Interfacial Interactions between Reservoir Brine and

CO
2
at High Pressures and Elevated Temperatures
Daoyong Yang, Paitoon Tontiwachwuthikul, and Yongan Gu*
Petroleum Technology Research Centre (PTRC), Petroleum Systems Engineering,
Faculty of Engineering, University of Regina, Regina, Saskatchewan S4S 0A2, Canada
Received August 18, 2004. Revised Manuscript Received October 26, 2004
In this paper, an experimental technique has been developed to study the interfacial interactions
of the reservoir brine-CO
2
system at high pressures and elevated temperatures. Using the
axisymmetric drop shape analysis (ADSA) for the pendant drop case, this new technique makes
it possible to determine the interfacial tension (IFT) and visualize the interfacial interactions
between the reservoir brine and CO
2
under practical reservoir conditions. More specifically, the
dynamic IFT between the reservoir brine and CO
2
is measured as a function of pressure at two
different temperatures. It is found that the dynamic IFT gradually reduces to a constant value,
which is termed as the equilibrium IFT. The equilibrium IFT decreases as the pressure increases,
whereas the same parameter increases as the temperature increases. The major interfacial
interactions observed in this study include interface disappearance, the swelling effect, the
shrinking effect, and wettability alteration. At an elevated temperature (T ) 58 C), the pendant
brine drop cannot be observed in the CO
2
phase at a pressure of P g 12.238 MPa. It is also found
that CO
2
solubility in the brine phase, which is measured using the PVT system, approaches its
maximum value under the same conditions. Further increases in pressure do not noticeably
increase the CO
2
solubility in the brine phase. The brine swelling effect is observed at all the
pressures and temperatures tested, whereas the brine shrinking effect occurs only at high
pressures and a lower temperature (T )27 C). In addition, the wettability of the reservoir brine-
CO
2
system changes from the hydrophilic case to the hydrophobic case when the CO
2
changes
from the gas phase to the liquid phase.
Introduction
Geological sequestration of anthropologic CO
2
is a
potential technology for greatly mitigating greenhouse
gas emissions. In this way, CO
2
is either sequestrated
in a depleted oil/gas reservoir or disposed from station-
ary sources into a saline aquifer. Successful sequestra-
tion of CO
2
is largely controlled by the interfacial
interactions among brine, CO
2
, and the reservoir miner-
als.
1
The major interfacial interactions include the
interfacial tension (IFT), wettability, capillarity, and
interface mass transfer. It has long been recognized that
these interactions govern both the distribution of fluids
and their flow behavior in porous media.
2,3
As a first
step, it is of fundamental and practical importance to
thoroughly study the interfacial interactions between
the reservoir brine and CO
2
at high pressures and
elevated temperatures.
Recently, a field-scale project for CO
2
enhanced oil
recovery (EOR) and CO
2
sequestration has been under-
taken in the Weyburn oil field
1
and a large-scale CO
2
sequestration project is underway in the Sleipner saline
aquifer.
4
The International Energy Agency (IEA) Green-
house Gas (GHG) Weyburn CO
2
Monitoring and Storage
Project is recognized as the worlds largest joint field
test for sequestrating CO
2
in a depleted oil reservoir,
although it is currently still at the EOR stage.
5
After
CO
2
is injected into a depleted reservoir or saline aquifer
under the supercritical condition, most of the injected
CO
2
remains in the supercritical state, whereas the
remainder dissolves in the crude oil and/or brine phase
and interacts with the native minerals. The IFT phe-
nomenon under high pressures controls the migration
of CO
2
and brine in the porous media. Although there
are numerous dynamic and/or equilibrium IFT data for
the water-CO
2
systems at different pressures and
temperatures,
6-9
no IFT data are made available for the
reservoir brine-CO
2
system under practical reservoir
conditions.
An updated literature search shows that few attempts
are made to relate the interfacial properties of the
* Author to whom correspondence should be addressed. Telephone:
1-306-585-4630. Fax: 1-306-585-4855. E-mail: Peter.Gu@Uregina.Ca.
(1) Emberley, S.; Hutcheon, I.; Shevalier, M.; Durocher, K.; Gunter,
W. D.; Perkins, E. H. Energy 2004, 29 (9-10), 1393-1401.
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2004, 47 (17-18), 3649-3657.
(3) Yang, D.; Gu, Y. Interfacial Phenomena of the Oil-Fluid-Rock
Systems in Carbon Dioxide Flooding Reservoirs. In Recent Develop-
ments in Colloids and Interface Research; Pandalai, S. G., Ed.;
Transworld Research Network: Kerala, India, 2003; Vol. 1, pp 115-
127.
