Article

pubs.acs.org/jced

The Gas−Oil Interfacial Behavior during Gas Injection into an

Asphaltenic Oil Reservoir
Mehdi Escrochi, Nasir Mehranbod, and Shahab Ayatollahi*,§
EOR Research Center, School of Chemical and Petroleum Engineering, Shiraz University, P.O. Box 7134851154, Shiraz, Iran

ABSTRACT: Oil displacement and recovery efficiency during

gas injection depends on the competition between driving
forces and capillary resistance that is governed by gas−oil
interfacial behavior. Detailed study of the interfacial forces
during gas injection is the main objective of this research work.
The effects of injecting gas composition and the possibility of
asphaltene precipitation in a wide pressure range were
determined through comprehensive experimental study. This
was performed by measurement of interfacial tension of a
highly asphaltenic Iranian crude oil in three surrounding gas
mediums. The results showed that as pressure increases, the rate to reach miscibility reduces in the vicinity of the asphaltene
precipitation onset. As the surface coverage of the asphaltene at the gas−oil interface exceeded a threshold value the rate was
reduced furthermore. Component extractions, noncondensable gas film formation, asphaltene precipitation, and asphaltene
accumulation at the interface are found to be the main parameters affecting the miscibility. The observations showed that
miscible displacement is practically impossible for this asphaltenic crude oil. Dimensional analysis proved that pressure increase
in N2 and flue gas injection is not effective in improving oil recovery; however, CO2 tests revealed the presence of optimum
pressure range with highest gravity drainage potential and minimum capillary resistance.

■ INTRODUCTION
The world energy supply extremely depends on sustainable oil
production from the challenging fractured giant carbonate
reservoirs in the Middle-East. High oil viscosity, oil−wet matrix,
large matrix blocks, low matrix permeability, poor matrix-
fracture interactions, and highly asphaltenic crude are among
the challenges to mention. These are the main reasons behind
very low recovery efficiencies during primary and secondary
recovery stages especially in the naturally fractured carbonate
reservoirs (e.g., Bangestan formation in Iran). Therefore, in
most of the Middle East naturally fractured carbonate oil
reservoirs, proven oil recovery efficiencies through primary and
secondary oil recovery methods rarely exceeds a few percent of
the oil in place.1−5 Such reservoirs thus require implementation
of enhanced oil recovery (EOR) methods to increase recovery
efficiency. The selection and implementation of any EOR
method require careful studies considering possible risks
concerning sweep efficiency (microscopic and volumetric)
and formation damage. Asphaltene precipitation is among the
main factors affecting sweep efficiency during the application of
an EOR process, especially during gas injection into reservoirs
with high asphaltene content. Asphaltene precipitation due to
the EOR methods causes fouling, pore blockade, and wettability
alteration within the formation and adversely affects the sweep
efficiency.5−8 Prolonging the oil production from asphaltenic
crude reserves and extending the recovery factor require careful
application of EOR methods, and asphaltene precipitation and
deposition within the formation must be considered during any
development plan (EOR process). In the past decade, different
aspects of asphaltene related problems have been studied
through thermodynamic modeling and laboratory tests.5,9−13
However, detailed studies on the different aspects of
asphaltenes during the EOR process is mandatory to monitor
the oil recovery factor for any specific oil reservoirs under the
considered production scenario.
Oil resevoir BGA-13 located in the southwest of Iran was
screened for different EOR processes. The gas injection process
was approved to compensate the reservoir’s low primary
recovery efficiency. The reservoir suffers from serious
asphaltene problems: the mass ratio of asphaltene to resin in
this crude oil is considerably high (as presented in Table 1),
which indicates a high risk of asphaltene precipitation.11,14
Therefore, different aspects of gas injection and asphaltene
challenges should be studied prior to any development
decisions for this case. The high cost of hydrocarbon gases
along with the lack of gas supply during the winter time are
among the challenges for the implementation of a successful gas
injection project. Besides, the environmental and technical
benefits of using alternate gases has motivated the use of carbon
dioxide, flue gas, and nitrogen (air) as the EOR agent in this
giant oil reservoir. However, the possibility of asphaltene
precipitation, which may affect the main oil recovery
mechanisms, required better understanding of the different
aspects of the gas injection process into this oil reservoir.
Asphaltene and Gas Injection. It is commonly believed
that gas injection generally increases the risk of asphaltene
Received: April 25, 2013
Accepted: July 16, 2013

