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Miscible Fluid Displacement--Prediction of Miscibility

A. L. BENHAM
JUNIOR MEMBER AIME

W. E. DOWDEN'

W. J. KUNZMAN

THE OHIO OIL CO.


LITTLETON, COLO.

JUNIOR MEMBER AIME

ABSTRACT

The mechanism involved in creating a miscible fluid


displacement of typical reservoir fluids through porous
media by light hydrocarbon mixtures usually involves a
number of mixing and separation stages in the contact
area. This mechanism has been illustrated on ternary
diagrams for miscible displacement of reservoir fluid
by rich hydrocarbon gases.
A relatively simple method has been devised for calculating the approximate conditions for a miscible displacement of reservoir fluid by rich, light hydrocarbon
gases or by LPG mixtures. Miscibility is favored by increased pressures, decreased temperatures, light reservoir fluids and light hydrocarbon-displacing fluids rich
in the heavier components.
The conditions for miscible displacements of five
typical reservoir fluids by various light hydrocarbon
mixtures were determined for a range of temperatures
from 70 to 260F and pressures from 1,000 to 3,000
psia. A correlation of these conditions was obtained
using the variables of temperature, pressure, C,+ molecular weight of the reservoir fluid, C,+ molecular
weight of the displacing fluid, and mol per cent methane
in the displacing fluid. This correlation has been applied
to data appearing in the literature with very good success. A partial check of the correlation has been made
using a step-wise procedure with a windowed PVT cell.
INTRODUCTION
The term, "miscible fluid displacement", may be defined as any oil-recovery displacement process where
there is an absence of a phase boundary or interface
between the displaced and displacing fluids. A water
flood would not be a miscible fluid displacement, although cycling in a condensate reservoir would be. Another example is displacement of oil by gasoline. Not
so obvious, however, are the conditions under which
fluids (such as propane, mixtures of propane and methane, or other similar systems) will give a miscible fluid
displacement of oil.
There are four standard miscible-fluid-displacement
Original manuscript received in Society of Petroleum Engineers
office March 17 1960. Revised manuscript received July 7. 1960.
Paper presented at AIChE-SPE Joint Symposium. Dec. 6-9. 1959.
in San Francisco.
*W. E. Dowden is now with the Continental Oil Co. in Ponca
City. Okla.
'References given at end of paper.

SPE 1484-G

VOL. 219, 1960

processes being used for the recovery of oil frem ~n


underground reservoir-( 1) high-pressure dry-gas mIscible displacement, (2)' rich-gas miscible displacement,
(3) miscible slug using a slug of LPG followed by a
lean dry gas under miscible conditions, and (4) gas
driven-slug process using a slug of LPG followed by a
lean dry gas under immiscible conditions.
The first problem faced by the engineer designing a
miscible displacement process is to determine the c~n
ditions for miscibility. A number of papers have mcluded discussions of the process of obtaining miscibility
in these processes:-s However, methods for calculating the conditions for miscibility have not been published.
This paper includes a method for calculati';1g t~e
conditiens for a miscible displacement of reservoir flUId
by a rich gas (LPG diluted with methane or natural
gas). In this paper, a rich-gas miscible displaceme?t
process is defined as an oil-recove~y. proc.ess III
the reservoir. The cost of a rich-gas miSCIble dIsplacement will be decreased by diluting the LPG with methane or natural gas as much as possible. Therefore, it
is important to be able to predict the maximum dilution
for miscibility.
MECHANISMS
The mechanisms for obtaining miscibility between a
displacing mixture of light hydrocarbons a.nd di.splaced
reservoir fluid often involve a number of dlsplacmg and
mixing stages. As stated previously, the co~t ~f a ric~
gas miscible displacement is decreased by d~lutmg ava.Ilable LPG with natural gas. The problem IS to predIct
the maximum dilution allowed while maintaining miscibility.
To get a picture of the displacing and mixing stages,
it is helpful to consider these complex hydrocarbon
mixtures as pseudo-ternary systems. Graphical representation of a cemplex system as a pseudo-ternary system
can be thermodynamically rigorous if enough variables
are used to describe the character of each pseudo-component in one of the phases. However, ~ven if the
characterization of each pseudo-component IS not cemplete, pseudo-ternary representation does serve to illustrate the mechanism for obtaining miscibility and can
be used to make some general conclusions concerning
the conditions for obtaining miscibility.
A phase diagram for the ternary system, methane229

