Case Studies in Thermal Engineering 24 (2021) 100880

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Case Studies in Thermal Engineering

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Effect of supercritical carbon dioxide adsorption on oil

displacement in tight reservoir
Guangsheng Cao a, Yujie Bai a, *, Xiaohan Nan a, Hongxin An a, Lei Wang b, Tong Du c,
Dan Li a
a
MOE Key Laboratory for Enhanced Oil and Gas Recovery, Northeast Petroleum University, Daqing, Heilongjiang Province, China
b
PetroChina Jidong Oilfield Company, Tang Shan, Hebei Province, China
c
School of Science, Zhejiang University, Hangzhou, Zhejiang, China

A R T I C L E I N F O A B S T R A C T

Keywords: The effect of CO2 adsorption on oil displacement in tight reservoirs is analyzed. The composition
Adsorption of clay minerals in a reservoir is analyzed, and a molecular model of the formed rock structure is
Tight oil established to investigate the adsorption characteristics of different clay minerals on the fluid.
Supercritical carbon dioxide
The effect of CO2 adsorption on oil displacement is investigated through a CO2 injection exper­
Water gas alternative flooding
Molecular dynamics
iment. The results show that the adsorption capacity of reservoir minerals is greater for light
Gas channeling hydrocarbons than for heavy hydrocarbons as well as for water and CO2 than for hydrocarbons,
indicating that the oil recovery rate of the reservoir composed primarily of silica is higher when
supercritical CO2 and water are alternately injected. The oil recovery can reach 23.78% by water
and CO2 alternate flooding. Intermittent stop injection enable CO2 to enter rock samples more
easily, and crude oil can subsequently be discharged more easily. As the mixing of CO2 and crude
oil cannot be realized under the experimental conditions, the intermittent stop injection time is
short and the gravity migration in tight cores is slow. Hence, we infer that the adsorption of CO2
significantly affects the displacement of tight reservoirs.

1. Introduction

Carbon dioxide is a typical greenhouse gas, whose storage and utilization has been investigated widely. Using supercritical CO2 to
drive a fractured tight oil reservoir [1] can not only result in a more efficient development of tight oil reservoirs, but also enable CO2
storage. Several scholars have investigated the principle of CO2 flooding. Hao et al. [2] inferred that under certain conditions, CO2 and
crude oil can be miscible, thereby reducing the viscosity of the formation fluids and enhancing their flow capacity. Ding [3] reported
that supercritical CO2 exhibits gas-like diffusion and liquid solubility, i.e., low viscosity, low surface tension, high diffusion coefficient,
and strong solubility. Li [4] inferred that supercritical CO2 can alter the properties of crude oil, such as its expansion, reduction in
interfacial tension, reduction in viscosity, enhancement in crude oil migration ability, and extraction of nonpolar components of crude
oil, thereby improving oil recovery. These properties yield good results from the application of supercritical CO2 in the oil
displacement process, thereby resulting in better permeability compared with water flooding alone. Additionally, the extraction rate is
higher and more effective than that of liquid, resulting in enhanced oil recovery.
The abovementioned studies pertain to investigations into the mechanism of supercritical CO2 flooding. However, with recent

* Corresponding author.
E-mail address: sygcbyj@163.com (Y. Bai).

https://doi.org/10.1016/j.csite.2021.100880
Received 20 January 2021; Received in revised form 1 February 2021; Accepted 4 February 2021
Available online 12 February 2021
2214-157X/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
G. Cao et al. Case Studies in Thermal Engineering 24 (2021) 100880

Fig. 1. Schematic diagram of scanning electron microscope.

