Enhanced oil recovery in reservoirs via diffusion-driven CO2 flooding:

Experimental insights and material balance modeling

Xiaoyi Zhang (张晓祎),1 Rui Xu (徐锐),2 Qing Zhao (赵庆),3 Qian Cheng (程倩),4 Rui Shen (沈瑞),2, a)
and Yanbiao Gan (甘延标)1, b)
1) North China Institute of Aerospace Engineering, Langfang 065000, China
2) Research Institute of Petroleum Exploration and Development, PetroChinaCompany Limited, Beijing 100083,
China
3) No.2 Drilling Engineering Branch, PetroChina Bohai Drilling Engineering Co. LTD., Langfang 065007,
China
4) Beijing Deep Green Energy Technology Co. LTD., Beijing 100083, China
arXiv:submit/6579801 [[Link]-dyn] 29 Jun 2025

(Dated: 29 June 2025)

CO2 flooding is central to carbon utilization technologies, yet conventional waterflooding models fail to capture the
complex interactions between CO2 and formation fluids. In this study, one- and two-dimensional nuclear magnetic
resonance experiments reveal that CO2 markedly enhances crude oil mobility during miscible displacement via mul-
tiple synergistic mechanisms, yielding a recovery factor of 60.97%, which surpasses that of immiscible displacement
(maximum 57.53%). Guided by these findings, we propose a convection–diffusion model that incorporates the dif-
fusion coefficient (D) and porosity (φ ) as key parameters. This model captures the spatiotemporal evolution of the
CO2 front and addresses a key limitation of conventional formulations—the omission of diffusion effects. It improves
predictions of gas breakthrough time and enables optimized injection design for low-permeability reservoirs. Extend-
ing classical material balance theory, we develop an enhanced CO2 flooding equation that integrates critical transport
phenomena. This formulation incorporates CO2 diffusion, oil phase expansion, reservoir adsorption, and gas compress-
ibility to describe the dynamic transport and mass compensation of injected CO2 . Validation through experimental and
numerical data confirms the model’s robustness and applicability under low-permeability conditions. The proposed
framework overcomes limitations of physical experiments under extreme environments and offers theoretical insight
into oil recovery enhancement and CO2 injection strategy optimization.

I. Introduction behaviors can be summarized as follows2–15 (1) Crude oil

property modification: CO2 dissolution reduces crude oil vis-
According to the latest Statistical Review of World Energy, cosity and induces oil swelling, enhancing its mobility. (2)
fossil fuels account for approximately 81.5% of global pri- Interfacial tension reduction and extraction: CO2 lowers the
mary energy consumption, resulting in an estimated annual interfacial tension between the gas and oil phases, extracts
carbon dioxide (CO2 ) emissions of nearly 40 billion tons1 . light hydrocarbons, and facilitates dynamic miscibility at the
Under the urgent need to address climate change, it is im- displacement front. (3) Mobility ratio improvement: CO2 in-
perative to establish a multi-path collaborative carbon man- jection adjusts the mobility ratio between crude oil and forma-
agement technology system through carbon capture, utiliza- tion water, improving sweep efficiency. (4) Solution gas drive
tion, and storage (CCUS) technologies. For example, inject- effect: Dissolved CO2 generates a solution gas drive that pro-
ing captured CO2 into oil reservoirs for enhanced oil recov- motes oil displacement. (5) Molecular diffusion: The natural
ery (CO2 -EOR) can effectively reduce carbon emission inten- diffusivity of CO2 enhances mass transfer across oil–gas in-
sity in industrial sectors. Accordingly, leveraging CO2 uti- terfaces. (6) Carbonation reaction: CO2 reacts with formation
lization within CCUS frameworks and investigating the un- water and carbonate minerals (e.g., CaCO3 + CO2 + H2 O →
derlying mechanisms of CO2 flooding for improved oil re- Ca2+ + 2HCO− 3 ) increasing reservoir permeability by dissolv-
covery present significant technical opportunities and broad ing cementing materials.
application potential. With the depletion of conventional oil Significant progress has been made by both domestic and
and gas resources, unconventional hydrocarbon development international scholars in understanding the mechanisms and
has become a strategic priority in the global energy transition. flow behavior of CO2 flooding. These advancements can be
Against this backdrop, CO2 flooding, owing to its favorable categorized as follows:
geological adaptability, is increasingly replacing traditional 1. Theoretical modeling and steady-state flow: Badriyev
methods such as horizontal well fracturing and water flood- et al.15 developed a two-dimensional mathematical model for
ing. It is emerging as a core technology for improving oil incompressible fluid flow in homogeneous porous media un-
recovery in unconventional reservoirs. der steady-state conditions. They derived analytical expres-
Based on extensive field trials and theoretical studies on sions for regional flow boundaries assuming a constant pres-
CO2 flooding, the primary displacement mechanisms and flow sure gradient modulus. Yi et al.16 applied unsteady-state seep-
age experiments and confirmed that water displacing gas fol-
lows Darcy’s law under the tested conditions.
a) Corresponding author: shenrui523@[Link] 2. CO2 -reservoir interactions: Narayanan et al.17 in-
b) Corresponding author: gan@[Link] novatively constructed a long-core physical model that ac-
 2

