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IEfkct d Oil Composition on Minimum

IIWliscibility
lPressuh3-Part 2: Correlation
F,M. Orr Jr., SPE, Stanford U.
M.K. Silwa, * SPE, New Mexico Petroleum

Recovery Research

Center
W?

/4/5d

SutIimary. .A new correlation for C02 minimum miscibdify pressure (MMP) is proposed and tested. ,The comdation is. based
on experimental evidence that extraction of hydrocarbons from a cmde oil depends most strongly on the size of the hydrocarbon
molecules. Thus, an oil rich in hydrocarbons that are efficiently extracted shotdd show a lower MMP than a heavier oiJ. The only
crude-oil data needed for use of the correlation are a carbon-number distribution, which can be obtained easiJy by chromatography.
The density of C02 at the MMP is correlated agaimt a weighted-composition parameter. The MMP of any oil at a given
ikmperahtre is estimated as the pressure required to yield that C02 density. The effects of contaminants in C02 can be estimated
easily by calculating the pressure rcquiroi to give a mixture densig equal to that required for pure COZ.
Correlation accuracy was tested by comparing predicted and measured MMPs for 35 oifs. The proposed correlation produces
MMP estimates accurate to witMn about 10% for most oils. Comparison of correlation predictions with those of other commonly
used correlations indicates that the proposed correlation is significantly more accurate, pariictdarly for recombined oik.
Introrfuation

Development of miscibility in a C02/crude-oil displacement is the


result of extraction of some hydrocarbons from tie oil by dense
C02. 1.6 There is considerable evidence that extraction of hydrocarbons from a cmde oil isstrongly influenced by the densi~ of
the C02. As its density increases, COZ extracts more and heavier
hydrocarbons than does lower-density C02. 5-7 Improvement of
extraction with the increase in C02 density that accompanies increasing pressure accounts for the development of miscibility. 8
Slim-tube displacement experiments. which suppress adverse effects of viscous instabilities and hence are m+rly one.dimensional,
are commonly used to determine an MMP for a given crude oil.
While exact procedures for MMP determination vary,9 all yield
a pressure above which little additional improvement in oil recovery occurs tiith further increases in pressure, and thus area measure of the pressure (density) at wh,ch extraction is cffecfive enough
to produce high local displacement efficiency. fn this paper, we
examine how variationsin crude oil compositioninfluenceMMP.
The size and stmcbme of hydrccabo molecides presmt in a crude
oil must also affect how such components partition in C02ihydmcxbon mixtures, and hence must influence the density required for
efficient extraction. Helm and Josenda17 developed a correlation
for prediction of MMP based on the idea that the density of C02
at the MMP could be correlated with tie amount of C5-tJmoughC30 hydrocarbons present in the oil. Aczordmg to their correlation, oils containing Jarge C@hrough-t330 fractions cequire lower C02 densities than heavier oils. Ofr and Jensen8 agreed that
C02 density determines extract@r eftlciency, but argued that at
low tempen+ures fbelow about 120F [49C]), the density of C02
increases so rapidly with pressure near the extrapolated vapor pressure (EVP) that effects of oiJ composition on MMP are sntalJ. Thus,
they sggestti that at low te,rnperatures, tie vapor pressure, extrapolated if necessa~, is a good estimate of the MMP. Yellig and
Metcalfe0 also offered an MMP correlation for west Texas oits
that depended on temperamre onty. Johnson and Pollin i1 sugge&d
another empirical MMP correlation that included contributions of
the oil moleculaf weight and ammaticity. Helm and JosendaJ also
speculated that aromatic content might influence the l@vfP.Alston
et il. 12 proposed a different empirical MMP correlation that included composition contributions based on the mokutar weight
of the C5+, fmctio jmd the ratio 06 volatile (C, and N2) to intermediate (C2-rhmugh-C4, C02, and H2S) mole fractions. A correlation for the effects of contaminants in the injecti C02 was
reported by Sebastian et af. 13
-Now at U. d Kan,zs.
Cwright 1987S@ely01Pet,oleum
Engineers
SPE ReservoirEngine@g, November 1987

kr a companion paper, 14 we present results of ,an investigation


of the effects of molecutar size and sfmcmre on component pamitioning in C02/hydrocarbon mixmres. That study indicates. that
while the chemical structure of a hytimcarb6n molecufe (paraffin,
naphthene, or aromatic) does influence partitioning in the presence
of C02, for the distribution of molectdar types and ski present
in mzny cmde oits, the size distribution of bydrocxbons present
in the oiJ has the greatest effect. Jtr this paper, we apply that resuk
to the development of a correlation for MMP that accounts for tiiatiorts in crude-oil composition. The correlation proposed here
parallels the one offered by Helm and Josenda17 in that we comelate tie density of C02 at the MMP with a pammctcr ifrat reflects
the composition of the oil. To con.wmct the pamnkfer, we use
component-wrionig data for a COzkmdmil system of the type
presemed i Part 1.14 Jn the secdc+ that follow, we describe the
stmcture of the correlation and the assumptions behind it, present
results of experiments to tsstthe,vaJidity of the assumptions, and
compam correlation predicdomswith measured values. ye ako offer
a simple procedure for estimation of the impact of contmninyus
in the C02 on MMP, also based on the idea that there is a characteristic densi~ of C02 at the MMP for a given ofl.
Correlation of MMPs
Jighter than C13 are individttaly miscible with Jiquid C02.
AJkmes
If an oil contains sufficient hydrocarbons heavier than C,3, two
phases wilJ forin over a wide range of pressures. Jn such cases,
the light hydrocarbons wI1 partition between the phases. The
component-partitioning data reported in Part 114 indicate cle,arly
that for hydrocarbon in Ore C@brough-C30 range, smaller
mokmdes are extracted more efficiently by dense C02. Lmge
molecules are extacted less efficiently, regardless of whether they
are parafiitic. naphtbmic, or arynatic. Became aromatic aid
naphrhenic components occur:predornimntly in heavier fractions,
from which extraction will be poor regardless of molecular type,
and because any aromatics and naphtbettes that do occur in the
C5-through-C12 range frequently have akyl side groups, it ssems
Iiiely that the cyctic character of such molecules has a relatively
smalf effect on the solubilify of those molecutes extracted most effectively by C02. It should be possible, therefore, to account for
variations in oil composition by considering in more defait fk effects of molecular size on partitioning. 14 Component-partitioning
data, Jike those shown in Figs. 10 and 12 of Part 1, can be used
to assess how much more effectively small hydrocarbon mokules
are extracted than large ones. We propose, therefore, a mcdiiica-
tion of Hobn and JosendaYs correlation based on the following assumptions.
479

Loo,

Ij

omined from theparametcras are nonhydrocarbon cotiponenti,


and hence rionba.ked weight fractions in the C?+ tlaction ate
giveri by
lvi

Wjq+=

~,.

,. . . . . . . . . . . . . . . . . . . . . .

. ... . . ...

(7-)

,~wi
log ki = [-4.175

10

x 10-21Ci + 0.7611

where Wi k weight fraction of Carboi Number iiri. ~e oil, and


the sum in the dcmominator of Eq. 2 specifically excludes C 1, N*,
FJ2S, CO>, and &y other nonhydmcarbon mmponents. Here
weight fmctions are used becau.scihey can be obmneddkctJY fmm
chrorwitography measurements made witi a .fl~e io!@ion detegor. Cdir&sion of those data to mole fractions, on the other hand,
wotid require an assumption about molecular weights of iiuiividuaf
carbon-number cuts.
,:
. We adopt tie same restriction used by Yel!.igand Metctife 10and
Hoimtid
Josendti7 concerning the effects of, nb?condensable
gases if @e corcekwionprdkts a value below the bubble@int pressure f3PP), ihen the bubbIepointistken
as the estimate of.the
MMP. Becauw.slim-mte displatemems are geiie+y not.pxfonned
at pressures below the bubblcpoiut, it is not known. whether high
displatirnent efficiencies could be obtained at lower pressures.
Partition coefficients, defined as the weight Jmctidh of hydrocarbons with Carbon Number i in the CO@ch phase dkided by the
wei@ttlaction.bi theoil-rich pbase, =shown in Fig. l. fhevalues
repmtcdinFig. Ihavebcen normali%d tortmovet heamomttof
COzpresent iqeachphase, sothat K~ is given by

. .

,.
.,= ~..
\
:
~N \
s
,:

>:
,!
.x
0.1

0.01
O

1 I
8

1. 1 !
12

.16

CARBON

I
20

24

28

3236

Wco2

NUMBER

1WC02

79. lNormalizedhydrocarbon equilibrium values for CO,{


i?aljamar-crude-oil mixtures at 3,000 psia and 160F.

, . . . . .............................(3)

Ki=

Wio
I WC020

1. The density,of CO,. at the MMP is a knction ofa weight.&


composition parameter krdy.
2, The weighted-composition parameter has the form
37

F=zKiwic2+,

. . . . . . . . . . . ... . . . ... . . . . . . . . . . . . . .

