Petroleum Research 8 (2023) 1e10

Contents lists available at ScienceDirect

Petroleum Research
journal homepage: http://www.keaipublishing.com/en/journals/
petroleum-research/

Estimation of the minimum miscibility pressure for CO2ecrude-oil

systems by molecular dynamics simulation
Wuge Cui a, Yunfeng Liang a, *, Yoshihiro Masuda a, **, Takeshi Tsuji a,
Toshifumi Matsuoka b, Haruka Takahashi c
a
Department of Systems Innovation, School of Engineering, The University of Tokyo, Tokyo, 113-8656, Japan
b
Fukada Geological Institute, Tokyo, 113-0021, Japan
c
JX Nippon Oil & Gas Exploration Corporation, Tokyo, 100-8163, Japan

a r t i c l e i n f o a b s t r a c t

Article history: CO2 injection is an effective enhanced oil recovery technique for energy security with the benefits of
Received 4 August 2022 carbon neutrality. To reach the maximum oil recovery, the miscible condition between CO2 and oil needs
Received in revised form to be maintained in the reservoir, which requires the operation pressure to be higher than the minimum
11 August 2022
miscibility pressure (MMP). There are two types of MMPs: the first-contact MMP (FC-MMP) and the
Accepted 11 August 2022
Available online 15 August 2022
multi-contact MMP (MC-MMP). In this study, molecular dynamics simulations were performed for the
CO2eoil interface system using two simplified digital oil models: a Bakken dead oil with four lumping
components and a live-crude-oil model with 50 types of oil molecules but with no asphaltenes and
Keywords:
CO2-EOR
heavy oil fractions. The vanishing interfacial tension method was used to predict the MMP. Different CO2
Minimum miscibility pressure eoil volume ratios were considered to mimic the different degrees of vaporization. To estimate the MMP
Molecular dynamics simulations accurately and rapidly, the interfacial tension in the low-pressure regime was used for the prediction.
Condensing and vaporizing mechanism Consequently, different MMPs were obtained, where the MMP value increased with increasing CO2eoil
CO2eoil volume ratio volume ratio. FC-MMP can be predicted when the CO2eoil volume ratio is sufficiently high. When the
Crude oil CO2eoil volume ratio was approximately 9e10, MMP was closest to the actual MC-MMP value. The
condensing and vaporizing mechanism was also studied at the molecular scale. Because pure CO2 was
used, only the vaporizing effect on MMP occurred. It was found that the intermediate C2eC6 components
have the main effect on the MMP calculation. This study can help to establish a computational protocol to
estimate FC-MMP and MC-MMP, which are widely used in reservoir engineering.
© 2022 The Authors. Publishing services provided by Elsevier B.V. on behalf of KeAi Communication Co.
Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/
by-nc-nd/4.0/).

1. Introduction
CO2 injection is an effective enhanced oil recovery (EOR)
method for energy security with the benefits of carbon neutrality
(Takagi and Okatsu, 2009; Kuuskraa et al., 2011; Yu et al., 2015; IEA,
2020; Knapik and Chruszcz-Lipska, 2020). Injecting gas into the oil
zones in a reservoir can improve oil recovery by maintaining the
reservoir pressure, displacing oil, or vaporizing the intermediate
and heavy fractions of the oil (Danesh, 1998; Yonebayashi et al.,
2021). During the injection process, contact between the two
* Corresponding author. .
** Corresponding author.
E-mail addresses: liang@sys.t.u-tokyo.ac.jp, liang@race.u-tokyo.ac.jp (Y. Liang),
masuda.yoshi@sys.t.u-tokyo.ac.jp (Y. Masuda).
phases induces mass transfer, which gradually makes the proper-
ties of the gas and oil phases similar. In the ideal state, the two
phases will achieve complete miscibility, that is, the gaseliquid
interface will disappear (Danesh, 1998). Usually, increasing the
pressure and enriching the gas can achieve miscibility. The injected
gas will vaporize the intermediate components in the oil through
multiple contacts and become enriched to achieve miscibility with
the oil. This process is known as vaporizing gas drive. At the same
time, the gas achieves multiple contact miscibility by condensing in
the oil, especially if the injection gas is rich, which is known as
condensing gas drive. In practical engineering, it is desirable to
obtain miscibility between CO2 and oil because it improves the local
displacement efficiency to 100%, hence maximizing oil recovery
(Dindoruk et al., 2021).
In petroleum engineering, two types of miscibility have been
studied: first-contact miscibility (FCM) and multi-contact

