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Enhanced oil recovery mechanism of CO2 water-alternating-gas

injection in silica nanochannel
Youguo Yan a, Chuanyong Li a, Zihan Dong a, Timing Fang a, Baojiang Sun b, Jun Zhang a,⇑
College of Science, China University of Petroleum, 266580 Qingdao, Shandong, People’s Republic of China
School of Petroleum Engineering, China University of Petroleum, 266580 Qingdao, Shandong, People’s Republic of China

h i g h l i g h t s

 Molecular dynamics simulation was firstly used to address CO2 WAG in nanochannel.
 The different roles of scCO2 slug and water slug in CO2 WAG injection were revealed.
 The synergistic effects of scCO2 slug and water slug were proposed.

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

Article history: CO2 water-alternating-gas (WAG) injection has been proven as a promising and effective technology to
Received 16 July 2016 significantly enhance the recovery of the residual oil. However, the detailed displacing process and exqui-
Received in revised form 31 October 2016 site interaction mechanism still remain ambiguous. By using Nonequilibrium Molecular Dynamic
Accepted 3 November 2016
Simulation (NEMD), three comparative displacement processes of adsorbed oil layer in nanoslit using
Available online xxxx
water, supercritical carbon dioxide (scCO2), and CO2 WAG injection were conducted to study the
enhanced oil recovery (EOR) mechanism of CO2 WAG injection. Simulation results indicate that the
scCO2 and water play different roles in CO2 WAG: the scCO2 slug could selectively dissolve apolar oil com-
ponents, and the water slug provides stable water/scCO2 promoting interface, which compels the misci-
Nanoslit ble oil/scCO2 slug out of the nanoslit. Furthermore, the synergistic effects of scCO2 slug and water slug
EOR were found to account for a decreased injecting pressure and an improved dissolution capability of
Molecular dynamics simulation scCO2 slug, which endows the CO2 WAG higher oil recovery efficiency than that of both scCO2 injection
and water injection. Our work here provides a comprehensive interpretation of EOR mechanism of CO2
WAG, and the results could provide insights into the optimization of the engineering process.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction happens and causes an early breakthrough, resulting in low volu-

metric sweep efficiency [2,9]. To disentangle this problem, CO2
Enhancing oil recovery (EOR) is an unremitting pursuit in the WAG technique was developed. Experimental researches demon-
petroleum field. After an initial quick extraction, most of the resid- strated that, in CO2 WAG injection, the water slug could improve
ual oil stays inside the reservoir on adsorption status [1,2]. In order the volumetric sweep efficiency, and the scCO2 slug could enhance
to displace the residual oil, numerous oil-displacing agents have the oil displacement ratio [10–12]. In current opinions, the CO2
been developed [2–5], such as the surfactant, the polymer, could diffuse into and swell the crude oil to reduce its viscosity
nanoparticles, and the scCO2. Among them, scCO2 exhibits great [13]; meanwhile, the CO2 also distributes at the interface between
advantages due to its unique properties, such as its large diffusion oil and water to reduce the interfacial tension [14,15], which favor
rate approximately equal to gas, and high dissolving capability forming of their miscible phase. In addition, the water dissolved
similar to liquid [6,7]. ScCO2-EOR has been confirmed to be a suc- with CO2 could corrode and broaden the channel. These advantages
cess technique to reduce the residual oil saturation [5,8]. will facilitate improving the EOR. However, limited to the detecting
However, due to the extremely low viscosity, the displacement method to observe the displacing process of crude oil in opaque
front of scCO2 is inherently unstable and viscous fingering often and nanoscale channel, the underlying mechanism of microscopic
interaction mechanism and the synergistic effect between the
⇑ Corresponding author. scCO2 and the water slug is not very clear. Therefore, the in-
E-mail addresses: (Y. Yan), (J. Zhang). depth understanding the microscopic mechanism of the WAG is
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.