(n) and a vapor phase of companion (a). As gas is first


injected, it will tend to move both liquid and vapor
until eventually the gas velocity is greater than the
liquid velocity. The first mixing will be between the
liquid (m) and rich gas (RG). The over-all composition of this mixture could be Point IX. This mixture separates into two phases represented by Points nand b.
As more rich gas is injected, it displaces the gas (b)
and mixes with the liquid (n). These may mix to an
over-all composition (3) which separates into liquid (0)
and vapor (c). Injection of more rich gas will result
in displacement of the vapor (c) and mixing of the
liquid (0) with the injection fluid (RG) to form the
mix (y). This continues until injection fluid (RG)
mixes with the liquid (tL at which time a miscible displacement. begins. Injection fluid (RG) miscibly displaces the liquid (t) which miscibly displaces the liquid
(s) which miscibly displaces r, etc. The gases will also
be miscibly displaced by the rich gas; therefore, a completely miscible displacement has been achieved. The
liquids will gradually build up in saturation with displacement until a completely single-phase miscible displacement is achieved.
It may be shown that the leanest mixture which will
give a miscible displacement is represented by a point on
the extension of the limiting tie-line (A-B) which passes
through the critical point (c).
At this point, a discussion of the limitations of pseudoternary representation is in order. It previously was
stated that pseudo-ternary representation can be rigorous
if the character of the intermediates and of the pentanes-and-heavier pseudo-components are completely
specified and held constant in one phase for the diagram. One diagram cannot be used for the representatation of all the stages involved in obtaining miscibility
because it would be extremely fortuitous if the character
of the intermediates in the reservoir fluid in question
were the same as that in the displacing mixture. As
displacing and mixing stages are carried out, the character of the intermediates will change from that for the
reservoir fluid to that for the displacing mixture. During
these steps, the character of the C, + fraction at any
given point may change also as some of these components are vaporized into the gas phase. The manner
in which these things change for a given reservoir will
depend upon the particular material balance placed
upon the system at any point and is principally determined by the relative flows of the two phases. Therefore,
it would appear that any calculation procedure based
upon the pseudo-ternary concept would suffer from

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MOL %

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70

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100

PROPANE

I-TERNARY COMPOSITION DIAGRAM FOR METHANE-PRO


PANE-PENTANE SYSTEM AT 100F AND 1,500 PSIA.'

propane-pentane at lOOF and 1,500 psia, is given in


Fig. 1." Under these conditions, there is a critical
point within the diagram.
Calculated pseudo-ternary phase diagrams for three
different reservoir fluids at different reservoir conditions
of temperature and pressure are given in Fig. 2. These
were calculated using NGAA equilibrium constants.'o
The y axis contains the percentage of methane in
the mixture. The x axis represents the sum of the mole
percentages of ethane, propane and butanes in the mixture. The remainder of the mixture (pentanes and
heavier) may be determined by subtracting the per
cent methane and intermediates from 100. The composition or character of the C, + and C'_4 fractions was
maintained constant in the liquid phase. It should be
noted that the shapes of the phase envelopes for these
systems are similar to the one given for the true ternary
system, methane-propane-pentane, in Fig. 1.
Assuming that a phase diagram of this general shape
is an appropriate representation, the mechanism for obtaining miscibility may be illustrated by reference to
Fig. 3. This figure has been prepared to demonstrate the
mechanism involved in obtaining miscibility between reservoir fluid represented by Point R and an enriched gas
represented by Point RG. The reservoir fluid is in the
two-phase region and has a liquid phase of composition

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INTERMEDIATES COMPOSITION, MOL Of.

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INTERMEDIATES COMPOSITION. MOL %
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RES 1't'lOl

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COMPOSITION INTERMEDIATES
MOL. %

FIC. 2-CALCULATED PHASE DIAGRAMS FOR THRlE RESERVOIR FLUIDS. (A) FOR FLUID B AT 3,000 PSIA AND 182, MW', = 38.8 AND
FOR FLUID C AT 2,200 PSIA AND 250F, MW,=39.4 AND MW H =220; AND (C) FOR FLUID E AT 1,500
PSIA AND 173F, MW, = 49.4 AND MW H = 241.

MII'.-202.6; (B)
230

PETROLEUM TRANSACTIONS,

AIME

these limitations. However, some generalizations can be


made independent of these assumptions. The degree to
which the character of the Co + fraction changes during these stages depends upon the distance of the point
in the reservoir being considered from the injection
point. Positions close to the injection point will change
their C. + character due to vaporization of C" C 6 , etc.,
more than those farther away. Therefore, if one considers a position some distance from the injection point,
the character of the C. + fraction in the liquid phase
probably will not change by an appreciable amount
during its approach to miscibility. It is true that the
character of the intermediate fraction (ethane-butane)
in the liquid phase will vary from an initial value equal
to that in the reservoir fluid to something approaching
that in the injection mixture when miscibility is finally
ac::hieved. However, if considerations are limited to the
region close to the critical point and the associated limiting tie line, the character of the intermediate fraction
will be close to that of the injection mixure. Therefore,
a pseudo-ternary phase diagram (drawn using intermediates of character equal to that of the injection mixture