developments related to oil fields, the method of CO2 flooding has changed considerably. Nasir [5] compared changes in CO2 oil
recovery under different displacement modes. Wei et al. [6,7] investigated the oil displacement process of supercritical CO2 and
adsorption characteristics through nuclear magnetic resonance. They conjectured that under the alternate injections of water and CO2,
the interaction between the fluid and rock wall will affect the distribution of crude oil in the rock pores. Furthermore, the adsorption
characteristics of different clay minerals on oil, gas, and water will affect the displacement of alternate supercritical carbon dioxide and
water injection. However, no detailed study has been conducted regarding the adsorption mechanism of CO2 molecules and crude oil
on rock surfaces. Fang et al. [8] investigated the oil displacement mechanism of CO2 on the surface of silica via molecular simulation.
Because of the high clay mineral content in tight reservoirs, further detailed analysis of the adsorption process of formation fluids for
different types of clay minerals and displacement modes must be performed to understand the mechanism of CO2 displacement.
Mahmoud et al. [9] investigated the effect of rock minerals on CO2 flooding but did not fully reveal the reasons contributing to the
observed differences. Hafiz [10–12] et al. investigated the diffusion characteristics of CO2.
CO2 flooding has resulted in numerous engineering problems. The problem of wellbore freezing and plugging has been investigated
previously [13,14]. In fact, the distribution of oil and water in dense rocks is more complex. In addition to the silica matrix, many clay
minerals exist in rocks, such as montmorillonite and kaolinite. The imbibition of tight rock has been investigated [15], but the
stimulation effects of different minerals and water as well as gas alternation has not been investigated. The clay mineral content in tight
oil reservoir is high, and the effect of water and CO2 alternate flooding is more complex than that of conventional gas injection
flooding. Therefore, the aim of this investigate is to study the effect of CO2 adsorption on oil displacement in tight reservoirs. In this
study, natural rock samples were used, and their clay composition was analyzed via scanning electron microscopy (SEM). A formation
rock model was established to investigate the effects of different clay minerals on the adsorption characteristics of the formation fluid.
To understand the mechanism of CO2 adsorption and oil displacement, we segmented the tight reservoir rock and then conducted an
oil displacement experiment under a pressure lower than those of CO2 and crude oil. Hence, issues pertaining to the miscibility of CO2
and crude oil can be avoided, and the low permeability characteristics of the tight oil reservoir reduced the expansion effect of CO2 on
crude oil. The effect of fluid adsorption on oil displacement was analyzed in this experiment, and the previous simulation results were
verified to further improve the oil displacement mechanism of CO2. This study is associated with the field of petroleum exploitation
and provides a theoretical basis for the wide application of CO2 flooding technology as well as the utilization of greenhouse gas storage.

2. Materials and methods

2.1. Experimental details

2.1.1. Experimental materials

The rocks used for reservoir clay mineral analysis were natural core samples (provided by Daqing Yushulin Oilfield, China). The
CO2 used in the experiment was provided by Daqing Xuelong Gas Co., Ltd., China. The purity of CO2 was 99%. The rocks used in the
experiment involving the alternate injection and flooding of water and CO2 were natural rock samples provided by the Daqing
Yushulin Oil Field, China. The simulated oil was compounded by kerosene and crude oil provided by the Daqing Yushulin Oil Field,
China, and the viscosity of the compounded crude oil was 3 mPa s.

2.1.2. Analysis of reservoir clay minerals

SEM functions similar to a television camera. Using an electron beam as a light source, a beam is deflected and focused by an

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Table 1
Basic parameters and experimental scheme of rocks.
3
Scheme Permeability (10− μm2) Porosity (%) Oil saturation (%) Irreducible water saturation (%) CO2:Water Stop injection time (min)