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2 Y. Yan et al. / Fuel xxx (2016) xxx–xxx

fundamentally significant for improving EOR. Whereas, due to the the adsorbed asphaltene molecules [26–29], as presented in
nano- and micro-scale size of the porous reservoirs, conventional Fig. 1d–f.
fluid theory (such as Darcy’s law) is no longer suitable in such
small scale [16]. Further, because of the invisibility of rock reser- 2.3. Fluid
voirs and the great difficulty in preparing the synthetic core with
a comparable porous structure to the real core, it is still a formid- Based on the typical reservoir condition, a temperature of 330 K
able challenge to obtain the detailed information of the displacing and pressure of 20 MPa were selected in our simulation, and the
process. corresponding density of scCO2 (0.743 g/cm3) and water (0.993 g/
In the past decades, molecular dynamics (MD) simulation has cm3) were adopted in the initial model, according to National Insti-
been fully developed and exhibits great advantages offering tute of Standards and Technology’s (NIST) database (2011) [30]. By
dynamic atomic-level information. In addition, some studies have adding certain number of CO2 and water molecules into box, the
been conducted to investigate the influence of the residual water pressure (20 MPa) at 330 K could be maintained. The amount of
[16], surface wettability [17], polarity of oil components [18], added CO2 and water molecules could be calculated from the
and various additives [4,17] on the oil displacement. And, the Peng–Robinson equation according to their density [31], and is
behavior of the scCO2-substituted nanopore oil has drawn dramat- listed in Table S1 in SI. As shown in Fig. 1d (scCO2) and e (water),
ically increasing research interest [19–21]. These studies shed light a fluid box with dimensions (xyz) of 24.6  81.1  130.0 Å3 was
on the oil displacement behavior in water injection and scCO2 set on the left side of silica nanoslit which was also filled with
injection. However, to the best of our knowledge, there exist very the fluid. As to the CO2 WAG model (Fig. 1f), it is composed of a
limited studies on the CO2 WAG injection in nanopore [22,23]. water slug (left) and a scCO2 slug (middle) with same length of
The detailed displacing process and microscopic interaction is still 65 Å, and the nanoslit filled with water. In these three models, a sil-
unclear. ica sheet was placed on the left of the fluid as slab to push the fluid
In this work, under the employment of NEMD simulations, across the channel.
three parallel displacing processes using scCO2, water and CO2
WAG injections were investigated. The roles of scCO2 and water 2.4. MD simulation
slugs in the CO2 WAG injection were analyzed, and some synergis-
tic effects of scCO2 slug and water slug were found to be responsi- The NEMD simulation was performed with LAMMPS package
ble for high oil recovery efficiency. Our work provides an atomic- [32] through employing EPM2 CO2 model [33] and a simple point
level understanding of the CO2 WAG process, and the results would charge (SPC) water [34]. The CLAYFF force field [35] and CHARMM
be useful to realize some engineering phenomena in CO2 WAG and force field [36,37] were used for silica and oil molecules, respec-
guide the application of scCO2 in the tertiary oil recovery tively. Detailed parameters could be found in Table S2 in SI.
efficiency. The MD simulations were conducted in NVT (the number of
molecules, volume and temperature are constant) ensemble at
2. Experimental and simulation 330 K with the Nosé–Hoover thermostat [38]. During simulation,
the leftmost silica sheet was defined as a rigid body and a constant
2.1. Nanoscale slit velocity 1 m/s along z axis was applied to it to push the fluid across
the channel; and the two silica slabs of nanoslit were kept frozen
The initial silica lattice was derived from the database of the except for the modified hydroxyl. The periodic boundary condition
Material Studio software, and a a-quartz silica supercell with was applied in all directions. The particle-particle particle-mesh
orthorhombic dimensions (xyz) of 24.6  81.1  97.6 Å3 was con- (PPPM) algorithm [39] with a convergence parameter of 104
structed, the detailed building process could be seen in Supporting was used to treat the long-range electrostatic interactions. The
information (SI). Considering there are abundant nanoscale pores van der Waals interactions were calculated with a cutoff (10 Å).
in the size range of 30–80 Å in rock reservoir [24], a nanoslit with A time step of 1 fs was used, and the corresponding data was col-
a height of 63 Å along y-axis was built through deleting the middle lected in every 5 ps. A 13 ns simulation was conducted for all three
part of silica supercell, and the exposed surface was (0 0 1). The sil- systems. The configuration snapshots were rendered by VMD soft-
ica surface was hydroxylated by hydroxyl with a density of ware [40].
9.6 nm2, which is consistent with the result of crystal chemistry
calculations (5.9–18.8 nm2) [25]. 3. Results and discussion