(4) Arts, R.; Eiken, O.; Chadwick, A.; Zweigel, P.; van der Meer, L.
Energy 2004, 29 (9-10), 1383-1392.
(5) Moritis, G. Oil Gas J. 2004, 102 (14), 45-52.
(6) Jho, C.; Nealon, D.; Schobola, S.; King, A. D., Jr. J. Colloid
Interface Sci. 1978, 65 (1), 141-154.
(7) Chun, B. S.; Wilkinson, G. T. Ind. Eng. Chem. Res. 1995, 34 (12),
4371-4377.
(8) Hebach, A.; Oberhof, A.; Dahmen, N.; Kogel, A.; Ederer, H.;
Dinjus, E. J. Chem. Eng. Data 2002, 47 (6), 1540-1546.
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216 Energy & Fuels 2005, 19, 216-223
10.1021/ef049792z CCC: $30.25 2005 American Chemical Society
Published on Web 12/13/2004
binary systems to their miscibility and solubility under
reservoir conditions. In practice, miscibility is consid-
ered to occur if there is no interface between the two
phases involved (i.e., zero IFT) or if the two phases can
be mixed together at any ratio.
10
On the other hand,
solubility of CO
2
in the reservoir brine represents how
much CO
2
dissolves in the reservoir fluids at the
equilibrium state, depending on the pressure and tem-
perature. To date, the miscibility between reservoir
brine and CO
2
has not been reported in the literature.
Although the solubility data of the water-CO
2
systems
covering large pressure and temperature ranges can be
found elsewhere,
11-16
few data are available for the
reservoir brine-CO
2
systems at high pressures and
elevated temperatures.
16,17
Generally, it has been as-
sumed that CO
2
solubility in the brine phase is low
because of its high salinity.
11
Furthermore, the complex
relationships among the equilibrium IFT, miscibility,
and solubility are not explored.
In this paper, an experimental technique is developed
to study the interfacial interactions of the reservoir
brine-CO
2
system under practical reservoir conditions.
Based on the axisymmetric drop shape analysis (ADSA)
for the pendant drop case, this new technique is used
to measure the IFTs and visualize the interfacial
interactions between the reservoir brine and CO
2
at
high pressures and elevated temperatures. More specif-
ically, the dynamic and equilibrium IFTs between the
reservoir brine and CO
2
are measured at different
pressures and two temperatures. Several important
physical phenomena are observed after the fresh brine
phase is made in contact with CO
2
. The measured IFT
data and the visualized interfacial interactions under
reservoir conditions should facilitate design of the CO
2
EOR and CO
2
sequestration processes. Certain relation-
ships also are found to exist among the equilibrium
IFT, miscibility, and solubility for the reservoir brine-
CO
2
system at high pressures and elevated tempera-
tures.
Experimental Section
Materials. The brine sample was collected from the Instow
field in Saskatchewan, Canada. Its density is 1.003 g/cm
3
at
15 C, and its pH value is 8.66 at 22 C. This brine sample
mainly contained 1500 mg/L of sodium, 2050 mg/L of chloride,
and 928 mg/L of bicarbonate, and the total dissolved solids
(TDS) content was 4270 mg/L at 110 C. The densities of CO2
at different pressures and temperatures are calculated from
a standard property table.
18
The purity of CO2 and nitrogen
(each from Praxair, USA) was 99.99% and 99.998%, respec-
tively. For CO2, its critical pressure is 7.38 MPa and its critical
temperature is 30.95 C.
18
Apparatus. In this study, the ADSA technique for the
pendant drop case is used to measure the dynamic and
equilibrium IFTs of the reservoir brine-CO2 system at differ-
ent pressures and temperatures. The ADSA technique is
probably the most advanced and accurate method for measur-
ing the IFT in a large range of pressures and temperatures.
19,20
In principle, the ADSA technique determines the IFT from the
pendant drop shape analysis. In experiment, a pendant brine
drop in CO2 phase is formed at the tip of a syringe needle. Its
digital image then is acquired, using a digital image acquisi-
tion system. Through application of computer digital image
analysis and processing techniques, an accurate interfacial
profile of the pendant brine drop is obtained. Finally, the IFT
of the pendant brine drop surrounded by CO2 phase is
determined by solving the Laplace equation of capillarity and
finding the best fit of the numerically calculated interfacial
profile to the physically observed drop profile. In comparison
with the other existing methods, the ADSA technique for the
pendant drop case is accurate for the IFT measurement ((0.05
dyne/cm), fully automatic, and completely free of the operators
subjectivity. At present, this technique becomes a standard
method for measuring the IFT.
