Journal of Petroleum Science and Engineering 35 (2002) 247 – 262

www.elsevier.com/locate/jpetscieng

Application of the new vanishing interfacial tension technique to

evaluate miscibility conditions for the Terra Nova Offshore Project
Dandina N. Rao a,*, J.I. Lee b,1
a
The Craft and Hawkins Department of Petroleum Engineering, Louisiana State University, 3516 CEBA Bldg., Baton Rouge, LA 70803, USA
b
Petro-Canada Oil and Gas, P.O. Box 2844, Calgary, Alberta, Canada T2P 3E3
Received 4 December 2001; accepted 25 April 2002

Abstract

Terra Nova oil pool is the second largest oil pool discovered in the Grand Banks of the Canadian East Coast and is under
development. As a part of the oil recovery process selection criteria, miscibility conditions were determined for Terra Nova oil
with various enrichment levels of gas available from the offshore production facilities using the recently developed vanishing
interfacial tension (VIT) technique. The VIT technique is based on the concept that the interfacial tension between the gas and
crude oil phases at reservoir temperature must reduce to zero as these two phases approach the point of miscibility. The concept
of zero-interfacial tension at miscibility is, in turn, based on the well-accepted fact that the interface between the phases must
vanish, as they become miscible with one another. Thus, the minimum miscibility pressure (MMP) and minimum miscibility
composition (MMC) can be determined precisely by measuring gas – oil interfacial tension as a function of pressure and gas
composition, down to as low an interfacial tension as the measurement technique allows, and then extrapolating the data to zero-
interfacial tension. This paper presents the details of this new VIT technique and its evaluation against slim-tube tests, and
discusses its application to the Terra Nova gas injection scheme. The interfacial tension data obtained at reservoir conditions
using the computerized axisymmetric drop shape analysis (ADSA) technique are presented as a function of pressure, gas
composition, and the mode of gas – oil contact (first-contact or equilibrium). In addition to providing visual evidence of
miscibility as the point of zero-interfacial tension is approached, the VIT technique is rapid in that it enables the experimental
determination of MMP and MMC within about 2 – 3 days as against 4 – 6 weeks required by the slim-tube technique. D 2002
Elsevier Science B.V. All rights reserved.

Keywords: Minimum miscibility pressure; Minimum miscibility composition; Miscibility; Interfacial tension; Phase behavior; Terra Nova
Offshore Reservoir

1. Introduction secondary waterfloods. This amounts to a staggering

Nearly two-thirds of the original oil in place is left
behind in reservoirs at the end of primary recovery and
*
Corresponding author. Tel.: +1-225-578-6037; fax: +1-225-
578-6039.
E-mail addresses: dnrao@lsu.edu (D.N. Rao),
JONGLEE@petro-canada.ca (J.I. Lee).
1
Tel.: +1-403-209-4567; fax: +1-403-296-5176.
351 billion barrels of unrecovered, known-to-exist oil
in the US alone and 2 trillion barrels of oil in the world
(Green and Willhite, 1998). Gas injection EOR projects
account for about 40% of EOR production in the US,
with the remaining 60% of EOR production coming
from steam injection projects (Moritis, 1998). A sum-
mary of gas injection projects in the past decade and
their design considerations have been provided else-