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Journal of Chemical & Engineering Data
Table 1. General Specifications of the Crude Oil
a
The expended uncertainty (U(ρ)) is 9 kg·m−3. bThe expended
uncertainty (U(μ)) is 5·10−5 Pa·S. cThe expended uncertainty is 5·
10−4. dThe expended uncertainty is 5·10−3.
precipitation.15−17 It has been already shown that precipitation
occurs if the concentration of gas in the oil (or gas pressure)
exceeds a threshold value16,18−24 or resin content falls below a
specific concentration.19,25 Recent experimental results showed
that the remediation of asphaltene induced formation damage,
and the cleaning of wellbore and production facilities imposes
great economic and technical challenges.6,26−29 Therefore, prior
to the implementation of any new production scenario, careful
considerations are required to minimize any asphaltene
challenges, by the selection of suitable injecting fluid and
conditions. Several laboratory tests must be performed to find
the asphaltene content, asphaltene structure, reservoir con-
dition effects on asphaltene precipitation and deposition, and
fluid behavior as well as the interfacial behavior (fluid−fluid and
fluid−solid) during the gas injection process.
The Gas−Oil Interfacial Behavior. Reservoir fluids
interfacial properties strongly affect oil recovery efficiency for
any production scenario. They affect the displacement
mechanisms, flow regimes, capillary pressure, phase effective
permeabilities, and residual oil saturation and control the
distribution of fluids within porous media, the sweep
efficiencies, and matrix−fracture interactions. Interfacial tension
(IFT) is an important property of multiphase systems that can
be considered as a measure of the interfacial behaviors.30 For
instance, efficient semi-miscible displacement (emulsion-like)
with low residual oil saturation occurs in a very low IFT system;
while at high IFT the displacement changes to a low efficiency
capillary dominated flow.31
The behavior of IFT at different pressures was first studied
during the 1980s.32 These studies proved that the existence of
asphaltene in oil considerably affects the interfacial behavior
resulting in higher gas−oil IFT especially at high pressures. The
effect of IFT on oil recovery from the fractured media by gas
injection has been investigated later, and the criteria for efficient
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displacement mechanism were already discussed based on
interfacial behavior.30 Later, in another study, it was shown that
at lower pressure, IFT decreases with increasing temperature,
while the decline rate is reduced at higher pressure.33 The
results of this study also showed that the vanishing IFT curves
meet the pressure axis near the observed miscibility in the cell;
however, this was not stated in the text.33 The vanishing
interfacial tension (VIT) method as a novel technique for the
determination of the minimum miscibility pressure (MMP) was
first developed at the end of the 20th century and has been
employed for studying different aspects of gas injection.34−37
The VIT technique was validated against slim-tube exper-
imental data and employed to determine the minimum
enrichment concentration of injection gas.35,36,38 Later, a new
method for the analysis of the interfacial interactions of crude
oil and CO2 using the VIT technique was offered and showed
that the time needed for attaining equilibrium between the
small liquid droplets (maximum volume is 10−8 m3) and the
surrounding gas is about 80 s, which was reduced by
temperature.39 A mass transfer model was then presented to
analyze the dynamic behavior of the droplets during VIT
experiments and showed that the concentration of the interface
quickly tended toward equilibrium.40 Four important onset
pressures were then detected through comparison of VIT
experiments, coreflooding tests, and asphaltene precipitation
observations, and the slope change of the VIT curve was
reported just above the onset of asphaltene precipitation.21
Significant behavior of the VIT was determined by tests
performed by Wang and co-workers.41,42 In their experimental
results a different slope change was detected within the pressure
range of the experiments. The slope increased at the onset of
asphaltene precipitation and inception of light component
extraction. Then, the slope decreased considerably at the
pressure denoted as the onset of extensive extraction. However,
a detailed technical explanation of the reason behinds the slope
changes was not provided in their study. It was shown
experimentally that oil recovery increases in the pressure range
where the slope of the VIT curve increases. The recovery was
increased again to the maximum value in the third range with
reduced VIT slope.41,42 It was also illustrated experimentally
that the MMP by VIT technique for recombined live oil is not
highly affected by usual sampling and recombination differences
and the resulting different gas oil ratios.38,43,44 The effect of
temperature and oil composition on the miscibility was
investigated in two different publications recently using the
VIT method.45,46 The applicability of the VIT technique
through binary mixtures and synthetic fluids was examined, and
the relation of decline rates of VIT curve with temperature was
investigated. It was stated that the dual rate VIT curve was
observed only for the diesel fuel at low temperatures.45
Moreover it was shown that the interfacial tension of pure
hydrocarbons (C7 and C16) and a fuel mixture (diesel fuel) with
CO2 are practically independent of temperature at a special
pressure.45 Temperature was reported as the most important
parameter that affects the decline rate of the VIT curve and the
magnitude of MMP.44 It was also illustrated that contamination
of the injection CO2 with CH4 above a threshold value affects
the MMP values and the decline rate considerably.44
More recently, it was experimentally proved that the VIT-
MMP for a crude oil shows good consistency with the MMP
that is determined through core flooding tests; moreover, the
point of slope change was close to the asphaltene deposition
pressure.46
Journal of Chemical & Engineering Data
Although numerous reports on miscible/immiscible flooding
have been published in the literature, the mutual effects of
asphaltene and injection gas composition on interfacial
behavior, miscibility (MCM or FCM), and the feasible
mechanisms of oil recovery is rarely addressed, particularly in
the case of N2 impurities in the injection CO2 streams. In this
work, the effects of the injection gas composition on interfacial
properties, asphaltene precipitation, the VIT curve, and possible
recovery mechanisms are studied for a giant reservoir with
severe asphaltene challenges. Also, a quick and reliable
technique to investigate the effects of different parameters on
the interfacial properties as well as the optimum oil recovery
conditions and the related mechanism are presented.
■
MATERIALS AND METHODS
A challenging crude oil with high asphaltene content from a
giant midcretaceous limestone oil reservoir located in the
southwest of Iran (BGA-13) is used in this study. The general
properties of the crude oil are presented in Table 1. CO2 and
N2 gases (mole fraction purity + 0.999) from a local company
(Pars Balloon Co.), and an enriched flue gas mixture (FG-619)
with CO2 mole fraction of 0.619 and N2 mole fraction of 0.318
are utilized for the tests, the uncertainty of the flue gas
composition was ±0.01 (mole fraction).
In this study, the VIT technique is employed to investigate
the effect of gas composition and the role of asphaltene on
crude oil−gas interfacial properties. This method is based on
the concept that the equilibrium IFT between two distinct
phases vanishes at conditions of miscibility, on the basis of the
definition of miscibility.35 In this technique the equilibrium
interfacial tension of the crude oil and the injected gas is
measured at reservoir temperature and different equilibrium
pressures. The trend of IFT versus pressure finally leads to the
determination of the MMP. The reliability, accuracy, and
repeatability of this fast MMP determination technique has
been verified satisfactorily versus the well-recognized exper-
imental and simulation approaches.21,34,37,41,45,47−50 Never-
theless, a few concerns have been raised on the validity of
this technique based on simulation studies; however, they were
not experimentally verified.51
A simple schematic of the experimental setup is illustrated in
Figure 1. The setup consists of a high pressure/high
temperature view cell equipped with a high quality image
acquisition system and accurate image processing module,
pressure, and temperature control system, liquid and gas
Figure 1. Schematic illustration of the experimental setup.
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transfer vessels, and a high pressure positive displacement
pump (IFT-700 Vinci-Technologies). Density variations of the
utilized gases and crude oil were determined experimentally by
high pressure oscillating tube densitometer (AntonPaar-mPDS
2000 V3) (Table 2); a detailed description of the employed
experimental setup is illustrated elsewhere.45
During the tests, the high pressure view cell and the bulk
floating piston were initially filled with the gas phase and the
drop floating piston was filled with fresh crude oil at a constant
temperature of 322 K and desired pressure. The temperature
was controlled at the set point by a well-tuned PID controller,
with uncertainty of 0.2 K, the pressure was held constant by
using the constant pressure mode of the positive displacement
pump through injecting water at the opposite side of the bulk
floating piston that was previously filled with gas (Figure 1).
The well-tuned PID controller of the pump and the gas phase
in the floating piston caused pulse-free pressure control at the
desired set point with maximum fluctuations of 0.07 MPa (10
psi) at 40 MPa.
Crude oil was initially introduced into the gas filled cell
(almost 10 % of the cell volume) and allowed to interact
overnight to attain equilibrium, as recommended previously.35
A fresh oil drop was then formed at the needle tip, the drop
valve (K4 in Figure 1) was closed, and then the image of the
drop was captured and analyzed automatically every 2 s to 3 s at
least for 3600 s (1 h). This procedure allowed a dynamic IFT
measurement between the oil drop and the surrounding gas.
Besides, the drop volume was monitored automatically for
swelling. It is worth mentioning that the dynamic behavior of
the VIT experiments was previously investigated and it was
declared that the equilibrium IFT values would be attained after
80 s in such an experiment;38 however, the drop behavior was
recorded carefully for at least one full hour to check if any
changes occurred during long-time interactions. The measure-
ment was repeated at least twice for each pressure, and
repeatability of both dynamic behavior and IFT values and their
accuracy was ensured. Then the pressure was increased
gradually through the positive displacement pump and the
same measurements were repeated for any new pressure set
point. This procedure was continued until either low IFT values
were obtained at high pressures or formation of stable droplet
at the needle tip was practically impossible. An example of the
visual changes of the drop shape with pressure and gas
composition is shown in Figure 2 as it was captured in the view
cell.
In any stable pressure, the IFT of the fresh drop which was
obtained just after the introduction of the drop (FD-IFT), the
final equilibrium IFT value which was acquired after 600 s of
interactions (EQ-IFT), and the drop volume at both conditions
were used in this study. The measured values were then plotted
against pressure to investigate the interfacial behavior of the
system at different pressures. IFT values were carefully
extrapolated linearly to zero, which was previously defined as
the VIT-MMP of the crude oil−gas system.35,42
Special complexities of this technique were reported in the
literature where the slope of the VIT curve was changed when
the asphaltene onset pressure was in the pressure range of the
tests or the crude oil was a multicomponent mixture with wide
molecular weight varieties.21,36,37,42,50,52 It is reported that in
this situation, the VIT curve deviates from its linear trend
during the experiments. However, it is stated that the
extrapolation of the low pressure IFT data points satisfactorily
determines a VIT-MMP value that is close to the slim-tube
Journal of Chemical & Engineering Data Article