1 0.3265 5.12 47.98 52.65 0:1 0

0.4126 5.61 56.13 61.34 0:1 0
2 0.2658 4.28 55.87 58.69 1:1 0
0.3659 5.06 49.13 65.11 1:1 0
3 0.6596 5.72 51.61 57.99 1:1 20
0.2581 4.66 56.31 51.46 1:1 20

electromagnetic field. Subsequently, the sample is bombarded, and the electronic signal image is received. The morphology of the clay
minerals in the rock can be observed, and the elemental composition of the rock sample can be analyzed. Subsequently, based on the
morphology and elemental composition of the clay minerals, the main types of clay minerals in the rocks can be further analyzed. The
schematic diagram of a scanning electron microscope is shown in Fig. 1.
Owing to the low porosity and permeability of tight reservoirs, the interaction between the injected fluids (water and CO2) and the
clay minerals of the formation rocks significant affect the oil displacement. To investigate the adsorption characteristics of the for­
mation fluids in the tight reservoir rocks, we observed the clay minerals via SEM, and a basis for subsequent molecular simulations was
obtained.

2.1.3. Alternate CO2 and water flooding experiment

In this study, a natural core of compact grade was used to perform an oil displacement test. In tight oil reservoirs with low porosity,
permeability, and poor water injection capacity in injection wells, water flooding is not cycled effectively. Therefore, we partitioned
the cores to enhance their adsorption area and increase the water flow capacity.
To evaluate the effects of CO2 and water adsorption on oil displacement in the tight reservoir, we used a tight reservoir rock of
extremely low permeability and partitioned the core such that the injected fluid flowed along the fracture instead of through the rock
interior (Fig. 3(b)).
Furthermore, the fluid temperature and pressure inside the rock were relatively low, thereby preventing the formation of crude oil
and CO2 owing to miscibility, and the properties of crude oil did not change significantly (Fig. 3(c)). During the experiment, the
interaction between the crude oil in the formation rock and the foreign fluid gradually ejected the crude oil in the porous medium, i.e.,
percolation and absorption occurred. The seeped crude oil was adsorbed on the rock wall, and the oil droplets adsorbed on the rock
surface were displaced through the alternate injections of CO2 and water. The specific experimental device is shown in Fig. 3(a).
First, the core was placed in an oven to dry, and the dry weight was measured. Subsequently, the core was placed in a jar containing
distilled water and vacuumized using a vacuum pump at a pressure of − 0.1 MPa. After 12 h, the core was removed, the wet weight of
the core was weighted, the pore volume and porosity of the core were calculated, and the core was introduced into the connected
experimental unit. Subsequently, the crude oil was displaced to calculate the oil saturation of the rock. Aged core crude oil was allowed
to stand at 50 ◦ C for 24 h. The rock was removed, split, and then introduced back into the experimental apparatus. The pressure of the
constant-pressure valve was set to 2 MPa [16], and the ring pressure was set to 6 MPa. After adjusting the gas pressure to the
displacement pressure, the gas stabilized and was then injected into the core for the CO2 oil displacement experiment. The
displacement pressure difference was 0.2 MPa, and the displacement time was 5 min. CO2 was injected alternately through a quick
switch valve, and then water was injected. The time of CO2 injection, water injection, and stopping of injection were periodically
adjusted until no oil flowed out during the displacement. In this process, the amount of displaced oil and displaced water, gas volume,
cumulative injected gas, water volume, and time were measured. The basic parameters and experimental scheme of the rocks are
shown in Table 1.

2.2. Theory

2.2.1. Diffusion models of CO2 in rocks

When water and CO2 was injected into the formation, CO2 entered the rock matrix through convection diffusion. The fluid flow in
the formation rock (i.e., a porous medium) satisfies Darcy’s seepage equation as follows [17]:
k
u= − ∇P (1)
μ

where u is the flow velocity of the fluid in the formation, [m/s]; k is the permeability of formation rock, [10− 3 μm2]; μ is the fluid
viscosity, [Pa⋅s]; P is the production pressure difference, [MPa].
The flow of water and CO2 in the crack is in a normal turbulent state, and its flow equation is as follows [18]:
∂u { [ ]}
ρ + ρ(u · ∇)u = ∇ · − pI + μ ∇μ + (∇μ)T + F + ρg (2)
∂t

where ρ is the fluid density, [kg/m3]; u is the fluid velocity, [m/s]; μ is the fluid viscosity, [Pa⋅s]; t is the dimensionless time; pI is the
outlet fluid pressure, [Pa]; T is the temperature, [K]; F is the volume force applied to the fluid, [N/m3]; g is the acceleration of gravity,

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G. Cao et al. Case Studies in Thermal Engineering 24 (2021) 100880

Fig. 2. (a) Silicon, (b) kaolinite, and (c) montmorillonite molecular models. (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article.)