0920-4105/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 4 1 0 5 ( 0 2 ) 0 0 2 4 6 - 2
248 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262
where (Rao, 2001). For gas injection projects to be
successful economically, they need to maximize micro-
scopic displacement efficiency by operating at or near
the conditions required for miscibility between reser-
voir crude oil and injected gas. Hence, the need to
assess gas –oil miscibility pressures and compositions
at the operating temperature.
1.1. Gas – oil miscibility
The following are some definitions of miscibility
appearing in the literature. Miscible displacement is a
process where there is an absence of phase boundary or
interface between the displaced and displacing fluids
(Benham et al., 1965). Two fluids are miscible when
all mixtures of these two fluids in all proportions
remain in a single phase without any interfaces, and
consequently with no interfacial tension between the
fluids (Stalkup, 1983). Miscibility is that physical
condition between two or more fluids which permits
them to mix in all proportions without the existence of
an interface (Holm, 1987). Two fluids that mix
together in all proportions within a single fluid phase
are miscible (Lake, 1989).
While these definitions generally refer to first-con-
tact miscibility between reservoir crude oil and
injected gas, similar discussion of multicontact mis-
cibility in terms of gas –oil interfacial tension have
been provided by Zhou and Orr (1998) and Poettmann
et al. (1992). In their analysis of the rising bubble
experiments, Zhou and Orr (1998) note that for gas –
oil systems in which multicontact miscibility is possi-
ble, changes in interfacial tension will have the largest
effect on bubble appearance and that the interfacial
tension declines much more rapidly as a critical
composition is approached than does density differ-
ence. Poettmann et al. (1992) use a qualitative plot of
gas – oil interfacial tension to explain the deterioration
of bubble shape in rising bubble experiments.
1.2. The vanishing interfacial tension (VIT) technique
The above discussion clearly conveys a consensus
that miscibility, whether by first-contact or by multiple
contacts, refers to the absence of an interface between
the injected fluids and the reservoir crude oil. The
absence of an interface means, in terms of a measur-
able variable, the value of the interfacial tension
between the displacing and displaced fluids is zero.
Therefore, it may be argued that the condition of zero-
interfacial tension is necessary and sufficient to attain
miscibility. However, none of the presently used
techniques for miscibility evaluation, namely the
slim-tube test, the rising bubble technique, or the
method of constructing pressure – composition dia-
gram, is capable of yielding direct and quantitative
information on interfacial tension. Hence, the vanish-
ing interfacial tension (VIT) technique, being pre-
sented in this paper, fills a void that has existed in
miscibility determination.
The fundamental premise of the VIT technique is
that the approach to miscibility between two fluids can
be closely observed by simply following the behavior
of their interfacial tension as a function of either
pressure or composition. The details of the develop-
ment of the VIT technique and its comparison with
slim-tube tests are provided elsewhere (Rao, 1997).
The VIT technique has been utilized in optimizing the
injection gas composition for the Rainbow Keg River
miscible flood in Alberta (Rao et al., 1999). In this
paper, we provide additional comparisons between VIT
and slim-tube tests and the experimental results
obtained by applying the VIT technique to determine
minimum miscibility pressure and composition for
Terra Nova offshore formation.
1.3. Terra Nova offshore field
The Terra Nova oil field is the second largest oil
pool discovered in the Grand Banks Jeanne d’Arc
basin of Canadian east coast in a water depth of about
95 m, located 350 km east – southeast of St. John’s,
Newfoundland, 35 km southeast of Hibernia. It was
discovered in 1984 and by 1988 a total of nine wells
were drilled to delineate the pool. Six of the nine wells
drilled were successful.
In December 1995, Petro-Canada, as project oper-
ator, announced a project of nearly 400 million barrels
of oil reserves. This was followed by a project
sanction announcement in February 1998. Currently,
an FPSO (steel floating production, storage and off-
loading) vessel is under construction. Development
wells are being drilled for an average rate of 115,000
barrels of oil per day starting in 2001.
This study was conducted as part of a depletion
plan to select the most economical oil recovery
 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262
mechanism. Waterflood, solution gas injection and
enriched gas injection, or miscible flood were in
consideration. The project was approved for water-
flooding the majority of the pool and solution gas
injection in part of the pool for gas conservation
purposes.
2. Apparatus and procedures
The apparatus used and the experimental proce-
dures followed in this study are quite similar to those
reported previously (Rao, 1997). Fig. 1 shows the
schematic of the high-pressure optical cell and its
accessories used in the experiments. The salient
features are repeated here for sake of completeness.
The experimental system consists of a high-pressure,
high-temperature cell, made up of titanium and Has-
telloy parts, with glass windows on opposite sides.
The cell is capable of operating at pressures up to 70
MPa (10,000 psi) and temperatures up to 200 jC
( f 400 jF). 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-handling system consisting of pistoned-pressure
vessels, high-pressure pumps and a backpressure
regulator. Elevated temperatures are achieved by
Fig. 1. High-pressure optical cell used in VIT experiments.
249
using an 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 used in calculating inter-
facial tensions. A side arm is used to position an inert
ruby sphere at the desired location within the view of
the camera for the purpose of image calibration. The
cell housing also contains a live oil reservoir equipped
with a piston driven by high-pressure water to enable
the maintenance of the fluids at reservoir temperatures
and pressures at all times during the course of the
experiments as well as to flow the oil in the form of
droplets within the field of view of the camera which
sends the drop profile images to be captured by the
computer.
The density of live oil was measured using a PAAR
DMA 45 density meter equipped with a PAAR DMA
512 external cell. The external cell is connected to a
high-temperature circulating bath, which is capable of
maintaining the cell at the desired temperature. The
outlet of the cell is connected to a backpressure
regulator. The inlet of the cell is connected to a
high-pressure pistoned vessel and a pump, which
introduces the fluids into the cell at the desired
pressure.
The density of the gas phase, at each pressure or
enrichment level, was calculated using a commercial
property package (Computer Model Group, 1994) by
250 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262
feeding the program with the chromatographic com-
positional analysis of the gas samples collected from
the optical cell.
The pendant drop technique, which consists of oil
drops hanging from a capillary tube within the sur-
rounding gas space as shown in Fig. 1, was used in
this study. The image of the drop profile is then
captured in a frame buffer and its digital representa-
tion is then saved on the computer hard drive. After a
set of images has been saved on the computer hard
drive, each image is individually recalled, digitized,
and analyzed for IFT using the axisymmetric drop
shape analysis (ADSA) calculation procedure (Roten-
burg et al., 1983).
3. Results and discussions
3.1. VIT versus slim-tube comparisons
Before employing the VIT technique to optimize
gas injection projects in Rainbow Keg River and Terra
Nova fields, the technique was calibrated against the
conventional slim-tube tests. These comparisons are
shown in Fig. 2 for the Gilwood stock-tank oil (STO)
with ethane as the solvent phase, and in Fig. 3 for
propane as the solvent. The slim-tube oil recoveries
obtained at 1.0 and 1.2 pore volumes of gas injection
(PVI) are plotted against the test pressure. Separate
Fig. 2. MMP from slim-tube and VIT tests for Gilwood STO with ethane.
linear regression lines, of the type y = ax + b, have been
fitted to the data in miscible and immiscible regions.
The points of intersection of these lines, which yield the
MMP, can be easily calculated (for better accuracy than
reading from the plots) by making use of slopes and
intercepts of these regression lines. The MMP value
can be derived from the condition that it should
simultaneously satisfy both equations to be:
ST
MMP ¼ ða2
a1 Þ=ðb1
b2 Þ ð1Þ
where a1 and a2 are intercepts, and b1 and b2 are slopes
of the two intersecting regression lines corresponding
to the immiscible and miscible regions, respectively.
The interfacial tensions measured at various pressures
for the two systems are also plotted and the data
extrapolated to zero-IFT points in Figs. 2 and 3. For
the straight line decline of gas –oil IFT, the MMP (or
the zero-IFT point) can be calculated from:
VIT
MMP ¼
a=b ð2Þ
where a and b are the intercept and slope of the
regression line drawn through the IFT data. The VIT-
MMP value of 7.53 MPa with ethane agrees well with
the slim-tube MMP of 7.2 – 7.4 MPa. The VIT-MMP of
2.83 MPa with propane solvent falls within the slim-
tube MMP range of 2.0 –3.1 MPa. Similar comparisons
of VIT results with slim-tube tests have been reported
by Rao et al. (1999) for the Rainbow Keg River field.
Their study also reported a slim-tube confirmation of
 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262 251

Fig. 3. MMP from slim-tube and VIT tests for Gilwood STO with propane.