Table 2. Experimental Values of Density (ρ) at Temperature of 322 K and Pressure (P) of the Gases (CO2, N2, and Mixture with
CO2 Mole Fraction of 0.619 (FG-619)) and Crude Oila
crude oil CO2 N2 FG-619
−3 −3 −3
P/MPa ρ/(Kg m ) P/MPa ρ/(Kg m ) P/MPa ρ/(Kg m ) P/MPa ρ/(Kg m−3)
0.1 931.1 0.3 8.0 1.7 18 1.9 30.1
2.7 933.6 2.4 46.5 3.4 36 2.9 44.2
5.4 935.8 5.1 114.4 5.1 53.9 5.1 78.9
8.2 938.0 7.5 212.4 8.5 89.1 6.8 105.2
10.9 940.0 8.8 369 10.2 105.8 8.5 131.5
13.6 942.1 9.5 451.5 11.9 122.3 10.2 157.3
17.0 946.0 11.9 592.2 17 170.5 11.9 184.1
20.3 948.3 13.6 664.3 20.3 200.6 13.5 209.5
27.1 954.1 15 704.1 23.7 228.3 16.9 261.9
31.8 958.0 17 746.8 27.1 254.2 20.3 314.3
36. 9 962.3 20.4 796.7 33.9 301.5 23.8 366.2
23.8 830.4 40.6 341.6 30.5 470.1
a
Maximum expended uncertainties in pressure measurements (U(P)) is 7·10−2 MPa and in temperature measurement (U(T)) is 0.2 K. The
maximum expended uncertainty of density measurement (U(ρ)) is 8.6 kg.m−3.

results.35,38 Therefore, VIT-MMP is measured in this study by

Figure 2. Visual change of drop shape with pressure in CO2
surrounding at 322 K (from left to right pressure is (7.4, 7.8, 10.3,
13.8, and 17.7) MPa).
using low pressure data points before the slope change of the
curve.
Accuracy and Precision of the Experimental Data. The
method and the employed experimental apparatus was already
evaluated successfully compared to published literature data,
and it is verified that they are both accurate and precise, the
details of the verification are presented elsewhere.45 To ensure
satisfactory repeatability, accuracy, and precision of the
obtained experimental results, every measurement was repeated
for at least two different pendant oil drops. Standard deviation

Table 3. Summary of the Experimental Results at a Temperature of 322 Ka

CO2 N2 FG-619
property (unit) FD-IFT EQ-IFT FD-IFT EQ-IFT FD-IFT EQ-IFT
DR (109 m) 2.21 1.96 0.62 0.66 1.00 0.95
VIT-MMP (MPa) 10.55 10.76 39.42 37.13 20.98 21.86
SC0 (MPa) 2.9
IFTSC0 (mN/m) 18.1 18.0
DR1 (109 m) 0.92 0.90
MMPP1 (MPa) 23.39 23.46
MMPP1/ MMP 1.1 1.1
DR1/DR 0.92 0.95
SC1 (MPa) 7.8 8.5 11.9
IFTSC1 (mN/m) 6.1 6.0 19.2 18.9 11.0 10.9
DR2 (109 m) 0.90 0.73 0.34 0.34 0.32 0.29
MMPP2 (MPa) 15.16 15.23 66.26 65.07 45.67 47.97
MMPP2/ MMP 1.4 1.4 1.7 1.8
DR2/DR 0.41 0.37 0.55 0.52 0.32 0.31
SC2 (MPa) 10.3 27.1 30.5
IFTSC2 (mN/m) 3.6 4.4 13.7 13.3 5.1 5.2
DR3 (109 m) 0.15 0.13 0.20 0.22 0.08 0.07
MMPP3 (MPa) 31.50 32.84 102.02 93.85 97.31 109.81
MMPP3/ MMP 3.0 3.1 2.6 2.5 4.6 5.0
DR3/DR 0.07 0.07 0.32 0.33 0.08 0.07

a
Abbreviations: DR, initial decline rate; DR1, decline rate after formation of noncondensable gas film; DR2, decline rate after asphaltene
precipitation; DR3, decline rate after extensive accumulation of asphaltene at interface; SC0, slope change after the inception of noncondensable gas
formation; SC1, slope change after asphaltene precipitation; SC2, slope change after extensive accumulation of asphaltene at interface; VIT-MMP,
MMP calculated by IFT values below the slope changes; MMPP1, VIT-MMP after the noncondensable gas formation; MMPP2, VIT-MMP after the
asphaltene precipitation; MMPP3, VIT-MMP after extensive accumulation of asphaltene at interface. The maximum expanded uncertainty of IFT
measurement (U(γ))was 5.2·10 −4 N/m.

