You are on page 1of 14

HIIIDPHAS[

EOglHDIHA
ELSEVIER Fluid Phase Equilibria 139 (1997) 311-324

A new technique of vanishing interfacial tension for miscibility


determination
D a n d i n a N. R a o *
HydroFlame Engineering Consultants. 196 Hawkwood Blrd. N.W., Calgary, Alberta, Canada, T3G 2TI
Received 16 December 1996; accepted 17 June 1997

Abstract

A new technique is presented in this paper to enable rapid and cost-effective determination of minimum
miscibility pressure and composition. This new technique, called the Vanishing Interfacial Tension (VIT)
technique, consists of measuring the interfacial tension between the injected gas phase and the crude oil at the
temperature of the reservoir and at varying pressures a n d / o r enrichment levels of the gas phase. These
interfacial tension measurements are carried out by computer digitization of the image of the profiles of the
sessile and pendant drops of crude oil enclosed in the surrounding medium of injection gas. By fitting these
actual drop profiles with the iterative solution of the Laplace capillary equation, the value of interfacial tension
is obtained at each pressure or enrichment level. By making a plot of the interfacial tension against the
independent variable (either pressure or enrichment), accurate values for the minimum miscibility pressure
(MMP) or composition (MMC) are then obtained by extrapolation to zero interfacial tension. The paper
provides experimental evidence for the validity of the new VIT technique by comparing the results with
slim-tube displacement tests. While the slim-tube technique requires 4 - 6 weeks for obtaining MMP or MMC,
the VIT technique yields the MMP in about 4 - 6 h, and MMC in about 16-24 h. The paper also presents an
application of the VIT technique to optimize injection gas composition for an Alberta field project. The Alberta
Energy and Utilities Board (a Government of Alberta agency) has accepted the optimized composition based on
the VIT technique. © 1997 Elsevier Science B.V.

Keywords: Experimental method; Liquid-Liquid equilibria; Interfacial tension; Miscible gas flooding; Crude oil

1. I n t r o d u c t i o n

Operating at or near the conditions of miscibility of the reservoir crude oil with the injected gas
stream (either natural gas or carbon dioxide) is essential for the technical and e c o n o m i c success of the

* Corresponding author.

0378-3812/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved.


PH S0378-38 l 2(97)00 180-5
312 D.N. Rao / Fluid Phase Equilibria 139 (1997) 311 324

improved oil recovery processes involving gas injection. Therefore, assessment of miscibility pres-
sures and compositions at reservoir temperature through laboratory tests constitutes an integral part of
the design of the gas injection projects.
Miscibility between two phases means that there is no interface separating the phases, or in other
words, the value of interfacial tension between the two phases is zero. However, none of the presently
used techniques for miscibility evaluation, namely, the Slim-Tube Test (STT), the Rising Bubble
Apparatus (RBA), or the method of constructing Pressure-Composition Diagram (PXD), is capable of
yielding direct and quantitative information on interfacial tension, and, hence, on miscibility, between
injected gas stream and reservoir crude oil at reservoir temperature and pressure. The new technique
described in this paper, on the other hand, is entirely based on acquiring this direct evidence of
vanishing interfacial tension as the miscibility of the two fluids is approached. Thus, it fills a void that
has long been existing in this field of miscibility evaluation. For petroleum reservoirs, miscibility is
defined as that physical condition between two or more fluids that permits them to mix in all
proportions without the existence of an interface [1]. Two fluids that mix together in all proportions
within a single fluid phase are miscible [2]. The term, 'miscible 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 [3]. This absence of an interface between miscible fluids means, in
terms of a variable amenable to easy laboratory measurement, that the interfacial tension between the
two miscible fluids is zero. Therefore, it may be argued that the condition of zero interfacial tension is
necessary and sufficient to attain miscibility.
An obvious question then, is what happens to interfacial tension when two fluids approach
miscibility from an initial immiscible state. In the initial immiscible state, the two fluids are separated
by an interface possessing a certain interfacial tension governed by the thermodynamic conditions
(pressure, temperature and composition) of the system. For the two fluids to approach miscibility,
their interfacial tension must approach zero. This means that the thermodynamic state of the system
must change, or that changes in either pressure, temperature or composition will have to be imposed
on the system under consideration. This is exactly what is involved in the measurement of minimum
miscibility pressure and composition associated with improved oil recovery processes involving
injection of gases. Thus, it appears reasonable to think that we can closely follow the approach to
miscibility of fluids by simply following the behavior of their interfacial tension as a function of the
imposed thermodynamic variable. This is the fundamental premise of the new Vanishing Interfacial
Tension (VIT) technique to determine miscibility pressure and composition at the temperature of the
candidate reservoir.