the minimum miscibility composition (MMC)
obtained from VIT tests using Rainbow Keg River
live oil and multicomponent field gas mixtures.
They have also compared VIT results with predic-
tions from an equation of state tuned with 17
components representing the crude oil. In the
present study, we have applied the VIT technique
to determine minimum miscibility pressure and
composition for Terra Nova Offshore Reservoir
using live oil and field gas mixtures.
3.2. Compositions and phase behavior of Terra Nova
fluids
The compositions of the Terra Nova live oil and the
five solvent gas mixtures are given in Table 1. In order
to account for phase behavior effects during the inter-
facial tension measurements, two-phase envelopes
were calculated, using CMGPROP property package,
for the four gas mixtures as shown in Fig. 4. None of the
gas mixtures exhibit a two-phase behavior at the

Table 1
Compositions of Terra Nova fluids used in phase behavior calculations
Component Mol% in Mol% in Mol% in Mol% in Mol% in Mol% in Mol% in
live oil solution reinjected 30% C2+ 40% C2+ 50% C2+ rich gas
gas gas solvent solvent solvent used
Nitrogen 0.15 0.27 0.33 0.22 0.17 0.12 0.21
Carbon dioxide 0.69 1.18 1.10 1.13 1.14 1.15 1.18
Methane 45.06 78.80 90.11 69.75 59.57 49.95 51.55
Ethane 5.37 8.82 6.01 9.40 11.09 12.69 12.80
Propane 5.44 7.15 2.09 9.48 13.17 16.66 16.31
i-Butane 0.98 0.84 0.12 1.40 2.04 2.65 2.63
n-Butane 2.85 2.02 0.21 3.75 5.51 7.18 6.71
i-Pentane 1.24 0.37 0.02 1.06 1.58 2.07 2.12
n-Pentane 1.80 0.40 0.0 1.34 2.01 2.63 2.35
n-Hexane 9.13 0.15 0.0 2.33 3.49 4.59 3.86
Heptanes plus 27.29a 0.0 0.0 0.16 0.23 0.30 0.29
Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00
CO2 + C2 + (mol%) 54.79 20.93 9.56 30.03 40.26 49.93 48.24
Molecular weight of C7+ fraction in live oil = 241.
a
Specific gravity of C7 + fraction in live oil = 0.879.
252 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262

Fig. 4. Phase behavior of Terra Nova fluids using CMGPROP 95 property package.

reservoir temperature of 96 jC except the rich gas
mixture containing 50% C2 + , which was not used in
any of the experiments. This facilitated single-phase
additions of rich gas to lean gas contained in the optical
cell during enrichment experiments.
3.3. Gas – oil equilibrium time determination
The time required for attaining gas –oil equilibrium
was determined by analyzing gas samples taken from
the cell at different times during the experiments in the

Fig. 5. Effect of gas – oil contact time and pressure on gas composition, molecular weight and density at 96 jC for 21% C2+ gas mixture.
 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262 253

first pressure series using the 21% C2 + gas mixture.
The results are plotted in Fig. 5. As can be seen, the
C2 + enrichment level and the molecular weight of the
gas displayed very little change with pressure over an
aging time range of 1.5 h to 65.5 h. Hence, a time of at
least 1.5 h was allowed in all the tests for reaching gas –
oil equilibrium. The unchanging gas composition in
Fig. 5 also indicates that mass transfer of components
between the vapor and liquid phases of the multi-
component mixture of live oil and gas mixture, after
reaching equilibrium, is not significantly affected by
pressure over an extended period of gas –oil contact.
The main reason for the little change in gas composi-
tion with pressure appears to be the injection of original
gas mixture (containing 21% C2 + ) to accomplish the
desired pressure increases. This procedure, of course, is
similar to that of a slim-tube run where a gas of a given
composition is continuously injected to carry out the

Table 2
A. Effect of pressure on equilibrium gas – oil interfacial tension at 96 jC for the Terra Nova live oil against a gas mixture with C2 + of 9.08 –
9.49 mol% (IFT in mN/m)
Drop # Pressure
26.2 MPa 26.20 MPa 31.0 36.0 41.0 46.0 51.0 56.0 60.7 MPa
(First contact) (equilibrium) MPa MPa MPa MPa MPa MPa
1 4.41 3.83 3.47 2.81 2.46 1.96 1.47 0.66 Unable to
2 4.11 3.89 3.43 3.09 2.00 2.22 0.84 0.89 form drops.
3 4.39 3.86 3.47 2.88 2.28 1.34 1.34 0.45 Approaching
4 4.60 3.81 3.38 2.65 2.49 1.96 0.97 0.96 miscibility.
5 4.04 3.87 3.25 2.40 2.54 1.88 1.20 0.84 See photograph
6 4.12 3.84 3.41 3.00 2.37 1.73 1.60 0.66 in Fig. 7.
7 4.61 3.86 3.42 2.90 2.59 1.57 1.06
8 4.00 3.76 3.37 2.93 2.10 1.82 0.77
9 4.74 3.92 3.40 2.91 2.35 1.79
10 4.41 3.82 3.28 2.90 2.56 2.16
11 4.45 3.87 2.66
12 4.53 3.88
Average 4.37 3.85 3.39 2.83 2.37 1.84 1.16 0.74
Standard deviation 0.23 0.04 0.07 0.18 0.19 0.25 0.28 0.17

B. Chromatographic analysis of gas composition (in mol%) corresponding to panel A

Component Pressure
26.2 MPa 26.20 MPa 31.0 36.0 41.0 46.0 51.0 56.0 60.7
(first contact) (equilibrium) MPa MPa MPa MPa MPa MPa MPa
C1 90.53 90.43 90.43 90.32 90.32 90.28 90.28 90.33 90.10
C2 5.67 5.72 5.72 5.72 5.72 5.73 5.73 5.73 5.73
C3 2.00 1.93 1.93 1.96 1.96 2.01 2.01 1.99 2.16
i-C4 0.12 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.16
n-C4 0.15 0.23 0.23 0.22 0.22 0.22 0.22 0.23 0.24
i-C5 0.00 0.04 0.04 0.03 0.03 0.04 0.04 0.04 0.04
n-C5 0.08 0.06 0.06 0.05 0.05 0.06 0.06 0.06 0.07
n-C6 0.07 0.13 0.13 0.13 0.13 0.13 0.13 0.12 0.09
n-C7 0.06 0.03 0.03 0.04 0.04 0.07 0.07 0.07 0.07
CO2 0.93 0.94 0.94 0.96 0.96 0.96 0.96 0.94 0.94
N2 0.39 0.35 0.35 0.41 0.41 0.35 0.35 0.35 0.41
C2 + 9.08 9.22 9.22 9.27 9.27 9.37 9.37 9.33 9.49
Gas density (g/cm3) 0.1660 0.1660 0.1904 0.2130 0.2328 0.2505 0.2682 0.2825 0.2947
(from CMGPROP)
Mixture mol. wt. (g/mol) 17.96 18.02 18.02 18.06 18.06 18.08 18.08 18.07 18.11
Critical pressure (MPa) 6.39 6.46 6.46 6.48 6.48 6.5 6.5 6.49 6.53
Critical temperature (jC)
60.98
60.41
60.41
60.47
60.47
60.36
60.36
60.46
59.91
254 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262