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Journal of Chemical & Engineering Data
and combined standard uncertainty of the results are calculated
and reported accordingly. The uncertainty of the IFT values
associated with the uncertainties in pressure measurement and
gas composition is given by eq 1:45,53
⎛ ⎛ ∂γ ⎞2 ⎞
uc2(γ ) = ⎜⎜∑ uc2(xi)⎜ ⎟ ⎟⎟
⎝ i ⎝ ∂xi ⎠ ⎠ (1)
where uc(x) is the combined standard uncertainty of variable x,
γ is the interfacial tension and xi’s are the variables that affect
the IFT measurement (e.g., gas composition and pressure). On
the basis of the measuring devices used in this study, the
uncertainty of pressure measurement (uc1(p)) is 3.5·103 Pa
(3.5·10−3 MPa), uncertainty of pressure control (uc2(p)) is 3.5·
104 Pa (3.5·10−2 MPa) and for gas composition the uncertainty
(u(C)) is 5·10−4 (mole fraction) for pure gases and 0.01 (mole
fraction) for the flue gas mixture. These values are half of the
least count of the measuring devices. The numeric values of ∂γ/
∂C and ∂γ/∂P were determined through the experimental
results, and the combined standard uncertainty is then
calculated accordingly.
■ RESULTS AND DISCUSSION
The interfacial behavior of the crude oil and different gases was
determined at a constant temperature of 322 K and wide
pressure range using the VIT technique. Table 3 presents a
summary of the results, and the crude oil VIT curves are
plotted in Figures 3 to 5 for CO2, N2, and FG-619, respectively.
Figure 3. The VIT curve for CO2 at 322 K (circles are the FD-IFT
data and squares are EQ-IFT data).
Figure 4. The VIT curve for N2 at 322 K (circles are the FD-IFT data
and squares are EQ-IFT data).
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Figure 5. The VIT curve for FG-619 at 322 K (circles are the FD-IFT
data and squares are EQ-IFT data).
The results showed that the maximum combined standard
uncertainty of IFT measurement in all the experiments was for
the CO2 crude oil system where the numerical value was 2.6·
10−4 N/m (0.26 mN/m), considering the maximum affecting
parameters in eq 1 which were observed during the
experiments. The maximum ∂γ/∂C was 0.205·10 −3 N/m (at
40 MPa), and the maximum ∂γ/∂P was 2.21·10 −9 m (for
CO2); the pressure uncertainty was 0.07 MPa, and maximum
gas concentration uncertainty was 0.01 (mole fraction). The
standard deviation of the experimental data has been calculated
for the whole experimental data, the maximum observed
standard deviation of IFT data was 2.95·10 −4 N/m and the
average standard deviation over the whole domain was 2.02·
10−4 N/m. The magnitude of the standard deviation and the
combined standard uncertainty show that the obtained
experimental results are reliable and results and conclusions
cannot be affected by the experimental errors.
The Effects of Gas Composition on Miscibility. The
minimum miscibility pressure by the VIT technique (VIT-
MMP) for CO2 obtained with the use of the FD-IFT data was
determined to be 10.55 MPa, while use of the EQ-IFT data
resulted in 10.76 MPa (1.9 % greater). The VIT-MMP values
for CO2 were calculated on the basis of the low pressure IFT
data points (below 8 MPa). The same MMP calculation
procedure for N2 through FD-IFT data resulted in 39.42 MPa,
which was 6.2 % greater than the MMP obtained by EQ-IFT
data (37.13 MPa) that were calculated using IFT data points
below 8.5 MPa. The MMP for the flue gas (FG-619) using FD-
IFT was found to be 20.98 MPa, which was 4.0 % lower than
the MMP calculated using EQ-IFT data (21.86 MPa). The
measurements were based on the data points between 3 MPa
and 11.9 MPa. The results for FG-619 presented in Figure 5
showed an exceptional singularity around 3 MPa, which will be
discussed later in this section. The slopes of the best fitting
curves for the FD-IFT data points used for the MMP
determination were 2.21(·10−9 m), 1.00 (·10−9 m) and 0.62
(·10−9 m) for CO2, FG-619, and N2, respectively. The results
are presented in Table 3 and show similar trends for the
equilibrium IFT data points.
The results show that the difference between the MMP that
is calculated using FD-IFT data and the one calculated using
EQ-IFT data are on the order of experimental errors. This
means that the dynamic behavior of the drop and the
corresponding mass transfer (for the crude oil (BGA-13)
used in this study) during VIT experiments does not affect the
magnitude of VIT-MMP. The dynamic drop behavior after the
first 600 s of exposure was carefully monitored for at least 1 h,
and the maximum observed changes were 5 % of its reported
Journal of Chemical & Engineering Data
equilibrium value. An illustration of the long time dynamic
behavior is presented in Figure 11. It has been previously stated
Figure 6. Chronological changes of IFT (circles) and drop volume
(triangles) in the case of CO2 injection at 322 K.
Figure 7. Chronological changes of IFT (circles) and drop volume
(triangles) in the case of N2 injection at 322 K.
Figure 8. Chronological changes of IFT (circles) and drop volume
(triangles) in the case of FG-619 injection at 322 K.
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Figure 9. Chronological changes of IFT (dashed blue line) and drop
volume (contineous red line) for CO2 at 7.16 MPa and 322 K.
Figure 10. Chronological changes of IFT (dashed blue line) and drop
volume (contineous red line) for CO2 at 9.06 MPa and 322 K.
(Keeping the drop at the tip of the needle was impossible after
approximately 4 min, the test was repeated 3 times and similar results
were obtained.)
Figure 11. Chronological changes of IFT (dashed blue line) and drop
volume (continuous red line) for CO2 at 10.83 MPa and 322 K.
that equilibrium state is achieved in less than 600 s in
hydrocarbon gas systems.39,54 Therefore, it is concluded that
the VIT-MMP can be obtained directly by fresh drop IFT
values in a couple of hours, without waiting for the equilibrium
IFT in each pressure step to be reached. This observation relies
on the fact that IFT is an interfacial property and depends only
on the local properties of the interface, which are being
chronologically modified due to mass transfer, while MMP is a
state property and depends on the composition of oil and gas
phases. It was already stated that the IFT versus pressure (the
trend of VIT curves) depends only on the phase properties and
oil and gas amounts do not affect the calculated miscibility.36,38
Journal of Chemical & Engineering Data
The results show that the case of CO2 at 9.06 MPa was an
exception, where stabilization of the drop at the tip of the
needle for more than 240 s was practically impossible, as shown
in Figure 10. In this case IFT was increased during this time;
therefore the reported equilibrium IFT value for this point is
the IFT after 240 s of exposure.
Visual examination of the liquid drop through the cell
showed that within the low pressure range, stable well-shaped
drops were easily formed and stayed at the tip of the needle for
several hours as shown in Figure 2. Volumetric measurement of
the drop in this region showed mostly swelling behavior for the
liquid during the first 10 min of gas−oil contact in the high
pressure cell. The rate of drop enlargement as the sign of liquid
swelling was increased by pressure, except for N2 at its critical
pressure (3.4 MPa). In this region, swelling was due to
dissolution of the gas molecules into the drop. Besides, the
equilibrium concentration in the vicinity of the gas−oil
interface is reached and consequently IFT is reduced by time
to its equilibrium value as shown in Figures 6 to 11.
Note that there are some exceptional observations in this
region; in the case of flue gas it is caused by the additional mass
transfer resistance of noncondensable gas film at the droplet
interface. It can be argued that during the mass transfer process
of a gas mixture containing both a soluble and nonsoluble
component (N2 and CO2), the soluble components dissolve
faster into the liquid phase. Therefore, the composition of the
nonsoluble gas increases in the vicinity of the interface, resulted
in larger mass transfer resistance in the gas phase, which is
known as the noncondensable gas film effect, a well-known
phenomenon mostly reported in heat transfer applications.55−57
Therefore, the droplet behaves as it is placed in a N 2
surrounding as schematically shown in Figure 12. Similar
Figure 12. Schematic illustration of noncondensable gas film
formation (N 2-rich film) around the pendant drop and CO2
dissolution in the case of FG-619.
phenomenon may cause formation of a noncondensable gas
bank at the leading edge of the gas front during flue gas
injection in oil reservoirs, which certainly affects the sweep
efficiency; however, the detail of its technical aspects should be
investigated later.
The Effects of Asphaltene on Miscibility and VIT
Curves. In some cases as the pressure exceeds a threshold
G dx.doi.org/10.1021/je400403y | J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Article
value, IFT does not decrease with its preceding decline rate,
and the slope of the IFT curve was changed. The experimental
observations in this study showed a triple decline rate for CO2
and N2, where the slope of the FD-IFT curve for CO2 test was
once reduced to 0.90 (·10−9 m) at 7.83 MPa; then changed at
10.2 MPa, where the final slope was 0.15 (·10−9 m). For the N2
test the slope was first reduced to 0.34 (·10−9 m) at 8.5 MPa,
and decreased again to 0.2 (·10−9 m) at 27.1 MPa. The results
of the FG-619 test showed quadratic decline rates: the slope
was initially changed to 0.92 (·10−9 m) at 2.86 MPa, decreased
again to 0.32 (·10−9 m) at 11.9 MPa, then it was reduced to
0.08 (·10−9 m) at 30.45 MPa (Table 3).
These results were compared with a part of the available
literature data as presented in Tables 3 and 4. There is different
reasoning on the changes of the IFT decline rate presented in
the literature. It is illustrated that the slope change of the VIT
curve for crude oil during C2 injection occurred just above the
onset of asphaltene precipitation, where the initial slope (2.1·
10−9 m) was reduced to 17 % of its initial value (0.35·10−9 m).
The same dual rate decline was not observed for propane
injection or crude oil as shown in Table 4. It is stated that the
MMP was below the onset of precipitation, therefore, no
change in the slope was observed.34 The relation of the dual or
triple decline rate behavior of the VIT curve and the asphaltene
precipitation has been already accredited.36,41,46,47,50 Moreover,
it was recently shown that the change in the decline rate
corresponds to the considerable decrease of the concentration
of asphaltene in the produced oil in core flooding tests.46
On the other side, other researchers suggested that the slope
change may be attributed to light component extraction and the
change in the composition of the droplet at higher pressures.
Previously, visualization of the onset of asphaltene precipitation
in two dimensional view cell (4.8 MPa) was compared to the
slope change of the VIT experiment (7.2 MPa).21 Similar crude
oil at the same condition was tested in another VIT
experimental work where asphaltene precipitation was reported
at 3.8 MPa without noting any slope change at this point.41
Inspection of their data points in more detail shows a disorder
near the onset of asphaltene precipitation. Slope change was
also observed at the onset of asphaltene precipitation for
another crude oil used in that study.41 Multiple rate VIT curves
were related to the component extraction; however, the
affecting mechanism that reverses the trend is not explained
well.21,41,42 A survey in the literature shows that the change of
the decline rate was not observed when pure hydrocarbons
were used;38,45 while, in other circumstances, dual rate VIT
curves were observed even in synthetic oil studies.45,58,59
Considering these observations, the multiple decline rate VIT
curves should have a direct relation with the impurities;
however, more clarification is necessary (as shown in Tables 4
and 5).
It is already known that in the crude oil below the onset of
asphaltene precipitation, asphaltene molecules are randomly
suspended in the oil and stabilized by the surrounding adsorbed
resin molecules forming a homogeneous solution.60 At higher
pressures, the concentration of gas molecules increases and
results in resin concentration reduction; consequently,
asphaltene molecules flocculate and precipitate due to the
mutual effect of pressure and composition. However, the
concentration of resin is still high enough to keep the
precipitated solids stabilized in a colloidal state.60 The
interfacial activity of colloidal solutions is usually improved
due to the tendency of the particles to accumulate at the
Journal of Chemical & Engineering Data Article