A schematic diagram of the ADSA system for the pendant
brine drop case used in this study is shown in Figure 1. The
major component of this system is a high-pressure cell with
two see-through windows (IFT-10, Temco, USA). The maxi-
mum operating pressure and temperature of this pressure cell
are 69 MPa and 177 C, respectively. The temperature during
the test is maintained by wrapping the pressure cell with two
heating tapes (HT955041, Electrothermal, USA), which are
connected to a stepless temperature controller (CN45515,
Thermolyne, USA). There are a total of six ports around the
pressure cell. In this study, the top port is used to introduce a
pendant brine drop in the presence of the CO2 phase, and the
bottom port serves as a draining outlet. Among the other four
ports on the side, one is for pressure measurement, using a
digital pressure gauge (DTG-6000, 3D Instruments, USA),
one is for temperature measurement using a thermocouple
(JMQSS-125U-6, Omega, USA) and a temperature display
(MDSS 41-T-A, Omega, USA), one is for installation of a
rupture valve (P-7019, Oseco, USA), and the last port is for
the injection of CO2.
In the ADSA system, the see-through windowed high-pres-
sure cell is placed between a light source and a MZ6 microscope
camera (Leica, Germany). A pendant brine drop is formed in
the CO2 phase at the tip of a stainless-steel needle, which is
installed at the top of the pressure cell. The entire experimen-
tal setup is mounted on a vibration-free table (RS 4000,
Newport, USA). A Dell desktop computer is used to acquire
the digital image of the pendant brine drop and perform the
subsequent drop image analysis, digitization, and computation.
Figure 2 shows a block diagram of the experimental setup
used to measure the IFT and visualize the interfacial interac-
tions of the reservoir brine-CO2 system at high pressures and
(10) Green, D. W.; Willhite, G. P. Enhanced Oil Recovery; SPE
Textbook Series, Vol. 6; Society of Petroleum Engineers: Richardson,
TX, 1998.
(11) Klins, M. A. Carbon Dioxide Flooding: Basic Mechanisms and
Project Design; International Human Resources Development Corpora-
tion: Boston, MA, 1984.
(12) Mori, Y. H.; Mochizuki, T. Energy Convers. Manage. 1998, 39
(7) 567-578.
(13) Teng, H.; Yamasaki, A. J. Chem. Eng. Data 1998, 43 (1), 2-5.
(14) Dhima, A.; de Hemptinne, J.; Jose, J. Ind. Eng. Chem. Res.
1999, 38 (8), 3144-3161.
(15) Diamond, L. W.; Akinfiev, N. N. Fluid Phase Equilib. 2003,
208 (1-2), 265-290.
(16) Enick, R. M.; Klara, S. M. Chem. Eng. Commun. 1990, 90, 23-
33.
(17) Li, Z.; Dong, M.; Li, S.; Dai, L. J. Chem. Eng. Data 2004, 49
(4), 1026-1031.
(18) Jarrell, P. M.; Fox, C. E.; Stein, M. H.; Webb, S. L. Practical
Aspects of CO
2 Flooding; SPE Monograph Series, Vol. 22; Society of
Petroleum Engineers: Richardson, TX, 2002.
(19) Rotenberg, Y.; Boruvka, L.; Neumann, A. W. J. Colloid Interface
Sci. 1983, 93 (1), 169-183.
(20) Cheng, P.; Li, D.; Boruvka, L.; Rotenberg, Y.; Neumann, A. W.
Colloids Surf. 1990, 43 (2), 151-167.
Figure 1. Schematic of the axisymmetric drop shape analysis
(ADSA) system for the pendant brine drop case.
Reservoir Brine-CO
2
Interfacial Interactions Energy & Fuels, Vol. 19, No. 1, 2005 217
elevated temperatures. This setup consists of the ADSA
system, a control panel, and a fluids handling system. Mounted
on the vibration-free table, the control panel has eight needle
valves that are used to control the flow rate and direction. In
the fluids handling system, three cylinders are used, to clean
the pressure cell and the entire tubing system with acetone
(EM Science, USA), pressurize the pressure cell with CO2, and
introduce the pendant brine drop, respectively.
