experimental values for 39 diffexent ndx-
tures. The comparison k shown in Table 2.- Maxhnum
deviation in the 39 mixtures was 2.6 per ~nt.
VISCOSITY OF CO,-CRUDE OIL MIXTURES
Experimental viscosity data for CO,-crude oil systems
xco~
IN OIL WITH UOP K= II,7
F[c. 2-CO, VOLUBILITY IN OIL.
TEMPERATURE, F
FIc. s--CQ ~OLUEILITY RSTIO.
,
1
!
- J
. I
.-,
. ,
LY .. -.
,.
.....
.
r
have been published,)ti)ti Welker and Dunlop presented a
method (limited to SOF) for predicting viscosity of car-
bonated oils? Johnson, et al. gave data for a system at
7SF. The data in Ref. 1 are for one oil. Ref. 13 reported
new viscosity data for two oils.
The authors obtained experimental viscosity information
from 20 difTerent CO,-oil mixtures, These mixtures, whose
properties arc summarized in Table 2, included five differ-
ent oils. Measurements were made in a temperature range
from 110 to 250F. A two-step experimental procedure was
used to obtain the data. Fkst, the atmospheric-pressure vis-
cosity of the oil was measured in a Zeitfuchs cross-arm
viscometer at a fixed temperature. Second, q mixturs$ of
CO, and oil was prepared, and the bubble-point pressure
and viscosity of the mixture were determined at the same
fixed temperature. E1evated pressure viscosity measure-
ments were made in a rolling ball viscorneter.
Using the data in Table 2 as a basis, a correlation re-
lating the viscosity of a CO,-crude oil mixt~e (P.) ~ the
mixture saturation pressure and to the original oil viscosity
r
(~.) was prepared. This correlation is for 120F and is
shown in Fig, 5, For mixtures at other temperature& the :
viscosity of the mixture is first calculated from Fig. 5 for,
120F and then corrected to the other temperature with
the aid of Figs, 6 and 7.
Use of the viscosity prediction method is illustrated in
the following example,
Ce,lculate the viscosity (p. ) of a C02-20API crude oil
mixture saturated with CO, at 500 psia and 100F. The ,
viscosity of the crude oil (p. ) is 92 cp at lOOF.
Step 1: Determine the viscosity of the oil at 120F. If ~
speeitlc data are not available, use the line x~~2= 0,0 in
Fift. 6 as a paralIel guideline. TMs will Ave 53 CP as Shown
G Step 2: Determine the saturation pressure at 120F by
using the middle line in Fig. 7 as a parallel guideline, A
saturation pressure of S00 psia at 100F is equivalent to
560 psia at 120F as shown in Fig. 7. .
Srep 3; Read the ratio N./~. from Fig. 5. If ~ = S3 at
TABLE 24 LIMAIARY OF EXPERIMENTAL DATA AND A COMPARISON OF EXPERIMENTAL JAND PREDICTED VALUES
Experimental Ckmpon$on of Experlmenfml and Pmdkkd VaIUe$
_vrscOsfw
L_
Solubl[lty Swelllne v15c.5sity
.
B
011
ii-
C
D
.E
F
G
H
[
2
3
4
5
6

110
200
,120
160
120
120
250
120
200
120
130
130
145
200
290
460
~;g
2361
412
910
12S5
495
1010
1570.
467
861
129[
203/
461
8?2
153s
.2376
47 I
996
1496
549
1124
140Q
2293
403
759
1553 ,
17S2
.415
790
2055
1710
518
Ills
551
I 093
1540
2321
401
1335
1856
331
S20
1472
2200
,g;;
.455
.667
.423
.625

.235
W: ,
..675
.313
.495
.667
.717
.299
.508
.632
.215
.366
.430
.571
f;,
669
.k77

,2S3
.498
.356
.555
.65s
.70s
.251
.5s4
.650
.191
.41 s
.59s
.681
.32B
,553

1.Es
1.104
1.193
1.370
1.053
1.112
1.220
1.303
1.040
1.116
1.202
1.031
1.072
1.092
1.163
1.024
1.0s1
1.14s
1.163
,_

-
1.049
1.129
1.052
1.12s
1.205
1.252
1.013
;.; V;
1.06S
1.1.52
1.232
1.049
!.133
Gxcrx = id imcffon of C@z in fix of COZ- + oil. -:
* *SW9.. focf. =
vol. .of Cf22 + 011 mix af sofn prass. & femp.
VOI of 011 of afm & ~of% temp.
, tA.
(
Experimental valve - prakfad VOIV8
..-.
Experimental volue -
)
K 100
104.