Table 4. Summary of the VIT Literature Data for Crude Oila

oil crude crude crude crude crude crude crude crude crude crude crude crude crude
gas CO2 CO2 CO2 CO2 C2 C3 CO2 Eq. gas Eq. gas Eq. gas CO2 CO2 CO2
temp (K) 300 300 300 300 358 358 300 366 311 355 416 416 323
Pmax (MPa) 10 15 12 12 18 4 14 35 35 35 26 26 20
DR (109 m) 3.35 2.26 3.47 3.36 2.1 5.42 3.55 0.89 1.12 1.16 0.45 0.58 2.04
MMP (MPa) 7.3 9.3 7.6 7.9 10.3 3.9 11.7 23 19.6 16.5 24.2 24.1 10.6
IFTSC1 (mN/m) 4.6 6.8 6.6 1.9 5.4 5.5 12 11.9 10.4 4.5
SC1 (MPa) 4.8 6.3 12 12 8
DR2 (109 m) 5.18 9.06 0.43 0.53 0.71
DR2/DR 1.55 2.61 0.48 0.47 0.61
MMPP2 (MPa) 7.4 7.6 34.6 28.5 23.1
MMPP2/MMP 1.0 1.0 1.5 1.5 1.4
SC2 (MPa) 6.4 6.6 7.2 7.2 8.1 9.8 23.8 18.8 17.1 8.4
DR3 (109 m) 1.48 0.6 0.59 0.23 0.35 0.38 0.19 0.16 0.19 0.31
DR3/DR 0.44 0.27 0.17 0.07 0.16 0.11 0.21 0.14 0.16 0.15
MMPP3 (MPa) 10.1 18.2 13 15.9 19.9 27.8 47.8 46.2 37.4 23.1
MMPP3/MMP 1.4 2.0 1.7 2.0 1.9 2.4 2.1 2.4 2.3 2.2
reference 41 41 42 21 34 34 70 33 33 32 43 43 46
a
Abbreviations: DR, initial decline rate; DR1, decline rate after formation of non-condensable gas film; DR2, decline rate after asphaltene
precipitation; DR3, decline rate after extensive accumulation of asphaltene at interface; SC0, slope change after the inception of non-condensable gas
formation; SC1, slope change after asphaltene precipitation; SC2, slope change after extensive accumulation of asphaltene at interface; VIT-MMP,
MMP calculated by IFT values below the slope changes; MMPP1, VIT-MMP after the non-condensable gas formation; MMPP2, VIT-MMP after the
asphaltene precipitation; MMPP3, VIT-MMP after extensive accumulation of asphaltene at interface; and Eq. Gas, equilibrium gas.