curately simulated reservoir alteration during CO2 flooding, II. Experimental results and analysis of carbon dioxide
with strong agreement between experimental and numerical flooding in Berea cores
results. Wang et al.18 systematically investigated the chem-
ical alteration mechanisms induced by CO2 , elucidated the In this section, CO2 flooding experiments were conducted
carbonation reaction process, and quantified the permeabil- under oil-saturated conditions using highly homogeneous
ity changes in sandy conglomerates with varying clay mineral Berea sandstone cores. A controlled-variable approach was
contents during supercritical CO2 soaking. adopted to systematically investigate the effect of injection
pressure on CO2 flooding efficiency. The use of standardized
3. Multiphase flow and relative permeability: Zhang19 Berea cores effectively minimized permeability variability,
determined relative permeability curves for the CO2 -oil sys- ensuring reliable comparison across experimental runs. Ad-
tem using unsteady-state displacement tests and analyzed how vanced characterization techniques were comprehensively ap-
injection parameters affect gas–liquid flow behavior. Dong20 plied, including one-dimensional nuclear magnetic resonance
extended these experiments to assess the influence of injec- (1D NMR), two-dimensional T1 − T2 NMR, and chromato-
tion pressure, rate, and volume on the relative permeability graphic analysis of crude oil components. These methods
of CO2 -water and CO2 -oil systems. Lun21 showed that in- enabled a detailed investigation into the interaction mecha-
creasing displacement pressure significantly reduces oil–gas nisms between CO2 and crude oil. By varying the injected
interfacial tension and enlarges the two-phase co-permeability pore volume (PV), the influence of injection quantity on dis-
zone, offering theoretical support for optimizing injection placement performance was quantitatively assessed, provid-
strategies. ing experimental support for optimizing CO2 flooding param-
eters.
4. Modeling and numerical simulation: Jafari et al.22
proposed a four-component material balance model (oil, as-
A. Experimental principles, equipment and samples
phaltenes, light hydrocarbons, and water) based on multilayer
adsorption theory to predict asphaltene behavior during CO2
flooding. Ampomah et al.23 utilized neural network algo- CO2 flooding technology is primarily categorized into two
rithms to accurately forecast CO2 storage efficiency and in- types: miscible flooding and immiscible flooding. The key
cremental oil recovery. Zhu24 used nuclear magnetic reso- distinction lies in whether the injected CO2 can form a sin-
nance (NMR) imaging to visualize flow evolution during near- gle phase with crude oil under specific reservoir conditions.
miscible displacement and discovered that, at sufficiently high Immiscible displacement is suitable for low-to-medium per-
displacement pressures, the velocity ratio of the displacement meability reservoirs (1 − 50 mD) where formation pressure
front to injected volume stabilizes. is below the minimum miscibility pressure (MMP), typically
20−35 MPa. It primarily improves oil mobility through phys-
ical effects induced by CO2 dissolution, causing 15 − 35%
Existing models predominantly rely on ideal miscibility as- oil swelling and 30 − 80% viscosity reduction, thereby en-
sumptions and neglect the impact of diffusion on displacement hancing microscopic displacement efficiency25 . Miscible dis-
fronts, resulting in significant errors in CO2 flooding recov- placement, however, requires stringent geological and engi-
ery predictions. And the CO2 flooding process is governed neering conditions: Injection pressure must exceed MMP but
by the interplay of multiple coupled mechanisms, making it remain below the reservoir fracture pressure threshold (typi-
challenging for any single model to fully capture the system’s cally 1.2 MMP). The reservoir must exhibit favorable porosity
complexity. While significant progress has been achieved in (> 15%) and permeability (> 10 mD).26 The key mechanism
modeling CO2 flooding under various pressure conditions, lies in the multiple-contact miscibility process CO2 gradually
a unified and comprehensive theoretical framework remains extracts light (C1 − C6 ), intermediate (C7 − C15 ), and heavy
elusive. (> C16 ) hydrocarbon fractions from crude oil through succes-
sive contacts. Under supercritical conditions (T > 31.04◦ C,
This study aims to leverage one-dimensional and two- P > 7.38 MPa), a pseudo-single-phase flow forms, creating
dimensional nuclear magnetic resonance (NMR) experimen- a fully miscible CO2 -oil displacement front at the interface,
tal results, focusing on the viscosity reduction and extraction enabling more efficient oil displacement and higher recovery
effects during CO2 flooding, with emphasis on analyzing the rates—though at significantly higher operational costs.
underlying mechanisms under different displacement states. This study utilized high-homogeneity standard Berea cores
Further considering the diffusion effects in porous media flow, to conduct CO2 flooding experiments with oil-saturated cores,
we quantify the coupling mechanism between diffusion and effectively eliminating the influence of core permeability vari-
miscibility conditions, thereby addressing the limitations of ations on experimental results. Relevant core data are pre-
existing models that overlook diffusion. Additionally, by inte- sented in Table I. During the experiments, the control vari-
grating the diffusion coefficient (D) into a novel CO2 flooding able method was systematically employed to investigate the
material balance equation and cross-validating experimental impact of displacement pressure on CO2 flooding efficiency.
data with numerical simulations, this research provides new The NMR experiments on Berea cores were performed using a
insights for advancing CO2 flooding theory and optimizing Reccore-04 core NMR analyzer, with measurement standards
operational processes. following SY/T 6490-2014 "Laboratory Measurement Spec-
 3