displacement. The density change observed in Fig. 5
can be attributed to the pressure changes imposed on
the system. This density change of the gas phase due to
changing system pressure influences the gas – oil inter-
facial tension as presented later. However, whatever
effects that may occur in the gas composition due to the
system pressure change and the effect of pressure itself
on density are well accounted for (through measured
compositions) in the calculation of the gas density
which is used as an input in calculating the gas – oil
interfacial tension using the ADSA technique.
3.4. Determination of minimum miscibility pressures
at reservoir temperature
Tables 2B, 3B, 4B, 5B, and 6B show the actual
composition of the solvent gas mixtures prepared for
use in the following series of experiments. These
tables also give the composition of gas samples taken
from the optical cell at various times during the
experiments. The high-pressure optical cell was
charged with the gas mixture of desired composition
and the cell brought to the reservoir temperature (96

Table 3
A. Effect of pressure on equilibrium gas – oil interfacial tension at 96 jC for the Terra Nova live oil against a gas mixture with C2 + of 20.4 –
20.66 mol% (IFT in mN/m)
Drop # Pressure
26.2 MPa 26.20 MPa 34.0 40.0 45.0 45.0 50.0
(first contact) (equilibrium) MPa MPa MPa MPa MPa
1 2.79 2.15 1.67 1.61 0.59 0.40 0.28
2 2.46 1.97 1.46 0.80 1.33 0.65 0.63
3 2.9 1.75 1.94 1.3 0.42 1.15
4 2.83 1.95 1.68 1.15 0.63 0.93
5 2.98 1.8 1.90 1.41 0.41 0.56
6 2.74 1.73 1.32 1.61 1.15
7 2.93 1.98 0.82
8 2.04 1.21
9 1.93 0.82
Average 2.80 1.92 1.66 1.31 0.82 0.74 0.46
Standard deviation 0.16 0.13 0.22 0.28 0.32 0.27 0.18

B. Chromatographic analysis of gas composition (in mol%) corresponding to panel A

Component Pressure
26.2 MPa 26.20 MPa 34.0 40.0 45.0 45.0 50.0
(first contact) (equilibrium) MPa MPa MPa MPa MPa
C1 78.99 78.99 78.99 78.99 79.32 79.32 79.32
C2 8.33 8.33 8.33 8.33 8.32 8.32 8.32
C3 6.63 6.63 6.63 6.63 6.97 6.97 6.97
i-C4 0.82 0.82 0.82 0.82 0.82 0.82 0.82
n-C4 1.94 1.94 1.94 1.94 1.95 1.95 1.95
i-C5 0.47 0.47 0.47 0.47 0.47 0.47 0.47
n-C5 0.60 0.60 0.60 0.60 0.57 0.57 0.57
n-C6 0.89 0.89 0.89 0.89 0.44 0.44 0.44
n-C7 0.24 0.24 0.24 0.24 0.12 0.12 0.12
CO2 0.73 0.73 0.73 0.73 0.75 0.75 0.75
N2 0.35 0.35 0.35 0.35 0.28 0.28 0.28
C2 + 20.66 20.66 20.66 20.66 20.40 20.40 20.40
Gas density (g/cm3) 0.2130 0.2130 0.2573 0.2840 0.3028 0.3028 0.3193
(from CMGPROP)
Mixture mol. wt. (g/mol) 21.85 21.85 21.85 21.85 21.57 21.57 21.57
Critical pressure (MPa) 10.65 10.65 10.65 10.65 10.00 10.00 10.00
Critical temperature (jC)
22.96
22.96
22.96
22.96
24.03
24.03
24.03
 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262 255

Table 4
A. Effect of pressure on equilibrium gas – oil interfacial tension at 96 jC for the Terra Nova live oil against a gas mixture with C2 + of 21.24 –
21.65 mol% (IFT in mN/m)
Drop # Pressure
26.2 MPa 26.20 MPa 27.2 29.0 34.0 40.0 45.0 50.0
(first contact) (equilibrium) MPa MPa MPa MPa MPa MPa
1 3.38 2.14 2.06 1.83 1.59 1.47 0.74 0.37
2 3.14 2.22 2.04 2.10 1.53 1.34 0.77 0.52
3 3.34 2.03 2.11 1.93 1.61 1.22 1.02 0.59
4 3.11 2.15 2.10 1.89 1.58 1.47 0.80 0.49
5 3.07 2.29 2.14 1.92 1.57 1.32 0.86 0.57
6 2.19 2.08 2.04 1.54 1.24 0.96 0.46
7 2.22 2.10 2.06 1.50 1.46 0.86 0.48
8 2.13 2.10 2.06 1.68 0.53
9 2.34 2.16 2.08 1.60 0.51
10 2.26 2.11 1.90 1.53
11 2.25 1.96
12 2.27 2.11
13 2.25 2.04
14 2.26
15, 16 2.15, 2.12
Average 3.21 2.20 2.09 1.98 1.57 1.36 0.86 0.50
Standard Deviation 0.13 0.08 0.05 0.09 0.05 0.10 0.09 0.06