interfaces. This accumulation may occur at oil−water, oil−rock
and oil−gas interfaces, and it alters the interfacial behavior
(mainly interfacial tensions and wettability) critically. Tambe
and Sharma,61 showed that the interfacial tension of a fluid
system containing colloidal particles increases as the interfacial
concentration of the particles is increased (concentration at the
interface). They have also illustrated that the increasing trend of
the IFT is critically amplified when the surface coverage of the
particles exceeded a threshold value (e.g., + 60 % surface
coverage). It was also stated that the asphaltene forms two-
dimensional thin islands or nets at the interface at low
concentrations (low surface coverage), the structure transmutes
to three-dimensional arrangements at higher concentra-
tions.62,63 It is concluded that the multiple decline rate VIT
curves occur if the liquid phase contains small colloidal particles
or if it was contaminated by any surface active materials during
the tests (e.g., it may be due to practically negligible
contaminations in the apparatus). However, such contami-
nation does not affect the VIT curve considerably and does not
lead to large deviations as shown in Table 5.
Accordingly, it is concluded that the tendency of the colloidal
asphaltene particles to accumulate at the oil−gas interface
critically affects the multiple decline rate behavior of the VIT-
curves. In this mechanism, the effect of gas dissolution and
decreasing density difference between the phases that tend to
reduce the gas−oil IFT with its previous rate, is partially
compensated by the asphaltene layer at the interface
(accumulation of the colloids at the interface), since the effect
of the asphaltene layer is to increase the IFT; therefore, the
decline rate is changed. It is worth mentioning that the slope of
the VIT curves is undoubtedly affected by component
extraction and composition revolution at high pressure;21,41
however, there are other mechanisms such as asphaltene
precipitation that may be dominant in special cases.
Theoretical modeling suggested by Alizadeh et al.,64 and
Roshanaei Zadeh et al.,17 was used to double check the effect of
asphaltene precipitation on the point of decline rate change. A
H dx.doi.org/10.1021/je400403y | J. Chem. Eng. Data XXXX, XXX, XXX−XXX
mixture with a total composition of 90 % gas and 10 %
(volume) oil was modeled using a commercial PVT software,
the amount of asphaltene precipitation by pressure was
determined in an increasing pressure fashion. The onset
pressure of asphaltene precipitation and the pressure with
maximum precipitation were determined. The onset of
asphaltene precipitation is predicted at 8.16, 9.18, and 11.9
MPa for CO2, N2 and FG-619 respectively, which are in the
locality of the slope change of the VIT curves and confirms the
effect of asphaltene onset pressure on the decline rate, as
illustrated in Figure 13.
On the basis of these explanations, the first slope change (the
second in FG-619 test) is attributed to the asphaltene
precipitation or destabilization and accumulation of the
asphaltene particles at the interface. At this condition the
slope is reduced utmost by an order of magnitude which
depends critically on the intensity of precipitations, the
tendency of such molecules to accumulate at the gas−oil
interface and their structure at the interface. Therefore, this
effect may not be pronounced in some cases as shown in Tables
4 and 5.
The other indication of asphaltene precipitation is the
volume of the stable droplet, as it is illustrated in Figure 14. The
volume was decreased by pressure below the onset of
asphaltene precipitation, the trend was revolved above the
onset point, and the drop volume remained practically constant
between the two slope changes. It is already proved that drop
volume and interfacial tension are technically independent of
each other.65
The exceptional decline rate which was detected in FG-619
test was initially considered as an experimental error; however
this was rejected through several repeated observations. This
slope change was then considered as the asphaltene
precipitation onset; however, an analogy with the observations
of pure gas tests, the magnitude of slope changes and the results
of asphaltene modeling (Figure 13), made the second slope
change more appropriate for the onset of asphaltene
 Table 5. Summary of the VIT Literature Data for Synthetic Oilsa
oil C10+C1 C10 C7 C16 diesel C7 C16 diesel C7 C7 C16 C16 C16 C7
gas CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2 CO2
temp (K) 344 311 393 393 393 313 313 313 333 353 354 403 443 323
Pmax (MPa) 12 7 7.5 11.4 15.5 6.9 9.3 11.4 7.6 7.6 11.0 16.0 23.0 9.5
DR (109 m) 1.25 2.8 0.79 0.91 0.92 2.16 2.21 2.27 1.64 1.27 1.52 1.05 0.76 2.0
MMP (MPa) 10.5 8.0 12.4 18.4 17.8 7.9 9.3 11.4 9.0 10.0 14.5 17.6 20.0 8.5
IFTSC1 (mN/m) 1.3 5.8 3.4 8.0 6.2
SC1 (MPa) 9.9 11.6 8.3 10.6 12.0
DR2 (109 m) 0.65 0.59 0.72 0.65 0.47
DR2/DR 0.52 0.64 0.32 0.62 0.62
MMPP2 (MPa) 11.9 21.4 13.3 21.9 24.8
MMPP2/MMP 1.2 1.2 1.2 1.2 1.2
SC2 (MPa) 19.6
Journal of Chemical & Engineering Data

DR3 0.29
DR3/DR 0.38
MMPP3 (MPa) 28.1
MMPP3/MMP 1.4
purity (mole ? ? + 0.99 Merck + 0.99 Merck + 0.99 Merck + 0.99 Merck + 0.99 Merck + 0.99 Merck + 0.99 + 0.99 + 0.99 + 0.99 Merck
fraction) S.Aldrich S.Aldrich S.Aldrich
ref 38 38 45 45 45 45 45 45 45 45 59 59 59 54
a