https://doi.org/10.1016/j.ptlrs.2022.08.001
2096-2495/© 2022 The Authors. Publishing services provided by Elsevier B.V. on behalf of KeAi Communication Co. Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
W. Cui, Y. Liang, Y. Masuda et al.
miscibility (MCM) (Dindoruk et al., 2021). At a given pressure and
temperature, FCM refers to the process in which two fluids mix in
all proportionsdat any concentration of either fluiddsuch that the
resulting mixture remains a single phase. The first-contact MMP
(FC-MMP) is the pressure at which two fluids mix in all proportions
at a given temperature. In the conventional displacement process,
MCM occurs between a reservoir fluid and an injected gas through
a dynamic mixing process with complex component exchange. The
multi-contact MMP (MC-MMP) is the pressure at which two fluids
mix in a porous medium at a given temperature. This is usually
determined to be the pressure with 90%e95% oil recovery after 1.2
pore volume injection of the solvent phase in a slim-tube experi-
ment (Dindoruk et al., 2021). In practice, FC-MMP and MC-MMP are
the same for a binary system, but their magnitudes can be very
different for CO2ecrude-oil systems (Dindoruk et al., 2021). The
condensing and vaporizing mechanism is very important for
describing MC-MMP.
Many experimental studies to predict MMPs have been per-
formed (Zhang et al., 2019; Dindoruk et al., 2021), including by
slim-tube experiments (Yarborough and Smith, 1970; Yellig and
Metcalfe, 1980; Stalkup, 1983; Hawthorne et al., 2016), using a
rising-bubble apparatus (Christiansen and Haines, 1987; Zhang and
Gu, 2016), and by the vanishing interfacial tension (VIT) method
(Rao, 1997; Rao and Lee, 2002; Ayirala and Rao, 2006; Orr and
Jessen, 2007; Jessen and Orr, 2008; Nobakht et al., 2008;
Hawthorne et al., 2016). The MMP can also be estimated through
analytical models based on the equation of states (EOS) (Zick, 1986;
Wang and Orr, 1997; Orr and Jessen, 2007; Jessen and Orr, 2008;
Zhang et al., 2018; Dindoruk et al., 2021) or by correlation models
based on experimental data (Benham et al., 1960; Yellig and
Metcalfe, 1980; Alston et al., 1985; Shokir, 2007; Valluri et al.,
2017). The correlation models have been further developed based
on machine learning (Shokrollahi et al., 2013; Chen et al., 2014;
Kamari et al., 2015; Tian et al., 2020). All of these theoretical studies
help to better understand the mechanisms (Orr and Jessen, 2007;
Jessen and Orr, 2008; Dindoruk et al., 2021) or determine the key
influencing factors of the MMP (Tian et al., 2020).
Molecular dynamics (MD) simulations can effectively simulate
the properties of CO2 and oil under different thermodynamic
conditions to provide insights that cannot be obtained from ex-
periments alone and to guide engineering operations (Kunieda
et al., 2010; Makimura et al., 2012; Liang et al., 2017; Iwase et al.,
2019; Fan et al., 2020; Jia et al., 2022). MD simulation has the po-
tential to speed up estimation of the MMP and reduce costs by
avoiding some conventional laboratory experiments. Previous
molecular modeling studies have focused on rapidly and accurately
predicting MMPs that are close to experimentally measured values
(Peng et al., 2018; Choudhary et al., 2019; Zhu et al., 2021; Li et al.,
2021; Toutouni et al., 2022; Qu et al., 2022). MMP predictions of a
binary mixture under different calculation conditions using the VIT
method have been successful (Peng et al., 2018; Choudhary et al.,
2019; Toutouni et al., 2022; Qu et al., 2022). Furthermore, Peng
et al. (2018) successfully calculated MMP of Bakken crude oil. MD
simulation has also shown that the miscibility degree can be
determined from the diffusion ability of the gas molecule (Zhu
et al., 2021). However, none of the previous studies have consid-
ered the difference between FC-MMP and MC-MMP, and it is also a
challenge to elucidate the condensing and vaporizing mechanism
from a molecular perspective.
Digital oil is a molecular model based on analytical data, and it
can be used to determine the connection between micro-
simulations and macro-experiments in petroleum engineering
(Sugiyama et al., 2018; Iwase et al., 2018, 2019; Liang, 2019). Using
digital oil, the reservoir fluid properties can be rapidly and accu-
rately verified, evaluated, and predicted, and actual production and
2
Petroleum Research 8 (2023) 1e10
development issues in oil fields can be solved. The combination of
digital oil and MD simulation opens a new door to support more
complicated, molecular-scale studies (Liang, 2019; Iwase et al.,
2019; Mizuhara et al., 2020; Fujita et al., 2022).
In this study, MD simulations of the CO2eoil interface system
were performed using two simplified digital oil models: a Bakken
dead oil with four lumping components and a live-crude-oil model
with 50 types of oil molecules but no asphaltenes and heavy oil
fractions. The interfacial tension (IFT) of the CO2eoil interface
system as a function of the pressure was calculated and the VIT
method was used to predict the MMP. In the simulations, the oil
content was kept constant, while the CO2 content was varied to
investigate the condensing and vaporizing gas drive mechanism in
the miscibility process (Fig. 1). An attempt was made to determine
whether it is possible to reproduce FC-MMP and MC-MMP using
MD simulations. This study will help to establish a computational
protocol to estimate MMPs, which are widely used in reservoir
engineering.
2. Computational methods
Two oil models were constructed. The first model was a
simplified Bakken-dead-oil model (Table 1), for validation of the IFT
calculation and MMP prediction, because there is a large and
publicly available experimental data (e.g., Hawthorne et al., 2016).
The second model was a live crude oil A containing 50 different
types of molecules. Because it was derived from real field data, only
the components up to C6 were listed (Table 2). Peng et al. (2018)
calculated MMP of Bakken crude oil with united-atom models for
the oil molecules. However, their model cannot be readily used for
describing aromatics, as well as oil molecules with heteroatoms.
Thus, the Bakken dead oil with all-atom models was studied again.
The GROMACS package (version 5.1.5) was used for the simu-
lations (Abraham et al., 2015). The CHARMM general force field was
used to describe the interatomic potentials of the oil molecules
(Vanommeslaeghe et al., 2010), and the TraPPE force field was used
for the CO2 molecules (Potoff and Siepmann, 2001). The CHARMM
force field can reproduce the density of the liquid oil phase
(Kunieda et al., 2010; Caleman et al., 2012; Iwase et al., 2018, 2019)
and the oilewater IFT (Kunieda et al., 2010), and it can describe
asphaltenes with complicated structures and heteroatoms
(Mizuhara et al., 2020; Fujita et al., 2022). Periodic boundary con-
ditions were applied to minimize the boundary effects caused by
the finite size of system. A linear constraint solver, known as the
LINCS algorithm, was used to constrain the chemical-bond lengths
(Hess et al., 1997). The long-range electrostatic interactions were
computed using the particle-mesh Ewald method (Essmann et al.,
Fig. 1. Simulation design. Different CO2eoil volume ratios were simulated by different
CO2 lengths to mimic different degrees of vaporization. The effect of the density of the
various light oil components in the CO2 phase on the IFT and MMP was investigated.
W. Cui, Y. Liang, Y. Masuda et al. Petroleum Research 8 (2023) 1e10

Table 1 interfaces were formed during the simulation. These data were
Composition of the simplified Bakken-dead-oil model. discarded in the analysis. Using the VIT method, a straight line was
Number Name Mole (%) Number of molecules fitted. When IFT becomes 0, the pressure at that condition is the
1 C6 8.83 53
value of MMP.
2 C10 47.67 286 The method for calculating IFT (g) was based on the Gibbs
3 C19 30.17 181 equation (Van Buuren et al., 1993; Kunieda et al., 2010; Makimura
4 C30 13.33 80 et al., 2012; Liang et al., 2017):