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A METHOD OF PREDICTION
An examination of Fig. 2 reveals that the limiting
tie line has a negative slope for each of the cases shown.
The sign of the slope of this tie line is determined by
the value of the equilibrium constants for the intermediates as the system approaches its critical composition. If the equilibrium constants are less than one, the
slope is negative; if they are greater than one, the slope
is positive. For most typical reservoir-fluid and displacing-fluid compositions, the equilibrium constants for the
combined intermediates will be less than one in this
region for typical reservoir temperatures and pressures.
This results in negative tie-line slopes. Individually, this
is true for pr<'pane and butane in the range of temperatures to 250F and pressures from 1,000 to 3,000 psi;
however, it is not always true for ethane. At 1,000 psi,
ethane will give a negative slope for the tie line for all
temperatures below lOOF, while the tie-line slopes are
negative at all temperatures below 250 P at 3,000 psi.
However, most typical injection fluids will contain less
than 75 per cent ethane so that this is not a serious
limitation.
These observations on the slope of the ~ie line serve
as the basis for a relatively simple method for caJcuhting the conditions f<'r miscibi1ity. Assuming a tie line
of infinite slope, the limiting injection-fluid composition
for a miscible displacement may be determined at a
certain reservoir temperature and ~ressure, knowing the
mixture of methane, injection-fluid intermediates and
reservoir fluid C.+ which gives a critical point at the
reservoir temperatures and pressure. All fluids having
an intermediates concentration equal to or greater than
that of the critical composition are either immediately
miscible or capable of becoming miscible with the reservoir fluid. Those containing fewer intermediates will
be assumed incapable of achieving miscibility. It was
explained in the previous section that, if the intermediates fraction is assumed to have a character close to
0

l&J

and Co + fractions having a character equal to that


in the reservoir fluid) will have quantitative significance
in the region of the critical point.

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B
MOL

INTERMEDIATES

FIG. 3-MISCIBLE DISPLACEMENT OF RESERVOIR FLUID

VOL. 219. 1960

By

RICH GAS.

231

that in the displacing mixture and the heavier C 5 +


fraction has a character close to that in the reservoir
fluid, the pseudo-ternary representation will be nearly
exact in the region of the limiting tie line. The assumption of a vertical tie line is being used for this calculation, while the light hydrocarbon components individually exhibit negative limiting tie-line slopes for typical
reservoir conditions. Therefore, this method of calculation will give a conservative number for the maximum
safe dilution of LPG with methane.
The limiting, miscible, injection-fluid composition may
be calculated by combining reservoir fluid with various
mixtures of potential displacing-fluid LPG and methane
in various proportions and calculating the critical temperature and pressure for those mixtures. Fig. 4 serves
to illustrate the method using Reservoir Fluid E and
mixtures of methane and propane. In this case, propane
would represent the LPG available for dilution with
methane as an injection fluid. The points on the diagram
represent various mixtures of Reservoir Fluid E, propane and methane. The temperatures and pressures given
for each point represent the calculated critical temperature and pressure for those compositions. Taking Point
A as a specific example of the interpretation of these
points, it represents a composition having a critical temperature of 164F and a critical pressure of 2,837 psi a
and contains 38.5 per cent intermediates, predominantly
propane. According to this method of calculating the
conditions for miscibility, a mixture of 61.5 per cent or
less methane with propane would give a miscible displacement of this reservoir fluid if the reservoir temperature is less than 164F and if the pressure is greater
than 2,837 psia. The points in the diagram may be
cross-plotted to determine the miscibility conditions at
other temperatures and pressures.
It should be pointed out that the accuracy of this
method is heavily dependent upon the accuracy of the
critical pressure and temperature correlation used in
the calculations.

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RESERVOIR
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SI7PSIA

MOL % INTERMEDIATES
FIG. 4--CRITICAL POINTS FOR MIXTURES OF RESERVOIR FLUID
E, PROPANE AND METHANE.

232

CORRELAnON
Five reservoir fluids of different compositions were
chosen for a study of the possibility of correlating the
conditions for a miscible displacement as a function of
reservoir-fluid properties, injection-fluid properties, reservoir temperature and pressure. Table 1 contains a
complete analysis of each of these reservoir fluids. Perhaps the best measure of the differences in character of
these fluids is the molecular weight of the C 5 + fraction.
This ranges from 182.6 for Reservoir Fluid A to 241
for Reservoir Fluid E.
The LPG's or intermediates used in this study are
listed in Table 2. The mixtures designated as 1, 2 and
3 were used for the calculations with Reservoir Fluids
A, B, D and E, while Mixtures 4, 5 and 6 were used
for the calculations with Reservoir Fluid C.
The procedure previously set forward was used for
each series of calculations. The critical temperatures
and pressures were calculated using the Kurata and
Katz method" as modified by Davis, Bertuzzi, Gore and
Kurata. 12 The results were cross-plotted to obtain the
conditions for miscibility at even pressures for a given
reservoir fluid and displacing fluid. The results for the
different reservoir fluids and LPG's were compared, and
it became evident that the controlling variables in determining the miscibility conditions were temperature,
pressure, reservoir-fluid C, + character and displacingfluid C,+ character.
The next problem considered was that of characterizing the C, + fraction of reservoir fluids and the C, +
fraction of methane-LPG mixtures. Due to the limited
results available as compared to the many variables required for a rigorous characterization, the average molecular weight of these fractions was used for the correlation. Using this interpretation, the maximum permissible methane concentration in the displacing fluid for a
miscible displacement of reservoir fluids has been correlated as a function of (1) temperature, (2) pressure,
(3 r C,+ molecular weight of the reservoir fluid and
(4) c, + molecular weight of the displacing fluid.
The final correlation of results is given in Figs. 5
through 16. These figures cover the range from 1,000
to 3,000 psi, 70 to 260F, reservoir fluids having C 5 +
molecular weights from 180 to 240 and displacing fluid
having C,+ molecular weights from 34 to 58.1. Due
to the characterization of the C,+ fraction by molecular
weight and to the use of mixtures of ethane with propane and propane with butane for the calculations, the
correlation may be applied only when the C,+ intermediates in the displacing fluid are composed principally of ethane and propane or propane and butane;
however, small amounts of butane can be tolerated with
ethane and propane, small amounts of ethane can be
tolerated with the propane and butane, and small
amounts of other hydrocarbon substances such as would
exist in a natural gas may be tolerated without sacrificing accuracy. The correlation should not be expected to
apply for large amounts of non-hydrocarbon components in the displacing fluid.
The dashed line in Fig. 5 represents the critical locus
at 1,000 psi for various displacing-fluid C,+ components mixed with methane. Miscibility at temperatures
below this dashed line is assured if the displacing fluid
is a saturated liquid.
In general, the preferred method for using these
charts to predict miscibility involves the following.
1. Calculation of the reservoir-fluid or saturated resPETROLEUM TRANSACTIONS,