(I)

where Ki IS a weighting factor obtained from partiiion-coefficient


data for mblecules witi i carbon atoms and w~c2+ is the nommlized weight fraction of Component i in the C*+ fraction of the
cmde oil.
3. The weighting yskes, K;, are independent of temperature or
pressure at pressures cfose to the MMP.
This correlation differs from that of Helm and Josenda17 OUIY
in that their p~rameter, tbc weight fraction of C@rough-CSo
hydrocarbons m.tiie C$+ fraction, is replaced by a new pammetcr, a weighted Cz+ fraction, with partition coefficient: ~ tie
weighting fimction. Cdinponent 37 represents C37+ hydrocar~ns.
TIIUS,oils rich in components with large values of K; (relauvdly
smatl hydrocarbommolcculei) wiU have hrge value.s of F, while
heavy oils will have small values. Thus the modified form of tie
correlation accounts for the fact that within the C@hrough-C30
fraction, C IO is ex~actkd more effectively than CM.
Hydrwarbons in the C2-t&ough-C4 range were included in the
calculations botkb~cause tie oils contained substantial amounts b!
these components and because a review of the literature. sug$e@
thatthey contribut~ to the extraction proc~s. 15-17A more debiled
discussion of this poirit is given by SiJva. 18 To caJculate the parameter for .a rccdrnbinid ri?sefvoir fluid, compositions were normaked to remove nonbydrocarbon fractions and Cl. JfCI has any
effect, it probably iaiies the MMP. In the weighted-composition
parameter US$ here, however, the high partition coeffi:ieh; o: C I
would yield a large vake of F, which corresponds to improved
hydrocarbon extraction and therefore Iower MMF. Jn.stead,we limit
the calculation of tbc weighti-composition parameter to those coinF@entst hat increase C02 density when extmcted. Thus, Cl is
480 ..

where Wicoa arid WC0,2 are the weight fficti?ns of Carbon


Nmbe: j and C02 in the C02-rich phase, ~d Wio ~ wc020 we.
ke corresponding weight fractions in the oikich phase. The data
in Fig. 1 wereobtained formixtures of C02with Ma!jamarcmde
oi,, aPernianbasinoit,
at 160F [71-C] and 3,000 psia [20.7
Mpa].l$' Thedemity of C02atthose condb.iijnswas
O.66glcni3,
~
high enough to ensure good extraction of hydfo~rbons from the.
oit. Jmaddition, phase-composition mcasurementi at the same dasity but at a lower temperamre were available for comparison.
Carbon-ktnber distributions for the samples were obiained by gas
chromato~apby according to the procqiime ckscribcd by Orr apd
Taber,2 The~ti@t lkeshowti
Fig. i WaSUSd*tiaViMe
rePr~entitiono ftierelationtipb
ewemcarbonn umber.ndpmtition cocfticierm
log Ki=aCi+b,

.. . . . . . . . . . . . . . . . . ... . . . . . . . . ... . ...(4)

where a= 0.04175 and b=O.7611.


The use of such a relationship implies sevemJ sknpl@iig assurnp
tions. Variations in partition uxfticient witti mixtik compnsiiion
=ei@orti,
asareiff~tio fchangesi ntempera~re? n~pr~mre.
Jn effect, we have assumed that in the neighborhood of the M.MP,
the relative cnse with which molecules of i given size are extra@e@
can reestimated fmmtheline in Fig. I,regaqlless of,tie temperatuie or MMP. ,4n exccrimental veriticiiion of that asstinmtirm wiu
be reported.
Next, we cocrdate the weiehted C,. composition mikdeter, F,
with C02 den.sity atthe W-P fora&m&; ofcmckoik. To ilo
that, we use data gjyen by Helm and Josenda17 to esthate
tbe,relationsbipbehveen C02densityand F. Composition dataasdetaikd
m%. 1 ~s for, however, were not avaikzble. Iristead, HOlm tid
JmeudaJ rep,onti oiJ compositions as wei@ .fracdoim of
C5-tirough-C12, C13-througb-C30, ad CSl+cuti.T ablelgiv?s
weighted C2+ parameters cahdatcd for iach of the O;S forwhich
HOIm md Josendd reported MMPs, .To calculate the. weigb$d
C2+ vake with tie C@mugh-C ,~, C #hrough-Cso, and C3L+
SPE

Reservoir Engineering,November 19S7


--

TABLE 1-WEIGHTED

C2+ PARAMETER

CALCULATED

FROM OATA OF HOLM AND JOSENDAL7

,,

Field

C6-through-C,z

C ,3-through.C20

(weight fraction)

(weight fraction)

0.154
,0.267

0.416
0.384

Farnsworth
Wilmington
Ford Zone

c%, +
(weight fraction)
.

C5-through-CaolC5+
(weight fraction)

Run,
Temperature

at MMP

XW;K,

(F)

(g/cm)

0.43
0.35,

0.57
0.65

0.768
1.001

165
.130
165
165
171

0.778
0.701
0.698
0.651
0.561
0.582
0:592.
0.552
0.515
0.553
0.521
0.420

0.513

North Dundas

0.231

0.469

West Poison
Spider
Dominguez

0.392

0.308

0.30
0.30

0.70
0.70

0.960
1.239

0.365

0.365

0.27

0.73

i .206

Bandini

0.336

0.464

0,20

0.80

1.13.7

Mead-Strawn

0.342

0.473

0,165

0.815

1,205

2,466

150
185
165
,137
135
190
165

1.595

165

Mead-Strawn
(C5-throughC 12 cut)
Mead-Strawn,
(C,-throughC30 cut)

- For these s.mpl;s,

the weightedc,+

PC02

Weighted C2+
Parameter

pmmew wai determinedfmm a detailedcOmPosiIionalanalysls01 Mead*traw..

,,
cuts, a value of Ki correspondingto m averagenumberof carbon
atoms for each cut was used. Tbe weighting value for the
C5-through-C,2 cut was taken to be th~ v.&e for C9; for
C @hrough-C30, the ,value for C22; aid for C31+, tbe value for
C33. A more detailed compositional analysis of two of the oils
showed these to be reasonable values. The more detailed analyses
yieldeda Cz+ parameterof 0.840 comparedwith 0.768 for Farnsworth and 1.2Cilcompared witi 1.205 for M&-Stmwn. The more
detailed analysis was used to calculated C2+ parameters for the
C5-fhrou h-C12 and C#trough-C30 cuts dmcossed by Helm and
Josendal. 3. Fig. 2 ts a plot of the weighted C2+ pammeter vs. the
density of C02 at the MMP for the seven oils. A Iiie through the
points was determined by least squares for F< 1.467. For larger
values, a constant value of 0.42 g/cm3, &e critical density of C02,
was ued. That vatue ensures that for very light oils, the corr.latio gives the critical density of C02 as the density at the MMP.
Tbe restittant relationship between F and density required at tie
MMP is
,q,tMp=-0.524F+

l.189

II

1.2

~.,

&
0
D
0
W
v
&
9

1.0 -

E
6

~,8

E
.
~

~,6 _

FARNSWORTH
WILMINGTON FORD ZONE
NORTH DUNDAS
MEAD-%TRAWN
MEAD-STRAWN 1,5-,,2 <UT]
MEAD- STkAWN lC$,Cm CUT)
WEST POISON SPIDER
DOMINGUEZ

,0

:
E
F
.

0.4

N.
8

~,z

. . . . . . . . . . . . . . . . . . . . . . . . .. (5a)

II

where F< 1.467, and


m,tMP=0.42
.. .......................

0.4

. . . . . . . . . ..(5b)

where F> 1.467.


Representation of the effect of contandnanw in C02 is 6130based
on the idea that there is a characteristic COZ density at the MMP
for a given oil (see the following section for a test of this assumption). The density required for pure C02 at the MMP is evduatcd
fiok the correlation previously descrited. Then the estimated MMP
for a mixtore of C02 with contaminants is calculated as the pressure required to produce the same mixture density at a given tern:
pwmture. Mixture densities cari be calculated with any suitable
equation ,of state (EOS).
Correlation Sun@ry. To apply the proposed correlation, tftefollowing steps ~e performed.
1. Obtain, carbon-number distribution data for the recombined
reservoir fluid. Calculate nhtalized weight fractions with Eq. 2.,
2. Evaluate &eweighted-composition parameter, F, with Eq. 1
and values of Ki given by Eq. 4,
3. Cdmdaie pMMp, the density of C02 at the minimti miscibility prestire, with l?q. 5.
4. Given the reservoir temperature, find the pressure at which
tie C02 density is pm
by use of densi~ data such as those given
by Michels et al. 21 or Newitt et al. 22,
3PE Ses-srvair Engimering, November 1987

0.8

!.2

(.6

F = 2

wiki

2.,0

2.4

2.8

Fig. 2C02 density atthe MMP.