2.2. Adsorbed oil layer In the WAG injection process, the scCO2 slug and water slug will
alternately pass through the reservoir pore. Sometime the pore
Here, decane and asphaltene were selected as representative was filled with the scCO2 slug, and in the next period, the pore will
apolar and polar components of crude oil. The molecular configu- be occupied by the water slug. Hence, the displacement behaviors
rations of decane and asphaltene are displayed in Fig. 1a and b, in the single scCO2 injection and single water injection were ana-
respectively. A detailed explanation for the selection of these two lyzed firstly to unveil their roles in the displacement process.
oil components could be found in SI. To obtain equivalent adsorbed And then, a detailed CO2 WAG injection process was studied to
oil layer, 10 asphaltene and 40 decane molecules was spread unveil the EOR mechanism of the CO2 WAG.
evenly onto the silica surface with dimensions (xz) of
24.6  68.0 Å2, and an energy minimization and a subsequent 3.1. The displacement behavior of scCO2 and water
1 ns MD simulation were performed [27]. In order to conveniently
observe the displacement consequence, these two adsorbed oil lay-
ers were placed onto the left side of the nanoslit. In the adsorbed 3.1.1. Displacement phenomena
oil layer, due to the strong interaction between the polar asphal- Fig. 2 presents several sequential snapshots in the scCO2 injec-
tene and the hydroxylated surface, asphaltene molecules could tion. As shown, nearly all decane molecules dissolve into the scCO2
preferentially adsorbed onto the surface, meanwhile the decane phase, and asphaltene molecules could only slip on but cannot
molecules adsorb onto the unoccupied silica surface and wrap detach from the silica surface. Detailed observation manifests that

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Fig. 1. Snapshots of initial system configurations: (a) decane (C10H22); (b) asphaltene (C27H23O2N1); (c) silica surface; (d) scCO2 injection model; (e) water injection model; (f)
CO2 WAG injection model. Atom color code: O, red; Si, yellow; H, white; N, blue. For clarity, CO2 molecules are represented as cyan points; water molecules are represented as
red points; decane, gray; asphaltene, green. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 2. Snapshots of displacement process of adsorbed oil layer in the scO2 injection.

after all scCO2 slug is injected, most of the decane molecules are water injection, the interactions between oil components, silica
pulled out of the nanoslit. However, it is also clearly showed that surface and the fluid were calculated as diagrammed in Fig. 4.
there still are some decane molecules resided inside the nanoslit. The interaction energy can be estimated by following equation
As to the water injection, Fig. 3 demonstrates that no oil molecule [41]. Here, the interaction energy between decane and water is
was displaced after the injection, and the only notable change was shown as follow.
that the oil layer shrank and displayed a semi-spherical configura-
tion. These results indicate three facts: (1) the scCO2 could selec- Edeca-wat ¼ Etotal  ðEdeca þ Ewat Þ ð1Þ
tively dissolve the apolar oil component; (2) the expulsion
where Edeca-wat is the interaction energy between decane and water,
outcome of scCO2 to decane molecules is undesirable; and (3)
Etotal is the total energy of the decane and water, and Edeca and Ewat
the water injection is not beneficial to displace the adsorbed oil.
are the energy of individual decane and the water, respectively.
Increasingly negative energy represents increasing interaction
3.1.2. Displacement mechanism between the two components.
To reveal the essence of above mentioned displacement phe- (1) scCO2 displacement mechanism: In the case of the scCO2
nomena, i.e. dissolution of decane and retention of asphaltene in injection, Fig. 4a shows that the interaction energy between decane
scCO2 injection, and retention of both decane and asphaltene in and scCO2 is far larger than that between asphaltene and scCO2,

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Fig. 3. Snapshots of displacement process of adsorbed oil layer in the water injection.