spectrum measurement and two-dimensional T1 −T2 spectrum

TABLE I. Reservoir CO2 flooding natural cores data
detection.
Core ID Lithology Length Diameter Porosity Permeability (4) The crude oil-saturated Berea cores were reassembled
(cm) (cm) (%) (mD) into the CO2 flooding system. The inlet and outlet pressures
were controlled separately using a high-pressure Quizix pre-
Berea-1 6.056 2.495 17.36 41.64 cision pump and back-pressure regulator, while the confining
Berea-2 Medium 6.066 2.495 17.63 42.29 pressure was maintained at 23.11 MPa via a manual pump.
Under constant net confining pressure, CO2 flooding experi-
Berea-3 permeability 6.025 2.495 17.26 44.28
ments were conducted through three injection stages with dif-
Berea-4 sandstone 6.061 2.495 17.34 48.14 ferent PV numbers: 0.2 PV, 0.4 PV, and 2.0 PV (cumulative
Berea-5 6.084 2.495 17.45 44.84 2.6 PV).
(5) After each CO2 injection stage, one-dimensional NMR
T2 spectra and two-dimensional T1 − T2 spectra of the cores
ifications for NMR Parameters of Rock Samples". The CO2 were measured.
flooding experiments on oil-saturated Berea cores were com- (6) NMR T2 and T1 − T2 spectra were plotted for both pre-
pleted using an SL-2018 CO2 core experimental system, with flooding and post-flooding states at different stages for com-
the experimental procedure illustrated in Fig. 1. parative analysis.
NMR T1 − T2 mapping serves as a non-destructive tech- (7) Portions of the produced oil were selected for NMR and
nique for distinguishing hydrogen-containing components in compositional analysis to investigate CO2 enhanced oil recov-
sandstone. The color intensity in two-dimensional maps un- ery mechanisms.
der the same scale enables qualitative analysis of shale oil (8) Systematic CO2 flooding experiments were subse-
fluid composition content and distribution within core sam- quently performed on all five cores at designated pressures:
ples. Free oil, adsorbed oil, and heavy components reside in 24.00 MPa, 22.00 MPa, 20.00 MPa, 18.00 MPa, and 16.00
organic pores, while bound water occupies inorganic pores. MPa.
The transverse relaxation time (T2 ) spectra of these fluids in
rocks exhibit overlapping phenomena, making it difficult to
B. Experimental Study on carbon dioxide Flooding
effectively differentiate them using one-dimensional T2 spec- Mechanisms Using 1D NMR
tra alone. Analysis of NMR characteristics of fluid compo-
nents reveals significant differences in longitudinal relaxation
times (T1 ) among fluids in different rocks. Particularly, the By systematically evaluating the displacement efficiency at
T1 /T2 ratio proves effective for evaluating oil-bearing infor- different injection volumes, CO2 flooding recovery data were