Fig. 3. Schematic diagram of alternate water and CO2 oil displacement experimental device.

[m/s2].
When CO2 enters the porous rock, part of it dissolves in water and convection diffusion occurs. The convection diffusion of CO2 in
water satisfies the following formula [19]:
∂ci
+ ∇ · (− Di ∇ci ) + u · ∇ci = Ri (3)
∂t

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Fig. 4. SEM and energy spectrum analysis of clay minerals.

Ni = − Di ∇ci + uci (4)

where ci is the diffusion coefficient, [m2/s]; Di is the initial concentration of the microelement segment, [mol/m3]; ▽ is the
Hamiltonian operator; Ri is the end concentration of the microelement segment, [mol/m3].
The CO2 entering into the stratum will change the original state of the stratum and the adsorption state of the silica matrix, clay
minerals such as kaolinite and montmorillonite on the rock surface will change significantly, and the oil phase will gradually disappear
from the rock surface. In addition, under the action of CO2, the interfacial tension and capillary force between oil and water will
change. Therefore, the oil phase in the rock porous media will be expelled from the rock pore channel and then enter the simulated
fracture, before being driven out by the water phase. During this process, the capillary force acting on the oil phase in the rock pore
throat can be expressed as follows [20]:
( )
1 1
Pc = σ + (5)
R1 R2

where Pc is the additional pressure on the droplet, i.e., the capillary force between oil and water, [Pa]; σ is the capillary force between
oil and water, [mN/m]; R1 and R2 are the radii of curvature of the thin pipe where oil and water are located, respectively [m].

2.2.2. Construction of molecular model

Based on the composition analysis of the clay minerals in the reservoir, silica quartz, kaolinite, and montmorillonite were primarily
identified. The silica in the reservoir was primarily silicon dioxide. Owing to the effect of the external fluid, particularly CO2, the
adsorption state of the formation fluid on the formation rock affected the oil displacement. We used different types of clay minerals as
adsorption layers to analyze the distribution of different types of formation fluids in the adsorption layers. The model is shown in Fig. 2
(a). The kaolinite structure parameters of Bish [21] were used to establish the kaolinite model, as follows: cell parameter of a = 0.515
nm, b = 0.894 nm, and c = 0.739 nm; and edge intersection angles of α = 91.926◦ , β = 105.046◦ , and γ = 89.797◦ . The chemical
formula was Si4Al4O10(OH)8, as shown in Fig. 2(b). The montmorillonite model was constructed based on the montmorillonite model
of Skipper. The cell parameters were a = 0.523 nm, b = 0.906 nm, and c = 1.25 nm; and the edge intersection angles α = γ = 90◦ and β
= 99◦ . The molecular formula was Na0.75(Si7.75Al0.25) (Al3.5Mg0.5)O20(OH)4, as shown in Fig. 2(c).
To analyze the adsorbability of clay minerals with respect to hydrocarbon mixtures in the formation, an adsorption model was
established. We assumed that C1–C4 was gaseous under the stratigraphic conditions in the investigated region, and that the phase state
of C5 was unknown under these stratigraphic conditions. Therefore, the molecular model of C6–C14 was first established, followed by
those of C6–C14 in the silicon cracks, kaolinite cracks, and montmorillonite pores. The distribution of C6C14 was random, as shown in
Fig. 2(d).
First, the surface of the rock was enlarged using 4 × 2 × 2 supercells. Subsequently, the conjugate algorithm was used to minimize
the energy of the split system to obtain the balanced configuration of the entire molecule by adjusting the position of the atoms. The
force field was simulated in COMPASS, and the intermolecular forces were calculated using van der Waals forces. The boundary
condition was periodic, and the cutoff radius was 12.5 Å. The system temperature was set to 355 K, and the pressure was set to 18 MPa