ðlz
pxx ðzÞ þ pyy ðzÞ 1 Pxx þ Pyy
Table 2 g ¼ ðpzz ðzÞ  Þdz ¼ ðPzz  ÞLz
Composition of the live crude oil A modela. 2 2 2
0
Number Name Mole (%) Number of molecules

1 CO2 0.3 3 where Pii (i ¼ x, y, z) are the pressure tensors in different directions,
2 N2 0.16 2 Lz is the simulation box size along the z direction perpendicular to
3 C1 31.88 319
4 C2 1.15 12
5 C3 0.31 3
6 IC4 0.18 2 different directions from the simulation to calculate IFT. The data
7 NC4 0.28 3 was recorded every 0.1 ps for the IFT calculations.
8 IC5 0.41 4
9 NC5 0.42 4
10 C6 1.25 13
11 C6þ 63.66 637
a
C6 is n-hexane. C6þ includes other C6 molecules, such as benzene, methyl-
cyclopentane, and cyclohexane, in addition to all the C7þ components.
1995). The cutoff distances were 1.2 nm for both the Lennard-Jones
and electrostatic potentials. To remove the excess potential energy
before the production runs, energy minimization steps were first
performed using the steepest descent method. The time step was 1
fs. The equilibrium of a single phase was confirmed after 10 ns of
simulation with the isothermaleisobaric (NPT) ensemble using the
Berendsen thermostat and barostat (Berendsen et al., 1984). Each
IFT calculation was based on a 20-ns simulation using the canonical
ensemble (NVT) with the BussieDonadioeParrinello thermostat
(Bussi et al., 2007), and the results of the final 3 ns were used for the
IFT calculation. The temperature was 315.15 K for the Bakken-dead-
oil model system, because the experimental data at this tempera-
ture are available (Hawthorne et al., 2016). The reservoir temper-
ature of 354.25 K was used for the light crude oil A system.
The strategy of the simulation was firstly to prepare two CO2
boxes and one oil box (Fig. 2), all of which were under the same
temperature and pressure. Secondly, the three boxes (note that CO2
was in a single phase according to the periodic boundary condi-
tions) were combined with at least 0.4 nm between two boxes to
prevent the molecules from overlapping. Thirdly, simulations of the
combined box were performed. The CO2 box was prepared by
referring to the experimental density data of CO2 at the target
temperatures and pressures (Lemmon et al., 2009). Two different
lengths of the CO2 phase were used for the Bakken-dead-oil model
system (Table 3), and four different lengths of the CO2 phase were
used for the light crude oil A system (Table 4). As mentioned above,
the CO2 box was equilibrated in advance by using the NPT ensemble
and then combined with the oil box. The data inside the brackets
(Tables 3 and 4) are the lengths of the CO2 phase in the simulation
due to the size change during pre-equilibration of a single phase
and the space left for preparing the interface system. The NVT
ensemble was used to calculate IFT. The interface between CO2 and
the oil is more stable when the volume of the box is kept constant.
In this way, large fluctuations of the system are avoided, and a more
accurate IFT is obtained. Owing to use of the NVT ensemble, the
pressure of the simulated system is solely an output, and hence it is
not fixed. But the pressure was within a certain pressure range after
equilibrium. Three independent runs at six pressures for each
model system were performed. In some cases, more than two
3
the interface, and lz is an arbitrary length of a segment along the z
direction containing an interface. P needs to be obtained in
3. Results and discussion
3.1. Bakken-dead-oil model: validation of the calculation scheme
The variation of the IFT of the Bakken oil with pressure is shown
in Fig. 3. IFT gradually decreased with increasing pressure. By fitting
the data at low pressure, MMP can be estimated. When the length
of the CO2 phase reached 50 nm, the MMP value was 6.7 MPa
(Table 3). When the length of the CO2 phase reached 200 nm, the
MMP value was 7.3 MPa, which is closer to the experimental value
of 8.8 MPa (capillary-rise VIT method) (Hawthorne et al., 2016).
This is because a smaller CO2 length increases the density of the
light oil component (e.g., C6) in the CO2 phase and decreases IFT,
thus leading to a lower estimate of MMP.
In the simulation, a new simulation box was used for each
calculation of IFT at a different pressure, rather than gradually
adding CO2 to the low-pressure box. We designed to maximize the
independence of each simulation, but this also sacrificed the
coherence of the fitted curves to some extent. During the simula-
tion, there was always an interface between the oil and CO2 phases
because the controlled pressure did not reach the MMP value. Such
a condition is necessary to calculate IFT. CO2 was initially on both
sides of the oil block and entered the oil phase during the simu-
lation. At the same time, the light molecules in the oil phase moved
into the CO2 phase. In the process of changing the composition of
each phase, IFT became smaller, and when the pressure reached a
certain level, it gradually approached the miscible state. This
mechanism is called the condensing and vaporizing gas drive.
With methodological confirmation of the Bakken-dead-oil
model, MMP of live crude oil A in the presence of injected CO2
was further investigated. There are few light components in the
Bakken dead oil, so the oil components do not greatly move into the
CO2 phase. In contrast, there are many light oil components (e.g.,
methane and C2eC6) in the live crude oil A. Owing to their
comparatively volatile nature, they will move more easily into the
CO2 phase, which will have a greater effect on IFT.
3.2. Live-crude-oil model: influence of the CO2eoil volume ratio
The live-crude-oil model contained 50 different types of mole-
cules, and it included molecules with different structures but
having the same number of carbon atoms. Compared with the
Bakken oil, live crude oil has more light oil molecules, which can
move into the CO2 phase. Among these molecules, the content of
C2eC6 molecules in the CO2 phase has been considered to be a key
W. Cui, Y. Liang, Y. Masuda et al. Petroleum Research 8 (2023) 1e10

the relevant data were measured. In previous experiments

Fig. 2. (a) Simulation strategy. (b) Density profile and a snapshot of the Bakken-dead-
oil model with CO2.
(Nobakht et al., 2008), pressures from 2.4 to 7.2 MPa were used to
obtain an accurate MMP. In our simulations, the pressure range
from 2.0 to 7.0 MPa was found to give an accurate MMP. This
pressure range was chosen for the following reasons. When the
pressure is higher than 7.4 MPa, which is the critical pressure for
CO2, the calculated IFT fluctuates significantly. This is because CO2
extracts much more of the oil phase in this pressure range than at
lower pressure (see Section 3.4 for more discussion). This causes a
change in the simulated pressure, which, in turn, affects the IFT
value. Therefore, considering the pressure fluctuations during the
simulation, the maximum value of the chosen pressure interval was
not greater than 7 MPa in order to eliminate the uncertainty caused
by the supercritical behavior of CO2.
The variation of the MMP for different CO2 lengths (i.e., different
CO2eoil volume ratios) is shown in Fig. 5. When the length of the
CO2 phase was 200 nm, a large MMP value of 22.45 MPa was pre-
dicted, but it was still slightly less than the FC-MMP predicted by
the EOS model (25.5 MPa). It is expected that when the length of
the CO2 phase in the simulation is sufficiently long, the density of
the oil component in the CO2 phase is almost negligible, in which
case the situation is close to the FC-MMP. In the simulation, we
could only make the CO2 phase a finite length. Theoretically, when
the CO2-phase length is infinite, the measured value is the FC-MMP.