B. Chromatographic analysis of gas composition (in mol%) corresponding to panel A

Component Pressure
26.2 MPa 26.20 MPa 27.2 29.0 34.0 40.0 45.0 50.0
(first contact) (equilibrium) MPa MPa MPa MPa MPa MPa
C1 78.34 78.12 78.12 78.09 78.40 78.40 78.41 78.04
C2 8.79 8.71 8.71 8.71 8.80 8.80 8.82 8.86
C3 7.04 6.96 6.96 6.91 6.99 6.99 7.04 6.95
i-C4 0.90 0.86 0.86 0.88 0.86 0.86 0.87 0.91
n-C4 2.02 2.52 2.52 2.60 2.05 2.05 2.00 2.19
i-C5 0.63 0.58 0.58 0.59 0.56 0.56 0.56 0.65
n-C5 0.48 0.46 0.46 0.45 0.44 0.44 0.45 0.53
n-C6 0.20 0.26 0.26 0.21 0.25 0.25 0.22 0.30
n-C7 0.10 0.01 0.01 0.01 0.05 0.05 0.05 0.03
CO2 1.24 1.23 1.23 1.22 1.23 1.23 1.23 1.24
N2 0.27 0.30 0.30 0.34 0.36 0.36 0.36 0.31
C2 + 21.40 21.58 21.58 21.57 21.25 21.25 21.24 21.65
Gas density (g/cm3) 0.2126 0.2126 0.2186 0.2295 0.2559 0.2829 0.3018 0.3184
(from CMGPROP)
Mixture mol. wt. (g/mol) 21.71 21.79 21.79 21.79 21.63 21.63 21.61 21.82
Critical pressure (MPa) 9.89 9.96 9.96 9.95 9.82 9.82 9.78 10.00
Critical temperature (jC)
22.64
21.32
21.32
21.26
23.3
23.3
23.42
21.33

jC) and the desired pressure of the experiment. The
temperature was observed to be constant at 96 jC
throughout the duration of this study. Fresh live oil,
which was maintained at reservoir temperature and
desired pressure of operation in a pistoned-pressure
vessel within the housing around the optical cell (as
shown in Fig. 1), was then allowed to enter the gas
phase in the optical cell in the form of small pendent
drops from a capillary tube. During this live oil
addition, the drop profile images of the first few drops
256 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262
Table 5
A. Effect of pressure on equilibrium gas – oil interfacial tension at 96 jC for the Terra Nova live oil against a gas mixture with C2 + of 28.90 –
29.80 mol% (IFT in mN/m)
Drop # Pressure
26.2 MPa 26.20 MPa 27.2 28.2 28.5 29.6 30.6
(first contact) (equilibrium) MPa MPa MPa MPa MPa
1 1.01 1.10 0.76 0.58 0.71 0.37 Unable to
2 1.15 1.13 0.74 0.66 0.55 0.47 form drops.
3 0.95 0.97 0.75 0.53 0.63 0.44 Approaching
4 0.80 1.01 0.85 0.65 0.55 0.38 miscibility. See
5 1.02 1.06 0.84 0.57 0.69 0.49 photograph in
6 1.26 1.07 0.78 0.56 0.66 0.46 Fig. 7.
7 1.18 0.94 0.79 0.63 0.64 0.35
8 1.16 1.10 0.69 0.60 0.67 0.33
9 1.19 1.02 0.75 0.70 0.54 0.33
10 1.10 0.97 0.91
11 1.12 1.08
12 1.04 0.94
Average 1.08 1.03 0.79 0.61 0.63 0.40
Standard deviation 0.12 0.06 0.06 0.05 0.06 0.06

B. Chromatographic analysis of gas composition (in mol%) corresponding to panel A

Component Pressure
26.2 MPa 26.20 MPa 27.2 28.2 28.5 29.6 30.6
(first contact) (equilibrium) MPa MPa MPa MPa MPa
C1 69.98 70.65 70.65 70.74 70.27 70.27 70.44
C2 9.32 9.34 9.34 9.35 9.34 9.34 9.32
C3 9.35 9.31 9.31 9.48 9.61 9.61 9.86
i-C4 1.50 1.43 1.43 1.46 1.49 1.49 1.42
n-C4 3.13 2.95 2.95 2.98 3.12 3.12 2.94
i-C5 1.22 1.09 1.09 1.08 1.20 1.20 1.13
n-C5 1.58 1.35 1.35 1.40 1.51 1.51 1.43
n-C6 2.35 2.30 2.30 1.80 1.84 1.84 1.85
n-C7 0.20 0.17 0.17 0.21 0.21 0.21 0.16
CO2 1.14 1.11 1.11 1.12 1.11 1.11 1.13
N2 0.22 0.32 0.32 0.36 0.31 0.31 0.33
C2 + 29.80 29.03 29.03 28.90 29.42 29.42 29.24
Gas density (g/cm3) 0.2646 0.2594 0.2657 0.2695 0.2747 0.2816 0.2872
(from CMGPROP)
Mixture mol. wt. (g/mol) 25.66 25.27 25.27 25.08 25.32 25.32 25.17
Critical pressure (MPa) 12.8 12.69 12.69 12.45 12.53 12.53 12.42
Critical temperature (jC) 18.4 14.27 14.27 12.17 14.82 14.82 13.28

of live oil were captured on a video tape for later
determination of ‘first-contact’ interfacial tension.
Then about 6 ml (or about 10% of cell volume) of
the live oil was added to the cell. The gas and live oil
are then allowed to interact for over 18 h (overnight)
in each of the experiments for attaining gas –oil mass
transfer equilibrium. Then pendent drops of fresh live
oil are formed in the gas phase, which has been
previously equilibrated with the live oil phase. These
drop profile images are first recorded on a video
recorder and then analyzed using the Axisymmetric
Drop Shape Analysis (ADSA) technique to determine
equilibrium interfacial tension between the gas mix-
ture and the live oil.
The pressure in the optical cell is then increased
to the next desired value by injecting the gas
mixture contained in the heated (to 96 jC) barrel
of a high-pressure hand pump. The gas phase in the
 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262 257