5. Estimate the effects ofconfantinants in the C02 by use of an


EOS or experimental data to estimate the pressure at which the density of the mixture of C02 plus contaminants is the same as the.
density obtained in Step 4.
ff available composition data are not as detailed as called for in
Eq. 1, then average vatues of Ki may be used for lumped cuts. Tbe
carbon number in the middle of a lumped cut gives a reasonable
e.sdmate of the average Ki for the cut. The sum in Eq. 1 may also
be truncated at a carbon number less than C36e.g., at C30. If
so, an average K; for the remaining fraction, C3, +, should be
used. The value obtained fpm Step 4 for i=33 would be a reasona:
ble estimate of an appropriate Ki for the C3, + fraction. ,
Validation of Aaaumptions
A key assumption in the construction of the correlation is that partitioning - for a given C02/hydrocarbon mixture is, controlled
primarily by the density of the C02, regardless of the temperature and pressure at which that density occurs. That assumption
431

TABLE 2EXPERIMENTAL
CONDITIONS FOR PHASECOMPOSITION MEASUREMENTS
FOR MIXTURES OF
CO, WITH MALJAMAR CRUDE OIL

&__
90
160
160
160

Pressure
(psia)
1,200
1.600
2;000
3,000

(!%)
0.66
0.29
0.43
0.66

.,
3

was tested with continuous multiple-contact phase-composition


~=~remet~ W23W for Mdjamar cmde oil at several COZ densities. Table 2 reports temperatures, pressures, and C02 densities
at which measurements were ma&. Comparison of the component
partitioning for the two runs at a C02 density of 0..66 glcm3 is
a test of the assumption that one set of partition coefficients can
& used at different teinpermues and pressures. 19,= Comparison
of the results for COZ densities of 0.29,25 0.43,M and 0.6619.M
glcm3 Mustrates the dependence of component partitioning on
COZ density.
Pseudotemmy phase diagmms for the three experiments at 160F
[71C] are shown in Figs. 3 through 5. Simitar diagrams for phasecomposition measurements at 90F [32CI, including the phase diagram for a C02 density of 0.66 g/cm3 (1,2C0 psia [g.27 MPa]),
are reported by Orr et al. 5 The phase diagrams show the effect
of increasing density @essure) on extraction of hydrocarbons into
the C02-rich phase and on solubili~ of C02 in the oil-rich phase.
At 1,60+2psia [11:0 MPa], the C02-rich phases contained only
small amounts of extracted hydrccarbm?.. At 2,LW2psia [13.8 MFa],
tie-line slopes have, changed as extraction of C3-thmUgfI-C12
hydrocarbons has increased at the higher C02 density. At 3,000
psia [20.7 MPa], both the volubility of C02 in the oil-rich phase
and the extraction of hydrocarbons in the C02-rich phase have increased further.
,
More detailed representations of the component partitioning are
given in Figs, land6through8.
Fig. Ishowsfhedistributionof
normalized partition coefficients obtained in the experiment at lf13F
[71C] and 3,000 psia [20.7 MPa],. where the density of C02 is
0.66. The normafiz.ationto remove C02 from the weight fractions
in theupper and lower phases substantially reduces tbe variation
in partition coefficients with changes in composition. Fig. 6 gives
a normalized partition coefficient for the experiment at 90F [32C]
and 1,200 psia [g.27MPa], for whichtbe CO* densiy was also
0.66 g/cm3. In fhat case, the C02-rich phase was a liquid, while
fh? C02-rich phase at 160F [71C] was a dense supercrificai
phase. Comparison of Figs. 1 and 6 indicates. that the normalized
partition coefficients at constant C02 densi~ were nearly the same,

even ~ough the pressures and temperamres were quite different.


The line shown in Fig. 6 is the least-squares fit to the data shown
in Fig. 1. Clearly, that line also agrees with the dam in Fig. 6. Thus
the assumption that the normalized partition coeftlcients of Fig. 1
can be used over a range of temperatures appem to be justified.
The effect of changing C02 density on partition coefficients is
sAown in Figs. 7 and 8, which show values for the experiments
at 160F U1 C] and 1,600 and 2,000 psia [11.0 and 13.8 MPa].
At 1,600 psia [11.0 MPa], the C02 density was 0.29 g/cm3, too
low to produce efficient extraction of any but the lightest components. The scatter in dm for compcmentsfighter than C5 or heavier
than about %8 is large because the amounts of those components
mesent in one or both of the rdmses were vew small. The&ta show
~onclusivcly, however, hat ~ydrocarbcms $ the range C8 through
C20 were extracted much less effectively at a COZ density of 0.29
than at Ij,66 g/cm3, as the larger negative <ope of the least-squares
line indicates. Similar data for C02 of 0.43 glcm3 are shown in
Fig. 8. Again, the slope of the least-squares line is significantly
more negative. At all C02 densities, large hydrowbon molecul=,
are extracted less effectively than small ones, and at low density
the dtiference between tie extraction of large and small molecuks
is greater. Whiie the values of Ki clearly depend on CO* density,
for co@adon purposes we assume that the data for P =0.66 glcm3
give a good indication of the relative extraction of hydrocarbons
in the neighborhood of the MMP.

Fig. 4Pseudoternaty
phase diagram for mixtures of CO *
and Matiamar separator oil at 160F and 2,ooO psia (compo.
sitions in mole fractions).

Fig. 5Pkeudoternary
phase diagram for mixtures of CO,
wtd Matjamar separator oil at 160F and 3,000 psia (compositions in mole fractlons).

482

3+

CO.mslnn.

,,-<

Fig. 3Pseudoternary
phase diagram for mixtures of CO,
and Maljamar separator oil.at 160F and 1,600 pSia (COtIIpO.
sitions in mole fractions).

SPE Reservoir Engineering,November 1987

!00

.100

k,

1 .[

,1

Ij

Ibg ki = (-9.819

x 10-21 Ci + 0.852%-

,:
10 :
10
. .

;
2

\
~

$
A
\

u
,%

>Q

:
g

2. .

,,
,,

G-

. ..
0,1

0,1

0,01

048,2,62024

0.01

048!2162024

2832?,6

283236
CARBON

CARBON NUMBER
39. 6NOrmaFned hydrocarbon equfbbrium values for COJ
!Jaljamar-crude-oil mixtures at 1,200 psia and 90QF.

The assumption that a given oil requires a characteristic injec.


tion fluid density, even if that fluid is a mixture of C02 and contaminant, was tested with Metcalfes27 data. He investigated the
effect of the addition of such contmninams as C,, H2S, C2, C3,
and G o MMPs for CO, dbvkacernems of two oils at seveml
temperatures. For each of&e oiis, the densiq of the injected gas
at the highest reported MMP is probably the most reliable estimate
of the required density because there is less uncertainly in the density for the systems at the highest temperamre and pressure. The
inherent uncertainty is illustrated in Fig. 9, which reports ijectiom
mixture density at the MMP for one of the systems studied by Metcalfc. Mixture debsities in Fig. 9 were calculated with the keK@ler EOS. 28 The uncertainty arises because the slim-tube displacements are mm with typical pressure increments of at least 104I
psi [689 kpa]. Thus the MMP is determined only to the resolution
of tie pressure increment. At low temperatures, a small change
in pressure can lead to a large difference in density, as is shown
by the error bars correqmndig to the densities of C02 at 100 psi
[689 Wa] above and below the reported MMP. Hence the density
at the MMP is determined less accurately at low temperature. Thus,
despite the scatter, the data shown in Fig, 9 are consistem with the
assumption of a characteristic density at the MMP, despite wide
variations in composition

i9. 7Normalized
Jafjamar-crude-oil

100 ,

NUMBER

hydro-rbon
equilibrium values for
mixtures at 1,600 psia and 160 F.

CO, I

I
g

log k: = [-7.995

0
y

x 10-21CI + 1.037 _

.:
0
$
>,

g >
.3
%
,,
2-.
0. [

Correlation Accuracy
Pure C02. Samples or analyses of oils for which measured
MMPs were available were obtained for 21 oils. 29 ID addition,
MMPs and composition data reported by Yellig md Metcalfe 10
for four oils at several temperatures were used. Table 3 summarizes the results for 25 o,ik, some containing dissolved gas and others
without. Tiie companies that supplied the MMP data for the mcombimd reservoir thids also provided a debited breakdown of the
Iigbt components through C6 and indicated the total amount of
C7+, In some cases, the information given included a hailed
analysis of the C7+ fraction, and in others we amdyzed the. C7+
fraction by sipndated distillation. 20 For tbc calculation in Table
SPE

Res-emoirEngimerimg, November 1987

0,01

04012,162024

28

32

,36

CARBONNUMBER
i9. sNO~afized
tia~amar-crude-oil

hydro-rbon
equilibrium values for co J
mixlwes at 2,OOO psia and 1600F.