AIME

TABLE I-PROPERTIES OF RESERVOIR FLUIDS USED IN STUDY


A

12.93
3.74
7.04
8.68
7.01
6.72
53.88
209
0.8400
144
682

48.96
4.18
1.98
1.36
1.40
1.36
40.76
211
0.848
182
3,206

59.12
9.19
4.55
3.42
C5+ 23.72

Mol Per Cent

CH,
C,H.
C,Ho
c..H'0
CSH12

C.H14

C'lH16 +

MWC1+
Density C1+
Reservoir Temperature, 0 F
Reservoir Pressure, psia
Pseudo-Ternary Components Composition
CH.4, mol per cent
C2-C4, mol per cent
C5

+,

mol per cent

MWC,-,
MWC5+

12.93
19.46
67.61
47.6
182.6

TABLE 2-MIXTURES OF INTERMEDIATES USED IN STUDY


Mol Per Cent
1
2
3
4*
5*
75
38.21 .
48.78
C,H.
C,H8
25
100
25.00
61.79
27.85
C,H'0
75.00
23.37

48.96
7.52
43.52
38.8
202.6

6*
100

*Used only for calculations for Reservoir Fluid C.

ervoir-liquid c,+ molecular weight MW II


2. Calculation of the LPG C, + molecular weight in
the displacing fluid MW/.
3. Determination of the allowable methane content
in the displacing mixture from the correlation chart for
the reservoir temperature and pressure, reservoir-fluid
pentane-plus molecular weight MW II , and injection-fluid
ethane-plus molecular weight MW/.
For example, if the reservoir-fluid C.+ molecular
weight were 200, the LPG were pure propane of molecular weight 44, the reservoir temperature were 180F
and the reservoir pressure were 2,000 psi, then the maximum methane allowed in the displacing fluid would be
determined as 51.5 per cent (from Fig. 7). If the displacing fluid has this much or less methane, miscibility
is assured.
CORRELATION ACCURACY
There are two general experimental methods which
can be used to determine whether a certain injection
fluid would miscibly displace a certain reservoir fluid.
The first method involves carrying out displacement of
the reservoir fluid from a long core using the potential
injection mixture. If the recoveries are high (90 per
cent or greater), miscibility is indicated; however, if
the recovery is low, then the indication is that the
injection fluid used did not miscibly displace the reservoir fluid from the core. The second method involves
carrying out injection, equilibration and displacement
steps in the PVT cell to simulate the mechanism involved in obtaining miscibility between a reservoir fluid
and a certain injection fluid during flow in a reservoir.
There are some published data giving the results of
core flooding studies which can be used to test the accuracy of the correlation presented in this report. A

FIG. 5-PREDICTED PHASE CONDITIONS AT 1,000 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C.+ MOLECULAR WEIGHT OF 180 TO 240.