I
Abbreviations: DR, initial decline rate; DR1, decline rate after formation of non-condensable gas film; DR2, decline rate after asphaltene precipitation; DR3, decline rate after extensive accumulation of
asphaltene at interface; SC0, slope change after the inception of non-condensable gas formation; SC1, slope change after asphaltene precipitation; SC2, slope change after extensive accumulation of
asphaltene at interface; VIT-MMP, MMP calculated by IFT values below the slope changes; MMPP1, VIT-MMP after the non-condensable gas formation; MMPP2, VIT-MMP after the asphaltene
precipitation; MMPP3, VIT-MMP after extensive accumulation of asphaltene at interface; and Eq. Gas, equilibrium gas.
Article

dx.doi.org/10.1021/je400403y | J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data
Figure 13. Comparison of the first change of decline rate (black
dashed line with star markers), second change of the decline rate
(purple dashed line with square markers), with the onset of asphaltene
precipitation from the model (blue line) and critical pressure of gas
(dashed red line with triangle markers) at 322 K.
Figure 14. Volume of stable droplets as soon as formation at 322 K for
CO2 (blue circles), N2 (red squares), and flue gas with molar CO2
mole fraction of 0.619 (green triangles).
precipitation (the same crude oil was used). Modification of the
decline curve at this pressure (3 MPa) as it was stated in the
previous part may be referred to as the inception of
noncondensable gas film formation (N2 rich film) at the drop
interface, which made the interfacial behavior similar to the
drop in a nitrogen surrounding. Rapid swelling was also
observed, which may be attributed to the fast CO2 dissolution
in competition with the noncondensable gas (N2).
The size of asphaltene clusters increases with pressure during
gas injection, until tolerable values are exceeded at the onset of
asphaltene deposition. Above this pressure the surface
accumulation of the asphaltene at the gas−oil interface
exceeded the threshold at which the rate of IFT enhancement
for the asphaltene surface layer was considerably increased.61
Otherwise, the semisolid three-dimensional asphaltene islands
are formed at the oil/gas interface62,63 and reverse the VIT
trend due to reimbursing the effect of gas dissolution and
density difference. During the experiments at such considerably
high pressures oil initially rose up the needle and then gently
J dx.doi.org/10.1021/je400403y | J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Article
glided down and formed a well-shaped drop after one or two
minutes. The trend of drop volume versus pressure was
changed again at the second onset in an increasing fashion as
shown in Figure 14, this phenomenon was more evident in the
pure gas tests.
Mechanisms of Displacement and Optimum EOR
Condition. In this section the mechanisms that may affect
oil recovery in different conditions are discussed and optimum
circumstances for each type of gases are suggested based on the
results of the VIT experiments and dimensionless indicators of
flow through porous media.
Capillary number has been successfully employed to
correlate microscopic sweep efficiency during the EOR process:
the displacement efficiency is increased with NCA (complete
capillary number), which is defined as eq 2:
vgasμgas l
NCA =
γGO kφ (2)
where l is the characteristic length of the porous media, k is the
absolute permeability, φ is the porosity, vgas is the gas phase
velocity, μgas is the gas viscosity, and γGO is the gas−oil
interfacial tension.52 In low pressure immiscible gas injection,
the recovery is reported to be almost independent of capillary
number: constant at the lowest value (e.g., 15 % of the oil in
place). In this zone the NCA slightly depends on the pressure.
At higher pressure (near miscible displacement) a transition
zone is expected, where oil recovery dramatically increases with
pressure and where the NCA is very dependent on the pressure.
When miscible displacement is reached (above MMP), both oil
recovery and capillary number are at their highest value and do
not change considerably with the pressure. This is called the
“higher invariable NCA zone”.52 Theoretically, NCA should be
infinity for miscible displacement processes; however, when it is
on the order of unity we may assume miscible (or semi-
miscible) displacement efficiency. Previous experimental studies
showed that the VIT-MMP is correlated well by the initiation
of the upper invariable NCA zone, and the efficiency of miscible
displacement was achieved in core flooding experiments, even
in the presence of asphaltene precipitation.42,52 Therefore, the
increasing trend of the complete capillary number curves can be
considered an indication of the near miscible zone, which
approaches the miscibility conditions; however, miscible
displacement is not attainable below the higher invariable
NCA zone.
Another dimensionless indicator, the ratio of gravity to
capillary forces, is defined through eq 3 as bond number (NBA).
It is successfully employed to evaluate the recoverable oil
through the gravitational forces:33
ΔρGO gl kφ
NBA =
γGO (3)
where l is the characteristic length of the porous media, k is the
absolute permeability, φ is the porosity, ΔρGO is the density
difference between oil and gas, g is the local gravitational
acceleration, and γGO is the gas−oil interfacial tension. It is
clearly illustrated that the influence of gravitational forces on oil
recovery and the recovery factor is increased by NBA.33,66−68
Therefore, the magnitude of such dimensionless indicators,
which are calculated using the interfacial behavior of the gas oil
system and reservoir properties, can be used for preliminary
evaluation of gas injection for the mentioned oil reservoir prior
Journal of Chemical & Engineering Data
to any costly and time-consuming detailed studies. In this work
a cylindrical core sample from a Bangestan Reservoir with
length of 0.0883 m, diameter of 0.0369 m, porosity of 4.6 %,
permeability of 2.35 mD (2.32·10−15 m2) and gas injection rate
of 3.1·10−6 m·s−1 (0.2 cm3·min−1) was considered for
preliminary evaluation of gas injection in such a reservoir.5
NCA and NBA were calculated for different gases in the pressure
range of the experiments as the results are presented in Figures
15 and 16; the feasible displacement mechanisms is discussed
for each case accordingly.
Figure 15. The effect of gas composition and pressure on complete
capillary number: a measure of microscopic sweep efficiency for CO2
(blue circles), N2 (red squares), and flue gas with molar CO2 mole
fraction of 0.619 (green triangles).
Figure 16. The effect of gas composition and pressure on bond
number and gravity drainage performance for CO2 (blue circles), N2
(red squares), and flue gas with molar CO2 mole fraction of 0.619
(green triangles).
As it is illustrated in the figures, in the low pressure region
(below 5.4 MPa for CO2, below 8.5 MPa for FG-619, and
almost the entire pressure domain of the experiments for N2),
high IFT values guarantee low capillary and bond numbers
which resemble immiscible displacement. Therefore, capillary
dominated flow is the main displacement mechanism that
would cause low recovery rates and high trapping and residual
oil saturations. It is also shown that gravity drainage is not
reliable in this region as well. Oil recovery might be only
K dx.doi.org/10.1021/je400403y | J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Article
marginally enhanced because of oil swelling and viscosity
reduction in such regions and slightly improved by pressure
maintenance, if the pressure is selected carefully on the basis of
the results of Figures 6 to 8.
Figure 15 shows that NCA and consequently the microscopic
sweep efficiency are practically independent of the pressure for
N2 and FG-619 gases in this region (lower invariable NCA
zone). However, a slight increasing trend in the case of CO2 is
observed, which shows the potential of increased oil recovery