Fig. 4. Interaction energy profiles between oil molecules, fluid, silica surface. (a) scCO2 injection, (b) water injection. For clarity, asphaltene, decane, silica surface, scCO2 and
water were denoted with asph, deca, surf, CO2 and wat, respectively.

hence scCO2 could selectively dissolve decane over asphaltene indicates the dissolving ability (Edeca-CO2) is dramatically stronger
[42]. And the high attraction between decane molecules and CO2 than the adsorption ability (Edeca-surf + Edeca-asph). Consequently,
phase (seen in Fig. 4a) enables the decane molecules dispersing the decane could be quickly dissolved into the scCO2 phase.
into the CO2 phase, meanwhile the large diffusion coefficient As to the dissolution of the asphaltene, after the quick dissolu-
(0.83  108 m2/s) of decane in low viscosity scCO2, which is tion of the decane, the driving force (Easph-CO2 + Easph-deca) coming
nearly 4 times of that of water ((2.30 ± 1.5%)  109 m2/s) at the from the attraction of the miscible CO2/decane phase is slightly lar-
room temperature and 1 atm [43,44], ensures the quick diffusion ger than the resistance force (Easph-surf). In principal, the asphaltene
of decane in CO2 phase, allows decane molecules quickly to dis- should be slowly dragged into the miscible decane/scCO2 phase
perse into the scCO2 phase, and the detailed calculation method rather than adsorbed onto the silica surface. A detailed explanation
could be found in SI. is given below. Generally, if there are hydrogen atoms and nega-
Further, in terms of the different adsorption status of decane tively charged atoms between two adjacent molecules, they tend
and asphaltene, a quantitative analysis of the interaction energy to form H-bonds. In our case, there are three type of strongly neg-
could provide us a rational explanation. Firstly, as to the dissolu- atively charged atoms N (0.6200 e), O1 (0.5700 e) and O2
tion of decane, the driving force derives from the interaction (0.6500 e) in asphaltene molecule as well as abundant positively
between decane and scCO2, while the resistance force comes from charged hydrogen atoms on the hydroxylated silica surface.
two parts, one is the interaction between decane and silica surface, Herein, we ascribed the adsorption of asphaltene molecules to
the other is the interaction between decane and asphaltene. Fig. 4a the formation of hydrogen bond. Fig. 5 shows radical distribution

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Y. Yan et al. / Fuel xxx (2016) xxx–xxx 5

Firstly, owing to the strong interaction and the formed H-bonds

(described above) between asphaltene and silica surface, asphal-
tene could be firmly adsorbed on silica surface. Secondly, decane
has slightly smaller interaction with silica surface than that with
water, which means decane could dissolve into water phase. How-
ever, due to the fact that there is strong interaction between
asphaltene and decane, the adsorbed asphaltene will acts as an
‘‘anchor” for the adsorption of decane. In terms of the dissolution
of decane, the driving force (Edeca-water) is smaller than the resis-
tance force (Edeca-surf + Easph-deca). As a consequence, decane mole-
cules would absorb onto the adsorbed asphaltene molecules,
resulting into the exposure to the water phase. Giving a hypothesis
that there are only decane molecules in the adsorbed oil layer,
based on the value of the interactions, without the ‘‘anchor” effect
of asphaltene molecule, the decane molecules should dissolve into
water phase and is pushed out of the nanoslit [45,46]. Our simula-
tion results indeed confirm this inference (see Fig. S7).
Fig. 5. Radial distribution functions of H atom of the silica surface with O1, O2 and N
atoms of the asphaltene (shown in Fig. 1b). 3.2. The displacement behavior in WAG injection