VOL. 219, 1960

C.+220
C5+ 0.825
250
4,000
59.12
17.16
23.72
39.4
220

46.59
9.72
6.46
3.92
2.21
4.77
26.33
258.7
0.854
148
3,440

15.77
1.54
2.20
4.79
4.36
4.73
66.61
263
0.8511
173
1,128

46.59
20.10
33.31
40.0
221.6

15.77
8.53
75.70
49.4
241

paper by Stone and Crump" contains enough information about displacing fluids, displaced oil and displacement efficiency to be able to make a test of the reliability of the correlation. Table 3 contains pertinent compositions and properties along with the per cent recovery
obtained in a core displacement. The correlation indicates miscibility with composite gas, propane-rich gas,
and ethane-rich gas and indicates something less than
miscibility with separator gas and condensate gas. This
correlates with recoveries of 91, 90 and 96 per cent
obtained with the miscible systems, and 57 and 63 with
the immiscible systems.
A paper recently presented by Wilson" also contains
enough information concerning the conditions of the displacement so that the correlation may be tested. Table
4 contains these comparisons. The correspondence between high recovery and a prediction of miscibility is
good except for Run No.6 where the recovery was 72
per cent, although the correlation indicated that miscibility should have been obtained.
The second method for determining miscibility which
involves the use of a PVT method has been carried out
using Reservoir Fluid E to check the accuracy of the
prediction method and the generalized correlation. This
test was carried out in the following manner so that the
mechanism of displacement in a porcus medium which
produces miscibility was approximately duplicated in a
PVT cell. Recombined reservoir fluid was placed in a
visual PVT cell. If an initial gas phase existed at the
test conditions, this was displaced from the cell at constant pressure. The system then was returned to its origi?al volume, rel?r~ssured with the potential displacing
mIxture to the ongmal test pressure, while being brought
to equilibrium. If a gas phase existed after this step, the
previous displacement, injection and equilibration steps
were repeated until either the percentage gas stopped
decreasing after injection or the liquid swelled to 100
per cent. If the liquid swelled to 100 per cent, the system volume was increased before carrying out another
step. This procedure was followed until either the liquid
quit swelling after injection or the further injection of
fluid at constant pressure did not result in formation of
a ~as phase to indicate the achievement of miscibility.
ThIS procedure forced the system in the cell to follow
TABLE 3-MISCIBILITY CORRELATION APPLIED TO DISPLACEMENT DATA
OF STONE AND CRUMp13
Mol Per
Cent CH,
Displacing Displacement Mol Wt.
Allowed for
Mol Per
Fluid (Gas)
Recovery
C, +
Cent CH,
Miscibility
Miscible
Separator
57
~
~ ~~ ~
63.8
Condensate
63
48.9
67.4
No
64.0
Coonposite
91
49.9
55.0
Yes
60.0
Yes
Propane-Rich
90
42.7
55.9
45.0
Yes
Ethane-Rich
96
30.8
27.7
Crude Oil. 47.5API, MWC5+' 167
Pressure: 2,000 psia
Temperature: 128F

233

close to the saturated-liquid curve on its pseudo-ternary


diagram. The equilibrium gas phase, displaced from the
cell in the earlier steps, was analyzed using gas chromatography and served as an indication of the progress
across the ternary diagram.
Four tests were run with Reservoir Fluid E at 1,500
psia and 173F and potential displacing mixtures of
methane and propane. The conditions and results for
these tests are listed in Table 5.
The displaced-equilibrium gas phase analyses for each
of these tests are given in Fig. 17, where they are plotted as a function of the relative amount of potential
displacing mixture injected into the cell during the
experiment. It will be noted that Test 4 shows that the
70,---,---,---,---,---,---,---,---,---,---,---,
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percentage methane in the displaced-equilibrium gas


phase eventuatly drops below the percentage methane
in the injected fluid. This is to be expected if the saturated-vapor-phase curve of the phase envelope pulls
away frem the 0 per cent C. + line as the critical point
is approached. The correlation indicates that miscibility
with Reservoir Fluid E should be obtained with a displacing mixture of 40 per cent methane with propane
at 1,500 psia and 173 OF. Miscibility was obtained using
30 and 35 per cent methane with propane in Tests 1
and 2, respectively, but was not obtained in Tests 3 and
4 using 41.5 and 46 per cent methane with propane,
respectively. In Test 3, miscibility in the cell was not
achieved; however, the PV curves and the shape of the
vapor-liquid interface at the time the test was stopped
indicated that the system was close to the critical point.
Knowing the original composition of Reservoir Fluid

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~~0--~8~0--~10~0~~1~20~~1+'40~-160~-'80~~2~00~~2~2~0~2~4~0--2~6~0~2~80
RESERVOIR TEMPERATURE, T, OF
FIG. 6--PREDICTED PHASE CONDITIONS AT 1,500 PSIA FOR A
MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C,+ MOLECuLAR WEIGHT OF 180, 200, 220 AND 240.

40~--~-~~--I_--I---I_--I---I---==t'--=_I---H

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is

RESERVOIR TEMPERATURE, T, OF

FIG. 9--PREDICTED PHASE CONDITIONS AT 2,500 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C,+ MOLECULAR WEIGHT OF 180.

fZ

~ 70r-----1-"...~~~~~~

"-w
0l1.

z <5 i
~ ::i!:_ 50r[
f(j)9

o =>

u;

40r

~ 30

'"<t
fu

Cl

20'~0--~--~--~--~~,z,~~I~~~c+.~c+.~o~~
6
80
100
120
140
160
180
200
220
RESERVOIR TEMPERATURE, T, OF

-r--T-

80

~~

'" 301_--I1_--I---j---j---j-~-j--__t--__t--__t~~34
S
0..
<f)

RESERVOIR TEMPERATURE, T, OF

FIG. 10--PREDICTED PHASE CONDITIONS AT 2,500 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C,+ MOLECULAR WEIGHT OF 200.

t--t---+-r--

50

Ui~

58.1

o 2~~O--~OO~--l100~~12~0--~14=0--~16~0--~,8~0~2~0~0~2~2~0~2~4~0~260~~280

FIG. 7--PREDICTED PHASE CONDITIONS AT 2,000 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C 5 +
MOLECULAR WEIGHT OF 180 TO 200.

f-

60r---!----l----"!~.:__.;~"-<I=-~~"""''!'.