In addition, a mercury-free PVT system (PVT-0150-100-200-
316-155, DBR, Canada) is used to conduct the solubility
measurements of CO2 in the reservoir brine. Such measured
CO2 solubility in the brine phase is related to the physical
phenomena observed in the pendant brine drop experiments.
The maximum operating pressure and temperature of the PVT
system are 69 MPa and 200 C, respectively. The major
component of this PVT system is a visual PVT cell, where fluid
samples are encapsulated inside a glass tube and isolated from
the hydraulic oil by a moveable isolation piston. The cell
pressure can be readily adjusted by changing the pressure in
the hydraulic system to move the isolation piston down-
ward or upward. The visual PVT cell, together with a video-
based digital cathetometer, allows direct and accurate mea-
surement of the phase volumes. It is also equipped with a
magnetically coupled mixer, which can effectively mix the
fluid-liquid system. The PVT cell and two sample cylinders
are kept in a constant-temperature air bath: one cylinder is
filled with CO2, and the other is filled with the reservoir
brine. The constant temperature inside the air bath is
maintained using a microprocessor-based controller, in con-
junction with a resistance temperature device (RTD) sensor.
An automatic positive displacement pump (PMP-500-1-10-MB-
316-M4-CO, DBR, Canada) is used to generate high fluid
pressures and accurately displace prespecified amounts of fluid
samples from the sample cylinders to the PVT cell. A computer-
based data acquisition system is used to automatically record
the cell pressure, cell temperature, and pump displacement
volume.
Experimental Procedure
IFT Measurement. Prior to the first experiment, the
entire system is tested for leakage with deionized water,
then cleaned with acetone, flushed with nitrogen, and
finally evacuated. The pressure cell is then pressurized
with CO
2
to a prespecified pressure, using a manual
positive displacement pump (PMP-500-1-10-HB, DBR,
Canada). After the CO
2
is injected, usually 30-60 min
are needed for the pressure and temperature inside the
pressure cell to reach their stable values. Note that the
brine and CO
2
are not pre-equilibrated in the experi-
ments, because the purpose of this study is to determine
both the dynamic and equilibrium IFTs when CO
2
dissolves into a fresh brine phase. This is conducted to
model the process during which CO
2
is placed in contact
with the brine phase for the first time after CO
2
is
injected into a saline aquifer or an oil reservoir for CO
2
sequestration and/or CO
2
EOR.
The general experimental procedure for the IFT mea-
surements and visual observations is briefly described
as follows. A pendant brine drop is introduced from the
brine cylinder, whose pressure is maintained 0.1-0.5
MPa higher than that of CO
2
phase inside the pressure
cell. The pendant brine drop is formed at the tip of the
stainless-steel needle, using a specially designed high-
pressure syringe delivery system. After the pendant
brine drop is formed in CO
2
phase, its digital image is
well-focused, acquired sequentially, and stored auto-
matically in the computer memory. For each digital
brine drop image, a standard grid image is used to
calibrate the drop image and correct possible optical
distortion. The ADSA program for the pendant drop case
then is executed to determine the dynamic and equi-
librium IFTs of the pendant brine drop, as well as the
entire drop profile. The output data also include the
radius of the curvature at the apex point, and the
volume and surface area of the pendant brine drop. Only
the local gravitational acceleration and the density
difference between the brine phase and CO
2
are re-
quired as the input data for this program.
The IFT measurements are conducted for at least
three different pendant brine drops, to ensure satisfac-
tory repeatability at the specified pressure and temper-
ature. After each test, the pressure cell and the entire
tubing system are cleaned with acetone, then flushed
with nitrogen and finally vacuumed. In this study, nine
pressures are tested, in the range of 0.1-30.0 MPa, and
two temperatures (27 and 58 C) are selected to cover
most practical cases of interest.
Figure 2. Block diagram of the experimental setup used to study the interfacial interactions of the reservoir brine-CO2 system
at high pressures and elevated temperatures.
218 Energy & Fuels, Vol. 19, No. 1, 2005 Yang et al.
Solubility Measurement. Prior to each solubility
measurement, the PVT cell and the fluids handling
system in the PVT system are thoroughly cleaned with
acetone and then nitrogen three times and finally
evacuated, to remove any traces of the cleaning re-
agents. The temperature of the air bath is set to the
desired value 24 h before the measurement, to allow the
sample cylinders and the PVT cell to reach the preset
temperature.