3.3. Molecular-scale view of the condensing and vaporizing

factor affecting IFT and MMP in some studies (Alston et al., 1985;
Shokir, 2007; Shokrollahi et al., 2013; Tian et al., 2020). Methane
and nitrogen in the CO2 phase were thought to increase IFT in a
previous study (Tian et al., 2020). These factors will be considered
in the subsequent analysis.
IFT of live crude oil A as a function of pressure for different CO2-
phase lengths is shown in Fig. 4. When the length of the CO2 phase
reached 10 nm, the predicted MMP value was 10.16 MPa (Fig. 4a).
The intercept of the fitted straight line with the y axis was also
small and the slope was large. As the length of the CO2 phase
further increased, the predicted MMP value gradually increased
(Table 4). When the length of the CO2 phase reached 120 nm, the
predicted MMP value was 16.58 MPa, which was the closest pre-
dicted value to the experimental MC-MMP value of 17.8 MPa (slim-
tube test).
Interestingly, the oileCO2 volume ratio for a CO2-phase length of
120 nm is approximately 9e10. A volume ratio of 1:9 has been used
in several previous experimental studies, especially under low-
pressure conditions (Rao, 1997; Rao and Lee, 2002; Nobakht et al.,
2008). It can also be found that the same volume ratio in the
simulation could predict a similar MC-MMP to the actual value after
Table 3
MMP values of Bakken oil with different amounts of CO2.
System 1 System 2
Length of CO2 Phase (nm) 50 (56) 200 (211)
MMP (MPa) 6.7 7.3
mechanism
To analyze the miscibility process, the density profiles of each
component in the CO2eoil interface systems were calculated for the
case of live crude oil A (see Section 3.2). The calculated density
profiles of each component along the z direction at different pres-
sures for a CO2-phase length of 20 nm are shown in Fig. 6. For
clarity, the oil components from C2 to C6 were combined as C2eC6,
where C6 indicates n-hexane, and the oil components from C7 to
C10, as well as benzene, methyl-cyclopentane, and cyclohexane
because they belong to C7 by boiling point even though their car-
bon number is six, as C6eC10. As shown in Fig. 6, two interfaces can
be clearly defined. Two peaks of CO2 appeared at the interface
owing to adsorption of CO2. The middle part was the oil phase, and
the two side parts were the CO2 phase. The density of the oil
component in the oil phase decreased with increasing pressure,
which was mainly due to oil swelling. While a portion of the oil
molecules moved from the oil phase to the CO2 phase as the
pressure increased, they were all light oil molecules, which in
general leads to an increase in the oil density. Because the volume
was kept constant in the simulation, the CO2 box was prepared and
equilibrated in advance by referring to the experimental density
data of CO2 at the target temperatures and pressures (Lemmon
et al., 2009). Therefore, the pressure could not be accurately
controlled in each simulation, but the number of CO2 molecules
could be adjusted so that the pressure remained within a certain
Experiments
range. Thus, each pressure was not an integer value. The density
e profiles for a CO2-phase length of 200 nm are shown in Fig. 7.
8.8
Vaporization of the light oil fraction was different from that of the

Table 4
MMP values of live crude oil with different amounts of CO2.

Volume ratio (CO2/Oil) Length of CO2 phase (nm) MMP (MPa) Experiments (MPa)

0.8 (0.9) 10 (12) 10.2

1.5 (1.8) 20 (23) 11.5
9.2 (10.2) 120 (133) 16.6 17.8 (MC-MMP)
15.4 (17.1) 200 (222) 22.4
>15.4 >200 … 25.5 (FC-MMP)