3.2.1. Displacement phenomenon

functions of H atoms on the silica surface with O1, O2 and N atoms In the WAG injection, the interaction between water and scCO2
of asphaltene molecule. It can be observed that the first peak posi- slugs brings out a significantly different displacement perfor-
tions of both H-O1 and H-O2 are approximately same and equal to mance, as shown in Fig. 6. When the scCO2 slug enters into the
2.1 Å, which locate in the regime of typical H-bonds [44]. And, nanoslit, most of the apolar decane molecules dissolve into the
the high peak value indicates the formation of abundant H-bonds scCO2 phase, resulting into the formation of decane/scCO2 miscible
between asphaltene molecules and silica surface. This point could slug. When the frontier interface of water slug reaches the left
be further confirmed by an enlarged interface configuration entrance of the nanoslit, the whole miscible decane/scCO2 slug is
between several asphaltene molecules and silica surface (see propelled out of the nanoslit. Compared with that in the case of
Fig. S4 in SI). In general, the H-bond strength is stronger than that single scCO2 (some decane molecules residue inside the nanoslit
of the non-bond interaction. Hence, the formation of H-bonds after injection), it is unambiguous that the EOR in the CO2 WAG
strongly promotes the adsorption of the asphaltene molecules. is improved.
However, an interesting phenomenon that some decane mole-
cules still reside inside the nanoslit after injection draws our atten- 3.2.2. Displacement mechanism
tion, as displayed in Fig. 2. Thanks to the high dissolution and quick Here, we reveal the displacement mechanism through analyz-
diffusion features of scCO2, nearly all decane molecules diffused ing the detailed injection process.
into the scCO2 phase to form a miscible slug at initial injecting First, at the initial stage (0.5 ns), when the scCO2 slug starts to
stage (3 ns). At this time, it was found that there was a long scCO2 be injected into the nanoslit which is prefilled with water, the
slug at the upstream of the decane/CO2 miscible slug, which would hydrophobic interaction between the injected scCO2 and adsorbed
push this miscible slug across the nanoslit in the next injection. oil layer combined with the large viscosity difference between the
However, some decane molecules still stayed inside the nanoslit scCO2 and water together result in the formation of the backward
after injection. This result could be ascribed to the competitive meniscus (the right interface between the scCO2 and water slugs at
consequence between the random diffusion of decane and the 0.5 and 2 ns in Fig. 6). This induces the injected CO2 entering into
expulsing effect of injection fluid. The high diffusion coefficient the nanoslit from its two sides; while in scCO2 injection, the scCO2
of decane in scCO2 induces some decane molecules diffusing enters into the nanoslit through its whole channel. As a conse-
towards the left side; while the injection of scCO2 slug will compel quence, for one unit of injected scCO2, these scCO2 in CO2 WAG
the dissolved decane molecules moving to right side. So, at low injection has higher probability to contact with the adsorbed oil
injection rate (1 m/s) with weak expulsing effect, some decane layer than that in scCO2 injection. Hence, a higher dissolution effi-
molecules could diffuse to left and reside inside the nanoslit (seen ciency of injected scCO2 could be achieved.
Fig. 2) after injection. In addition, a higher injecting rate (5 m/s) Second, after a quick dissolution and diffusion of decane mole-
system was conducted and it was found that the strong expulsing cules in scCO2 phase, a miscible scCO2/decane frontier slug forms.
effect compels most of the decane molecules passing across the The dissolved decane molecules considerably increase the viscosity
nanoslit and only a few decane molecules residue inside the nano- of the scCO2 slug, and a semi-flat interface (the right interface
slit (see Fig. S5). Nevertheless, a higher injecting rate means a between the scCO2 and water slug at 4 ns in Fig. 6) is induced to
higher injecting pressure at the expense of more power and an form due to the decrease of viscosity difference between the mis-
inevitable high-cost. Meanwhile, it is reasonable to deduce that a cible scCO2/decane slug and the water slug. Compared to the back-
larger volume of scCO2 slug will generate a better displacement ward meniscus, in which the injected scCO2 preferentially pass
outcome. However, a larger injection volume of scCO2 also implies across the channel from two sides of nanoslit and bypass the resid-
a high cost for the unit product. ual water, the formation of semi-flat interface will make the
(2) Water displacement mechanism: As for the water injec- injected scCO2 passing across the nanoslit through the whole chan-
tion, the comparison of the interaction energies (Fig. 4b) indicates nel, and the residual water will be compelled out. So, once the
that there is no adequate driving force for the dissolution of both semi-flat interface forms, it will lead to an easy discharging of
the decane and asphaltene. We even tried a larger injecting rate the residual water. This process is clearly illustrated in the snap-
(5 m/s), and a similar adsorption configuration was also observed shots of 2–6 ns in Fig. 6.
(see Fig. S6). Here, a detailed inspection of the interaction energy In addition, compared with that all oil components shrink into a
could offer us some insights into the adsorption mechanism. semi-spherical configuration in the case of water injection (Fig. 3),