To measure the solubility of CO
2
in the brine sample,
the PVT cell is filled with CO
2
first. After the cell is
allowed to stabilize for 4 h, the initial CO
2
pressure (P
0
),
CO
2
temperature (T
0
), and CO
2
phase volume (V
0
) are
recorded. Next, a total brine sample volume of V
brine
)
35 cm
3
is injected into the PVT cell at the injection rate
of 2000 cm
3
/h, using the automatic positive displace-
ment pump. The magnetic mixer then is turned on, to
vigorously mix the brine sample with CO
2
. Finally, after
the brine-CO
2
mixture reaches the equilibrium state,
as indicated by constant cell pressure and temperature,
the mixer is stopped and the equilibrium CO
2
pressure
(P
e
), CO
2
temperature (T
e
), and CO
2
phase volume (V
e
)
are obtained. Note that, during the solubility measure-
ments, the equilibrium CO
2
temperature (T
e
) is almost
same as the initial CO
2
temperature (T
0
), because the
sample cylinders and the entire PVT cell are placed
inside the constant-temperature air bath. By applying
the conservation of mass and the equation of state for
a real gas, the solubility of CO
2
in the brine sample ()
can be determined from the following equation:
where R is the universal gas constant, M
CO2
is the
molecular weight of CO
2
, F
brine
is the density of the fresh
brine sample with no dissolution of CO
2
, and Z
0
and Z
e
are the compressibility factors (Z-factors) of CO
2
at the
initial state (P
0
, T
0
) and at the equilibrium state (P
e
,
T
e
), respectively.
Results and Discussion
Swelling Effect and Shrinking Effect. During the
experiments, the joint effect of brine swelling and
shrinking is manifested by a change in the volume of
the pendant brine drop. The pendant brine drop swells
after it is formed in the presence of CO
2
inside the
pressure cell. Figure 3a shows that, at P ) 0.121 MPa
and T )27 C, the pendant brine drop continues to swell
and its volume continues to increase from 7.954 mm
3
at t ) 0 s to 8.858 mm
3
at t ) 9022 s. This is mainly
ascribed to CO
2
dissolution in the brine phase. Finally,
the brine drop detaches from the needle tip due to the
force imbalance between the downward gravity and the
upward surface force. When pressure is increased to P
) 8.506 MPa, as shown in Figure 3b, or higher at T )
27 C, the brine drop initially swells, because of the CO
2
dissolution in the brine phase, and then shrinks,
because of the mass transfer from the pendant brine
drop to the CO
2
phase. A similar phenomenon has also
been reported by Kogel et al.
21
for the water-CO
2
system.
The observed swelling and shrinking effects are
explained as follows. In the brine-CO
2
binary system,
(21) Kogel, A.; Dahman, N.; Ederer, H. J. Supercrit. Fluids 2003,
29 (3), 237-249.
Figure 3. Sequential digital images of the pendant brine drop in CO2 with the swelling effect and shrinking effect: (a) P ) 0.121
MPa at T ) 27 C, (b) P ) 8.506 MPa at T ) 27 C, and (c) P ) 0.130 MPa at T ) 58 C.
)
M
CO
2
RF
brine
V
brine
(
P
0
V
0
Z
0
T
0
-
P
e
V
e
Z
e
T
e
)
100
Reservoir Brine-CO
2
Interfacial Interactions Energy & Fuels, Vol. 19, No. 1, 2005 219
CO
2
contacts the brine-CO
2
interface first, then trans-
fers across the interface and finally diffuses into the
pendant brine drop. It has been found that the solubility
of CO
2
in water is 4.0 mol %, whereas that of water
in CO
2
is <0.1 mol % at high pressures and low
temperatures (usually T e 10 C).
22
At the low temper-
atures, only one-way mass transfer (i.e., swelling effect)
is considered (i.e., CO
2
dissolves into water). As the
temperature increases, the solubility of water in CO
2
(i.e., the shrinking effect) increases.
22
Thus, the higher
the temperature, the greater the amount of brine that
transfers to the CO
2
phase. In this study, the mutual
saturation of the binary system is achieved through two-
way mass transfer: dissolution of CO
2
in the brine
phase and permeation of the brine phase into CO
2
.
Although two-way mass transfer occurs simultaneously,
the swelling effect is more pronounced at the beginning
(t e 85 s), whereas the shrinking effect becomes more
significant when t > 85 s at P ) 8.506 MPa and T ) 27
C. At equilibrium, there exists the mutual solubility
of CO
2
and brine.
The swelling effect is still observed when the tem-
perature is increased to T ) 58 C at P ) 0.130 MPa,
as shown in Figure 3c, although the brine shrinking
effect is expectedly stronger at a higher temperature.