4
W. Cui, Y. Liang, Y. Masuda et al.
Fig. 3. (a) IFT of the Bakken-dead-oil model as a function of pressure for a CO2-phase length of 50 nm. (b) IFT of the Bakken-dead-oil model as a function of pressure for a CO2-phase
length of 200 nm.
Fig. 4. IFT of the live crude oil A model as a function of pressure with CO2-phase lengths of (a) 10 nm, (b) 20 nm, (c) 120 nm, and (d) 200 nm.
20-nm-long CO2 phase case at all CO2eoil volume ratios. When the
simulation boxes were merged, a sufficient space was also left to
ensure that no molecules overlapped. Thus, the actual pressure was
lower than the predicted pressure. This was especially obvious
when the CO2 length was small. When the CO2 length was large, the
space left had less influence on the predicted pressure. The density
Fig. 5. Estimated MMP values for different lengths of the CO2 phase. The different CO2
lengths correspond to different densities of the oil components in the CO2 phase and
therefore affect the IFT. Thus, the IFT value equal to 0 for the fitted straight line (i.e., the
MMP value) is also different.
5
Petroleum Research 8 (2023) 1e10
of the oil in the CO2 phase for the 200-nm-long CO2 phase case was
lower than that for the 20-nm-long CO2 phase case. At the same
volume, the densities of CO2 in both the oil and gas phases
increased with increasing pressure because the pressure was
controlled by increasing the number of CO2 molecules, and the
solubility of CO2 in the oil phase increased with increasing pressure.
The density profiles of C2eC6 for different CO2-phase lengths
are shown in Fig. 8, clearly indicating the difference in the C2eC6
composition of the CO2 phase. For a CO2eoil volume ratio of 0.8
(CO2-phase length of 10 nm, Fig. 8a), the C2eC6 oil components had
a high density in the CO2 phase. In this case, the measured MMP
value was lower than the experimentally measured MC-MMP. As
the CO2eoil volume ratio increased, the IFT increased owing to the
decrease in the density of the oil components in the CO2 phase.
Therefore, the calculated MMP increased and gradually approached
the experimentally measured MC-MMP. When the CO2eoil volume
ratio was approximately 9:1 (CO2-phase length of 120 nm, Fig. 8c),
the calculated MMP value was 16.6 MPa, which was close to the
experimentally measured value. As the CO2eoil volume ratio
continued to increase, the predicted MMP value also increased and
approached the FC-MMP, but it still did not reach the experimental
FC-MMP value at a CO2eoil volume ratio of 15.4 (CO2-phase length
of 200 nm, Fig. 8d). When the CO2 length was larger, the total
W. Cui, Y. Liang, Y. Masuda et al.
Fig. 6. Density profiles of live crude oil A at pressures of (a) 3.64, (b) 4.77, (c) 5.80, and (d) 7.17 MPa. The CO2-phase length was 20 nm. Z is the coordinate of the simulated box along
the Z direction.
amount of C2eC6 moving to the CO2 phase was greater, as evi-
denced by the lower density of C2eC6 in the oil phase (Fig. 8aed).
Because the volume of the CO2 phases was larger, the density of
C2eC6 in them was lower. The density profiles of C6eC10 for
different CO2 lengths are shown in Fig. 9. The presence of C6eC10 in
the CO2 phase also decreased the IFT. Because it was relatively
difficult for C6eC10 to move into the CO2 phase, their density in the
CO2 phase was low in this pressure range. The density in the oil
phase was different at different pressures, which may be partly due
to oil swelling. The density profiles of nitrogen and methane for
different CO2 lengths are shown in Fig. 10. Nitrogen and methane
were distributed more in the CO2 phase than in the oil phase
compared with the other oil components. This can be seen from the
higher density in the CO2 phase than in the oil phase. Their pres-
ence in the CO2 phase increases IFT to some extent. However, the
dominant factor for IFT and MMP is the presence of oil molecules
Fig. 7. Density profiles of live crude oil A at pressures of (a) 2.07, (b) 3.90, (c) 4.95, and (d) 6.73 MPa. The CO2-phase length was 200 nm. Z is the coordinate of the simulated box
along the Z direction.
6
Petroleum Research 8 (2023) 1e10
(i.e., C2eC6) in the CO2 phase.
The density of C2eC6 in the CO2 phase changed with pressure in
the simulations for different CO2eoil volume ratios (Fig. 11), clearly
reflecting the degree of C2eC6 vaporization. The mechanism of
condensation and vaporization is strongly related to the composi-
tional changes between the oil and gas phases. In the molecular
simulations, it was possible to simulate such different degrees of
condensing and vaporizing. For larger CO2 length (i.e., higher
CO2eoil volume ratio), the density of the oil components in the CO2
phase was lower and the predicted MMP was higher, approaching
FC-MMP. As the CO2eoil volume ratio was gradually reduced, the
multiple contacts became more obvious, and once it decreased to a
certain value, the calculated MMP became closer to the experi-
mentally measured MC-MMP. For different types of oil, it is
important to determine an appropriate CO2eoil volume ratio to
estimate MMP.
W. Cui, Y. Liang, Y. Masuda et al. Petroleum Research 8 (2023) 1e10

Fig. 8. Densities of C2eC6 in live crude oil A at different pressures for CO2-phase lengths of (a) 10 nm (b) 20 nm, (c) 120 nm, and (d) 200 nm. Z is the coordinate of the simulated box
along the Z direction. By using different lengths of CO2, the different densities of the oil components in the CO2 phase can be observed. Note that the values in the density profiles are
small and appear to fluctuate because the figures are enlarged figures of Figs. 6 and 7.

3.4. Discussion studying CO2ecrude-oil systems.

Zick (1986) pointed out that a minimum of four components is
necessary for the condensing and vaporizing mechanism to occur.
In a ternary system, it is possible to observe the condensing or
vaporizing mechanism and obtain different IFTs when the mole
fraction of the injected gas is changed (Orr and Jessen, 2007). In a
binary system, MMP is the critical point on the top of the two-phase
region in the pressureecomposition diagram, which can be simu-
lated and measured relatively easily using the VIT method
(Dindoruk et al., 2021). By previous MD simulations (Peng et al.,
2018), it has been shown that by adjusting the interaction param-
eters of CO2 and the oil, the MMP value of the Bakken oil and CO2
can be accurately predicted. However, Qu et al. (2022) found that
adjusting the interaction parameters may not be necessary for the
CO2edecane binary system. From this perspective, obtaining the
MMP by varying the CO2eoil volume ratio has a clear advantage for
When CO2 is gradually added to the oil phase, the pressure in-
creases. Three pressure regions can be designated (Tsau et al., 2010;
Abdurrahman et al., 2015, 2019). The first pressure region is the
“condensation” region, in which the oil-phase volume steadily in-
creases owing to dissolution of CO2 in the oil. The second pressure
region is the “condensation/extraction” region, in which the oil-
phase volume decreases rapidly. The third pressure region is the
“extraction” region, in which the oil-phase volume decreases more
slowly with increasing pressure. In this study, the focus was on the
first pressure region, where IFT is well-defined. Thus, MMP can be
estimated more accurately and rapidly. It should be mentioned that
the above terminology is taken from Tsau et al. (2010), and it solely
reflects three regions of the oil-swelling data (Tsau et al., 2010;
Dindoruk et al., 2021). As shown in this work, vaporization of the
light oil components also occurs in the first pressure region (i.e., the
condensation region). It is important to estimate the MMP using

Fig. 9. Densities of C6eC10 in live crude oil A at different pressures for CO2-phase lengths of (a) 10 nm (b) 20 nm, (c) 120 nm, and (d) 200 nm. Z is the coordinate of the simulated
box along the Z direction. Note that the values in the density profiles are small and appear to fluctuate because the figures are enlarged figures of Figs. 6 and 7.