483

TABLE 3COMPARISON

Reported
T.
oil

BPP
(psia)

rF)

Waljarnar

Stock-tank oil
Stock-tank oil

Arco D 29

95
126
127

Kubikim
Amarume3Q
Ganado37
Cwtoco Ag
Gulf D=
Arco C=

165

Amoco Am

130,
142

Stock-tank oil
Stock-tank oil
Stock-tank oil
Not given
Not given

63
92
115

Arco B 29
Mobil A29

410
1,660
2,954
Not given

147
160

Amoco S,29
Gulf C29
CSOG A29

320

Measured
MMP
(psia)

Parameter

~WJKI

af:~p

0.705

1.186

0.567,

1,110

0.835

i .689
1.121

0.420
0.601

1.494
1.149

0.420

1,160
1,670
1,570

0.620
0.642

0.025

1,910
BPP

0.095
0.304

2,900
2,150
2,250

2;650

1.695
1.211

0.567
0.420
0.554

0.575
0.904

1.060
2.134

0.633
0.420

0.407
0.287

0.613
0.549

1.602
1.194

0.420
0.563

1,790
2,240

0.083
0.434

0.816
0.759
0.710
0.770

1.370
1.111
1.183

0,471
0.607,
0,569

2,120
3,190
3,170

1.379

0,466

2,590

0.147

0.601

, 1,155

0.5s4

3,440

3,150
2,500

0.227
0.235

0.721
0.696

1,307
1.474

0.504
0.420

3,210
2,690

Not given

Shell A29
Conoco B-

200
220

Mobil B=

220
240

1,269
Not iven
Not given

3,000
2,800

0.220
0.285

1,010
1,140
1,710
1,610

Not ciiven

4.300

245

Not given

3;500

0.320
0.339

0.630
0:749

1.134
1.563

0.595
0,420

4,320
3,000

253

2,225

3,650 ~

0.315

0.770

1.470

0.420

3,110

to192

Not given

T4.
C,+

0.23
N2+C0,

MMP

(psia)

0.100

194

95

C5-through-Cm/Cs+

0.913
0.814
0.711

Gulf B2g

Metcalfe A

(mO[e?&ction)

4,100
890
1,100

3,450
3,050

MMP

Calculated

1,500

Not giyen
Not given

Arco A2g
Yellig and

AND PREDICTED

Weighted C2.

1,100
1,090
2,100

183
194

COnOcO C29
Gulf Am

OF MEASURED

T4

-0.963

>1.696

0.420

-0.963

> i .896

0.420

T4

0.420

T4

Yelfig and
Not given

T4-

,Metcalfe C B 95 to 150

Not given

T4

Yellig and
Metcalfe D 10 95 to 150

Not given

T4.

Metcalfe B;o 95 to 192


Yelfig and

0.9.63

0,23
C, +N2.+C02

-0,963

1,69B
>1.69S

0.420

T4

.T4 - see TaMn 4.

PRESSURE[MPa]
0.8

10

15
I

20
I

Y
0.7

0.6

z
~

0.5

c
?3 0,4
i
.
0 .0,3
.
0.2

0.1

-0

t 500
PRESSURE

2500
(PsI,]

fig. glniect=f
fluid density at MhfPs measured by Metmlfe. 27 Errc.r bars indicate density at the MMp * 100 Psia.

464

3, tie parameters were determined by dc~ed ~dysis as opposed


to the three pseudocomponents used for Helm md Josend81s oils.
MMpk predicted by tic proposed correlation are Compared with
measured values and with medkdons of other correlations in Table
4. Fig. 10 also compares ~richctd with measured values. The BPP
exceeded the predicted MMP for ody two of the oils (Arco B,and
Amoco A). Those oils are identified in Fig. 10. The Amoco oil
contained more than 30% C,, and the Arco oit contained more
than 40% C,. Each oil also contained a considerable C2-throughC4 fraction. For tie &co oil, the measured MMP was, in fact,
close to the BPP. The MMP of the Amoco ol was specified only
a.$the BPP. Because such cases do not really test the performance
of the correlation, those oils were ort?lted from the assessment of
accuracy given kiter. The remaining oils were divided into three
data sem The fmt set conhined the five dead oils,.The second 8roup
included 16 recombined oils. Dktributions of hydmcarbom in the
C2-through-C36 range varied widely in those oils. The last group
contained the 14 MMPs reported for four oik, 811with the same
C,+ fraction, described by Yellig and Metcalfe. 10Because the distribution of iiydrocarbons in the C7+ fraction dld not vary in their
experiments 8nd because the original C7+ fmction was relatively
tight, their data provide a test of the performance of the cOmektion for light oils at a variety of temperatures.
The standmd md average absolute deviations reported in Table
4 for each of the correlations indicate that the proposed correlation
performed significantly better than those given by Yellig and Metcaffe, 10Hobn and JosendaJ, 7 Orr and Jensen,8 and A!ston et af. 12
for the first two groups of oils. For the third group, all the correlations except the EVP correlation jerftmned equally well. The accuracy of the Alston-Kokolis-James correlation could not be
evaluated for most of the oils in the tird group because a breakdown
of components in the C2-duough-C6 fraction was not repmied. 10

SPESeservou Engineedng,Novembei 1987

TABLE 4COMPARISON

~emu~d
T

&l

Yeltig & Metcaffe

OF MMP CORRELATIONS

MMP
(psia)

Pressure
(psia)

% Deviation

Pressure
(psia)

% Deviation

ProPosed

,A1ston et al.z
COrrelatirx

Helm & JosendaJ7

MMP
(psi.)

EVP

% De.laiion

Pressure
(P+

Correlation

% Deviation

PmssJre
(p+

% Deviation

Group 1
Mal@nar5

90

1,100

1,050

i.s

1,130

2,7

1,110

0.9

1,100

0.0

1,110

0,9

Arco D z

95

1,090

{,130

3.7

1,170

7,3

1,290

17.4

1,160

6.4

1,160

6.4

2,360

12.4

1,650

-21,4

1,870

-11:0

1,560

4.0

1,660

6.6

2,420

10,7
41.0

1,570
2,650.

4.7
-35.4

Kubik 30

126

2,100

1;540.