54
e 501_--I----I---j---j--~_=c_____.:r"'""":::-t-='"'"""===t-=i:-49
6: 3
44.1
:::;"8 ~ 401_--I---j---j---j---j-----f--""+=-__t----f=-+39

'

0'-"

....!

~::2:

I-

=:l

o......!

40

:::;"-

u ~

'"~

30f--.--'e-----!--+-

<t

20>r---t---t-

<f)

o
80

00

34

RESERVOIR TEMPERATURE, T, OF

FIG. 8-PREDICTED PHASE CONDITIONS AT 2,000 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C.+ MOLECULAR WEIGHT OF 220 AND 240.
234

80

100

120
140
160
180
200
220
RESERVOIR TEMPERATURE, T, OF

240

260

280

FIG. ll--PREDlCTED PHASE CONDITIONS AT 2,500 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C.+ MOLECULAR WEIGHT OF 220.

PETROLEUM TRANSACTIONS, AIME

Run
No.
1

2
3
4
5
6
7

TABLE 4-COMPARlsON OF MISCIBILITY CORRELATION PREDICTION WITH "WILSON'S"" CORE FLOODING RESULTS
MWC, + in
Per C.o' CWo in
Displacing
Reservoir Fluid
Displacing
Per Cent
Per Cent CH,
Fluid
C.+MW
Fluid
Recovery
Allowed
--2-3-39
60
27
228
39
60
28
27
228
39
60
32
27
228
7
39
98
27
216
43
42
45
36
216
33
43
72
36
21
216
44
100
36

---m-

E along with the amount placed in the PVT cell, it was


possible to calculate the over-all composition of fluid
in the cell at any time along with the composition of
the equilibrium vapor and liquid phases after each
stage, Pig, 18 contains a plot of the phase diagram obtained in a test in which the injection fluid was made
up of 35 per cent methane and 65 per cent propane. It
will be noted that the phase-boundary curves are quite
smooth and that the tie lines have negative slopes.
These properties of the phase diagram fulfill the basic
assumptions made in deriving the method for calculat..

Miscibility
Predicted?
No
No
No
Yes
No
Yes
Yes

TABLE 5-CONDITIONs FOR PVT DETERMINATION OF MISCIBILITY USING


RESERVOIR FLUID E

Pressure, psia
Temperature, OF
Mol Per Cent Methane
with Propane in
Iniected Fluid
Miscibility?

1,500
173

1,500
173

30
Yes

35
Yes

3
~
173

4
1,500
173

41.5
Not Quite

46
No

ing the conditions for miscibility described in this paper.


At this time, these PVT tests of miscibility indicate
that the correlation is accurate to within 5 per cent for
the condition studied.
Recent unpublished data obtained on a reservoir fluid
at 250 P using an injection fluid containing considerable amounts of ethane indicate that under these conditions the assumption of a vertical tie line is in error.
However, since the critical point usually lies close tc
the 0 per cent C,+ line, the error due to this discrepancy should not be extremely large. However, if the injection fluid does contain ethane and if the temperatures
are relatively high, this effect should be taken into account by using less methane than indicated by the correlation.
It should be emphasized that the method of calculation and the correlation included in this paper represent a first approximation to the limiting conditions
for miscibility. They should serve as a useful tool in

80~=~--~-~

'-'

71----'~~~~~~~-~+--+--+---+--+--+-'-'
c::

6~

60,1---+--+-"-..c+-~+-"'~~~-R;.::.y

...J

~ ~_ 50,1---+--+--+--.p...~-+-':::"'J-....::o,k-=hc-'p_____5B.l
M
e
49
~

u;

;r::;;"-~

40,i---i--i--i---+_-+_--'"k--+_--'"1-=-+_---'f-44 .1

39

u<!>

30f--+--+--+--+--+--+--+-...cch:--+--+-----1
34

...J

~ Z~~0-"8~0-~IOO~~12~0~~14~0~~16~0~~18~0~~20~0~~22S0~o24~0~'26~0~~200
o

RESERVOIR

TEMPERATURE, T, OF

FIG. 12-PREDICTED PHASE CONDITIONS AT 2,500 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C.+ MOLECULAR WEIGHT OF 240.

~ 80'f---..S::~~~~

"-W
00.
2

<5

t--i'"",,-r~'t-2:::f2::::-F:::::::t::===:f ~~' !