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Fig. 6. Snapshots of displacement process of adsorbed oil layer in CO2 WAG injection.

the dissolution of adsorbed apolar oil components (majority of profile in the WAG case stands for a slow planar flow. The slow pla-
crude oil) significantly broadens the fluid channel, which would nar scCO2 fluid implies the migration of scCO2 slug is controllable
largely decrease the injecting pressure [47] and is of the special and results in a prolonged contacting duration between these
significance to save cost for the oil exploration. scCO2 and adsorbed oil layer. As a result, the dissolution efficiency
Third, we pay attention to the effects of two scCO2/water inter- of unit volume of injected scCO2 is improved.
faces. As to the front interface, its influence on the scCO2 fluid was As to the back water/scCO2 interface, its function is to push the
studied. For comparison, the density and velocity distributions of scCO2 slug ahead. Due to the quick diffusion velocity of decane
CO2 inside the nanoslit along y-axis were calculated in scCO2 and molecules in scCO2 phase, the dissolved decane molecules nearly
CO2 WAG injections, as depicted in Fig. 7. The configuration at diffuse anywhere in the scCO2 slug. But, because of the insolubility
6 ns, which corresponds to the status that the nanoslit was just between water and decane, the decane molecules only stay inside
completely filled with injected scCO2 in the case of CO2 WAG, the scCO2 slug to form miscible scCO2/decane slug. Meanwhile, the
was selected. The two density peaks near to the silica surface refer stable propelling water/scCO2 interface will push the miscible
to CO2 adsorption layer, and the corresponding velocity in this scCO2/decane slug forward. Along with the water/scCO2 interface
adsorption layer can be found slower than that in the middle nano- passing across the nanoslit, all decane molecules merging in the
slit. The sharp and high velocity profile in the scCO2 case denotes a scCO2 slug will also be pulled out of the nanoslit. However, in
viscous fingering tendency, while the semi-flat and low velocity the case of scCO2 injection, there were some decane molecules
merging in the scCO2 slug still stayed inside the nanoslit after
injection (Fig. 2). This displacement consequence exhibits the
advantage of CO2 WAG injection over scCO2 injection.

4. Conclusion

In summary, by employing NEMD simulations, the displacing

processes of adsorbed oil layer in scCO2, water and CO2 WAG injec-
tions were investigated to unveil the EOR mechanism of CO2 WAG.
Simulation results demonstrate that the scCO2 and water play dif-
ferent roles in the displacing process. The scCO2 slug is responsible
for dissolving the apolar oil component, and the water slug pushes
the miscible decane/scCO2 slug out of the nanoslit. Furthermore,
several attracting synergistic phenomena between the scCO2 slug
and water slug, including of high dissolution efficiency, easy dis-
charging of residual water, broadening of the fluid channel, and
desirable displacement consequence, endow the CO2 WAG injec-
Fig. 7. Density and velocity distribution profiles of CO2 in scCO2 and CO2 WAG
injection in nanoslit, which is derived of the statistical average of eleven
tion a low injecting pressure and high oil recovery efficiency. Our
configurations in a range of 5.9–6.1 ns. The gray rectangles denote the CO2 study provides an atomic-level understanding of the CO2 WAG dis-
adsorption layer. placing process, and the results may be helpful to recognize the

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