Amacume

127

1,500

1,540

Ganado
Standard
deviatiom %

165

4,100

2,060

-26.7
2.7
-49.8

Average
abs..!u!e
deviation, %

1,690

.19.5

1,680
2,050

12.0
50,0

3,830

25,4

24.8

,10.2

17,5

18.3

8.3

21.4

17,0

15.6,

11,7

GrouP 2?9
Cono,co A

63

890

990

Gulf D

92

1,100

1,100

115

1,910

i ,430

Ako C

10.0
0.0
-25,1

1,010
7,170

i 3.5

6.4

1,400

27.3

1,0?0
1,120

2;160

13.1

2,410

26.2

1,460

13.5
1.3
-23.6

1,010

13,5

1,143

3.6

1,710

-10.5

Amoco A

130

1,660

1,620

1,650

1,320

1,720

1,610

Arco B

142

2,900

!,780

2,030

1,570

1,%0

1,790

Mali A
Amoco B

447
180

2,150,
2,250

2,150

3,550
2,250

62,3

3,?80

47.0

2,040

0,0

2,350

4.4

2,310

4,930

42.9

2,650

3,210

5.2

1,980

0.0
-12.0

Gulf C

183

3,450

2,280

-33.9

2,910

c30GA

194

3,050

2,400

-21.3

3,520

Gulf B

184

3,000

2,400

-20.0

3,070

2,3

3,900

30.1

3,I30
.3,130

Shell A

200

2,600

2,450

-12.5

4,560

62,9

3,s30

36.8

3,300

3,150

2,700

-14.3

3,880

28.3

3,976

Mobil B

220
220

2,700

COnOcOC

240

2,500
4,300

2,920

8.0
-32.i

4,150
5,370

66.0
24.9

3,260

30.4

3,670
4,510

Gulf A

245

3,500

2,960

-15,4

4,220

20.6

2,950

18.3

Arco A

253

3,65o

3,050

-16.4

4,200

15.1

2,950

C.....,

-15,7
15,4

-49.2

5.1

2,240

4.2

2.7

2,120

5.6

-17.4

3,190

3,170
2,590

3.9
-13.7

17.9

S.&o

22.9

22.9

3,210

1.9

54.8
4.6

2,690
4,320

7.6

4,660

33.7

3,000

-14:3

4,960

35.9

3,110

14.8

2.6
4,3

7.5

.0.2

Standarc!
deviation, %

18.6

32.9

29.3

23.0

10.6

Average
absolute
deviation, %

15.8

24.7

26,2

17.2

3.9

GiouP 310
Yelbg and
Metcdfe A

95
,13
150
182

Ye!lig and
Metcalle B

Yelllg and
Met@fe C
%llig and
Met&alfe D

95
.,,6

1,150
7,375
7,375
2,350

1,140
7,400
1,650
2,370

1,?50
1,300

i,150

0.9
1.3
7.3
0.9

1,410
,,770
2,270

1,?40

~ 0.9

1,460

12,3

0,0
2.5
5.8
6.0

1,?50

0,0

1,400

7.7

150

1,850

1,850

0.0

1,770

-4,3-

192

2;150

2,370

10,2

2,200

95

1,100

1,140

3.6

118

7,460

150

1,450
1,975

0,7
6,3

1,150
1,410
1,760

2,3
4.5

95

1,150

0.9

1,150

1,ffiO
1,140

1,160

0.9

1,160

0.9

I,si,o
2,100
3,,380

9,3
72,0
SI. I

1,Uo
1,870
2,3s0

4.7
0.3
0,4

1,510
2,100

73.5

1,670

1.1

42.3

2,360

9,s

20.0

3,080
1,160

5.5

I,lm

.20.0
13.4

1,510
2,100

4.1

1,440

6.3

~ ,870

1,160

0.9

1,i60

1,160

0.9

1,160

0.9

16.2

1,440

10.8

2.8

1,S80
1,740

9.9

2,240

0.0

7,510

16,2

1,#o

i 0.8

2,100

23.5

1,870

10.0

1,300

1,460

i 2,3

1,400

7.7

150

4,700

i ,850

8.6

1,770

4,1

5.5
0.7
5.3
0.9

6.2

5.1

17.8

6.1

4.4

4.1

13.2

4.4

TIIe poorer perfo~ce


of the EVP correlation is not 3u@sing,
betause myy of the temperatures at which MMPS were estimated
fell well oqt+ide the range of temperamres ( < 120F [c 50C]) for
which the EVP co~elation WAS
originally recommmded. 3 I addition, the deviations calculated for the third group show that as
temperature increases, the EVP generally errs with higher MMP
predictions t@n those measured. Fig. 11 provides an explanation.
It summarizes MMPs as a function of temperature for various
values of F, which,, of Course: correspond to fixed value$ of C02
density. Also shown in Fig, 11 is the EVP curve. At low,temperatures, the EVP curve lies close to the line corresponding to a C02
density of 0.42 glcm3, which the weighted C2+ correlation gives
as the required C02 density for all the oils in the third group. As
temperature increases, the EVP curve deviates from the 0.42 curve
toward curves representing higher C02 densities that are required
SPE Resemoir.Emgimering,Novmnber1987

116

Standard
de:.!:., %
Average
absolute
deviation, %

for heavier oils. This deviation explains why, at higher temperatures, the EVP gener#Iy predicts C02 densities that are too high
for the light oils found in tic third group.
The EVP correlation works well at low ttmperamres because it
provides a good estiqate of the pressure required m produce a liquid C02-rich phase. For most oils, hat liquid phase will be dense
enough to extiact hydrocarbons, because typical densities of
C02-rich Iiqtid phases exceed the C02 density required for all but
the heaviest of oils. T& correlation proposed here can also be used
at ternpemmres, below the critical temperamre of COi (88 F
[31,aC]). In such cases (e.g., Conoco A at 83F [28C]), the C02
density at the MMP is evaluated from Eq. 5 x before. If the densig
of liquid C02 at the vapor pressure exceeds the C02 densi~ obtzined from l?q. 5, then the vapor pressure, is taken as the MMP.
Thus this correlation reduces at low temperature to rhe.EVP corn485

ME,
s,mMMP
[W.)
,

,,

,,

TEMPERATURE

,0

z.

,,

40

60

80

OC

,00

,20

,40
i

4CU0
-

35

,/
,.,,, ,.
z
.-

30

,. ..,,, ,

,000

$
,
8
z

25

~
5

,,,,,, m

a.
.

,0;

..,,,,,,

. ,.

E
-

20

,5

to

&
:

moo -,
- ,,

.
,,..
,m.

3m.
MM.(,,!0)

..00
Wmwm,

I~

4.0,

100

)50

200

250

TEMPERATURE.

Fig. lo~omparison
of calculated
Dashed lines indicate *10%.

and measured

MMPs.

lation, as do those of Yellig and Metcalfe 10 and Helm and Josendal. 7 At bigher teniperamres, the EVP, ybich lies in the middle
range of values predicted by the other correlations, is still usefuI
as a rou@ estimate. It should be used, however, only if composition
data are not available.
As Table 4 indicates, only four of tie 35 MMPs reported showed
deviations greater thin 11% and only two greater than 15%. Five
of those six oils were recombined resemoir fluids and, of those,
four were at temperantres grtiter than 190F [88C]. Thus it appears that correlation predictions are somewhat more uncertain for
high-temperature systems containing significtit amounts of dissolved gas. Whether that uncertainly is because the correlation does
not account for the presence of C, is not known. More research
is needed to detineate the role of C,, particularly in hightemperature displacements. In any case, MMPs for most of the
oils were &timatcd to within 200 psia [1379 !&a]. Given the precision with which MMPs are determined, this agreement is probably all that can be expected. Slim-tube displacements kre often
performed with pressure increments of several hundred psia. For
instance, the MMP reported for Shell A was based on slim-tube
emplacement.s conducted at 2,000, 2,500, 3,000, and 3,400 psig
[13.8, 17.2, 20.7, and 23.4 MPa]. Thus, some of the relatively
large deviation for that oil may have been a result of un$eriakity
in the measur~ MMP. In addition, there are frequently differences
between laboratories in experimental technique and interpretation
of slim-tube displacements. 9 Dtierencesin the criteria. for determining the MMP have the largest impact at high temperatures,
where the increase in recovery with pressure is lower (primarily,
we argue, because the density of.C02 inc~eases more slowly with
increasing pressure), and for heavy oils, which often show a g?adual

Fig. 11MMPs
values of F.

as a function

.F

of temperature

for various

,.
increase in recoveiy over wide pressure ranges. 30 Thus there is
undoubtedly some uncertainty in the value reported for ,fhemeasured MfvfP. The values reported here were those given by the companies who provided samples or analyses.
As Table 4 also indicates, the proposed correlation is Subs@tiatIy better than the others for the recombined oils in Group 2.
The improvement is the result of including C2-through-C4
hydrocarbons in the correlation. For ex~ple, F values were recdctdated with norndzed C3+ and C5+ compositions, arid all the
MMPs were recalculated. The resultant average absolute and stare
dard deviations are reported in Table 5. The values change only
for Group 2, because the oils in Group 1 did not contain any
C2-thr0.3hLC4 hydroc=bons and beciuse the oils in Group 3 were
light enough tiwt F exceeded 1:467 for all the oiI compositions and
hence Pwp was independent of composition for those oils. For
the recombined oils, however, the accuracy of MMP predictions
declined sharply when C@fm5ugh-C4 hydrocarbons were ignored.
Hence, we rogue that the pm.sence of C2-Ouough-C4 hydrocarbons
in an oil aids the development of miscibility, though it is also clear
that the abscce of Cz.throu h-C4 hydrocarbons dms nOtPmhibh
development of miscibility.Y5-1
The semitivi~ of the correlation to changes in the normalized
partition coefficients, K;, was also investigated. Values of F were
recalculated with ffie data of Fig. 8, where the C02 density is 0.43
g/cm3, and all MMPs were recalculated. The resultant deviations
for the dead oils improved slightly (because the error for the Ganado
predict@. dropped from 35 to 22%), but the predictions for the
recombined oils in Group 2 were much less accurate. Thus, the
patition coefficient data at high COZ density produced the most
accurate correlation.

TABLE 5EFFECT
OF CHANGES IN THE WEIGHTED-COMPOSITION
PARAMETER ON CORRELATION ACCURACY
Group 1
WeightedComposition
Parameter

Average
Absolute
Deviation

C2+

lt.7
11.7
11.7

c 3.+
C5+
C2+ with K,

6.4

Group 2

Group 3

Standard
Deviation

Average
Absolute
Deviation

Standard
Deviation

17.0
17.0
17.0
10.4

8.9
11.1
20,5
14.6

10.8
13.2
27.7
16.6

Average
Absolute.
Deviation

4.4
4.4
4.4
4.4

Standard
Deviation
6.1
6.1
6.1
6.1

from

pco,
486

= 0,43

SPE ReserwoicEngineering,Noember 1987

m,

.,34

$,-0,,

Fig. 13 Pseudoternary
phase diagram for mixtures of CO,
and Gatado stock-tank oil at 160F and 3,000 psia (compositions in mole fractions).