2. Apparatus and procedures

2.1. Interfacial tension

The schematic diagram of the apparatus used in this study is shown in Fig. 1. It consists of a
high-pressure high-temperature cell, made of Hestalloy, with glass windows on opposite sides. The
cell is capable of operating at pressures up to 70 MPa and temperatures up to 200°C. The glass
windows allow the capture of drop/bubble profile images by using a light source on one side and a
camera system on the opposite side. Elevated pressures are achieved through the use of fluids
D.N. Rao / Fluid Phase Equilibria 139 (1997) 311-324 313

LIGHT
SOURCE
THERMOSTATEDOVEN

CALIBRATION _ _ __ I
SPHERE I '!'

PYCNOMETER
112
UJ

---T-- ~
'! /,il 1

BRINE ~-1
RESERVOIRL-~ I
PUMP ]~

LENS
COMPUTER NTSC MONITOR
BELLOWS

m __ CAMERA

Fig. I. Experimental system used for interfacial tension measurements at elevated pressures and temperatures.

handling system consisting of pistoned pressure-vessels, high pressure pumps and a back-pressure
regulator. Elevated temperatures are achieved by the use of a Blue M oven as a source of heat. The
camera system is connected to an NTSC monitor and a personal computer equipped with an image
capture board and the image analysis software including the A D S A program to iteratively calculate
the interfacial tension. The cell details of Fig. 1 are quite similar to the contact angle cell described
elsewhere [4]. One major difference from the contact angle apparatus is that only one quartz crystal is
used (instead of two parallel crystals in the contact angle tests) to position an inert ruby sphere at the
desired location within the view of the camera for the purpose of image calibration. The quartz
surface also serves as the solid phase for sessile drops/bubbles to rest on during sessile drop image
analysis experiments. However, only the pendant drop technique was used in this study which
consists of oil drops hanging from a capillary tube within the surrounding gas space. The bottom part
of the optical table supporting the test cell and the camera system is loaded with sandbags to minimize
vibrations and enhance clarity of the profiles of the drops and bubbles captured on the computer
hard-drive. The cell housing also contains a live oil reservoir equipped with a piston driven by high
314 D.N. Rao / Fluid Phase Equilibria 139 (1997) 311-324

pressure water to enable the maintenance of the fluids at reservoir temperatures and pressures at all
times during the course of the experiments.
Interfacial tension, being very sensitive to fluids contamination, imposes cleanliness as a basic
requirement during experimentation. The titanium and Hestalloy lines and valves were flushed with
large amounts of water to remove any excess brine or salt which may have accumulated within the
system. A dilute solution of nitric acid and hydrochloric acid can be used when required. The lines
were then flushed with acetone to remove residual water. The lines were then flushed with methylene
chloride (to remove trace hydrocarbons), and with acetone to remove any remaining methylene
chloride. A final flush with high purity HPLC grade isopropyl alcohol was used to remove any
remaining contaminants. The lines were then dried by purging with high grade nitrogen. The titanium
parts of the cell, crystal holders, and injection needles were cleaned using the same sequence of
solvents. The quartz windows, the ruby calibration sphere and the quartz crystals were cleaned in a
heated bath of sulphuric acid and ammonium persulfate for 2 h. These components were subsequently
rinsed with deionized water.
The density of live and stock-tank oils, required in the calculation of interfacial tension, was
measured using a PAAR DMA 45 density meter equipped with a PAAR DMA 512 external cell. The
external cell is housed within an oven which is capable of maintaining the cell at the desired
temperature. The outlet of the cell is connected to a back pressure regulator. The inlet of the cell is
connected to a pump which introduces the fluids into the cell at the desired pressure.
The density of the gas phase, at each enrichment level, was calculated using a commercial PVT
property package [5] using the chromatographic compositional analysis of the gas samples collected
from the optical cell.
Images are acquired using the digitization apparatus in the following manner. Drop images are
displayed and centered on the NTSC monitor. The video camera, optical cell, and light source are
arranged in a collinear fashion. When the light intensity is at the appropriate level, so that it is within
the dynamic range of the video camera, the drop profile can be brought into focus. The image of the
drop profile is then captured in a frame buffer and its digital representation is then saved on the PC.
Each image is individually recalled and analyzed. First, a low pass digital filter is used to smooth
out the jagged interface. Then a Laplacean two-dimensional second derivative is applied to the filtered
image to identify the drop edge. The image is now scanned along the drop edge. This supplies the
x-y coordinate data for a representation of the drop interface. The coordinate data are converted into
polar coordinates and then fitted using the method of cubic splines. Once the data has been
appropriately fitted, the fitted function is then converted back into Cartesian coordinates. It is this
fitted function that is used to obtain up to 50 or 60 points on the interface as input to the ADSA
program for calculating the interfacial tension.