efficiency at higher pressures. The same trend was also
observed in NBA for these gases; therefore, efficient gravity
drainage is not expected in this pressure region and gas
injection in this region should be avoided. It is also concluded
that N2 injection cannot be considered as an efficient oil
recovery process for this crude oil. It is shown that NCA and
NBA results are almost flat at the lower invariable zone within
the whole pressure domain of the experiments, with very low
values. Besides, these results do not reveal any sign of
miscibility close to the attained VIT-MMP value for N2, since
severe asphaltene precipitation and asphaltene accumulation at
the interface prevent the dissolution of gas molecules into the
oil and avoid the interfacial mass transfer. Therefore, in this
case the miscibility condition to higher pressure is completely
hindered and the approach to the miscibility trend is reversed.
Swelling and extraction potentials of N2 were also limited and
overcoming the difficulties created by asphaltene precipitation
is very unlikely. In this case, the synergic effect of capillary
resistance, enhanced viscous resistance, low swelling and
extraction, low gravity drainage features, and the possibility of
permeability reduction due to asphaltene plugging (formation
damage) are all contributing to low recovery efficiency. The
situation is somewhat different for the case of CO2, where some
promising signs are observed as the NCA and NBA showed
smooth increasing trends.
At higher pressures the behavior of these gases changed
substantially; therefore, it is discussed distinctly. Figure 15
illustrates the formation of a capillary transition zone, where
NCA exhibited an increasing trend for both gases (CO2 and FG-
619). The rate of increase is considerably lower in the case of
FG-619 compared to that of CO2, and inclined to terminate at
the second invariable zone at high pressure, while the
magnitude of the NCA was considerably low at such a condition
and high displacement efficiency is not expected due to a strong
capillary. On the other side, Figure 16 shows that NBA has an
increasing trend and the feasibility of oil recovery by gravity
drainage increases with the pressure; however, the magnitude of
maximum NBA in the pressure domain of the experiments was
not very promising. If the challenges of asphaltene precipitation
were also considered, one may conclude that such flue gas is
not appropriate for this oil reservoir. It is worth mentioning
that there are some promising features that may cause more oil
recovery: significant swelling around 5 and 15 MPa and the
enhanced extraction potential at high pressure flue gas
applications.
CO2 was completely different in all aspects as it shows a
sharp increasing NCA trend in the transition zone and reaches
considerable values at the edge of the pressure domain (Figure
15), which promises near-miscible displacement and probably
efficient and low capillary displacement. This compensates for
some of the challenges in the oil recovery processes caused by
asphaltene precipitation. Besides, the NBA trend showed
appealing variations in this case (Figure 16). Bond number
was decreased dramatically just above the onset of asphaltene
Journal of Chemical & Engineering Data
precipitation (above the critical pressure of CO2), which was
due to the increased equilibrium IFT in this region. NBA was
increased again at 11 MPa (maximum gravity drainage
potential), then experienced a decreasing trend at higher
pressures. Since the same trends are not observed in NCA
results, it is related to the gravitational forces (density
difference) and the transition of gaseous CO2 to a liquid
phase, which decreases the gravity drainage potential (this
changes was observed clearly in the view cell). The results
showed that through the use of CO2 at this pressure (11 MPa),
the highest recovery efficiency due to the reduced capillary
resistance, maximum gravity drainage potential, and enhanced
extraction behavior is anticipated. However, the possibility of
formation damage and higher viscous resistance due to
asphaltene precipitation increases for the case of CO2 injection.
At higher pressures, the capillary resistance and gravity drainage
potential is decreased; therefore, the optimum pressure for
EOR application should be considered based on the good
configuration, production scenario, thickness of the producing
layer, and the superiority of each mechanism (gravity drainage
or reduced capillary resistance).
■ CONCLUSIONS
The effects of gas composition, miscibility, and pressure on the
gas−oil interfacial behavior of a highly asphaltenic Iranian crude
oil are studied by the observation of pendant oil drop behavior
in a gas-surroundings cell. Also, the effective oil production
mechanisms and the phenomena involved during non-
hydrocarbon gas injection process into asphaltenic oil reservoir
are discussed based on the experimental results and dimen-
sional analysis. The most important findings of this
experimental work follow:
• Preliminary study of the applicability of enhanced oil
recovery can be easily performed through reservoir
condition observation of the interfacial properties, and
the behavior of a pendant oil drop in different gas
systems at various conditions such as compositions,
temperature, and pressure.
• The results showed that, the use of either the equilibrium
gas−oil IFT values or the instantaneous value does not
affect the quality and quantity of VIT-MMP results. The
observation showed that the very low alteration of IFT in
the period of 600 s up to 3600 s was noticed, hence the
600 s IFT results were considered as the equilibrium
values.
• The slope of the VIT curve as it shows the trend toward
the miscibility condition is affected by the accumulation
of asphaltene at the oil−gas interface for asphaltenic
crude oils. Therefore, asphaltene precipitation results in
slope reduction of the VIT curve and makes the
miscibility harder to be achieved. This effect was
amplified when the surface coverage of asphaltene
molecules exceeded a threshold value (e.g., 60 %). This
is one of the causes of the observation of dual and triple
rate VIT curves in different experimental works.
• Increasing the pressure above the acquired VIT-MMP
values does not lead to full miscibility of the oil drop in
the surrounding gas medium, for this severely asphaltenic
crude oil except for the case of CO2 injection. It means
that asphaltene accumulation at the interface can severely
affect the miscibility development during gas injection
and should be studied carefully.
L dx.doi.org/10.1021/je400403y | J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Article
• The effect of asphaltene precipitation and multiple
decline rate VIT curves on the dimensional analysis
was not noticed in the case of CO2 injection which also
does not expect to affect the displacement efficiency
because of the high solubility of CO2 and low IFT values.
Therefore, the VIT-MMP is expected to match the slim
tube results; however, asphaltene precipitation in the case
of other gases with lower solubility hinders the
miscibility, and the consistency with slim tube results is
not expected.
• Low recovery efficiency for the case of N2 and flue gas
injection is predicted compared to CO2 injection into
this asphaltenic oil reservoir, since different mechanisms
are contributing to higher residual oil saturation for both
capillary dominated displacement and gravity drainage
schemes.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: shahab@shirazu.ac.ir.
Present Address
§
(S.A.) Sharif University of Technology, Tehran, Iran.
Funding
We thank the National Iranian South Oil Company (NISOC)
for partial financial support.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We would like to acknowledge Dr. Shahin Kord for his valuable
comments. Moreover the assistance of Mr. Ahmadreza
Haghnegahdar and Mr. Ali Zolghadr during the extensive
experimental part of this study is deeply appreciated.
■
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