One of the stock-tank oik, Ganado, showed substantial deviation. AUthe correlations, except that of Alston et al., 12did a poor
iob of Drcdictin2tic MMP for that oil. Holm and Josenda131
agued tiat the ~eg high MMP for Ganado was the result of an
unusual carbon-number dkibution. For example, Fig. 12 compares carbon-number distributions for Farnsworth, an oil used in
comtructing the cmrekdio, and Gmado. The Farnsworth sample
was relatively heavy. Our amdysis showed dmt it contained about
19 wt% C@hrough-C 12and 37 W% C37+. The Gamdo sample
contied about the same amount of C#hrough-C 12(15 w%), but
it showed essentially no hydrocarbons heavier than C36. In contrast, alf the oils used to construct the correlation contained a substantial C37+ fraction, Vpically 20 ,WY. or more. Thus, the
Gamdo oil is unusual, not oPJy because it is relatively lean in the
C@.brough-C,2 range, but also because it does not contain any
C37+ fraction as would be expected for an oil containing little
C#hrough-C12, 32
The absence of C@hrough-C12 hydrocarbons is apparently important in determining the MMP. Hobn and Josenda151 performed
a series of slim-hrbc experiments in which they added naphthenic,
pm@tlnic, and aromatic cuts to Ganado. They found that adding
enough C@hrou&-C,2 to raise the fraction of that cut to a more
typical value brought the MMP in line with their correlation. Furthermore, it did not matter what type of C#mX@-C 12hydrocarbons was added. That result supports the contention that the
distribution of molecular sizes is more important than the distribution of molecular types.
Because the correlation offered here is an attempt to account for
the effects of the distribution of molecular sizes, it is important to
undersmnd why the correlation faifed for Ganado. One additiomf
phasecomposition experiment was performed to examine component partitioning for the Ganado oil. 32 The experiment was performed at a C02 densi~ of 0,66 glcm3. Tbe resultant pseudoternary phase diagram (Fig. 13) shows clearly the absence of
C@hmugh-C,2 hydrocarbons, because all the tie-lines obtained
fie near the C02/C,3 + side of the diagram. Normalized pmtition
coefficients for the Ganado oil are shown in Fig. 14. The values
obtained differed only slightly from those shown in Fig. 1. Re.calcufation of the Ganado MMP with the K; values given by the line
SPE Reservoir Engjneerhg, November 1987

in Fig. 14 increased the predicted MMP only slightly, from 2,650


to 2,780 psia [18.3 to 19.2 MPa]. Thus ,$e hydrocarbons that were
present partitioned in a way that is represented reasonably well by
the data in Fig. 1. f-fence the procedure used to calculate F was
also apparently reasonable. We speculate, therefore, that the inadequacy of the correlation for this oil stems from the fact that the
F and Pcoz was established with OiJ.3contain:
@Itiodip between
ing substantial C37+ fractions. The absence of that fraction in the
Ganado 01 caused the vafue of F m be relatively large because the
weight fraction of each carbon number in the C3-thmugh-C36
range was correspondingly higher. The high value of F then produced a low MMP. E, for example, the Ganado weight fractions
are normalized to include a C37+ fraction of 37 W%, the value
of F decreases to 0.771 and the predicted MMP increases to 4,600
psia [31.7 M.%], Thus, use of the correlation proposed here should
be limited to oits hat have carbon-number distributions dmt include
. reasonable C37+ fraction. If so, the procedure proposed will account for variations in composition in the oil. Fortunately, it is a
simple matter to check the carbon-number distribution experimentally, a task that must be completed anyway if this correlation is
to be used.
Contaminated C02. To test the procedure for estimating the effects of the presence of conta.mimnts in the injected C02, Metcalfes data27 for two oils were examined. No carbon-number
distribution was given for the C,+ fraction, so the CO* density
at the MMP could not be estimated with thecorrelation. fnstead,
the density was determined from plots like Fig. 9. For Oils A and
B, the injected fluids had densities of about 0.47 and 0.46 glcm3,
respectively, at the highest MMPs. MMPs for all the other injected gas titures
and temperatures were then predicted as the.
pressure at which the injected fluid had a densily of 0.47 for Oil
A and 0.46 for 01 B.
Densities of injected fluids were calculated with the Lee-Kestler
EOS28 or were estimated from experimental data. 33-35In a few.
cases, the injected fluids formed two phases at pressures near the
MMP. In such cases, the BPP of the injected fluid was obtained
from experimental data or was calculated with the Schmidt-Wenzel
EOS. 36,Resuks of the predictions are compared with tic measured
MMPs in Tables 6 and 7 and Fig. 15.
As Tables 6 and 7 indicate, all three correlations produced esti-.
mates of comparable accuracy for Oils A and B, though the AlstonKokolis-James correlation did a poor job of predicting the MMP
of Oif B for pure C02. The correlations of AMon et al.2 and Sebastian et al. 13both make use of changes in mixture average critical temperao.ues to estimate the change in MMP. Alston et al. used
weight fractions to obtain average critiwf iernperatures, while Sebastia.net al. used mole-fraction weighting. Both groups used Metcalfes experimental data to obtain a relationship between average
437

TABLE 6COMPARISON

100
90
90
812
80
75
75
50
50
67.5
67.5
45
45
60
60
40
40

10
10
20
20

90
105
135
t 05
135
i 05
135
i 05
i 35
105
135
105
135
105
135

25
25
50
50
22.5
22.5
45
45
20
20
40
40

10
10
10
10
20
20
20
20

AND ESTIMATEO MMPS FOR METCALFSS


density= 0.47 g/cm)27

Alston et al. 12
MMP

Measured
MMP
(psia)

(1%)(A%)
(rwo]b
100
100

OF MEASURED
(Characteristic

psia
1.110

1,000
1,200
1,700
1,600
2,220
2,150
2,700
1,070
1,480

940
1,290
1,490
1,800
1,290
1,490
2,050
2:500
1,760
1,800

1;300
1,700
1,590
2,070
2,1s0
2,850
1,120
1,460
980
1,290
1,330
1,740
1,140
1,490
1,740
2,270
1,430
1,870

% Deviation
11.0

8.3
0
0.6
- 6.8
1.4
5.6
4.7
- 1.4
4.3
0.0
-10.7
- 3,3
-13.2
0.0
-17.8
- 9.2
- 1S.6
3.9

absolute

detiatiort,

oh

Proposed
Correlation
MMP

Sebastian et a/,s
MMP
psia

1,520
2,160
1,940
2,750
1,080
1,530
960

1,360
1,390
1,940
1,250
1,800
1,780
2,530
1:630
2,300

8.5
6.4

Standard deviation, h
Average

OIL A

% Deviation

5.0
2,7
9,s
1.6
0,9
3,4
2.1
5.4
- 7.2
7.8
-3.1
20.s
-13.0
1.2
- 7.4
27.8
10.4
7.5

psia
1,090.

1;330.
1,760
1,680.
2,160
2,100
2,640
1,110
1,390
940,
1,220
1:320
1,880
1,31O*
1,450
1,800
2,380,
1.440
2:070,

oh

Deviation
9.0

10.8
3.5
5.0
- 2.7
- 2.3
- 2.2
3.7
- 6.1
0.0
5.4
-12.6
4.4
1.6
2.7
-12,2
4.8
-18.2
15,0
S.1
6.4

.Calculaled Press,. at whichQ= 0.47 @n,


dotilng
to lhe Lw.Kestler equa!lon.x
. . Estima!edfromthe expenmen!aldam .f Bwlin end KaYa
t CalculatedBP? according!. the Schmidt.WenzelEOS.=

!00

;0

k
,

log

ki =

(-4515

, 10-2) Ci

+ 0.7949

0
g
3
L
.3

,,
.x

0,!

densi~. Tho fact that the proposed correlation performed as well


as empirical correlations obtained by titdng the data directly is additional evidence @d injected-fluid density correlates. strongly with
development of miscibility.
The agreement shown in Fig. 15 suggests that the effects of the
addition of contaminants to CO* or other miscible gas or .of
changes in temperature can be estimated easily if it least some MMP
data are available. For instance, for the oils examined by Metcalfe,
the estimated effe$ts of the addition of C, or N* to CO* ae shovni
in Figs, 16 and 17. Contamination of the C02 by either Cl or N2
raises the MMP appreciably, At low temperatures, N* has a I~ger
effect. At high temperatures, there is little difference between C I
and N2.
As Fig. 15indicates, the effects of contamination on the MMP
can be estimated with an accuracy of better than about 10% as long
as the density required forthe particulx oil is known or can be
estimated. This sort of procedure should be used with care, however, if the changes in composition am large. For instsnce,
Stalkup37 reports a correlation for MMPs for C I displacements.
Calculated demi:ies of Cl at the measured MMPs for the tie oils
for which Stalkup gives experimental results (see Table 8) were.
sll close m 0.15 g/cm3, much lower than the 0.4 to 0.5 glcnt3
typical of C02 systems, though the difference in mol% densities
was smdlec 9.4 moI&/L for Cl vs. 9.1 m 11.4 moles/L for C02.
Estimates of MMPs based on the assumption of cottstant molar
den?.iV did not agree as well with Metcalfes measured values,
however.
Discussion

0,01

ill!!.!
0.?

l!l!l!l!l!l!
81216202*

CARBON

2832

NUMBER

=9. 14 Nomalized
hydrocarbon
equilibrium values
:021Ganado stock-tank mixtures at 3,000 psia and 160

critical temperabue ef the injection gas.and the ratio of the MMP


for the mixture to that of pure C02. Thus it is not smprising that
the two correlations based on averaee critical temnemture fit the
experimental data well. The correla~on proposed here made use
of only one MMP point for each oil to determine tic cha.mcteristic
486