Table 6 are needed in calculating interfacial tension using

A. Effect of pressure on equilibrium gas – oil interfacial tension the ADSA procedure.
at 96 jC for the Terra Nova live oil against a gas mixture with Fig. 6 shows the gas – oil interfacial tensions meas-
C2 + of 41.20 mol% (IFT in mN/m)
ured at varying pressure levels in the cell for all the
Drop # Pressure (MPa) three C2 + enrichment levels of 9.3%, 21.4%, and
26.2 MPa 26.20 MPa 29.4%. It also includes the results of a repeat test
(first contact) (equilibrium) conducted with 20.7% C2 + gas mixture. Linear least-
1 0.37 Unable to form square lines were fitted to each set of data and
2 0.40 drops. Approaching extrapolated to zero-gas – oil interfacial tension to
3 0.27 miscibility.
determine the minimum miscibility pressures. The
4 0.51
5 0.36 MMP was found to be 62.9 MPa when the C2 +
6 0.57 content of the gas phase varied from 9.08% to
7 0.50 9.49%, 57.8 MPa when the C2 + concentration range
8, 9 0.50, 0.63 was 21.24 – 21.65%, and 31.8 MPa at the C2 +
10, 11 0.70, 0.42
concentration range of 28.9 –29.8%. When the cell
11, 12 0.22, 0.23
Average 0.44 was charged with the gas phase containing 41.2%
Standard deviation 0.14 C2 + fraction, only the first-contact interfacial ten-
sion could be measured to be 0.44 mN/m at 26.2
B. Chromatographic analysis of gas composition (in mol%) corres- MPa. When the gas phase was equilibrated with
ponding to panel A
about 6 ml of live oil in the optical cell to determine
Component Pressure the equilibrium interfacial tension, gas –oil interface
26.2 MPa 26.20 MPa was observed to be unstable as the oil became
(first contact) (equilibrium) miscible with the gas phase as soon as it emerged
C1 58.60 58.75 from the tip of the capillary tube. Thus, even at the
C2 11.28 11.30 starting pressure of 26.2 MPa, gas phase containing
C3 13.96 13.95
41.2% C2 + was considered to be miscible with the
i-C4 1.86 1.86
n-C4 5.53 5.51 live crude oil.
i-C5 1.72 1.69 It can be noticed in Fig. 6 that the linear regression
n-C5 2.21 2.16 line corresponding to the 21.4% C2 + data set has a
n-C6 2.98 2.75 different slope than the other two lines. Hence, it was
n-C7 0.54 0.63
decided to repeat this test by recombining a new gas
CO2 1.12 1.12
N2 0.20 0.28 mixture and restarting the measurements in a thor-
C2 + 41.20 40.97 oughly cleaned experimental system. The new set of
Gas density (g/cm3) 0.3209 0.3209 data, which are also plotted in Fig. 6, lie very close to
(from CMGPROP) the old set clearly indicating the good reproducibility
Mixture mol. wt. (g/mol) 29.74 29.74
of these measurements. The new MMP for the 20.7%
Critical pressure (MPa) 12.28 12.28
Critical temperature (jC) 54.23 54.23 C2 + gas was found by extrapolation to be 57.2 MPa
which differed from the previously determined value
(of 57.8 MPa) by about 1%.
The three rows of drop images shown in Fig. 7
optical cell is then sampled, after allowing 1.5 h for correspond to the three C2 + enrichment levels in
oil – gas equilibrium, and analyzed on a gas chro- these tests. The pressures at which miscibility was
matograph. The composition from the chromato- visibly evident, as shown by the drop images in the
graphic analyses is then fed to the CMGPROP last column of Fig. 7, are also indicated by arrows in
property package to calculate the gas density at Fig. 6. It can be seen that in all three cases, the MMP
the operating temperature and pressure as well as at zero-interfacial tension was higher (by about 3 –
the gas molecular weight and the pseudocritical 5%) of the visually observed miscibility pressure.
temperature and pressure. The gas and oil densities Thus, MMP from the VIT technique appears to be
258 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262

Fig. 6. Effect of pressure on interfacial tension of Terra Nova live oil in three solvents at 96 jC.

Fig. 7. Video images of Terra Nova live crude oil drops at different pressures and solvent gas compositions.
 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262 259