2.2. Axisymmetric drop shape analysis (ADSA) technique

The theory of Laplace indicates that an attractive force exists between all atoms and molecules
bringing them as close together as the repulsion forces arising from overlapping electron shells will
allow. Both Young and Laplace recognized that the attraction forces between molecules would set up
a pressure difference across a curved liquid-fluid interface. Their derivation of this pressure
difference in terms of the liquid surface tension in the form of Eq. (1) below, forms the basis of all
methods of measuring surface and interfacial tension [6]. The principle of balancing the pressure
D.N. Rao / Fluid Phase Equilibria 139 (1997) 311-324 315

difference across an interface with the gravitational force has been known for over two hundred years,
resulting in the well known terminology of sessile (or captive) and pendant (or hanging) drops and
bubbles.
The method of Rotenberg et al. [7], known as the axisymmetric drop shape analysis (ADSA)
technique, relies on numerical integration of the Laplace capillary equation,
AP = T(1/R, + l/R2) (1)
where Y is the interracial tension, R 1 and R 2 are the principal radii of curvature and A P is the
pressure difference across the interface. The strategy employed in the ADSA technique is to construct
an objective function which expresses the deviation of the physically observed curve of the profile of
the interface from a theoretical curve which satisfies the above equation. This objective function is
then minimized numerically using the method of incremental loading in conjunction with the
Newton-Raphson iteration method. The input data required are the local gravity, densities of liquid
and fluid phases, and several accurate coordinate points that describe the observed profile of the
interface. Further details can be obtained from the reference of Cheng et al. [8].
The ADSA method differs from the others in that (1) the objective function, which is a measure of
the discrepancy between the calculated Laplacian curve and the measured curve, is the sum of the
squares of the 'normal' distances between the measured and the calculated curves; (2) the drop shape
can be measured from any convenient reference frame; (3) no particular starting values are needed for
the interfacial tension, radius of curvature at the apex, and the coordinates of the origin; (4) the
analytically determined integrands reduce the loss of accuracy in the calculation of the objective
function and its first and second derivatives; and (5) the numerical procedure unifies both the sessile
and pendant drop methods without the need for any table of shape factors.
The ADSA technique has been utilized in conjunction with other commercial image analysis
software for determining solvent-oil interfacial tensions reported in this study.

2.3. Slim-tube test for miscibility

The slim-tube displacement test, often considered as the 'industry standard' for miscibility
evaluation, has been well described in the literature. Elsharkawy et al. [9] present an overview of the
varied design and operating practices used with the slim-tube technique. They point out that in spite
of being referred to as the industry standard, there is neither a standard design, nor a standard
operating procedure, nor a standard set of operating criteria for determining MMPs with a slim-tube.

3. Results and discussion

3.1. Interfacial tension measurements at elevated pressures and temperatures

Calibration experiments were initially conducted to standardize the operating procedures and image
capture and analysis techniques. The pendant drop method was used with the direct image capture
technique (as against photographing the drop profiles) to measure n-octane-water interracial tension
at 85, 125 and 170°C in the pressure range of 1 to 70 MPa. At each pressure and temperature, five to
seven images of different pendant drops were analyzed for interfacial tension using the ADSA
program. These results are given in Table 1 and are plotted in Fig. 2. The excellent precision of the
interfacial tension measurements at all pressures and temperatures is clearly indicated by the low
316 D.N. Rao/ Fluid Phase Equilibria 139 (1997) 311-324

Table !
Interracial tension of n-octane in deionized-water at elevated pressures and temperatures from ADSA using the technique of
direct image capture of pendant drops
Pressure (MPa) Average interfacial tension
T = 85°C T = 125°C T = 170°C
y (mN/m) SD a ( m N / m ) No. h y (mN/m) SD(mN/m) No. y (mN/m) SD(mN/m) No.
1 44.57 0.19 7 39.60 0.15 6 32.39 0.12 6
10 45.58 0.05 c 5 39.49 0.10 7 32.33 0.06 6
20 46.12 0.17 6 39.50 0.21 6 32.76 0.14 6
30 46.90 0.07 5 39.38 0.14 6 33.37 0.09 6
40 47.24 0.19 7 39.94 0.31 d 6 33.69 0.14 6
50 47.80 0.29 7 40.65 0.16 6 34.36 0.12 6
60 47.32 0.28 7 41.31 0.13 6 34.39 0.08 6
70 47.35 0.22 5 42.36 0.16 5 36.00 0.12 9

aStandard deviation; bnumber of samples; Cminimum standard deviation of 0.05 m N / m or 0.11% of average IFT;
amaximum standard deviation of 0.31 m N / m or 0.78% of average IFF.

standard deviations in the range of 0.05 m N / m to 0.31 m N / m in Table 1. The minimum standard
deviation corresponds to a deviation of 0.1% from the average interfacial tension, and the maximum
corresponds to a deviation of 0.8% from the average. These measurements are plotted in Fig. 2 along
with the data of McCaffery [10] at 85 and 125°C. McCaffery's data at both these temperatures are
slightly lower than our measurements indicating the possibility of impurities in his system. It can be

50 5O

a~ .--,',--~i."- ~ -- ' , L...........