In the experiment, the pendant brine drop is observed
to detach quickly (t ) 223 s or less) from the needle tip
as the operating pressure increases. This is attributed
to a higher solubility of CO
2
at a higher pressure. The
brine swelling is an important effect, which should be
taken into account after CO
2
is injected into a previously
water-flooded oil reservoir or sequestrated in a depleted
reservoir or saline aquifer.
11,23,24
However, the brine
swelling effect is usually neglected in CO
2
flooding
processes, because increased salinity of the reservoir
brine results in significantly reduced CO
2
solubility.
11
Therefore, accurate determination of the brine swelling
effect is needed, to estimate the maximum sequestrable
amount of CO
2
in the depleted reservoir or saline
aquifer.
Wettability Alteration. It is observed that the
pendant brine drop is formed around the outer surface
of the needle, as shown in Figure 4a at P e 4.013 MPa
and T ) 27 C. At P g 8.506 MPa and T ) 27 C,
however, the pendant brine drop is formed from the
inner surface of the needle, as shown in Figure 4b. Note
that, at T ) 27 C, CO
2
is in a gas state when the
pressure is 4.013 MPa or lower, whereas it becomes
liquid when pressure is 8.506 MPa or higher. Obviously,
wettability between the reservoir brine and the needle
surface is altered when the CO
2
changes from a gas
phase to a liquid phase. The stainless-steel needle
surface is modified from a hydrophilic surface to a
hydrophobic surface. This is because the needle surface
is coated with an interfacial hydrate layer that is formed
between the brine phase and CO
2
at P g 8.506 MPa
and T ) 27 C. It has been reported that the interfacial
hydrate in a crystalline state is formed between water
and CO
2
at P g 4.5 MPa and T e 10 C,
9,22,25,26
whereas
the hydrate layer, probably in a quasi-crystalline state,
is formed at P ) 6.0-30.0 MPa and T ) 15-40 C.
9,22,26
This means that, in the depleted oil/gas reservoirs or
(22) Teng, H.; Yamasaki, A. Int. J. Heat Mass Transfer 1998, 41
(24), 4315-4325.
(23) Enick, R. M.; Klara, S. M. SPE Reservoir Eng. 1992, 7 (2), 253-
258.
(24) Ipsen, K. H.; Jacobsen, F. L. Energy Convers. Manage. 1996,
37 (6-8), 1161-1166.
(25) Ogasawara, K.; Yamasaki, A.; Teng, H. Energy Fuels 2001, 15
(1), 147-150.
(26) Ohgaki, K.; Hirokawa, N.; Ueda, M. Chem. Eng. Sci. 1992, 47
(8), 1819-1823.
Figure 4. Wettability alteration of the pendant brine drop in CO2 phase under different pressures at T ) 27 C: (a) CO2 in the
gas phase and (b) CO2 in the liquid phase.
220 Energy & Fuels, Vol. 19, No. 1, 2005 Yang et al.
saline aquifers, the interfacial hydrate may prevent CO
2
from closely interacting with the reservoir rocks. When
the temperature is increased to T )58 C, no wettability
alteration is observed in the pressure range tested in
this study.
Miscibility and Solubility. Figure 5 shows digital
images of the pendant brine drops that formed at
different pressures, from P ) 0.130 MPa (CO
2
in the
gas state) to 7.410 MPa at T ) 58 C (CO
2
in the
supercritical state). However, no pendant brine drop can
be formed and observed when P g 12.238 MPa. In this
case, miscibility between the reservoir brine and CO
2
seems to be achieved, because no interface exists
between the brine phase and the CO
2
, based on a
traditional definition that miscibility is obtained when
no interface exists between the two phases that are
involved.
10
The interface disappearance phenomenon
observed in this study has not been documented in the
literature, although CO
2
is claimed to be a water-
miscible fluid in a CO
2
sequestration process.
27
In fact,
the disappearance of such an observed interface may
result from the two-way mass transfer, i.e., mutual
saturation of the brine phase and CO
2
. In the literature,
it has been found that the mass transfer coefficient from
the water drop to the CO
2
phase is 2.173 10
-3
-2.404
10
-3
cm/s, whereas the mass transfer coefficient from
the CO
2
phase to the water drop is 1.412 10
-4
-1.562
10
-4
cm/s at P ) 23.0 MPa and T ) 62 C.