Thecorrelation proposed here estimates more accurately than other


available correlations the effects on the MMP of variatiom i the
composition of light ends (C.#hmugh-C4) of the C5+ iiaction and
of the injected fluid. The compositional dependence is based on
the use of measured normalized patition-coefficient data to weight
the snumnt of extractable material in a crude, and hence, is based
in part Ori knowledge of the physiial behavior of the COZI
hydrocarbon mixtures, although the relatiomhip between COZ dmsity at the MMP and the weighted-composition parameter was still
determined empirically. The correlation is simple, but doei require
more detailed compositional analysis that other correlations. Because those data ciin be obtained in about 1 hour by chromatograSPE Reservoir Engineering, Novemb.m1987

TABLE 7-COWARISON

co,
:mol%) (m%)

100

100
90
90

80

(m%%)

10
10

~o

AIston et al. 12MMP

(m%%)
&

20
20

Af4fJ ESTWATED
MMPS FOR METCALFEi
d~=O.46
g/cm)27

Measured
MMP
(psia)

--

80
20
90-10120
90
io
80

80

9010
9010
,80
-

OF M5AStNtED
(Characteristic

20

psla

120
150
120
150

1,600
1,940
i ,450
1.880
120
1;410
150,
1,S70
1,350
150
1,640
i 20
1,150
1,490
150
120
1.150
150
1;310
150 ~~1>160

1;910
2,420
1,720
2,180
,1,490
1,680
1.430
,1;810
1,520

Standard deviation, %
4verage absolute deviation, %
. MMP cdc.!aled for pure C% with ttw cvrmwan.{
,. Measuredvalue for tiMP 10,PureC& used.

35.5
2%4
27,4
36.3
29,6
26..2
24.0
23.2
28.8

0/9 Oeviation

1,510
1.830
1;420
1,73JI
1,260
1,560
1,110
1,350
1.070
1;290
1,090

33.0
22,6

4.1
- 3.2
1.4
- 7.5
- 4.4
- 25
- 3.5
-10.4
- 7.0
- 1.5
-7.6

OIL E

Proposed
Correlation
MMP

Sebastian et d,3
MMP
psia
.

% Deviation

1,600
1.940

1:560
1,920
1,380
1,680
1,220
1,470
1.250

10.3
2.7
12.1
2.7
3.0
5.6
6.1
1.3
8.7

1;510
1,220

15.3
3.4

psia

% Deviation

3 l,950t
1,550$
2.040$

4.4
0;5
&9
7,9
14,2
16.0.
7,4
5.0
--13.0
4.0

1:610+
2,170$
l,250t
1,660*
1,00@
l,420t
1,130$
l,470t
1,180s

1,8
12.3
0.0

7.8
.6.5

5.6
:4.8

8,8
7.2

AJ$t@n
e! aw

t Calculattiwas,.,. at whichQ-0,48 OIC!W.accnrding


1. !k Le%Kn%rEOS.=
* lnW@lled from!he exPerimenBldata ot Reams, et .s1.=

SE5timatw fromthe axw!ilrralal cifdad PDS!!mwmand KaIz,15

of estimated and IIIOaWred MM$.,S:


for two west Texas oils at a vattefy of temperatures.
Fig. 15-Comparison

~hy, 20,tie &@ ~q~meats

do riotseem excessive. Thus, wifi

a mcdest experimental effort. reasimable estimates of the W


cm
be obtainedm screen resemoir candidates for C02 flocding or to
guide additional slim-tube or phase-Lwhavicmwork. Simple schemes
for using more limited coinpositiooal &ta coold also be devised.
As with dl simple correl~ons for the behavicx of complex systems,
tbii one has limitation. Carbm-nuinber. distitwions should be
scrutinized carefoUy before application of the correlation. For oils
witi distributions roughly simik to time used to c&mm the correlation (w,hichshould include ~st oils), this correlatbn apprs
to produce more accurate MMP estimates than other COrmlations
currently used.
Concfukfom

Dettiled compositioml analyses of C02-rich and oil-rich phases


that form for C02/crude-oiI mixtures along with. similar data for
mixtures of C02 with weU-characterized hydrocarbon mixtures 14
3PE ReservoirEgimminE, November 1987

40

50

60

70

TEMPERATURE

80

90
[-C]

lg. 16EsNmated
MMP% for displacement
tasln oil by C02 cemtamlnated with Cl.

100
,,

of a Petmian

indicate that the distribution of molecular sizes presem in a cmde


oil has a signiiicaotly larger impact on tie MMP than variations
in hvdrcearbon strwmme. We use that conclusion &one with the
i~-that extractim of kwg.a hydrocarbon molecdes I.qkes$more
dense C02 to construct a correlation for MMP. 7 Tests of the per.formmce of the correlation for OUSwiti widely varying impositions lead to the following conclusions.
429

TABLE 8CALCULATED
DENSITY OF METHANE AT
MEASURED MMPS FOR VAPORIZING GAS DRIVES37
T

32

oil

27

(+)

2
3
4
5
6
7

264
242
176
242
142
142
250
212

a
9

MMP

(psi.)
3,310
4,740
5,430
3,234
4,580
4,030
4.440
4;730
,4,640

PMMP
(g/cm)

0.?46
0,150
0,174
0.130
0,152
0.171
0,183
0.154
0,163

, 22
,
i,

PC02 = densiw of Coz, g/cm3


>UMD=
densitv of COT at the MMP, glcm3
.......

,
:

17

Acknowledgments

12

40.

50

60

70

80

90

100

TEMPERATURE

1000

References

PC]

39. 17: Estimated MMPs for displacement


3asin cd by COZ contaminated with N*.

of a Permian

1. The presence in an od of C@hrough-C4 hydrccarb.ens, which


are easily extcacted by dense CO*, aids the development of miscibility, but development of miscibility does notrequire tie presence
of such hydrocarbons.
2.. MMP estimates from the proposed correlation are more accurate thatJ other correlations tested for 35 oils.
3. The effects on MMP of contaminants in the injected COZ can
be estimated easily on the bask of the idea that a given oil requires
a charactmkfic injected-fluid density. The MMP of the contaminated CO, is the messure reauirfd to bring the iniecticm fluid to
the same ~ensity mthat of p~re: CO* at ~e MMP.
4. Use of the proposed correlation should be limited to oils with
carbon-number dishibutions that Ml within the relatively wide range
of distributions used to construct the correlation. Correlation predictions for oils with unusual distributions (Jike Ganado) may be
significantly

less accucate.

Nomenclature
a = constant in Eq. 4, -0.(? 4175
b = constant in Eq. 4, 0.07611
C; = carbon number
F = weighted-composition parameter
Ki = normalized pactition coefflcierd for Carbon

Number i
T = temperature,

F ~C]

weight fraction of C02 in the C02-rich phase


WC02. = weight fraction Of COZ ~ fie Ofi-rich phase
Wi = weight fraction of Carbon Number i in oil
weight fraction of Carbon Number i in
iC2+ = normaked
tie C2+ fraction
wico2 = weight fraction of Carbon Number i in the. C02-rich
phase
Ww= weight fraction of C.wbon Number i in the oil-rich
phase
p = densiLy, g/cm3
WC02

490

This work was supponed by the U.S. DOE, the New Mexico Research and Development fnst., and a ccpsortinrn of companies and
foundations including the Abu Dhabi;.NatL Resecvoir Research
Foundation, Amoco, Arco, Cities Secvice, Concco, Elf Aquitaine,
Gulf, Japan Natl. 011Co., Marathon, Mobil, Petro-Canada, ShelJ,
Sobio, Sun, and Tenneco. We are particularly indebted to Amoco,
Arco, Cities Service,Conoco, Gulf, Mobil, Shell, and Union 011
for providing oil samples and analyses. We are grateful to L.W.
Helm and Unocal for providing deeded analyses of two oils.