7
W. Cui, Y. Liang, Y. Masuda et al.
Fig. 10. Densities of N2eCH4 in live crude oil A at different pressures for CO2-phase lengths of (a) 10 nm, (b) 20 nm, (c) 120 nm, and (d) 200 nm. Z is the coordinate of the simulated
box along the Z direction.
Fig. 11. Densities of C2eC6 in the CO2 phase at different CO2eoil volume ratios. Note
that three points overlapped at approximately 2 MPa and two points overlapped at
approximately 4 MPa for a CO2-phase length of 200 nm.
the VIT method. It has been reported that the intersection of the
lines for the second and third pressure regions can be used as an
estimate of MMP (Tsau et al., 2010; Abdurrahman et al., 2015, 2019;
Dindoruk et al., 2021). It will be very interesting to study the second
and third pressure regions directly by MD simulations using digital-
oil models.
Since the advent of the VIT method, two issues have been widely
discussed (Dindoruk et al., 2021). First, the composition path in the
VIT method is usually along the dilution line of the crude oil and
injected gas, which might differ from the composition after mul-
tiple contacts in the porous medium. Second, there are often small
but detectable IFTs even above the MMP (i.e., the MC-MMP). For the
first issue, IFTs and MMPs were studied using an interfacial system
with different CO2eoil volume ratios, consequently, it is possible to
obtain different MMPs. When the CO2eoil volume ratio reaches
approximately 9e10, MMP is closest to the actual MC-MMP value. It
is interesting to note that a similar CO2eoil volume ratio had also
been used in previous experimental studies (Rao, 1997; Rao and
Lee, 2002; Nobakht et al., 2008). Although the composition path
is still in the dilution line in this work, this study provides new
insights into the miscibility process in the VIT method. To address
the second issue, the low-pressure data was used for fitting. A
similar pressure range was used in a previous experimental study
(Nobakht et al., 2008). In the future, it is planned to study the
8
Petroleum Research 8 (2023) 1e10
CO2ecrude-oil systems between MC-MMP and FC-MMP in detail.
These systems may correspond to the above-mentioned second and
third pressure regions (i.e., the condensation/extraction and
extraction regions). Jessen and Orr (2008) determined the phase
behavior of multicomponent reservoir fluids and injected gases
based on the EOS model and calculated IFTs using the parachor
model (Schechter and Guo, 1998). The IFT calculation method used
in this study is more appropriate than the parachor model. It would
be fruitful if a molecular-scale study was performed with compo-
sitions according to the EOS-based phase diagram because the fluid
characterization is common to both methods.
4. Conclusion
CO2ecrude-oil systems with the Bakken-dead-oil model and a
live-crude-oil model were studied by MD simulations. MMPs were
calculated based on the VIT method. The computational protocol
for estimating FC-MMP and MC-MMP with digital oil is developed.
The key findings are:
(1) The degree of vaporization in the miscible processes can be
controlled by changing the CO2eoil volume ratio in the
simulation.
(2) To estimate the MMPs more accurately and quickly, IFT in the
low-pressure range was recommended during the linear
fitting for the prediction.
(3) When the CO2eoil volume ratio is approximately 9e10, MMP
is closest to the actual value of MC-MMP obtained by a slim-
tube experiment. FC-MMP could be predicted when the
CO2eoil volume ratio is higher than 15.
(4) Furthermore, the condensing and vaporizing mechanism is
shown on the molecular scale. It was found that the C2eC6
intermediate components have the main effect on the MMP
prediction.
However, it should be mentioned that there are some limita-
tions in this study. For example, only two crude oil models were
considered. In addition, the heavy fractions as well as asphaltenes
are not included in our oil models. In the future, more studies can
be performed to establish a protocol to estimate FC-MMP and MC-
MMP by using well-defined ternary and quaternary model systems,
W. Cui, Y. Liang, Y. Masuda et al.
as well as various crude-oil systems using the sophisticated digital
oil models.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This study was financially supported by JX Nippon Oil & Gas
Exploration Corporation. We thank the Japan Society for the Pro-
motion of Science (JSPS) for a Grant-in-Aid for Scientific Research A
(No. 24246148) and Grants-in-Aid for Scientific Research C (Nos.
16K06925, 17K06988, and 22K03927).
References
Abdurrahman, M., Bae, W., Permadi, A.K., 2019. Determination and evaluation of
minimum miscibility pressure using various methods: experimental, visual
observation, and simulation. Oil Gas Sci Technol.dRev. IFP Energies Nouvelles.
74, 55e63.
Abdurrahman, M., Permadi, A.K., Bae, W.S., 2015. An improved method for esti-
mating minimum miscibility pressure through the condensation-exaction
process under swelling tests. J. Petrol. Sci. Eng. 131, 165e171.
Abraham, M.J., Murtola, T., Schulz, R., Pa ll, S., Smith, J.C., Hess, B., Lindahl, E., 2015.
GROMACS: high performance molecular simulations through multi-level
parallelism from laptops to supercomputers. Software 1, 19e25.
Alston, R.B., Kokolis, G.P., James, C.F., 1985. CO2 minimum miscibility pressure: a
correlation for impure CO2 streams and live oil systems. Soc. Petrol. Eng. J. 25,
268e274.
Ayirala, S.C., Rao, D.N., 2006. Comparative evaluation of a new MMP determination