J t,
E
Z [
v
E
Z 40 i40
0 _ _._@. ......
• .......... • . . . . . . . . . . -@--.....
or)
Z ....... _&
LU 35 i35
I-- .... ~ .......... JE. . . . .
._1
......... l .......
& ........ -dr- . . . .
0
~ 30 30
I1:
ADSA Technique ADSA Technique McCaffery (1972)
LLI
I-- P e n d a n t at 85°C Sessile at 85°C P e n d a n t at 85°C

~ 25 i 25
ADSA Technique MeCaffery (1972) ADSA Technique
P e n d a n t at 125°C P e n d a n t at 125°C P e n d a n t at 1
i

20 _ _ ~ ~ .... ± . . . . . . . . . ~ _ _ ~ i 12o
0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0
PRESSURE (MPa)

Fig. 2. n - O c t a n e - W a t e r interracial tension measurements using ADSA technique.


D.N. Rao/Fluid Phase Equilibria 139 (1997) 311-324 317

seen in Fig. 2 that both the sessile and pendant drop measurements using ADSA agree quite closely
with each other at 85°C. The interfacial tension data at each of the three temperatures were separately
fitted with linear least-squares lines as shown in Fig. 2. The positive slopes of these fitted lines
indicate that the interfacial tension increases with increasing pressure which is in agreement with the
measurements of Neumann [ 11 ] and the theory of Adamson [ 12]. As expected, the interfacial tension
decreases with increasing temperature. These measurements clearly demonstrate the feasibility of
precise interfacial tension measurements at elevated temperatures and pressures by digitizing the
sessile or pendant drop profiles and by processing the digitized images through the ADSA technique.
3.2. Comparison of MMPfrom slim-tube and VIT techniques
In order to verify the M M P obtained using the VIT technique, several slim-tube displacement tests
have been carried out with Gilwood and Rainbow stock-tank crude oils with both propane and ethane
as solvents. Figs. 3 and 4 compare VIT and slim-tube results for Rainbow stock-tank oil (STO) with
propane and ethane, respectively, as solvents.
3.2.1. Slim-tube results
It can be seen that the slim-tube M M P for Rainbow STO with propane falls in the range of 2.6
MPa and 3.0 MPa, while that with ethane lies between 11.2 to 11.5 MPa. It should be pointed out that
in Fig. 4, the slim-tube recovery points corresponding to the injection pressure of 12.1 MPa, were
assumed to fall in the miscible region, although the oil recoveries were less than 90% of the original
oil in place (OOIP). For miscible slim-tube displacements, oil recoveries in excess of 9 0 % - 9 5 % are
expected at 1.2 PVI [13]. It can be further observed in Figs. 3 and 4 that the propane displacements
are somewhat more sensitive to whether the oil recoveries at 1.0 PVI or 1.2 PVI are used for
determining the MMP. It is also interesting to note that the lower recoveries at higher pressures
observed with ethane displacement did not occur in the case of propane displacement. This may be
due to asphaltene precipitation problems which are known to become more severe as the n-alkane
molecule in the solvent gets smaller [14].

100- ........ it4 . . . . . . . ~ ......

9O
~\ 3.0 MPa Slim-Tube Recovery Z
SO ~t / 2.6 i P a at !-2p V1 ~E
~" 7 / Slim-Tube Recovery 8
O Z
6O ~ 0 ,FT

~5o <
>
O t~- Slim-Tube MMP = 2.6 - 3.0 MPa lo
O 4o VIT MMP = 3.88 MPa
ILl
n-
. 30 | 3.88 i P a Z
5 ._l
2° T 9_

0 2 4 6 8 10 12 14 16 18 20
INJECTION PRESSURE (MPa)

Fig. 3. C o m p a r i s o n o f M M P f r o m sfim-tubc and V I T techniques f o r R a i n b o w s t o c k - t a n k oil w i t h propane.


318 D.N. Rao / Fluid Phase Equilibria 139 (1997) 3 1 1 - 3 2 4

100
11.5

O
O
z
o
~ 7o
UJ
W-
_J
O
W 5O
,<
~ £ ~ e MMP= 11.2- 11,5MPa
"""1 V/TMMP = 18.25MPa
O

P- 20 ~0" .-..i 18.25 MPa


Onset of asphaltenes?~ ' .... I " . o
_J 10
,<
0 (.9
2 4 6 8 10 12 14 16 18 20 22
INJECTION PRESSURE (MPa)
Fig. 4. Comparison of MMP from slim-tube and VIT techniques for Rainbow stock-tank oil with ethane.

Each slim-tube test required five working days to complete. Thus, each MMP determination,
requiring four to five slim-tube tests, needed four to five weeks of time.
3.2.2. VIT results
G a s / O i l interfacial tensions were measured by applying the A D S A technique to pendant crude oil
drops immersed in the gas phase of desired composition at reservoir temperature and varying
pressures. Gas and crude oil were pre-equilibrated in the high pressure optical cell before commenc-
ing the acquisition of drop profile images on the computer. About 5 to 7 images were captured on the
computer at each pressure. Including the cleaning of the optical cell and its accessories (which is
essential for obtaining accurate interfacial tension measurements), each determination of MMP for
one crude oil with one solvent gas (or gas mixture) took about 4 - 6 h to complete.
The results of VIT experiments for the Rainbow stock-tank crude oil with propane and ethane are
also included in Figs. 5 and 6, respectively. The data sets were fitted with regression equations. For

E 12 . . . . . . . .
Z
g C1/C3 Mixtures c1/c2_Ml.~ures
Z lO
O

""-..