1, Hutcbinso., C.A. Jr. and Braun, P.H.: Phase Relations of Miscible


Dkpiaceme.t and OD Recovery, AIChE 3. (1961) 1, M-72.
2. Rathmeil, J.J., SfaJkup,F. I., andHassinger,R.C.: 4ALaboratory Investigation of Miscible Displacement by Carbon Dioxide, paper SPE
3483 presented at fhe 1971 SPE Annual Meeting, New Orleans, Oct.
3-6,
3. Helfferich, F. G.: Theory of Multicomponent, Multi Phase Displacement i Porous Media,, SPEJ (Feb. 1981) 51-62.
4. Gardner, J.W., Orr, F.M. Jr., and Patel, P.D.: The Effect of Phase
Behavior.. CO,-F1cad Displacement= ficiency,, JPT (Nov. 1981)
2067-81.
5. Orr, F,M. Jr,, SiJva, M.K., and Lien, C.L.: Equilibrium Phase Compxidons of CO,lCrude OiJMixtu-Pzl
2 Comparisonof CondnuoUS
MultipkContict and 31im-Tube Displacement Tests,,, SPEJ (April
1983) 281-91..
6. Sigmund, P. M., Kerr, W.; and McPherson, R.E.: A Laboratov and
Computer Model Evacuation of Immiscible CO, Flooding in a LbwTmnperamre Reservoir, paper SPE 12703 presented at the 1984
SPEIDOE Symposiumon Enhanced Oil Recovery, Tuka;April 16-18.
7. Helm, L.W. and JosendaJ, V.A.: Effect of Oil Compasiticm on
Miscible;Typs Displacement by Carbcm Dioxide,, SPEJ (Feb. 1982)
,,0,
., -...
8. Orr, F.M. Jr. and Jensen, C. M.: .Interpretation of Pressure
Compxition Phase Diagrams for CO,lCmde OiJSystems, SPEJ (tit
1984) 485-97.
9. Orr, F.M. Jr. a al.: V-a.boratorj Experiments to Evaluate Field Pm~pecf.s for CO, FJocdhg, JPT (April 1982) 888-98.
10. Yellig, W.F. and MetcaJfe, R.S.: CDeterndmtion and Predicdon of
CO, Minimum Miscibility Pressures, JPT (Jan. 1980) 160-68.
11. Johnson, J.P. and Pollin, JS.: Measurement and Correlation of CO,.
MiscibiU@f
pressures,>,paper SPE 9790 presentedat the 1981SPE/DOE
Joint S9mmsium
on Enhanced Oil Recoven, TtJsa. April 5-8.
. .
12. Alston, R.B., KokoJis, G. P., and James, C. F.: CO, Minimum Miscibility Pressr% A Correlatim for Impwe CO, Streams zmdLive Oil
Systems, SPEJ (April 1985) 268-74.
13. Sebastian, H. M., Wenger, R. S.,and Renner, T. A.: Correlation of
Minimum Miscibility Presswe for Impure CO, Streams,,, JPT (Nov.
1985) 2076-82.
14, Sdva, M.K. and Ox, F.M. Jr.: EtTectof Oil Comwsition on Minimum
Miscibtity Pressure-Pasf 1: Solubilifyof Hydrmadxms in Dense CO,,
SPER2 (NOV. 1987) 469-78.
15. Hohn, L.W. and Jmmdal, V.A.: Mechanismsof Oil Displacement
by Carbon Dioxide, 99JPT (Dec. 1974) 1427-3ti Tmm., AJME, 257.
16. Holrn, L.W. and Josmdal, V.A.; Aulhors, Reply 10 Discussion of
Mechakns of OiJD!spl?.cemnt by Carbon Dioxide, JPT(Gec. 1974)
1437-3% Tram. , AIME, 257. .
SPE Resemoir Engineering, November 1987
,..

17. Metcalf., R.S. and Yarbomugh, L.: ,Discussion of Mcchinisms of


;.Dsp~Ft
by Carbm fliOtid%,, JF7(Dec. 1974) 143ti Trans.,
18, Silva, M. K.: component Partitioning in CO,+Jydrccarbm SystemS
The EffeGIsof ChemicalTyP% MS thesis, New Mexicohsi. of Mining
and TecbIIo]oa, Sc.corm, NM (1984).
19, Silva, M. K., Hutfer, C. E.. and Lien, C. L.: ,4Phase Compositions and
Densities of Mixtures of CO, witi MaJjSeparator Oil at 160F
and 3CKMpsia, Repmt 8S7, PetroleumRecoveryResearch Cenfer,
New MexicoJu.s.of Miningand Technology,Sccorm, NM fFeb. 1985).

20. Om, F.M. Jr. and Takr, J.J.: ,$Displacement of Oil by Carton
Dioxide, final report, Contract No. DOE/ET/12082-9, U.S. DOE,
Bartkville (May 1981).
21. Michels.A.@otzen, A., and *huunnan, W.: The VimmiLYofCarton
DioxideSetW&n OTCan&75C at Pressures up to 2030 Atmospheres,
PhJ.StC. (1957) 23, 95102.
Dbxide.,, 2kemdwu~ic
.Funcdons
22. Newitf. D.M. et .1.: cab
of Gases, F. Din (cd.), B.tterworkL ~ndon (1956) 1, 102-34.
23. Orr, F.M. Jr. and Silva, M.K.: F@ibrium Phase Composition of
CO,lHydrwarbod Mixmms-Part 1: Mezsuremet by a comiuous
Multiple-Cotact Experiment,. SPEJ (A@f 1983) 272-80.
24. Silva, M.K. 4 d.: Phase Compasitiom and Densities of MixNms
of CO, with MaJjamar Separator Oil at PLVFand 1200 psia,,. Repml
81-53, Peuoleum Recovery Resfarcb Cemer, New Mexico Inst. of Mining and Texhology, Sccorro, NM (Nov. 1981).
25. SiJva, M.K., Huiter, C.E,, and Lien, C. L.: -Phase Compositions and
Densitie$ of Mixtures of CO, with MaJjamar Separator Oil at MO-F
and 1603 psi.,,, Repmf 8S- 11, Petroleum RecoveIYResearch Center,
New Mexico Jnst. of Mining and TCCIIIIO1ORY.
SCCOrro,NM (Aprif
,0,.,
..w,.
26. Silva, M.K., MMter, C. E., and f.im, C.L.: Phase Compxitions and
Densities of Mixfures of CO, with Maljamar Separator Ofl at 160F
and 2LN30
psia,,, Reporf 85-8, Pe@Jlem Recovery Research Center,
New Mexico Inst. of Mid?g and Tezh@y, ,%orm, NM (March
1985).
27. Metcaffe, R.S.: Effwfs of Impurities on Minimum Mkcibifhy PresSUKSand Minimum Enrichment k,ek for CO, and Jfich-Oas DqJacements;, SPEI (April 1982) 219-25.
28, Walas, S.M.: Phase @Jli6ninn 61Chemical Enginwtikg, Buttenvwfh,
Boston (1985).

SPE Reserdr

En@neer@,

November

1987

29. Silva, M.K. and Hinter, C.E.: .Cmde Oil Amlysis for MMP co~.
lath.,,, ReparI 85-24, Petroleum Recovery Research Center, New
Mexim 2mt. of Mining and Tdumlogy, Soamm, NM (May 1985).
30. Mmii, S. et af.: Effect of Oil Composition on CO,-Flced Displa&
mem Performance, paw presented* the 1985FmropeanSympxirn
on Enhanced Oil Recovety, Rome, April 16-19.
31. Helm, L.W. andlosendal. V. A.: -Effect of Volatility and Molecular
Structure of Reservoir 03 on Oif Recovery Efficiency Using Carbon
Dioxide,, paper presenled al the 19S4Annual AJChE Mettig, .4na.
heirn. Mav 22.
32. Siiva, M.K., Hwter, C. E., and Lien, C.L.: tPb.aseCnmposition5md
Densities of Mixtures of CO, wifh Ganado Sbxk Tank Oil at 160F
and 3000 psia,, Report 85-12, Petmle.m Recovery ResearchCenter,
New Mexico Jmt. of Mining and Tecbnolom, Sccmro, NM (April
!0,.,
..-,.
33. Bierlin, J.A. and Kay, W.B.: PW-Equilibrium FWperdesof System
carbon Dioxide.Hydrogen Sulfide, Jnd. & E.g. Ch.m. (1953) 45,
618-23.
34. Reamer, H.J-I.efal.: Pbme E@iiria in HydrocarbonSysfmnx Volu.
metric Behaviorof Eibane-CartmnDioxideSystem,Ind & .Ens Clrem
(1945) 37, 688-91.
35. Pceomann, F.H. and Katz, D.L.: Pha.w Behavior of Binary Carh.m
Dioxide-Ptim
Sysfems, Ind. & Eng. Cfwm. (1945) 37, 847-53.
36. Fim.mabadi. A. et al.: EOS Predicdons of Commessibtifv and Phase
E&vim inSysfeIIE
ConkiiningWater,HYAQS
and ~0,, paw
SPE 15674 presemed at the 1986 SPE Annual Technical Conference
and Exhibition, New Orleans, Oct. 5-8.
37. SfalbJp, F.L Jr.: Miscible Di@cemenr, Monogaph Series, SPE,
RiChWi.$0,TK (1983) 8, 128.

S1 Metric Conuefaion Faators


=Oc,

F
(F32)/l.8
psi x 6.894757

E+OO = kpa
SPERE

Ofigina SPE m.wk.t

redwd

for review

S@

27, i9i5.

Papa

acceptedforpubtica.

lionOct. 24, 19ffi, Revisedmmwm-p! recdwd March16,1987.Papar(SPE14%50)


first
Pm50n10d
at !he 19S5AJn,d Technic@
C-mferemeandExhibition
held1. b Vegas
Pam.23-25

491

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