mation in sandstone. Experimental results demonstrate that obtained for five Berea cores under varying pressure condi-
various fluid components occupy distinct distribution ranges tions (see Table II). And Fig. 2 presents a line chart demon-
in T1 − T2 two-dimensional spectra. Through data segmenta- strating the evolution of recovery factors in different core sam-
tion of T1 − T2 spectra, detailed fluid component information ples as CO2 injection volume increases.
can be obtained. Based on this, existing research has proposed
standard NMR spectra for different fluid components, indicat- TABLE II. Recovery factors of CO2 flooding in five Berea sandstone
ing the existence of recognized two-dimensional NMR meth- cores under varying injection pressures.
ods for oil-bearing detection. Furthermore, by varying the in-
jected pore volumes (PV), this study quantitatively analyzes Pressure Recovery Factor (%)
Core ID
the influence of injection volume on CO2 flooding efficiency, (MPa) 0.2 PV 0.4 PV 2.0 PV
providing experimental basis for optimizing CO2 flooding pa- Berea-1 24.00 47.40 52.99 60.97
rameters.
This study follows the standard experimental procedure: Berea-2 22.00 46.62 51.80 57.53
(1) The five Berea sandstone cores used in the experiment Berea-3 20.00 45.16 51.32 57.26
were vacuumed for 2 hours, then saturated with kerosene. Berea-4 18.00 42.52 51.46 56.41
Subsequently, the five cores were placed in a pressure vessel
and pressurized to 15.00 MPa for additional kerosene satura- Berea-5 16.00 39.72 49.88 54.58
tion lasting over 12 hours.
(2) The cores were then loaded into the CO2 core flooding Comprehensive analysis of experimental data (Table II)
system. The system temperature was set to 97.3◦ C, and the and intuitive comparison shown in Fig.2 indicates that CO2
cores were flooded with crude oil from Block Hei 79 of Jilin flooding exhibits excellent displacement efficiency in low-
Oilfield (whose minimum miscibility pressure of 22.10 MPa permeability Berea sandstone cores, maintaining stable recov-
was determined through slim-tube experiments) until achiev- ery across varying injection pressures. Mechanistic investiga-
ing more than 5 pore volumes (PV) of injection, ensuring tions suggest that CO2 improves oil recovery through several
complete crude oil saturation. synergistic mechanisms: (1) selective extraction of light hy-
(3) The saturated cores were removed from the core holder, drocarbons reduces crude oil viscosity; (2) the pronounced
weighed and recorded, followed by one-dimensional NMR T2 expansion behavior of supercritical CO2 enables it to occupy
 4

FIG. 1. Schematic diagram of the experimental setup for CO2 flooding in saturated crude oil Berea core samples.