6 ., . .' . I ""'...... -.

42 ~'~~ 42.9% ............ . 825%


_J

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85
PROPANE OR ETHANE ENRICHMENT (Mole %)
Fig. 5. Effect of gas phase enrichment on gas/oil interfacial tension for Rainbow stock-tank oil at 17.2 MPa and 85°C.
D.N. Rao / Fluid Phase Equilibria 139 (1997) 3 1 1 - 3 2 4 319

E7
Temperature = 87"C
7
I -- - 14.8 MPa
3 " I Y = = + t=
"-'E 6 ....."~- ' L~# I Z 3 (at equilibrium)
Z " cc a~12 ~ a~
O
--
2 """" ", =
b
a62 z38 azz
-o.t29n .0.1,o7 -o.1377 14.0 M P a
(/)5 ............ "'... MMC 5t.o~ SZ~ ~.~ (at equilibrium)
1 . • . . .....................

U
Ji-_4 ~ .............. ""~.. 14.8 MPa

____.-J : ~ . . : "'....... (first_~ta__ct)


C)
~L~_. 3 .... L~ "-.

1-2 -
z_ .+ ......~

(.90 ....
10 15 20 25 30 35 40 45 50 55 60
G A S E N R I C H M E N T ( C 2 + mole %)
Fig. 6. Application of the V1T technique to optimize injection gas composition at Rainbow Keg River F Pool in Alberta.

the linear variations of g a s / o i l interfacial tension with pressure (as in the case of propane runs), it can
be easily shown that the M M P (which occurs at zero interfacial tension) is given by

MMPwT = - a / b (for straight line correlations) (2)

where a is the intercept and b is the slope of the regression lines.


While the Rainbow crude oil/propane interfacial tension exhibited a linear variation with pressure,
the data for the Rainbow oil/ethane system was best matched by a logarithmic function of the type,
y = a + b(ln x), as shown. The value of MMP at zero interfacial tension for such a logarithmic
function can be shown to be given by

MMPvlT = e (- a / b) (for logarithmic correlations) (3)


The V I T - M M P value of 3.88 MPa with propane compares well with the slim-tube value in the
range 2.6 to 3.0. However, the V I T - M M P value of 18.25 MPa for Rainbow oil/ethane system differs
markedly from the slim-tube value of 11.2-11.5 MPa. The reason for this appears to be related to the
asphaltene flocculation phenomenon. It is hypothesized that the initial rate of linear decline of gas/oil
interfacial tension with increasing pressure (as shown by the thin dashed straight line in Fig. 4)
decreases at a pressure of about 8 MPa as the asphaltenes begin to come out of the oil and migrate to
the g a s / o i l interface. Therefore, a slower linear decline (as indicated by the second dashed straight
line in Fig. 4) than the initial rate describes the behavior of g a s / o i l interfacial tension at pressures
beyond 8 MPa. The point of intersection of the two dashed lines (about 8 MPa) perhaps signifies the
onset of asphaltene flocculation in this system. It should be noted, however, that this type of dual-rate
decline of g a s / o i l interfacial tension does not affect the MMP determined from the VIT technique as
320 D.N. Rao / Fluid Phase Equilibria 139 (1997) 311-324

Table 2
Comparison of minimum miscibility pressures obtained from the VIT and slim-tube techniques
Crude oil Solvent V I T - M M P (MPa) Slim-tube-MMP (MPa)
At 1.0 PVI At 1.2 PVI
Gilwood STO Ethane 7.53 7.2 7.4
Gilwood STO Propane 2.83 3. I 2.0
Rainbow STO Ethane 18.25 11.2 11.5
Rainbow STO Propane 3.88 3.0 2.6

can be seen in Fig. 4. On the other hand, this type of dual-rate decline analysis, if proven by
additional testing, could possibly serve as a means of identifying the threshold pressure for the onset
of asphaltenes in miscible flooding processes.
Furthermore, it can be seen in Fig. 4 that the dashed straight line fitted to the initial interfacial
tension data up to a pressure of 8 MPa, intersects the zero interfacial tension axis at a pressure of
about 10.3 MPa. It is interesting to note that this value is within 1 MPa of the MMP determined from
the slim-tube tests.
Table 2 summarizes the comparison of MMP from VIT and slim-tube techniques for both Rainbow
and Gilwood stock-tank oils. For the Gilwood case, the agreement between the two techniques is
quite good for both propane and ethane solvents. Thus, in three out of a total four cases studied, the
V I T - M M P matched closely with slim-tube-MMP and the disagreement between the two techniques
in the fourth case appears to be related to asphaltene deposition.