technique. In: SPE/DOE Symposium on Improved Oil Recovery, Tulsa,
Oklahoma.
Benham, A.L., Dowden, W.E., Kunzman, W.J., 1960. Miscible fluid displacement e
prediction of miscibility. Transactions of the AIME 219, 229e237.
Berendsen, H.J.C., Postma, J.P.M., van Gunsteren, W.F., Di Nola, A., Haak, J.R., 1984.
Molecular dynamics with coupling to an external bath. J. Chem. Phys. 81,
3684e3690.
Bussi, G., Donadio, D., Parrinello, M., 2007. Canonical sampling through velocity
rescaling. J. Chem. Phys. 126, 014101.
Caleman, C., Van Maaren, P.J., Hong, M., Hub, J.S., Costa, L.T., Van Der Spoel, D., 2012.
Force field benchmark of organic liquids: density, enthalpy of vaporization, heat
capacities, surface tension, isothermal compressibility, volumetric expansion
coefficient, and dielectric constant. J. Chem. Theor. Comput. 8, 61e74.
Chen, G., Fu, K., Liang, Z., Sema, T., Li, C., Tontiwachwuthikul, P., Idem, R., 2014. The
genetic algorithm based back propagation neural network for MMP prediction
in CO2-EOR process. Fuel 126, 202e212.
Choudhary, N., Nair, A.K.N., Ruslan, M.F.A.C., Sun, S., 2019. Bulk and interfacial
properties of decane in the presence of carbon dioxide, methane, and their
mixture. Sci. Rep. 9, 19784.
Christiansen, R.L., Haines, H.K., 1987. Rapid measurement of minimum miscibility
pressure with the rising-bubble apparatus. SPE Reserv. Eng. 2, 523e527.
Danesh, A., 1998. PVT and phase behaviour of petroleum reservoir fluids. Dev.
Petrol. Sci. 47, 1e388.
Dindoruk, B., Johns, R., Orr Jr., F.M., 2021. Measurement and modeling of minimum
miscibility pressure: a state-of-the-art review. SPE Reservoir Eval. Eng. 24,
367e389.
Essmann, U., Perera, L., Berkowitz, M.L., Darden, T., Lee, H., Pedersen, L.G., 1995.
A smooth particle mesh Ewald method. J. Chem. Phys. 103, 8577e8593.
Fan, C., Jia, J., Peng, B., Liang, Y., Li, J., Liu, S., 2020. Molecular dynamics study on CO2
foam film with sodium dodecyl sulfate: effects of surfactant concentration,
temperature and pressure on the interfacial tension. Energy Fuels 34,
8562e8574.
Fujita, K., Liang, Y., Mizuhara, J., Masuda, Y., Kobayashi, K., Takabayashi, K.,
Yonebayashi, H., 2022. Evaluation of asphaltene adsorption free energy at the
oilewater interface: effect of oil solvents. Energy Fuels 36, 1338e1349.
Hawthorne, S.B., Miller, D.J., Jin, L., Gorecki, C.D., 2016. Rapid and simple capillary-
rise/Vanishing interfacial tension method to determine crude oil minimum
miscibility pressure: pure and mixed CO2, methane, and ethane. Energy Fuels
30, 6365e6372.
Hess, B., Bekker, H., Berendsen, H.J.C., Fraaije, J.G.E.M., 1997. LINCS: a linear
constraint solver for molecular simulations. J. Comput. Chem. 18, 1463e1472.
IEA, 2020. CCUS in Clean Energy Transitions. IEA, Paris. https://www.iea.org/
reports/ccus-in-clean-energy-transitions.
Iwase, M., Sugiyama, S., Liang, Y., Masuda, Y., Morimoto, M., Matsuoka, T., Boek, E.S.,
Ueda, R., Nakagawa, K., 2018. Development of digital oil for heavy crude oil:
molecular model and molecular dynamics simulations. Energy Fuels 32,
9
Petroleum Research 8 (2023) 1e10
2781e2792.
Iwase, M., Liang, Y., Masuda, Y., Morimoto, M., Matsuoka, T., Boek, E.S., Kaito, Y.,
Nakagawa, K., 2019. Application of a digital oil model to solvent-based
enhanced oil recovery of heavy crude oil. Energy Fuels 33, 10868e10877.
Jessen, K., Orr Jr., F.M., 2008. On the interfacial-tension measurements to estimate
minimum miscibility pressures. SPE Reservoir Eval. Eng. 11, 933e939.
Jia, J., Li, J., Liang, Y., Peng, B., 2022. Molecular dynamics study on performance of
olefin sulfonate at the decaneewater interface: effect of molecular architecture.
Fuel 308, 122013.
Kamari, A., Arabloo, M., Shokrollahi, A., Gharagheizi, F., Mohammadi, A.H., 2015.
Rapid method to estimate the minimum miscibility pressure (MMP) in live
reservoir oil systems during CO2 flooding. Fuel 153, 310e319.
Knapik, E., Chruszcz-Lipska, K., 2020. Chemistry of reservoir fluids in the aspect of
CO2 injection for selected oil reservoirs in Poland. Energies 13, 6456.
Kunieda, M., Nakaoka, K., Liang, Y., Miranda, C.R., Ueda, A., Takahashi, S., Okabe, H.,
Matsuoka, T., 2010. Self-accumulation of aromatics at the oilwater interface
through weak hydrogen bonding. J. Am. Chem. Soc. 132, 18281e18286.
Kuuskraa, V.A., Leewen, T.V., Wallace, M., 2011. Improving Domestic Energy Security
and Lowering CO2 Emissions with 'Next Generation' CO2-enhanced Oil Recov-
ery (CO2-EOR) (No. DOE/NETL-2011/1504). National Energy Technology Labo-
ratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR, USA.
Lemmon, E.W., McLinden, M.O., Friend, D.G., 2009. Thermophysical Properties of
Fluid Systems. NIST Chemistry WebBook: NIST Standard Reference Database.
Number 69.
Li, D., Xie, S., Li, X., Zhang, Y., Zhang, H., Yuan, S., 2021. Determination of minimum
miscibility pressure of CO2eoil system: a molecular dynamics study. Molecules
26, 4983.
Liang, Y., 2019. Development of digital oil for technological innovation in petroleum
engineering. J. Jpn. Assoc. Pet. Technol. 84, 425e436.
Liang, Y., Tsuji, S., Jia, J., Tsuji, T., Matsuoka, T., 2017. Modeling CO2ewateremineral
wettability and mineralization for carbon geo-sequestration. Accounts Chem.
Res. 50, 1530e1540.
Makimura, D., Kunieda, M., Liang, Y., Matsuoka, T., Takahashi, S., Okabe, H., 2012.
Application of molecular simulations to CO2-enhanced oil recovery: phase
equilibrium and interfacial phenomena. SPE J. 18, 319e330.
Mizuhara, J., Liang, Y., Masuda, Y., Kobayashi, K., Iwama, H., Yonebayashi, H., 2020.