ume from 0.6 PV to 2.6 PV continues to enhance recovery,

highlighting the importance of prolonged CO2 contact time in
low-permeability reservoir development. These findings pro-
vide an experimental basis for optimizing CO2 flooding strate-
gies: using smaller PV volumes during early development to
achieve rapid production, followed by higher PV injection to
maintain stable output and maximize long-term recovery effi-
ciency.
When the cumulative CO2 injection volume reached 2.6 PV
(including a secondary injection of 2.0 PV), all core samples
achieved favorable ultimate recovery. This result confirms
that large PV injection is a necessary condition for economi-
cally efficient development in low-permeability reservoirs us-
ing CO2 flooding. Based on these findings, it is recommended
that field-scale implementations adopt a reservoir-specific in-
jection strategy, whereby smaller PV volumes are used during
FIG. 2. Recovery factor as a function of total injected CO2 PV for the early development phase to achieve rapid production re-
five Berea sandstone cores. The Berea-1 core, subjected to miscible
sponse, followed by larger PV injections in the later stages to
flooding, exhibits a distinct upward deviation compared to the other
cores. Notably, its ultimate recovery factor is 3.44% higher than that ensure high ultimate recovery.
of the Berea-2 core, while the difference between Berea-2 and Berea- Based on the experimentally determined minimum misci-
5 is only 2.95%. bility pressure (MMP = 22.10 MPa), results show that only
the Berea-1 core (24.00 MPa) achieved miscible displace-
ment conditions within the tested pressure range, exhibiting
significantly higher ultimate recovery compared to the other
additional pore space; and (3) the solution gas drive effect, es- samples. Table II and Fig. 2 show that its recovery fac-
pecially under lower pressure conditions (16 − 18 MPa), fur- tor is 3.44% higher than that of Berea-2 (22.00 MPa). As a
ther contributes to enhanced recovery performance. comparison, recovery factor of Berea-2 is only 0.27% higher
During the cumulative injection of 0.6 PV of CO2 (includ- than that of Berea-3 (20.00 MPa) and even only 2.95% higher
ing a secondary injection of 0.4 PV), oil recovery continued than that of Berea-5 (16.00 MPa), which is still smaller than
to increase significantly, though at a slower rate than during the gap between it and Berea-1. This discrepancy cannot
the initial 0.2 PV stage. This trend reveals two important in- be solely explained by pressure differences. It can be con-
sights: (1) Substantial early-stage recovery can be achieved cluded that achieving miscible displacement conditions leads
in low-permeability Berea cores even with small PV injection to significantly enhanced flooding efficiency. The remaining
volumes, due to their favorable flow capacity and the rapid four cores (Berea-2 to Berea-5, with pressures ranging from
diffusion of CO2 . (2) Further increasing the injected vol- 16.00 to 22.00 MPa) operated under immiscible conditions
 5

but still demonstrated favorable displacement performance.

Notably, oil recovery in the immiscible group displayed pres-
sure sensitivity: as injection pressure decreased from 22.00
MPa to 16.00 MPa, the recovery factor declined correspond-
ingly. These findings confirm the superior efficiency of mis-
cible displacement in enhancing oil recovery and underscore
the importance of optimizing injection pressure even under
immiscible conditions to ensure effective reservoir develop-
ment.
Figure 3 presents the comparative T2 spectra of five Berea
sandstone cores under four distinct displacement conditions:
(1) the initial state saturated with crude oil; (2) after injection
of 0.2 PV CO2 (cumulative 0.2 PV); (3) after an additional
0.4 PV injection (cumulative 0.6 PV); (4) after a final 2.0 PV
injection (cumulative 2.6 PV).
As shown in Fig. 3, the T2 spectra of the five Berea sand-
stone cores exhibit substantial overlap during the initial crude
oil saturation stage, indicating excellent core homogeneity un-
der identical fluid conditions. This confirms that the intrinsic
physical properties of the cores had minimal impact on the ex-
perimental outcomes. As the CO2 flooding process advances,
the Berea-1 core—under miscible conditions—consistently
shows higher recovery efficiency compared to the immisci-
ble cores. However, with continued CO2 injection at large PV
volumes, the recovery performance of the immiscible cores
gradually converges and eventually becomes nearly identical,
emphasizing the importance of extended CO2 exposure. Fur-
thermore, the ultimate recovery achieved by miscible flood-
ing exceeds that of the immiscible cases, highlighting both
the advantage and necessity of achieving miscible displace-
ment conditions to maximize oil recovery in low-permeability
reservoirs.