70,i---i--+_'::""f"'-~-R~~~

~::;;

49

~ e- 6o'f--+--+--+--+-~h"""":::p..-='f=____~~~~ %~.1
1~.1

O::J

~~

u<!>

'_-+-_+~-+-~-+-=--+-_-=j'

39
50,f--f--+--+--+--+--+--+-~?-~~-+-~

34

44 I_
39
34

j4~~0~o8~0-'lk,OO,-'1~20,-'14~0,-'16~0.-"~OO.-020~0.-~22bo~o24~0'-~26~0'-~280
~
RESERVOIR TEMPERATURE, T, OF

280

FIG. 15.-PREf,ILl'LD PHASE CONDITIONS AT 3,000 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C 5 + MOLECULAR WEIGHT OF 220.

FIG. 13-PREDICTED PHASE CONDITIONS AT 3,000 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C.+ MOLECULAR WEIGHT OF 180.

90r---,---,---,---,---,---,---~--,---,----,--,

I
U

G 90~-_-~

!zw

....z

80t-~~~~

<>:

~ 80,1---""'~~k-

LLW

o a.. 70

66
i=

1-.-+--+--+---+-.:::,..d--':-,....-!O-::::"..j...;;:?--k2-~==-+~~.I
49
44.1

50f-----~--+_--+_--+_--+---+---'"~~+_--+_~~39

34

~ 4~~0--~---~-~-~--160~-,80~~2~OO~-~2~2~O~2~~~~2~OO~~280

e,

TEMPERATURE, T, OF

FIG. 14-PREDICTED PHASE CONnITIONS AT 3,000 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C. + MOLECULAR WEIGHT OF 200.

VOL. 219, 1960

~~

;n~
o~

60

56.1

~;;: 50f--+---+---I~-f_-~;:--t__=~~---=-:p-""""":!---'='f49

ao<!>

44.1

~ 40f---t---+_--+_--+_--+---+---~~+_--4_=~39

...J

34
6a. 306'';;0-'8;,;0~'1*00~'1*'20~'1-:!c40~-I;60;;-~,80;;-~2o:!:OO:;;-~2o:!:2;;-0~2~4-;;-0-::!26"'0~~200
RESERVOIR TEMPERATURE, T:F

FIG. 16-PREDICTED PHASE CONDITIONS AT 3,000 PSIA FOR A


MISCIBLE DISPLACEMENT OF A RESERVOIR FLUID CHARACTERIZED BY A C.+ MOLECULAR WEIGHT OF 240.

235

70

pMETHANE IN

DISPLACED GAS

-------~Q

RUN 4

f----.,~-t---+---..---2-

+-

METHANE

- j----1------j---~+_-_1

_ Y8.0PANl'-. -C
3

RUN 3
!-

u;
o

20

o=-

70

0..

~ 60

<f)

<!

C>

~SO

RUN 2

0..

QPA~~ ___MEIH!,NE..

-' 40
0

=-

30
20

-C

f---+-----f---i---- --t ~- t-------j----t

70

-- -.- - - - - l'BQPAHE' - - --C

~METHANE

~ 60
w
~ 50
w

'-.
RUN

0..

-,40
0

'" 30

stant-pressure and temperature ternary diagrams to illustrate the complete process rigorously. However, in
determining the limiting conditions for miscibility, the
conditions close to the critical point are the important
ones; nearly exact representation will be achieved by
using a C,_, intermediate fraction having a character of
that in the injection mixture and a C.+ fraction of
character equal to that in the reservoir fluid.
The limiting tie line is defined as a straight line drawn
tangent to the phase envelope in a ternary-composition
diagram at the critical point. Miscibility will be achieved
between a reservoir fluid and an injection fluid if the
point representing the latter lies to the intermediatecomponent side of the limiting tie line.
Typical reservoir fluids and injection mixtures give
negative slopes for the limiting tie line. Knowing the
critical composition for the reservoir pressure and temperature, a conservative figure for the maximum
methane concentration allowed in the displacing injection fluid is usually obtained by assuming that the minimum C,-4 intermediates allowed are equal to that existing in the critical composition. This is equivalent to
assuming a vertical, limiting tie line.
The approximate conditions for miscibility for five
different reservoir fluids were correlated using the reservoir temperature and pressure, reservoir-fluid C,-+
molecular weight, injection-fluid C,-C molecular weight
and the mentane concentration in the injection fluid.
This correlation may be used to predict the approximate conditions for a miscible displacement of reservoir
fluid by rich gas for temperature between 70 and
260 o P, pressures between 500 and 3,000 psia, reservoirfluid C, + molecular weights between 180 and 240
and displacing-fluid C, + molecular weight between
34 and 58. The correlation was partially checked using
published data. It also was checked using a stepwise
determination of miscibility using a PVT cell. The
correlation should be used with caution when the injection fluid contains ethane.
One general conclusion derived from the correlation is that miscibility between reservoir fluids and
rich-gas injection fluids is favored by high pressures,
low temperatures, light reservoir fluids and light hydrocarbon-displacing fluids rich in the heavier components.
The calculation method and correlation should be
extremely useful for the preliminary evaluation of field
rich-gas miscible-displacement projects and shOUld serve
as a starting point for laboratory studies if desired.
4

20
0

RELATIVE VOLUME INJECTED, CC


CC O~IGINAL RESERVOIR FLUID

10

12

INJECTED

14

FLUID /

FIG. 17-COMPOSITIONS OF DISPLACED EQUILIBRIUM GAS


PHASE IN PVT TESTS OF MISCIBILITY.