~
2.0
1.13
.66
1.3s
.s2
.50
-

19.5
S.5
:.:
1:18
1.03
245
g
2.4
16
8.6
-
20.1
15.0

.
X.4
~
.195
.296
.464
.417
.627
.747
.406
.538

.299
.513
.659
.296
.531
.633
.210
,368
.@!
I ,256
.434
.643

.287
.501
.334
.597
.63S
.235
.566
,
.190
.412
.594
.3X
.551
+1.4
- .3
5.1
-6.S
-1.3

i-4.5
-3.6
+1.2
+1.0
-4.5
--
.2
+2,3
- .5
+ 2.s
o
-2.0
+ 5.0
+ 3.4
-1.4
. .6
+ 6.2
- .4
i 3.0
+6.4
i 3.1
+ .5
+ 1.4
+ .?
+2.1
+ .4
I,19S -;2
1.020
1.104
1.197
1.367
1,Jf.43
1;102
1.220
1.276
- .2
-0.3
+ .2
+ .9
+ .9
0
+ .5
I .043
1.119
1.196
1.037
1.060
1.082
1.155
1.025
1,04s
1.152
1.171
1.050
1.128
1.050
1.126
1.204
1.256
1.025
1.0ss
1.144
- .3
- .3
,+.5
.+.4
+1.1
+ .9
+.,7
- ,1
+ .3
,4
- .s
- .1
+ .1
+ .2
+ .2
+ :1
- .3
1.2
+2.6
+1.3
2.07
1.1
..77
1.32
.s3
.60
1:.;
5:9
I .3
.85
.75

-.

i2 I
52
11.7
2.6
18.2
8.9
17
14.9
-
.-

.-
.
.. . . ... ,-_
-.
,?
.
JOtiRNAkO~ J~T~OJ-RuM TECfEfi?f@f;y .,
,.. ,. ..: . . . .. . .. . .,. . . . . . . .
1,.
{
. .
i
1
,.
175 225
XC02
Fm &-Swtvm~c FALdivsNOI. FIIACTION CO,.
[.0
,,9
.8
.7
.6
pm .5
iG-
.4
.3
,1
.1
.-
----J
PO= 1000
5
/
~~ - ..-
400
SATURATION PRESSURE, I%IA
...
... ..