C. Experimental study on carbon dioxide flooding

mechanisms using 2D NMR

As described in Sec. II A, to more clearly illustrate the ex-

perimental findings, two-dimensional nuclear magnetic reso-
nance (2D NMR) measurements were performed.
Fig. 4 and 5 display representative T1 − T2 relaxation maps
of two Berea sandstone cores, Berea-1 and Berea-3, at differ-
ent stages of the flooding process. Berea-1 was subjected to
miscible CO2 flooding, whereas Berea-3 underwent immisci-
ble CO2 displacement. These spectra provide insight into fluid
distribution evolution under different flooding mechanisms.
At the initial displacement stage (top-left spectrum in each
group), free oil accounted for the largest proportion. As CO2
flooding progressed, the 2D spectra evolved through the top-
right (after 0.2 PV), bottom-left (after 0.4 PV), and bottom-
right (after 2.0 PV) spectra, showing a clear left shift in the FIG. 3. Comparison of T2 spectra at different displacement states for
transverse relaxation time (T2 ) spectrum and a downward shift five Berea cores. Across all injection volumes, each core exhibits
a single peak in the T2 spectrum, indicating a highly uniform pore
in the longitudinal relaxation time (T1 ). The T1 − T2 2D NMR
size distribution. The area under each peak corresponds to the crude
spectra reveal that as the displacement progressed, the fluid oil volume retained in the core. As CO2 flooding progresses, the
content in the Berea cores gradually decreased. The propor- residual oil content in the cores gradually decreases, with Berea-1
tion of free oil reduced, while the relative proportion of ad- core showing the smallest remaining oil volume.
sorbed oil increased, with heavy components accumulating.
This trend was consistent with the changes observed in the
 6

FIG. 4. Comparison of T1 − T2 spectra at different stages of CO2 FIG. 5. Comparison of T1 − T2 spectra at different stages of CO2
flooding for the Berea-1 core. Compared to T2 spectra, T1 − T2 spec- flooding for the Berea-3 core. Berea-3 exhibits a similar spectral
tra offer more comprehensive insight into the behavior of different evolution trend to Berea-1, with enhanced displacement of lighter
crude oil components during flooding. In this study, the evolution of components, but retains substantially more total oil.
spectral features highlights the progressive displacement of lighter
hydrocarbons. In the T1 − T2 maps, lighter molecular weight com-
ponents appear in the upper-right region and are preferentially dis-
placed as CO2 injection proceeds.
 7