3.3. Determination of minimum miscibility composition (MMC) of injection gas using the VIT
technique

In order to optimize the injection gas composition, numerous VIT experiments have been
conducted, at reservoir pressure and temperature, by measuring g a s / o i l interfacial tension at various
gas phase compositions. The results for some of these experiments are plotted in Fig. 5 for RKR
stock-tank oil. Good straight-line correlations (with correlation coefficients near 0.99) were obtained
for both methane/propane and methane/ethane gas mixtures. When extended to zero gas/oil
interfacial tension, these correlations yielded a MMC of 42.9 mole % propane and 82.5 mole %
ethane in methane gas as shown in Fig. 5. Thus, the new technique offers a simple and rapid means of
optimizing the injection gas composition at reservoir temperature and actual operating pressure.
The consistent trends displayed by all the gas/oil interfacial tension data, against either pressure or
composition, presented, thus, far clearly demonstrate the reliability of the VIT technique for
evaluating miscibility pressures and compositions at reservoir conditions.

4. Application of the VIT technique at an Alberta reservoir

This section presents a practical application of the VIT technique to optimize injection gas
composition for the Rainbow Keg River F Pool in Alberta, using live reservoir crude oil and gas
mixtures representative of lean and rich gases available in the field.
D.N. Rao / Fluid Phase Equilibria 139 (1997) 311-324 321

Table 3
Compositions of Rainbow Keg River F Pool fluids used in this study
Component Mole % in live oil Mole % in lean gas Mole % in rich gas
Nitrogen 1.34 1.76 0.40
Carbon dioxide 0.80 1.24 0.80
Hydrogen sulphide 1.14 0.0 0.0
Methane 31.82 81.01 14.73
Ethane 10.12 11.14 21.34
Propane 6.30 3.95 41.83
/-Butane 1.60 0.50 7.35
n-Butane 3.83 0.34 11.67
Pentanes 3.60 0.07 1.89
Hexanes plus 39.45 - -
Total 100.00 100.00 100.00

4.1. Fluids compositions

The compositions of the Rainbow Keg River (RKR) F Pool live oil, lean gas and rich gas (NGL)
used in these experiments are given in Table 3. In order to experimentally determine the optimum
enrichment, the composition of the gas phase contained in the optical cell was varied by adding
different amounts of rich gas to the lean gas originally filling the cell.

4.2. VIT tests with liL'e crude oil and f i e l d gas mixtures

The experimental study began with the optical cell containing lean gas (with C2+ = 17.79%, where
all compositions are expressed in mole %) and about 6 ml (or 10% of cell volume) of live oil at 14.8
MPa. Crude oil was added to the cell to simulate the reservoir process where the solvent will be
injected into a lean gas flooded zone containing residual oil. When the first addition of the rich gas
was made to achieve C2+ concentration of 21.86% in the gas phase, a cloudy layer of the rich gas
was observed to form above the oil level. This cloudy layer was seen to gradually disappear as the
rich gas diffused into rest of the gas space and became clear in about 2 h. In order to determine the
time required for achieving homogeneous gas composition after each addition of rich gas, gas samples
were taken at 2 h and 3.5 h after the first rich gas addition and analyzed on the gas chromatograph.
The results indicated the absence of noticeable change in the gas composition between the two
samples. Hence, it was decided to allow a minimum of 2 h after each rich gas addition to the cell
volume before beginning interfacial tension measurements.
The gas-oil interfacial tensions measured using Rainbow (F Pool) live crude oil are plotted in Fig.
6 against the concentration (in mole %) of C2+ fraction in the gas phase. There are three different sets
of data in Fig. 6. The first set, marked 1 in the figure, presents the g a s / o i l interfacial tension
measured at 14.8 MPa when the mass transfer between the gas and oil phases had reached
equilibrium. This equilibrium was achieved by keeping a small volume (about 6 ml or 10% by
volume of the cell) of live crude oil at the bottom of the cell before beginning the interfacial tension
measurements. The same oil was retained in the cell all the time when the composition of the gas
phase was altered by rich gas additions, as well as when the pressure in the cell was dropped to 14.0
322 D.N. Rao / Fluid Phase Equilibria 139 (1997) 311-324

M P a to obtain the second set of data in Fig. 6. The third set of data in Fig. 6 was obtained separately
by starting the experiment with the cell filled with the gas of desired composition, and by capturing
the images of the first few drops of live oil as soon as they emerged from the capillary tube in the
optical cell, Hence, this data set is termed as 'first contact' in Fig. 6.
The results of equilibrium interfacial tension measurements at each gas composition and at 14.8
MPa are presented in Table 4, along with the actual measured composition of the gas phase at each
enrichment level. The low standard deviations in Table 4, at all gas compositions, indicate the
precision and repeatability of these measurements. All the data points are plotted in Fig. 6 using small
sized symbols and the average values are plotted with bigger sized symbols. The correlation
coefficients and the parameters of the linear equations for the three regression lines in Fig. 6 are also
summarized in the figure. The correlation coefficient ( R 2) was close to unity in all cases indicating
good accuracy of regression fitting. The equation parameter a represents the y-intercept which is the
value of g a s / o i l interfacial tension at zero C2+ concentration in the gas phase, or in a gas mixture
containing only methane and nitrogen. The slopes of the regression lines vary within a narrow margin
from - 0 . 1 3 to - 0 . 1 4 indicating that the three lines are very nearly parallel to each other. The
m i n i m u m miscibility composition ( M M C ) for each of the three data sets in Fig. 6 can be obtained