f
I .-
1
1
I
I
~ ~ 1000
1000 2000 3000

120F and saturation pressure is 560 psia at 120F, the .1

p,/p. = 0.197.
,,
(The insert in Fig. 5 is intended to facilitate reading the
graph from O to 500 psia. N,otc that the ordinate for the
insert is the reciprocal of the mdinate of the main graph. )
Step 4: Calculate the viscosity of the mixture at 120F.
/.1,,, = 0.197x p., /J,,,, =0.197x53= 10.5 Cpat 120F.
!
Step 5: Correct the p,. = 10.5 CP U 1XIF to 19 CP at
100F by using the line x,.,,, = 0.3 in FQ. 6 as a Parallel
I
guiqeiine.
Fig. 6, is based on two typical crude oils130 and
t
20 API. Viscosity of CO, mixtures with other crude oils , :
can be estimated by plotting the viscosity-temperattlre data
for the pure crude oil (x,,,,, =0) on Fig. 6.
,,
The viscosity calculation method illustrated above i: the
first available for reservoir engineering studies of CO,-
1
crude oil systems. Viscosities predicted by the method
were compared with measured viscosities for 20 different
CO,-oil mixtures, This compari~on is suromssrizcd in Table
2, For systenls at. 120F, viscosdies ctdcohitecl from Fig. 5
have an average devintion of 9 per cent, For systems at
other temperpturesj viscosities calculated with Figs. 5, 6
and 7 have an average deviation of 14 per cent. The aver-
tige deviation for all 20 mixtures was 1 I.7 pcr ceot, with
(1
z
o
.-i=
)~
3
I
I ,
,.
0 %00
1
200 300 400 500
T~M~ERATtJRE F
.
.....-.
!*
.
1 0 0
1(s9 J20 140 160 180 200 220 , ?40
G
m
SATURATION TEMPERATURE, F
.
,- .-, ._ ..>.
,
1
~.
OO.
SATURATION PRESilRE, PSIA
1 ;
~w.5-:-% M);lT% OF COX-CRLW @I. i!fixrLmk~s AI 120~.
1.
SAN Uhi{Y., 196S
. . . . . . . . . . ... - . ... . . .
1 ..>., ..- .,. .... ,. . . . . . .
._. /_ . -.,, ., -., -- -.
.
-.
105
.,
I
/
a :uuximum deviation of 28 per cent. A comparison of prc-
,dicted values with experimental values from the literature
showed a similar ,average deviation.
TCI improve the correlations accuracY,. it is necessarY to
conduct further studies which account for the molecular
type artd viscosity-temperature slope of each oil.
CONCLUS1ONS
Experimental data are presented which show the sohl-
bility, sweIling andviscosity behavior of CO,-crudeoiIsys-
terns. The data were used to develop correlations fo$ pre-
dicting these three properties when the viscosity and grav-
ity of the crude oil are knbwn. A comparison of values
predicted by the correlations with measured values showed
thedeviations in Table 3.
NOMENCLATURE
K 012 = eqililibriurn vaporization COr3StiUIt fot CO,
M = mol weight of oil
UOP K = LJOdpetroIeut;~ ch;racteri!mtimr factor
X,:,82= MO! fraction CO, in a CO:-crude oil mixture
.},,,, = mol fraction of CO, dissolved.in crude oil
wficw.c UOP K ~= 11.7
XF ==nloI fraction of CO, dissolved in crude o;
whose:UOP K ditlers from 11.7
~= Experimental wduc-predicted value
Experimental value
< I00
p,. = viscosity of CO,-crude oil mixture. cp
p,,, = viscosity of crude oil, cp
[J = density of crpdc oil, gn~/cc
,,
REFERENCES
1. fhsrm, 1). M. and OrtlOfT, G. O.: LulJO1-utur: Inw*ligation of
,the Watvr-i)l-iwrl, {ktrl)on I)ioxidv Prom+ for oil Ptceo Yin).
(
&
.
.
.1
..!
.-
.1
J
.-l
,!
:.
,,
I
TABLE 3 .
I
.
Property Average MOxlmum
_. . - --
Solubilify (%) 2,3 6.8
swelling
viscosity I :.; 2$.:
- .. . . . .. ..
lruns.,AIME ( 1959) 216, 388.
2. de Neum, N. 1-1: .4. Ctilrmlulion Metlwd Ior Carlmndld
Water Flooding-, SUc. Pet, Kng. lnw. ( March, 1964) 9.
3. Welker, J. R. and JJunloIi, 1). D.: Physid Prwperlies of Car-
bonated Oils, .fmr. Pet. lecA. (<lug., 1963) 873.
4. l?ifdiagraphy 0/ Vupor-1.iwid L<iuilibriunl Duks jor Iiydw
cur.hm Systems, .AP1, Oivision of Refining (Bitrliography No.
1, 1963) Table 18, 32,
5, En4inwring Dutu Bud, NGSJIIi ( 1957).
6, Poettmwm, F. H.and Kmz, f), 1..: CO, in a 3intnridl (;us. ,,
(knrlensutc System. IJCC ( 1946) 38,530.
;, Poettman, F. H.: ~aljiwizution (Iimrac[eristics of CO, in u
Nntnrd t2ss.CrudI: oil Systcm, Iruri., AIME ( 1951 J 192.
141,
8. Jacol,F, :R. H. uudILkr. 11.J.: flquilihrium Ya wirr.tirm
1 I{tit ins lor Ni[r{lgen. iletlwnr, (k! bc,u I)iuxidc, kt lm~e and
11}-L{r,,g*.1, Sujp}]i,[c in :jl,. udwrt)il.Xatulml (k zllld (11-U1114
oil-f fatutal (Lrs Systcvus, 2rnns., .\IJIE(1952) 19S, Y).
9. I)eming, W. E. and Dmin:, L. S.: fllP 17U&it) ?f ~()~:.
Phys.lieriw ( July 1, 19.39) 108.
10. \Vatson. K. 31., Nelson, Ii. F. UIIL1llurIJIy. G. B.: (l]oru[,tc,ri.
[E\ ( 1935) #7, 1460. zation of Petroleum kriirtion> ,
11. JIIIUWCMI. W. ~.. llac~irlu!w,, Ii. 11. WI(I Ilmt,m, J. X.: Prod.
Mon. i Nov., 195?) 15.
12. I-kmnw. f[. 11. LInd%gr. B. }1.: !t,lmt]rlril. and Pilusu Be.
huvior of IIIC n-l)ecunc-(:(), Syslem;, Jour. 0/ (Thcm. Eng
Data, (Qrt.. 196:3) 8, XI,. II, 508.
13. Crawford, il. R., et al: Ii[-!mil llioxi,lv-,\ Ill]ltil!urpusc
Acfditi! c for IHfccti~c l\c,ll SIimululil,n. .IImf. Pet. Trc6.
( JIarch, 196.3 ) 237.
14. lILJIIU, L. W.: uJ,-sI,I~ [mtFlowtiog Iur 11111IILI. (WI [.)ii I{W
I:OWW, fruns.. A 131J; (19.59) !216,?25.
***
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.. . -,, <.. .. ,-.
. .
,
.,,
., ._.. ,.>