1D NMR T2 spectra. For the immiscible CO2 -flooded Berea- To determine the position of the gas front xe1 , the Buck-
3 core, under insufficient CO2 injection, cores subjected to ley–Leverett (B–L) equation,27 based on the iso-saturation
higher displacement pressures exhibited higher recovery effi- front assumption, is employed. The B–L equation is given
ciency. This indicates that in the early stages of immiscible by:
CO2 flooding, higher displacement pressure results in higher
recovery under the same PV injection. In contrast, the mis- fg′ (Sg ) Z t
xe1 − x0 = q(t) dt, (1)
cible CO2 -flooded Berea-1 core yielded higher recovery than φA 0
the immiscible CO2 -flooded cores.
where fg′ (Sg ) is the derivative of the gas fractional flow func-
For CO2 flooding, increasing immiscible CO2 displacement tion, φ is porosity, A is the cross-sectionalRarea, and q(t) is the
pressure can improve recovery efficiency, while miscible CO2 volumetric injection rate. Assuming Q = 0t q(t) dt and x0 = 0,
flooding yields the best performance. At higher PV injection Eq. (1) becomes:
volumes, immiscible CO2 flooding exhibits a clear contrast in
efficiency compared to miscible CO2 flooding. Although in- fg′ (Sg )
creasing immiscible CO2 displacement pressure improves re- xe1 = Q. (2)
φA
covery efficiency, it does not significantly enhance the flowa-
bility of heavy crude oil components in the reservoir. In con- The gas fractional flow function fg (Sg ), defined through
trast, miscible CO2 flooding can markedly improve the flowa- the relative permeability–saturation relationship, establishes a
bility of heavy oil components, leading to superior oil recov- known correlation between gas saturation and fractional flow.
ery performance. Thus, the gas front location xe1 can be considered a deter-
minable quantity under given flow and saturation conditions.
The transport of CO2 components during diffusion can be
III. Theoretical Derivation of Seepage Processes
described by the mass conservation equation:
Incorporating Diffusion Effects ∂c
+ ∇ · (vc) = D∇2 c, (3)
∂t
To further investigate the advantages of miscible CO2 where c is the component concentration, v is the Darcy veloc-
flooding, a simplified flow model incorporating diffusion ef- ity, and D is the diffusion coefficient. This equation assumes
fects is proposed. Currently, most studies on CO2 flooding no source or sink terms, constant D, and incompressible flow.
focus primarily on displacement mechanisms and oil recov- The second term on the left-hand side represents convection,
ery efficiency. However, the theoretical modeling of CO2 de- while the right-hand side represents diffusion, based on Fick’s
velopment often continues to reference analytical frameworks second law. Equation (3) is thus referred to as the convec-
developed for water flooding, which may not accurately rep- tion–diffusion equation.
resent gas–oil interactions. Unlike water flooding, gaseous For one-dimensional flow, the equation simplifies to:
CO2 interacts with reservoir fluids through three key mecha-
nisms: dissolution, diffusion, and convection. These interac- ∂c ∂c ∂ 2c
tions, particularly at the displacement front, lead to fundamen- φ +v = Dφ 2 , (4)
∂t ∂x ∂x
tal differences in flow behavior. To account for these effects,
we establish a one-dimensional homogeneous porous media with the initial and boundary conditions:
model for two-phase CO2 –oil flow, as illustrated in Fig. 6. The

c(xe1 ,t) = c0 ,
 t ≥ 0,
model operates under the following assumptions: (1) Thermo-
dynamic equilibrium is maintained throughout the process; c(x,t = 0) = 0, x > xe1 ,

c(x → x ,t) → 0, t ≥ 0.
(2) Porosity and permeability remain constant; (3) Viscosity e2
reduction and compressibility effects of CO2 are neglected.
To generalize, the following dimensionless variables are in-
Under these conditions, the reservoir domain is conceptually
troduced:
divided into four distinct zones during the CO2 flooding pro- Z t
cess: (a) A pure CO2 gas zone; (b) A two-phase CO2 –oil v x c vL
tQ = dt, xQ = , cQ = , K= ,
coexistence zone; (c) A CO2 diffusion-dominated transition 0 φL L c0 φD
zone; (d) A pure crude oil zone.
where L denotes the total investigated depth of the zone, and K
is a normalization parameter. Substituting into Eq. ( 4) yields
the dimensionless form:
1 ∂ 2 cQ ∂ cQ ∂ cQ
2
− = , (5)
K ∂ xQ ∂ xQ ∂tQ
with boundary conditions:
FIG. 6. Schematic diagram illustrating the multi-phase seepage pro- 
cess during CO2 flooding, showing the interaction between the CO2 cQ (xQ = xe1Q ,tQ ) = 1,
 tQ ≥ 0,
gas phase, oil phase, and water phase, as well as the displacement cQ (xQ > xe1Q ,tQ = 0) = 0,
front dynamics. 
c (x → x ,t ) → 0, tQ ≥ 0.
Q Q e2Q Q
 8