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Fig. 5. Adsorption effects of formation crude oil on different clay minerals.

based on the formation conditions (actual formation conditions at the Yushulin oilfield). Dynamic simulations of 1 ns were performed
for the NPT ensemble to balance the system energy, and the silica wall was fixed. A 3 ns dynamics simulation was performed for the
NVT ensemble, and 500 steps were used for the calculation.

3. Results

3.1. Composition analysis of reservoir clay minerals

Based on the experimental scheme, the effects of the fracturing fluid system on the permeability and absorption rate were
determined. The core permeability, absorption process, and oil absorption effects during the permeability and absorption experiments
are shown in Fig. 2.
To investigate the fluid adsorption characteristics of the reservoir, the composition of the clay minerals in the reservoir must first be
understood. Therefore, the clay minerals in the near-well zone of the supercritical CO2 and water injection wells in the Yushulin oilfield
were subjected to SEM. Fig. 4 shows the SEM and energy spectrum analysis results of the clay minerals in a supercritical CO2 and water

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Table 2
Distribution of fluid density on rock surface under various development conditions.
Development conditions Reservoir fluid Density

Silicon dioxide Kaolinite Montmorillonite

Water flooding Hexane 0.04895 0.07764 0.15436

Octane 0.02161 0.06151 0.08944
Decane 0.03493 0.02065 0.04981
N-dodecane 0.04769 0.10423 0.09202
N-tetradecane 0.02983 0.13759 0.08114
Water 0.64200 0.24903 0.02068
Alternate injection of water and CO2 Hexane 0.06582 0.02813 0.04094
Octane 0.06564 0.07427 0.11859
Decane 0.06655 0.07213 0.10871
N-dodecane 0.07227 0.10222 0.12988
N-tetradecane 0.03972 0.04906 0.09882
Water 0.07443 0.10454 0.00141
CO2 0.54226 0.19141 0.00988

alternate flooding reservoir in the Yusulin oilfield.

The oxygen content in the formation rock was the highest, i.e., between 36.94% and 39.56%. Meanwhile, its silicon content was
between 36.25%–38.48%, whereas sodium and aluminum were present in lower quantities. It can be inferred that the block reservoir
contained more clay mineral contents of kaolinite and montmorillonite. Except the silica formation of the rock skeleton in the dense oil
reservoir, the clay mineral contents of montmorillonite and kaolinite affected the adsorption characteristics of the formation fluid.