slightly conservative and well supported by visual Table 7

observations. Effect of aging time on gas composition in the interfacial tension
cell
Component Gas analysis (mol%)
3.5. Determination of minimum miscibility composi-
tion at reservoir pressure and temperature Aging time Aging time
after rich gas after rich gas
addition = 1.5 h addition = 18.5 h
The next series of gas –oil interfacial tension meas-
C1 87.77 87.67
urements were conducted with the objective of opti-
C2 5.95 5.85
mizing the injection gas composition to attain C3 2.68 2.48
miscibility with the reservoir crude oil. For these i-C4 0.28 0.23
measurements both the pressure and temperature in n-C4 0.65 0.49
the optical cell were kept constant at the field operat- i-C5 0.36 –
n-C5 0.40 1.05
ing conditions of 30 MPa and 96 jC. The cell was
C6 0.58 0.54
first filled with the lean gas mixture (containing C7 0.09 0.24
9.49% of C2 + fraction). About 6 ml of live oil was CO2 0.93 0.92
added to the cell and the two phases were allowed to N2 0.31 0.54
reach equilibrium overnight. A gas sample was taken Total 100.00 100.00
C2 + ( = 100 C1 – N2) 11.92 11.79
from the cell and analyzed, its composition used in
calculating the CO2 + C2 + concentration, and its den-
sity for use in the interfacial tension calculations. literally to mean the first-contact between gas and
Fresh live crude oil drops were then brought into live-oil in the cell. This resembles the field situation
the previously equilibrated gas phase, and the drop where the gas injected down the well first meets the
images were captured on a videotape for later ADSA oil in the reservoir. As the gas advances in the
analyses for obtaining interfacial tension. A rich gas reservoir, it continues to interact with fresh oil resid-
mixture (previously prepared and its composition is ing ahead of the front. Meanwhile, the fresh gas that is
given in the last column of Table 1) containing 48% being continuously injected into the well meets the
C2 + fraction, was then added by means of a high- residual oil that has interacted with the gas previously.
pressure hand pump to the gas phase in the optical cell The addition of fresh gas during VIT experiment is an
to reach the next desired enrichment level. The system attempt to simulate this process. The ‘‘first-contact’’
was allowed to age for at least 2 h to equilibrate before points plotted in Fig. 8 correspond to the IFT of the
beginning the interfacial tension measurements. ‘‘first’’ 5– 6 drops of fresh live oil drops contacting
Table 7 shows the negligible change in composi- the gas phase in the cell without any oil at the bottom.
tion of the gas phase at 1.5 h and 18.5 h of aging Since the mass transfer is yet to occur when these first
subsequent to the addition of the rich gas to the optical few drop images were captured, the IFTs are higher
cell. Fresh live crude oil drops were then allowed to than for those drops lying on the line marked ‘‘equi-
flow into the cell at a low flow rate and the images of librium data.’’ However, when all the first-contact IFT
the drops were again captured on videotape for later data are extrapolated to zero-IFT, we arrive at the gas
ADSA analyses. This procedure of adding calculated phase composition (or enrichment) that is ‘‘first-con-
amounts of the rich gas to the optical cell, allowing 2 tact miscible’’ with the crude oil. This is because
h for equilibrium at the new enrichment level and beyond this zero-IFT point on the composition axis,
capturing images of fresh live crude oil drops, flowing the injected gas and reservoir crude oil would not
into the equilibrated gas phase and calculating the have an interface and hence, are first-contact miscible
gas – oil interfacial tension was repeated at each in the traditional sense of the term (that they are
enrichment level. The results are presented in Table miscible in all proportions). It is important to note
8 and plotted in Fig. 8. that on VIT plots, such as Figs. 6 and 8, miscibility
Fig. 8 also includes the first-contact interfacial occurs only to the right of the zero-IFT point on the x-
tension data measured at 26.2 MPa during the MMP axis. Regions to the left of the zero-IFT point repre-
determination steps. The term ‘‘first-contact’’ is used sent immiscible two-phase zones of gas and oil.
260 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262

Table 8
Effect of gas composition on equilibrium gas – oil interfacial tension at 30 MPa and 96 jC for the Terra Nova live oil (IFT in mN/m)
Drop # C2 + Concentration in gas phase (mol%)
9.49 11.79 14.22 18.57 24.64 27.77
1 3.21 3.06 2.65 2.01 1.13 0.61
2 3.24 3.02 2.58 1.99 1.20 0.66
3 3.21 3.13 2.60 1.89 1.44 0.55
4 3.15 3.00 2.59 2.04 0.85 0.88
5 3.14 3.11 2.67 1.92 1.10 0.67
6 3.19 3.14 2.63 2.09 0.88 0.99
7 3.20 3.08 2.60 2.11 0.85 0.44
8 3.19 3.07 2.49 1.98 1.06 0.68
9, 10 3.15, 3.14 2.59, 2.63 1.97, 2.14 1.21, 1.01 0.90, 0.89
11, 12 3.06, 3.09 2.58 2.07 1.11, 1.13 0.84
Average 3.19 3.09 2.60 2.02 1.07 0.73
Standard deviation 0.03 0.05 0.05 0.08 0.20 0.16

Chromatographic analysis of gas from IFT cell (mol%)

C1 90.10 87.67 85.45 81.14 75.10 71.98
C2 5.73 5.85 6.62 7.50 8.72 9.14
C3 2.16 2.48 3.84 5.32 7.78 8.78
i-C4 0.16 0.23 0.45 0.75 1.15 1.31
n-C4 0.24 0.49 1.06 1.83 2.88 3.30
i-C5 0.04 0.0 0.28 0.51 0.80 1.01
n-C5 0.07 1.05 0.37 0.59 0.87 1.17
n-C6 0.09 0.54 0.44 0.92 1.21 1.74
n-C7 0.07 0.24 0.18 0.15 0.19 0.30
CO2 0.94 0.92 0.98 1.00 1.04 1.02
N2 0.40 0.54 0.32 0.28 0.26 0.25
C2 + (mol%) 9.49 11.79 14.22 18.57 24.64 27.77
Density (g/cm3) 0.1877 0.2031 0.2093 0.2294 0.2565 0.2743
Mol. wt. (g/mol) 18.11 19.35 19.83 21.38 23.41 24.74
Critical pressure (MPa) 6.5 7.5 8.3 10.1 11.7 12.5
Critical temperature (jC)
59.9
57.0
46.9
29.6
5.37 8.9