preliminary evaluation of the process. The basic method


of calculation is based upon a limiting tie line of infinite slope. This usually will result in a conservative
number for the maximum permissible methane concentration in the injection fluid; but, under certain conditions such as high temperatures and the presence of
ethane in the injection fluid, it can lead to a non-conservative number. The calculation is based upon the accuracy of the critical pressure and temperature correlation used. Preliminary studies of the accuracy of the
correlation, as given by published displacement and
PVT studies, indicate that the correlation does give answers that are fairly reliable. A complete evaluation of
this work can result only from published comparisons
furnished by other people working in this research area.
CONCLUSIONS
The mechanism involved in creating a miscible displacement of typical reservoir fluids through porous media by light hydrocarbon mixtures usually involves a
number of mixing and separation stages. It is necessary
to take these processes into account in making predictions of miscibility during a displacement involving the
two fluids. If these complex mixtures are considered as
pseudo-ternary mixtures of methane, intermediates
(ethane, propane, and butane) and heavy components
(pentanes and heavier), the mechanism for obtaining
miscibility between reservoir fluid and various injected
fluids may be shown. Pseudo-ternary representation is
rigorous if the pseudo-components are completely characterized in one phase. Since the character of the pseudo-components actually change during the displacement,
it would be necessary to use a large number of con236

NOMENCLATURE
MW ll = average molecular weight of C,+ portion of
reservoir fluid
MW, = average molecular weight of C,-1 portion of injection fluid.
REFERENCES
1. Hutchinson, C. A., Jr. and Braun, Philip H.: "Phase
Relations of Miscihle Displacement in Oil Recovery",
Paper presented at AIChE-SPE Joint Symposium in San
Francisco (Dec., 1959).
2. Slohod, R. L. and Koch, H. A., Jr.: "Which to Use-'I'
Type or 'M' Type-in High Pressure Gas Injection ?".
Oil and Gas Jour_ (April 6, 1953) 51, 84, ll5.
3. Slohod, R. L. and Koch, H. A., Jr.: "High-Pressure Gas
Injection-Mechanism of Recovery Increase", Drill. and
Prod. Pmc., API (1953), 82.
4_ Whorton, Leonidas P. and Brownscomhe, Eugene R.:
U. S. Patents 2,724,437 and 2,724,438 (Nov. 22, 1955).
PETROLEUM TRANSACTIONS, AIME

901---~

80\-----l--~

EQUILIBRIUM
VAPOR
70~----~----+----+~

/' INJECTION
FLUID
EQUILIBRIUM
30 8~-........
..... LIQUID

.....

--

'RESERVOIR
FLUID
10~---l~~~----~----4-----+---~~---+---~----~

10

20

30

40

50

60

70

80

90

100

INTERMEDIATES, MOL %
FIG. 18-ExPERIMENTAL PHASE DIAGRAM FOR RESERVOIR FLUID E OBTAINED DURING STEP-WISE DISPLACEMENT TEST IN PVT CELL
-MISCIBLE DISPLACEMENT BY RICH GAS; RESERVOIR PRESSURE, 1,500; RESERVOIR TEMPERATURE, 173F.
5. Koch, H. A., Jr. and Hutchinson, C. A., Jr.: "Miscible
Displacements of Reservoir Oil Using Flue Gas", Trans.,
AIME (1958) 213, 7.
6. Clark, N. J., Schultz, W. P. and Shearin, H. M.: "Con
densing Gas Drive, Critical Displacement Process-New
Injection Method Affords Total Oil Recovery", Pet. Engr.
(Oct., 1956) 28, BAS.
7. Clark, N. J., Garms, K. M., Moore, J. L. and Shearin,
H. M.: "Miscible Drive-Its Theory and Application",
Jour. Pet. Tech. (June, 1958) X, No.6, 11.
8. Crump, James S.: U. S. Patent 2,880,801 (April 7, 1959).
9. Carter, R. T., Sage, B. H. and Lacey, W. N.: "Phase Be
havior in the MethaneProponenPentane System", Trans.,
AIME (1941) 142. 170.

VOL. 219, 1960

10. Engineering Data Book, Natural Gasoline Supply Men's


Association (1957).
II. Brown, G. G., Katz, D. L., Oberfell, G. G. and Alden, R.
C.: Natural Gasoline and the Volatile Hydrocarbons,
NGAA (1948).
12. Davis, P. c., Bertuzzi, A. F., Gore, T. L. and Kurata, F.:
"Phase and Volumetric Behavior of Natural Gases at Low
Temperatures and High Pressures", Trans., AIME (1954)
201,245.
13. Stone, H. L. and Crump, J. S.: "Effect of Gas Composi.
tion Upon Oil Recovery by Gas Drive", Trans., AIME
(1956) 207, 105.
14. Wilson, J. F.: "Miscible Displacement-Flow Behavior
and Phase Relationships for a Partially Depleted Reser
voir", Trans., AIME (1960) 219.

***

237