3.2. Adsorption characteristics of reservoir clay minerals to hydrocarbons

To investigate the adsorption characteristics of the reservoir clay minerals to hydrocarbons and subsequently obtain the fluid
migration state in the reservoir under the original state, the adsorption characteristics of different reservoir clay minerals to C6–C14
were simulated, obtained, and analyzed. As shown in Fig. 5(a), the density of hexane was the highest on the surface of silica, whereas
the density of n-tetradecane was the lowest. Meanwhile, with the increase in the carbon chain length, the density of alkane on the silica
surface decreased. This indicates the strong and weak adsorption capacities of silica for light and heavy hydrocarbons, respectively.
Furthermore, the density distribution of C6–C14 in the pores of silica was relatively uniform, indicating that the adsorption of hy­
drocarbon substances by nanosilica was primarily concentrated on the surface of silica, thereby forming an adsorption layer. As shown
in Fig. 5(b), hexane exhibited the highest density on the surface of kaolinite, whereas n-dodecane exhibited the lowest density.
Meanwhile, C6–C12 conformed to the law, where the surface density of kaolinite decreased with the increase in the carbon chain
length.
However, the density of C14 was higher; the random distribution of the initial configuration most likely resulted to its partial
location near the kaolinite surface, whereas the poor flow and diffusion capacity of C14 resulted in its high density in the kaolinite
pores. In addition, compared with the density distribution of the silica pores, that of hydrocarbons in the kaolinite pores fluctuated
significantly. These observations indicate that the adsorption of kaolinite was primarily concentrated on its surface, thereby forming
an adsorption layer. Meanwhile, when the carbon chain achieved a certain length, it was affected less by the adsorption of clay
minerals and more by the diffusion ability and flowability. As shown in Fig. 5(c), the adsorption characteristics of C6–C14 in the pores of
montmorillonite were similar to those in the pores of kaolinite. This indicates that the adsorption capacity of C6–C12 in the pores of
montmorillonite and in the formations with a high content of kaolinite weakened as the length of the carbon chain increased.
Additionally, the effect of the adsorption capacity was weak when the carbon chain reached a certain length. It was primarily affected
by the capacity of the flow and diffusion. This phenomenon is consistent with the results of Sung et al. [22], thereby supporting the
validity of our model.
Based on the density distribution of the reservoir fluid under the original conditions, the adsorption capacity of silica was the
highest, whereas those of montmorillonite and kaolinite were weak. This indicates that the reservoir with more silica had a stronger
adsorption capacity for light hydrocarbons, whereas that with more kaolinite and montmorillonite had a weaker adsorption capacity
for light hydrocarbons. The adsorption capacity of silica was weaker than those of kaolinite and montmorillonite. Furthermore, it was
observed that the adsorption capacity of the reservoir minerals for light hydrocarbons was generally high, whereas that for heavy
hydrocarbons was low. However, field practice indicated that most light hydrocarbons were produced first, likely because under the
effect of density difference, heavy hydrocarbons were distributed on the outside of the fluid during the flow. They occupied the mineral
surface of the reservoir, thereby reducing the adsorption capacity for light hydrocarbons; meanwhile, the migration state included
heavy hydrocarbons enveloping light hydrocarbons.
To investigate the adsorption characteristics of the reservoir clay minerals for hydrocarbons, water, and CO2 followed by the
migration state of various fluids in the reservoir, the adsorption characteristics were simulated and obtained for different development
modes. The migration state of the reservoir fluid under different development modes was analyzed, and the effect degree of the
reservoir fluids on oil recovery was obtained. The results are shown in Table 2.
The density distributions of the reservoir fluids under the original conditions show that the adsorption capacity of silicon dioxide

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Fig. 6. Oil displacement effects under different experimental schemes.