Each of the two data sets in Fig. 8 is fitted with a
linear least squares line, which when extended to the
zero-interfacial tension axis gives the minimum mis-
cibility composition (MMC). From these interfacial
tension data, a minimum enrichment of 32.33 mol%
of (CO2 + C2 +) for the equilibrium miscibility, and a
minimum enrichment of 42.68 mol% of (CO2 + C2 +)
for the ‘first-contact’ miscibility, are obtained. The
‘first-contact’ data set shows a wider scatter, which is
perhaps due to the very nature of these first-contact
experiments. However, the estimated MMC of 42.68
mol% appears to be a conservative value, considering
the fact that the measured interfacial tension value of
0.44 mN/m at 41.4 mol% C2 + is relatively high for
the close-to-miscible behavior observed during the
test. The difference between the ‘‘first-contact’’ and
equilibrium MMCs is about 10 mol% in C2 + con-
centration. It is interesting to note here that a differ-
ence of 9 mol% C2 + was observed between the
first-contact and equilibrium MMCs (both being
measured at the same pressure of 14.8 MPa) in
another study (Rao et al., 1999) conducted for the
Rainbow Lake F pool. That study also reported a
similar difference of 9 mol% between first and
multiple contact miscibility compositions calculated
from a ternary diagram generated using a commer-
cial PVT package. In this Terra Nova study, the
difference was 10.35 mol% (somewhat higher than
the 9 mol% of Rainbow study) due mainly to the
fact that the ‘first-contact’ data was measured at 26.2
MPa and the equilibrium data was measured at 30
MPa. It is reasonable to expect a lower difference
than 10.35 mol% had both data sets been measured
at the same pressure.
 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262
Fig. 8. Effect of gas phase enrichment on gas – oil interfacial tension for Terra Nova live oil at 96 jC.
3.6. Visual observations of miscibility
The fact that the VIT technique makes use of an
optical cell (for interfacial tension determinations)
provides an advantage in that visual observations of
miscibility can be made simultaneously during the
experiments. Fig. 7 shows some examples of images
of actual live oil pendent drops suspended in solvent
gas phase at different pressures and varying gas phase
compositions. The pressure, composition and interfa-
cial tension data are also shown on these images. The
approach to miscibility is clearly evident as interfacial
tension decreases. The last column of images displays
miscible conditions clearly because of the absence of
an interface between gas and oil phases. These visu-
ally observed miscibility pressures were identified in
Fig. 6 for comparison with MMP at the point of zero-
IFT. As noted before, the zero-IFT pressures were
about 3 –5% higher than the visual miscibility pres-
sures. Hence, the MMP and MMC values from the
VIT technique appear to be slightly conservative and
well supported by actual visual observations of mis-
cibility.
261
4. Summary and conclusions
A simple, recently developed technique, called the
vanishing interfacial tension (VIT) technique, has
been utilized in this study to determine minimum
miscibility pressure and composition for the Terra
Nova offshore field.
The main feature of the VIT 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 the
vanishing interfacial tension as the injected gas phase
approaches miscibility with the crude oil in the
reservoir, due to the imposed pressure or composition
changes. Since the technique involves visual image
capture and analysis for interfacial tension measure-
ments, it enables visual observations of the approach
to miscibility between the phases at actual reservoir
conditions. This provides evidence for miscibility
determined from the VIT technique. In this paper,
we have presented the minimum miscibility pressures
and compositions (MMPs and MMCs) determined
using the VIT technique along with visual observa-
262 D.N. Rao, J.I. Lee / Journal of Petroleum Science and Engineering 35 (2002) 247–262
tions of miscibility for three different field gases with
the Terra Nova live crude oil at reservoir temperature
of 96 jC.
The MMP was found to be 62.9 MPa when the
C2 + content of the gas phase varied from 9.08% to
9.49%, 57.8 MPa when the C2 + concentration range
was 21.24% to 21.65%, and 31.8 MPa at the C2 +
concentration of 28.9% to 29.4%. A repeat test con-
firmed the MMP within about 1% indicating the
reproducibility of the VIT technique. These MMPs
were within 3 – 5% of the pressures at which misci-
bility was visually observed in the optical cell during
the tests.
The injection gas composition was optimized for
miscibility by conducting VIT tests at varying gas
compositions at the operating pressure of 30 MPa and
temperature of 96 jC. The minimum miscibility
composition (MMC) of the injection gas in a gas –
oil equilibrium mode at these conditions was found to
be 32.33 mol% C2 + .
Additional data were recorded during several of the
experiments to enable the determination of first-con-
tact miscibility composition. These data were meas-
ured at the starting pressure of 26.2 MPa during
pressure series experiments and at the reservoir tem-
perature of 96 jC. From these limited number of data
points, the first-contact MMC was estimated to be
about 42.7 mol% C2 + . Similar differences between
first-contact and equilibrium enrichments of the gas
phase were observed in another field application of
the VIT technique.
This study has demonstrated that the VIT techni-
que is rapid, reproducible and quantitative in addition
to providing visual evidence of miscibility between
injected gas and reservoir live oil.
Acknowledgements
The authors thank the management of Petro-
Canada Oil and Gas for permission to publish this
work. Sincere thanks are due to Marcel Girard of
Petroleum Recovery Institute for making the inter-
facial tension measurements, and Jeanette Wooden,
Rajesh Pillai and Chandrasekhar Vijapurapu of
Louisiana State University for their help in preparing
the manuscript.
References
Benham, A.L., Dowden, W.E., Kunzman, W.J., 1965. Miscible fluid
displacement—prediction of miscibility. Petroleum Transactions
Reprint Series No. 8. Society of Petroleum Engineers of AIME,
p. 123.
Computer Modelling Group, 1994. Phase Behavior Package User’s
Guide. CMGPROP 95.00, Calgary, Canada, November 8.
Green, D.W., Willhite, G.P., 1998. Enhanced Oil Recovery. SPE
Textbook Series. Society of Petroleum Engineers, Richardson,
Texas.
Holm, L.W., 1987. Miscible displacement. In: Bradley, H.B. (Ed.),
Petrology Engineering Handbook. Society of Petroleum Engi-
neers, Richardson, TX, pp. 1 – 45.
Lake, L.W., 1989. Enhanced Oil Recovery. Prentice-Hall, Engle-
wood Cliffs, NJ, p. 234.
Moritis, G., 1998. EOR oil production up slightly. Oil Gas J., 49.
Poettmann, F.H., Christiansen, R.L., Mihcakan, I.M., 1992. Discus-
sion of methodology for the specification of solvent blends for
miscible enriched-gas drives. SPE Reserv. Eng., 154.
Rao, D.N., 1997. A new technique of vanishing interfacial tension
for miscibility determination. Fluid Phase Equilib. 139, 311.
Rao, D.N., 2001. Gas injection EOR—a new meaning in the new
millennium. J. Can. Pet. Technol. 41 (2), 11.
Rao, D.N., McIntyre, F.J., Fong, D.K., 1999. Application of a new
technique to optimize injection gas composition for the Rain-
bow Keg River ‘F’ Pool Miscible Flood. J. Can. Pet. Technol.,
Petroleum Society’s 50th Anniversary Special Edition 38 (13).
Rotenberg, Y., Boruvka, L., Neumann, A.W., 1983. Determination
of surface tension and contact angle from the shapes of axisym-
metric fluid interfaces. J. Colloid Interface Sci. 93 (1), 169.
Stalkup Jr., F.I., 1983. Miscible displacement. SPE Monogr., vol. 8.
SPE of AIME, New York.
Zhou, D., Orr, F.M., 1998. Analysis of rising-bubble experiments to
determine minimum miscibility pressures. SPE J., 19.