Table 4
Effect of gas composition on equilibrium gas/oil interfacial tension at 14.8 MPa and 87°C for the Rainbow F Pool live oil
(IFT in raN/m)
Drop # C2+ concentration in gas phase (mole %)
17.79 21.64 25.85 3 0 . 5 7 3 3 , 8 6 3 7 . 7 0 4 3 . 0 7 4 8 . 3 9 4 9 . 2 8 44.52a 41.41a
l 4.26 3.95 3.18 2.75 2.16 1.54 0.99 0.51 0.22 0.87 1.16
2 4.18 4.09 3.31 2.64 2.20 1.53 0.94 0.55 0.26 0.89 1.27
3 4.14 3.96 3.16 2.69 2.20 1.57 0.98 0.48 0.28 0.90 1.13
4 4.15 3.85 3.29 2.65 2.13 1.48 0.98 0.60 0.23 0.89 1.20
5 4.23 4.10 3.34 2.71 2.14 1.52 0.93 0.58 0.32 0.91 1.11
6 4.62 3.90 3.25 2.69 2.13 1.53 0.97 0.49 0.29 0.92 1.29
7 4.25 3.90 3.34 2.67 2.14 1.49 1.03 0.58 0.27 0.91 1.19
8 3.85 3.24 2.71 2.09 1.50 0.92 0.46 0.26 0.93 1.20
9 4.12 3.27 2.66 1.99 0.96 0.40 0.30 0.88 1.27
10 3.97 3.32 2.68 2.11 0.60 0.85 1.28
Average 4.26 3.89 3.27 2.69 2.13 1.52 0.97 0.53 0.27 0.90 1.20
Standard deviation 0.15 0.14 0.06 0.03 0.06 0.03 0.03 0.06 0.03 0.02 0.06

Chromatographic analysis of gas from IFT cell (mole %)


Cl 80.38 76.42 72.70 68.08 64.87 61.09 55.65 50.65 49.77 54.21 57.44
C2 11.19 1 1 . 8 4 1 2 . 5 8 13.37 1 3 . 9 5 1 4 . 6 8 1 5 . 5 2 1 6 . 6 2 17.13 15.5 14.89
C3 4.08 6.32 8.67 1 1 . 3 4 1 3 . 3 4 1 5 . 5 4 1 8 . 5 2 2 1 . 8 9 2 3 . 0 0 1 9 . 2 9 17.36
iC 4 0.55 0.93 1.32 1.78 2.09 2.47 2.96 3.33 3.19 3.18 2.88
nC 4 0.54 1.12 1.74 2.47 2.90 3.42 4.26 5.01 4.26 4.76 4.36
nC 5 0.20 0.25 0.35 0.45 0.46 0.53 0.65 0.58 0.66 0.94 0.84
CO 2 1.24 1.21 1.19 1.16 1.13 1,11 1.07 1.04 1.05 1.08 1.09
N2 1.83 1.94 1.46 1.36 1.26 1,20 1.28 0.97 0.95 1.06 1.15
Density(g/cc) 0.1157 0.1257 0.1372 0.1518 0.1626 0,1763 0.1977 0.2203 0.2217 0.2077 0.1931

aAdded lean gas to retrace the trend.


D.N. Rao / Fluid Phase Equilibria 139 (1997) 311-324 323

simply by the equation, MMC = - a / b obtained by setting y = 0 in the straight line regression
equation. The equilibrium MMC was, thus, determined to be 51 mole % C2+ at 14.8 MPa (which was
further reconfirmed by conducting a single slim-tube test) and 52.5 mole % C2+ at 14.0 MPa.
Equilibrium MMC means the composition of the gas phase (that has been equilibrated with live oil by
prior contact) with which 'fresh' live oil exhibits zero interfacial tension and becomes miscible. On
the other hand, 'first contact' miscibility represents that composition of the gas phase (which has not
been previously exposed to crude oil contact) with which 'fresh' live crude oil exhibits zero
interfacial tension. This first contact miscibility was estimated, based on the three separate tests
conducted with fresh gas of desired composition and fresh live oil each time, to be 59.7 mole % C2+
as shown in Fig. 6.
A total of over 200 interfacial tension measurements were made in this study within a time period
of 15 working days. The results clearly demonstrate the practicality of utilizing the VIT technique to
determine both the first contact and equilibrium interactions between live reservoir crude oil and
multicomponent gas mixtures usually available in the oil field for gas injection projects.