was the strongest, whereas those of montmorillonite and kaolinite were relatively weak. This indicates that the reservoirs with more
silica content had a strong adsorption capacity for light hydrocarbons, whereas those with more kaolinite and montmorillonite had a
relatively weak adsorption capacity for light hydrocarbons. The adsorption capacity of silica to heavy hydrocarbons was weaker those
that of kaolinite and montmorillonite. Furthermore, it was observed that the adsorption ability of the reservoir minerals for light
hydrocarbons was generally strong, whereas it was poorer for heavy hydrocarbons. However, it was observed in practice that most
light hydrocarbons were produced first. This is because heavy hydrocarbons were distributed on the outside of the fluid and occupied
the mineral surface under the effect of density difference to reduce the absorption capacity of light hydrocarbons. This is the migration
status of light hydrocarbons in heavy hydrocarbon packages.
The density distributions of the reservoir fluids under water flooding conditions show that the adsorption characteristics of C6–C14
on different rock walls in the reservoir under the effect of water changed significantly. Silica indicated the strongest adsorption ca­
pacity for water, and the density of water was the highest on the wall. However, the adsorption capacity of montmorillonite to water
was low, and the density of water on the wall was the lowest. This indicates that when traditional water flooding is performed, a water
adsorption layer is formed in the reservoir with high contents of silica and kaolinite, and oil is washed down from the wall surface. The
migration state of the fluid is oil in water, which enhances the recovery rate. In reservoirs with a high content of montmorillonite, the
adsorption capacity of the water in the reservoir is weak, and an adsorption layer cannot be formed easily; hence, the recovery rate
cannot be increased sufficiently.
The density distributions of the reservoir fluids under water and CO2 injection flooding show that the adsorption capacity of clay
minerals to water and CO2 was in the order of silica > kaolinite > montmorillonite, and the overall adsorption capacity was greater
than that for single water flooding. This indicates that for supercritical CO2 and water injection flooding, the silica and kaolinite
contents of the reservoir form CO2 and a water adsorption layer, thereby improving the recovery rate. Reservoirs with a high content of
montmorillonite have a weak adsorption capacity for water and CO2, rendering it is difficult to form an adsorption layer, and the
increase in the recovery rate is limited. Meanwhile, the alternate injections of supercritical CO2 and water can wash off more oil from
the rock surface than traditional water flooding, thereby further improving the recovery degree.
Furthermore, it was observed that the migration state in the reservoirs with high contents of silica and kaolinite was oil-in-water-in-
gas, namely O/W/G. The migration state in the reservoir with more montmorillonite was water-in-gas-in-oil, namely W/G/O. This
indicates when displacement occurred during alternate supercritical CO2 and water injections, CO2 and water encapsulated the oil,
thereby reducing the surface tension and improving the oil washing efficiency significantly during the displacement process and oil
recovery.

3.3. Comparison of alternate injection flooding of water and CO2

The oil displacement experiment was performed by alternating injections of water and CO2. Herein, scheme 1 refers to single water
displacement; scheme 2, alternate water and CO2 displacement; and scheme 3, alternate water and CO2 displacement after which the
injection was halted and the injection valve was closed for 10 min. To ensure the accuracy of the experimental results, a set of repeated
experiments was conducted for each group of experiments. The oil displacement effect under different experimental schemes was
measured, and the results are shown in Fig. 6.
Under the condition of only water flooding, the recovery degree was the lowest at only 7.969%–8.495%, and the average recovery
rate was 8.232%. The time from displacement to oil production was the shortest. The overall displacement time was approximately
100 min. When water and CO2 were injected alternately, the oil recovery was 18.844%–24.405% and the average recovery was
21.6245%, which was higher than that of single water flooding. However, the displacement time was longer, i.e., 300–350 min. As
observed in scheme 3, the intermittent cessation of injection during the alternate flooding of water and CO2 enabled CO2 to enter the
rock sample easily; hence, the crude oil was easily discharged. The recovery rate was 22.759%–24.801%, and the average recovery was
23.78%.
To further verify whether the adsorption of CO2 and water can enhance oil recovery, we analyzed the flow rate of the fluid and the

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G. Cao et al. Case Studies in Thermal Engineering 24 (2021) 100880

Fig. 7. Distribution characteristics of velocity and concentration of fluid in fracture during experiment.

distribution characteristics of CO2 concentration in the fracture, as shown in Fig. 7.

As shown in Fig. 7(a), the flow velocity of the fluid at the fracture was relatively high and that of the rock matrix was relatively low,
indicating that the injected fluid primarily flowed along the fracture during the experiment and did not enter the rock matrix. As shown
in Fig. 7(c), CO2 entered the rock matrix in a relatively short period. Subsequently, the adsorption property of the crude oil inside the
rock changed [23], and the rock was more likely to absorb CO2 and water, resulting in the crude oil being expelled. As this experiment
was performed using rock samples of permeability less than 1 × 10− 3 μm2, the gravity point shift function was almost negligible. In
another experiment involving injection, the extraction pressure difference was low, i.e., well below those of the mixed crude oil and
CO2. The properties of the stratum in the crude oil and CO2 did not change significantly, neither did they significantly reduce the
viscosity of crude oil. Furthermore, the density level of the rock oil droplets in the gravity points shifted slowly, and stop the 10 min
note did not affect the oil displacement effect. Therefore, the effects of CO2 adsorption and interfacial action on oil displacement can be
compared. In contrast to scenarios 2 and 3, the intermittent discontinuation of injection appeared to have accelerated the time to attain
the ultimate CO2 flooding recovery factor, thereby accelerating the displacement time to 107 min and slightly enhancing the oil re­
covery factor. Compared with the previous CO2 displacement oil experiment, this experiment yielded a lower recovery efficiency. This
is attributable to the condition of the rock after fracturing, in which the fluid displacement ability of the injected fluid through the rock
cracks improved, and the displacement effect weakened significantly. Hence, it would be preferable to demonstrate the adsorption of
CO2 and water for improving the recovery factor.