21
Furthermore, CO
2
solubility is measured using the
PVT system and is related to the interface disappear-
ance phenomenon observed in the pendant drop experi-
ments in which the volume of the pendant brine drop
is sufficiently smaller than that of CO
2
phase. As shown
in Figure 6, the solubility of CO
2
in the brine phase
increases as the pressure increases, whereas it de-
creases as the temperature increases. These two trends
have also been reported for the water-CO
2
system.
12-17
The solubility measured in this study for the Instow
reservoir brine-CO
2
system is similar to that of the
Weyburn reservoir brine-CO
2
system.
17
At T ) 27 C,
solubility cannot be measured when the pressure is
higher than the saturation pressure of CO
2
. This is
because, in this study, solubility is determined from the
equation of state for a real gas, which is not valid when
CO
2
becomes liquid. It is worthwhile to emphasize that
the brine-CO
2
interface disappearance phenomenon is
not observed in the solubility measurements in which
the volume of the brine phase is approximately one-half
of the volume of the CO
2
phase. Nevertheless, Figure 6
(27) Kaszuba, J. P.; Janecky, D. R.; Snow, M. G. Appl. Geochem.
2003, 18 (7), 1065-1080.
Figure 6. Measured solubility data of the reservoir brine-
CO2 system versus pressure at two different temperatures.
Figure 5. Digital images of the pendant brine drops in CO2 phase under different pressures at T ) 58 C: (a) CO2 in the gas
state and (b) CO2 in the supercritical state.
Reservoir Brine-CO
2
Interfacial Interactions Energy & Fuels, Vol. 19, No. 1, 2005 221
shows that the solubility of CO
2
in the brine phase
approaches its maximum value at T ) 58 C and P )
12.238 MPa, at which the interface disappearance
phenomenon starts to occur in the pendant brine drop
experiments. Further increases in pressure do not
appreciably increase CO
2
solubility in the brine phase.
Obviously, the maximum CO
2
solubility in the brine
phase is achieved as long as the pressure is higher than
a threshold value, which corresponds to the pressure
at which the brine-CO
2
interface disappearance phe-
nomenon starts to occur in the pendant brine drop
experiments.
Dynamic IFT. The measured dynamic IFTs of the
reservoir brine-CO
2
system versus time under different
pressures at T ) 27 C are shown in Figure 7. Note that
the dynamic IFT reaches a constant value (i.e., the
equilibrium IFT) after 10-100 s under different pres-
sures. In the literature, it has been concluded that the
dynamic IFT reduction is caused by both the adsorption
of CO
2
molecules onto the pendant water drop surface
and the reorientation of water molecules at the inter-
face.
9
In the experiments, at P ) 0.121 MPa, the IFT is
slightly reduced in a period of 100 s and then remains
constant for at least 2.5 h. However, the pendant brine
drops only stay at the tip of the syringe needle for 70
and 36 s at P ) 1.027 and 4.013 MPa, respectively,
probably because of a large force imbalance between the
downward gravity force and the upward surface force.
When the pressure is further increased to 8.506 MPa,
the dynamic IFT remains almost constant from the very
beginning. This means that the pendant brine drop and
liquid CO
2
can quickly reach the equilibrium state. Note
that the dynamic IFTs measured at P ) 8.506 MPa are
higher than those at P ) 4.013 MPa. A similar finding
has also been reported for the pure water-CO
2
sys-
tems.
6-9
This is attributed to the phase change of CO
2
from gas to liquid and the formation of a second CO
2
-
enriched phase
7,8
and/or CO
2
hydrates.
9,22,26
The dy-
namic IFT is further reduced when the pressure is
increased to P ) 12.907 MPa or higher. Also, the
dynamic IFT reaches its constant value more quickly
at a higher pressure. The faster establishment of the
equilibrium state may be attributed to a stronger
convective mixing at a higher pressure.
2
Figure 8 shows the dynamic IFTs of the reservoir
brine-CO
2
system versus time under different pres-
sures at an elevated temperature of T ) 58 C. During
the experiments, it is observed that the pendant brine
drop stays much shorter under a higher pressure. In
comparison with that at T ) 27 C, as shown in Figure
7, the dynamic IFT at T ) 58 C, as shown in Figure 8,
is higher under the same pressure. This is because CO
2
solubility in the brine phase is lower at a higher
temperature.
11,16
No IFT data are available if P g12.238
MPa at T ) 58 C, because there is no interface formed
between the brine phase and CO
2
in the pendant drop
experiments, as described previously.