Evaluation of asphaltene adsorption free energy at the oilewater interface: role
of heteroatoms. Energy Fuels 34, 5267e5280.
Nobakht, M., Moghadam, S., Gu, Y., 2008. Determination of CO2 minimum misci-
bility pressure from measured and predicted equilibrium interfacial tensions.
Ind. Eng. Chem. Res. 47, 8918e8925.
Orr Jr., F.M., Jessen, K., 2007. An analysis of the vanishing interfacial tension tech-
nique for determination of minimum miscibility pressure. Fluid Phase Equil.
255, 99e109.
Peng, F., Wang, R., Guo, Z., Feng, G., 2018. Molecular dynamics simulation to esti-
mate minimum miscibility pressure for oil with pure and impure CO2. Journal of
Physics Communications 2, 115028.
Potoff, J.J., Siepmann, J.I., 2001. Vapor-liquid equilibria of mixtures containing al-
kanes, carbon dioxide, and nitrogen. AIChE J. 47, 1676e1682.
Qu, B., Ma, X., Dong, Z., 2022. Interfacial characterization and minimum miscible
pressure study of CO2 flooding based on molecular dynamics. Improved Oil and
Gas Recovery 6. https://doi.org/10.14800/IOGR.1207.
Rao, D.N., 1997. A new technique of vanishing interfacial tension for miscibility
determination. Fluid Phase Equil. 139, 311e324.
Rao, D.N., Lee, J.I., 2002. Application of the new vanishing interfacial tension
technique to evaluate miscibility conditions for the Terra Nova Offshore Project.
J. Petrol. Sci. Eng. 35, 247e262.
Schechter, D.S., Guo, B., 1998. Parachors based on modern physics and their uses in
IFT prediction of reservoir fluids. SPE Reservoir Eval. Eng. 1, 207e217.
Shokir, E.M., 2007. CO2-oil minimum miscibility pressure model for impure and
pure CO2 streams. J. Petrol. Sci. Eng. 58, 173e185.
Shokrollahi, A., Arabloo, M., Gharagheizi, F., Mohammadi, A.H., 2013. Intelligent
model for prediction of CO2-Reservoir oil minimum miscibility pressure. Fuel
112, 375e384.
Stalkup, F.I., 1983. Status of miscible displacement. J. Petrol. Technol. 35, 815e826.
Sugiyama, S., Liang, Y., Murata, S., Matsuoka, T., Morimoto, M., Ohata, T., Nakano, M.,
Boek, E.S., 2018. Construction, validation, and application of digital oil: Inves-
tigation of asphaltene association toward asphaltene-precipitation prediction.
SPE J. 23, 952e968.
Takagi, S., Okatsu, K., 2009. International Joint Study on CO2-EOR Study on Appli-
cability of CO2-EOR to Rang Dong Field. In: Offshore Vietnam. IEA Collaborative
Project on Enhanced Oil Recovery Symposium, Canberra, Australia.
Tian, Y., Ju, B., Yang, Y., Wang, H., Dong, Y., Liu, N., Ma, S., Yu, J., 2020. Estimation of
minimum miscibility pressure during CO2 flooding in hydrocarbon reservoirs
using an optimized neural network. Energy Explor. Exploit. 38, 2485e2506.
Toutouni, R., Kubelka, J., Piri, M., 2022. Liquid-vapor interfacial tension in alkane
mixtures: improving predictive capabilities of molecular dynamics simulations.
J. Phys. Chem. B 126, 1136e1146.
Tsau, J.-S., Bui, L.H., Willhite, G.P., 2010. Swelling/extraction Test of a Small Sample
Size for Phase Behavior Study. SPE Improved Oil Recovery Symposium, Tulsa,
Oklahoma, USA.
Valluri, M.K., Mishra, S., Schuetter, J., 2017. An improved correlation to estimate the
minimum miscibility pressure of CO2 in crude oils for carbon capture, utiliza-
tion, and storage projects. J. Petrol. Sci. Eng. 158, 408e415.
Van Buuren, A., Marrink, S., Berendsen, H., 1993. A molecular-dynamics study of the
W. Cui, Y. Liang, Y. Masuda et al.
decane water interface. J. Phys. Chem. 97, 9206e9212.
Vanommeslaeghe, K., Hatcher, E., Acharya, C., Kundu, S., Zhong, S., Shim, J.,
Darian, E., Guvench, O., Lopes, P., Vorobyov, I., Mackerell Jr., A.D., 2010.
CHARMM general force field: a force field for drug-like molecules compatible
with the CHARMM all-atom additive biological force fields. J. Comput. Chem. 31,
671e690.
Wang, Y., Orr Jr., F.M., 1997. Analytical calculation of minimum miscibility pressure.
Fluid Phase Equil. 139, 101e124.
Yarborough, L., Smith, L.R., 1970. Solvent and driving gas compositions for miscible
slug displacement. SPE J. 10, 298e310.
Yellig, W.F., Metcalfe, R.S., 1980. Determination and prediction of CO2 minimum
miscibility pressures. J. Petrol. Technol. 32, 160e168.
Yonebayashi, H., Iwama, H., Takabayashi, K., Miyagawa, Y., Watanabe, T., 2021. Un-
even distribution of asphaltene deposits in CO2 flooding path: interpretation by
combining thermodynamic and micro-CT 3D geological porous models. Energy
Fuels 35, 329e340.
Yu, W., Lashgari, H.R., Wu, K., Sepehrnoori, K., 2015. CO2 injection for enhanced oil
10
Petroleum Research 8 (2023) 1e10
recovery in Bakken tight oil reservoirs. Fuel 159, 354e363.
Zhang, K., Gu, Y., 2016. New qualitative and quantitative technical criteria for
determining the minimum miscibility pressures (MMPs) with the rising-bubble
apparatus (RBA). Fuel 175, 172e181.
Zhang, K., Jia, N., Li, S., Liu, L., 2018. Millimeter to nanometer-scale tight oileCO2
solubility parameter and minimum miscibility pressure calculations. Fuel 220,
645e653.
Zhang, K., Jia, N., Zeng, F., Li, S., Liu, L., 2019. A review of experimental methods for
determining the Oil‒Gas minimum miscibility pressures. J. Petrol. Sci. Eng. 183,
106366.
Zhu, S., Yu, H., Yan, G., Li, J., Cao, A., Sun, C., 2021. Miscibility process of hydrocarbon
mixture gas and crude oil: insights from molecular dynamics. Ind. Eng. Chem.
Res. 60, 13710e13718.
Zick, A.A., 1986. A combined condensing/vaporizing mechanism in the displace-
ment of oil by enriched gases. In: SPE Annual Technical Conference and Exhi-
bition, Louisiana, USA.