4. Conclusions

Through adsorption simulations of different components of CO2, water, and crude oil under different rock minerals, combined with
alternating injection experiments of water and CO2 in fractured rocks, the following conclusions were obtained:

(1) Clay minerals generally exhibited high adsorption capacity for light hydrocarbons, but low adsorption capacity for heavy
hydrocarbons. Moreover, for longer carbon chains, the adsorption capacity deteriorated. The adsorption capacity for water in
the reservoir was greater than that for hydrocarbons. The surface of the reservoir dominated by silica was hydrophilic. The
adsorption capacity of the reservoir to water and carbon dioxide was greater than that in single water flooding. This indicates
that the recovery rate of the reservoir with high contents of silica and kaolinite will be higher if supercritical CO2 and water
injection flooding are used alternately.
(2) During oil displacement via the alternate injection of CO2 and water, the adsorption of CO2 on the rock surface enhanced the oil
displacement efficiency. This was primarily embodied in two aspects. First, it was reflected on the effects of CO2 and water,

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rendering it easier for crude oil to seep out by the effect of adsorption on the rock surface displacement. However, for alternate
CO2 and water injections, the oil displacement significantly prolonged the production time, even when crude oil was contin­
uously driven out at the end of production. Furthermore, adhering to the CO2 and water absorption line displacement function
enhanced the subsequent oil displacement effect.
(3) The recovery rate of alternating water and carbon dioxide flooding was 23.78%, whereas that of single gas flooding was
21.62%. Intermittent stop injection accelerated the time for attaining the limited CO2 flooding recovery rate and slightly
enhanced the oil recovery rate. We believe that intermittent stop injection during the water and CO2 alternate flooding process
would enable CO2 to diffuse easily into the rock sample and for oil to seep out more easily.
(4) With the widespread application of CO2 flooding technology, the challenges are becoming increasingly complex, and the
process of CO2 flooding will include various complex physical and chemical processes. Therefore, further investigations are
required to understand the mechanism of CO2 flooding based on various advanced experimental methods.

CRediT authorship contribution statement

Guangsheng Cao: Writing - original draftWriting – original draft, Writing - review & editingWriting – review & editing, All the
authors listed have approved the manuscript. Yujie Bai: Writing - original draftWriting – original draft, Writing - review & editing­
Writing – review & editing, All the authors listed have approved the manuscript. Xiaohan Nan: Writing - original draftWriting –
original draft, Writing - review & editingWriting – review & editing, All the authors listed have approved the manuscript. Hongxin An:
Writing - original draftWriting – original draft, Writing - review & editingWriting – review & editing, All the authors listed have
approved the manuscript. Lei Wang: Writing - original draftWriting – original draft, Writing - review & editingWriting – review &
editing, All the authors listed have approved the manuscript. Tong Du: Writing - original draftWriting – original draft, Writing - review
& editingWriting – review & editing, All the authors listed have approved the manuscript. Dan Li: Writing - original draftWriting –
original draft, Writing - review & editingWriting – review & editing, All the authors listed have approved the manuscript.

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.

Acknowledgements

The authors gratefully acknowledge the support of the >National Natural Science Foundation of China (No. 51574089).

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