Equilibrium IFT. A constant or equilibrium IFT
always exists at the end of each dynamic IFT measure-
ment. The equilibrium IFTs of the reservoir brine-CO
2
system, versus pressure at two different temperatures,
are plotted in Figure 9. This figure shows that the
equilibrium IFT generally decreases as the pressure
increases, whereas the same parameter increases as the
temperature increases. These two patterns have also
been observed for the water-CO
2
system.
6-9
This is
because CO
2
solubility in the brine phase, as shown in
Figure 6, is higher at a higher pressure and lower at a
higher temperature, respectively. Also, the pressure
effect on the IFT is comparable with the temperature
effect for the reservoir brine-CO
2
system. Note that,
at T ) 27 C, the equilibrium IFT at P ) 8.506 MPa is
higher than that at P ) 4.013 MPa. This is mainly
because of the phase change of CO
2
from gas to liquid
and the formation of a second CO
2
-enriched phase
7,8
Figure 7. Measured dynamic IFTs of the reservoir brine-
CO2 system versus time under different pressures at T )
27 C.
Figure 8. Measured dynamic IFTs of the reservoir brine-
CO2 system versus time under different pressures at T )
58 C.
Figure 9. Measured equilibrium IFTs of the reservoir brine-
CO2 system versus pressure at two different temperatures.
222 Energy & Fuels, Vol. 19, No. 1, 2005 Yang et al.
and/or CO
2
hydrates.
9,22,26
On the other hand, there is
a condensation process of CO
2
in the pressure range of
7.410 MPa < P < 12.238 MPa at T ) 58 C. In this case,
no clear digital image of the pendant brine drop can be
observed, and, thus, no IFT can be measured. When
pressure is increased to P ) 12.238 MPa and higher at
this temperature, no interface exists between the brine
phase and the CO
2
. This means that the equilibrium
IFT between the brine phase and the CO
2
becomes
zero.
10,28
In this case, the measured CO
2
solubility in
the brine phase, which is obtained using the PVT
system, approaches its maximum value.
Conclusions
In this paper, a new experimental technique has been
developed to measure the interfacial tension (IFT) and
visualize the interfacial interactions between the res-
ervoir brine and CO
2
under reservoir conditions. The
IFT measurements are conducted using the axisymmet-
ric drop shape analysis (ADSA) technique for the
pendant drop case. The dynamic IFT reduces to a
constant value after 10-100 s at T ) 27 C and after
10-60 s at T ) 58 C. The dynamic IFT reduction may
be explained by both the adsorption of CO
2
molecules
and the reorientation of water molecules at the pendant
brine drop surface. It is also observed that the equilib-
rium IFT decreases as the pressure increases, whereas
the same parameter increases as the temperature
increases. This is attributed to higher CO
2
solubility at
a higher pressure and lower CO
2
solubility at a higher
temperature, respectively. On the other hand, the
swelling effect, the shrinking effect, wettability alter-
ation, and interface disappearance are observed for the
reservoir brine-CO
2
system in the pendant brine drop
experiments. The swelling effect is caused by the
dissolution of CO
2
in the brine phase, whereas the
shrinking effect is due to the permeation of brine into
CO
2
. This means that two-way mass transfer exists
between the brine phase and CO
2
. Wettability alteration
occurs because of the interfacial hydrates formed be-
tween the brine phase and CO
2
at high pressures and
T )27 C in the pendant drop experiments. No interface
between the reservoir brine and CO
2
is observed at P g
12.238 MPa and T ) 58 C. Under the same conditions,
however, a clear interface is formed between the brine
phase and CO
2
and is observed using the PVT system,
while the measured solubility of CO
2
in the brine phase
approaches its maximum value. Further increases in
pressure do not lead to an appreciable increase of CO
2
solubility in the brine phase. In practice, the maximum
CO
2
solubility is achieved in a depleted reservoir or
saline aquifer as long as the operating pressure exceeds
a threshold value.
Acknowledgment. The authors acknowledge a dis-
covery grant from the Natural Sciences and Engineering
Research Council (NSERC) of Canada and an innova-
tion fund from the Petroleum Technology Research
Centre (PTRC) at the University of Regina to Y.G. The
authors also wish to thank Mr. Chaodong Yang, for his
assistance in the solubility measurements, and two
anonymous reviewers, for their helpful comments.
EF049792Z
(28) Adamson, A. W. Physical Chemistry of Surfaces, 6th Edition;
Wiley: New York, 1996.
Reservoir Brine-CO
2
Interfacial Interactions Energy & Fuels, Vol. 19, No. 1, 2005 223