5. Summary and conclusions

A simple new technique has been developed for rapid and cost-effective optimization of pressure
and composition of gases injected in miscible or near-miscible oil recovery processes. The new
technique is based on the principle of absence of an interface or, in other words, a condition of zero
interfacial tension, when fluids become miscible,
The main feature of the new technique, which clearly distinguishes it from the conventional
slim-tube, rising bubble and phase behavior techniques, is that it determines miscibility solely on the
basis of vanishing interfacial tension as the injected gas phase approaches miscibility with the crude
oil in the reservoir, due to imposed pressure or composition changes. Hence, the name Vanishing
Interfacial Tension (VIT) technique.
The VIT technique consists of measuring the interfacial tension of the live reservoir crude oil
against the injected gas phase at the temperature of the reservoir and at varying pressures a n d / o r
enrichment levels (composition) of the gas phase. By plotting measured interfacial tension against the
independent variable (either pressure or enrichment), accurate values of the minimum miscibility
pressure a n d / o r minimum enrichment are obtained by extrapolation of the data to zero interfacial
tension axis.
Minimum miscibility pressures (MMP) for two different Canadian reservoirs (Rainbow and
Gilwood), with ethane and propane as injection gases, were determined using both the VIT technique
and the conventional slim-tube technique. The MMP obtained using the VIT technique agreed closely
with that from slim-tube measurements for three of the four cases studied. In the fourth case (of
Rainbow crude oil with ethane), the discrepancy in MMP from the VIT and slim-tube techniques
appears to be related to the asphaltene flocculation phenomenon.
Each MMP determination using the VIT technique was accomplished within 4 - 6 h while 4 - 6
weeks were required for the slim-tube technique. The minimum miscibility composition (MMC) of
methane/ethane and methane/propane mixtures for the Rainbow and Gilwood crude oils, at the
respective reservoir temperature, were also determined using the VIT technique within about 3
work-days.
324 D.N. Rao / Fluid Phase I:'quilibria 139 (1997) 311 324

The new V I T technique was successfully utilized in optimizing the injection gas composition for
the ongoing miscible flood in the Rainbow Keg River F Pool. Live reservoir crude oil as well as lean
and rich gas mixtures, matching field gases in composition, were utilized in all the experiments. Both
'first contact' and 'equilibrium' miscibility compositions were determined using the V I T technique.
The V I T - M M P was c o n f i r m e d by conducting a single slim-tube displacement test.
The Alberta Energy and Utilities Board ( A E U B ) has accepted the r e c o m m e n d e d injection gas
c o m p o s i t i o n determined by the V I T technique.

Acknowledgements

Sincere thanks go to H u s k y Oil Operations, Frank M c I n t y r e and David Fong of H u s k y Oil


Operations, and the Petroleum Society of C I M for permitting the use of data and information
presented in this paper. Thanks are also due to Marcel Girard and Ann M c D o n a l d of Petroleum
R e c o v e r y Institute for carrying out the experimental work.

References

[1] L.W. Holm, in: H.B. Bradley (Ed.), Petroleum Engineering Handbook, Society of Petroleum Engineers, Richardson,
TX, USA, 1987, pp. 1-45.
[2] L.W. Lake, Enhanced Oil Recovery, Prentice-Hall, Englewood Cliffs, NJ, 1989, 234 pp.
[3] A.L. Benham, W.E. Dowden, W.J. Kunzman, Petroleum Transactions Reprint Series No. 8, Society of Petroleum
Engineers of AIME, 1965, p. 123.
[4] D.N. Rao, M.G. Girard, J. Can. Petrol. Technol., January 1996, pp. 31-39.
[5] Computer Modelling Group, CMGPROP 95.00, Phase Behavior Package User's Guide, Calgary, Canada, November 8,
1994.
[6] F.C. Goodrich, in: E. Matijevic (Ed.), Surface and Colloid Science, Vol. 1, Wiley-Interscience, New York, 1969.
[7] Y. Rotenberg, L. Boruvka, A.W. Neumann, J. Coll. Interface Sci. 93 (1) (1983) 169-183.
[8] P. Cheng, D. Li, L. Boruvka, Y. Rotenberg, A.W. Neumann, Coll. Surf. 43 (1990) 151-167.
[9] A.M. Elsharkawy, F.H. Poettmann, L.R. Christiansen, Energy Fuels 10 (1996) 443-449.
[10] F. McCaffery, J. Can. Petrol. Technol., July-September 1972, p. 26.
[11] A.W. Neumann, Final Report for Supply and Services Canada, No. 23440-9-9002/01-SS, University of Toronto,
Toronto, Canada, March 1991.
[12] A. Adamson, Physical Chemistry of Surfaces, Wiley, New York, 1976.
[13] F.I. Stalkup, Jr., Miscible Displacement, SPE Monograph Vol. 8, SPE of AIME, New York, 1983.
[14] R.B. Long, Chemistry of Asphaltenes, in: J.W. Bunger, N.C. Li (Eds.), American Chemical Society, Advances in
Chemistry Series, 195, 1981, pp. 17-27.