Applying the Laplace transform to Eq. 5 and solving with IV. Material Balance Equation for Carbon Dioxide Flooding
characteristic roots yields:
" p # Experimental studies often face inherent limitations, partic-
1 (xQ − xe1Q )(1 − 1 + 4s/K) ularly under extreme conditions such as ultra-low permeabil-
c̄Q (xQ , s) = exp (6)
s 2/K ity reservoirs, high-pressure environments, and geologically
complex systems (e.g., heterogeneous formations). Addition-
Taking the inverse Laplace transform gives the time-domain ally, experimental results are frequently constrained by equip-
solution: ment resolution, core heterogeneity, and limited control over
 ( ! boundary conditions, which hinders the ability to fully eluci-
xQ − xe1Q xQ − xe1Q + KtQ date the individual contributions of mechanisms involved in
cQ (xQ ,tQ ) = exp K erfc p
2 2 KtQ CO2 flooding.
!) To address these limitations, this study proposes a gener-
xQ − xe1Q − KtQ alized and scalable mathematical model for CO2 displace-
+ exp [K (xQ − xe1Q )] erfc p . (7)
2 KtQ ment that can quantitatively describe the coupled effects of
key physical mechanisms—including diffusion, extraction,
This solution is applicable for arbitrary values of K. Here, and dissolution—under a range of reservoir conditions. The
erfc(x) denotes the complementary error function. model is built upon the reservoir material balance equation,
Equation (7) enables calculation of the compositional front which serves as the theoretical foundation. By calibrating
during CO2 flooding with diffusion. Given a known diffu- the model against existing experimental data, a complemen-
sion coefficient and an initial concentration c0 at the satura- tary relationship is established, enabling mutual verification
tion front xe1 , the extent of CO2 diffusion can be determined. between simulation and laboratory observations. This ap-
The location where concentration approaches zero is defined proach compensates for the limited experimental capacity un-
as the diffusion front xe2 . der extreme conditions and improves overall understanding of
the displacement process. Furthermore, the proposed model
offers predictive capabilities for identifying potential opera-
tional risks, such as exceeding formation fracture pressure or
early CO2 breakthrough. It provides theoretical guidance for
experimental parameter selection and field-scale injection de-
sign, helping to avoid high-risk and low-efficiency operating
conditions while optimizing oil recovery performance.
In previous studies, material balance equations for reser-
voirs using traditional water flooding or N2 displacement have
been well-established. However, there are significant differ-
ences between the displacement models for CO2 flooding and
those for water flooding or N2 displacement. In gas displace-
ment processes, the gas flow rate is typically approximated
using an average pressure, which causes substantial differ-
ences between the gas and water flooding models. By ap-
plying material conservation principles to establish reservoir
FIG. 7. CO2 concentration profile over time. material balance equations, we can avoid the complexities of
analyzing phase-specific displacement mechanisms. This ap-
Figure 7 shows the evolution of the CO2 concentration pro- proach allows for a more comprehensive evaluation of overall
file over time, calculated using Eq. (7) with a diffusion coeffi- reservoir development, focusing on macro-scale strategies for
cient of D = 10−4 . As shown in Fig. 4, with the increase in dif- efficient oil recovery.
fusion time, the compositional front due to diffusion gradually Typically, it is assumed that the displacing fluid does not
shifts forward, expanding the CO2 displacement front. Mean- interact with any reservoir components, including formation
while, the concentration of CO2 within the already diffused crude oil, irreducible water, and the rock matrix. This as-
region also increases. The intersection of the curve with the sumption is reasonable for water flooding or N2 flooding pro-
horizontal axis can effectively predict the time and distance cesses. However, such a completely non-reactive two-phase
at which the CO2 breakthrough occurs during the displace- flow system does not apply to CO2 flooding. CO2 flood-
ment process. Furthermore, this illustrates that under miscible ing is inherently a reactive process, where CO2 interacts with
conditions, CO2 rapidly increases the contact area with crude formation crude oil through mutual mass transfer and diffu-
oil, enhancing mass transfer efficiency. This enables more ef- sive exchange. Additionally, CO2 reacts with the rock ma-
fective extraction of light components, thereby accelerating trix, leading to natural formation consumption as CO2 is ab-
the overall displacement process. These results are consistent sorbed by the reservoir. While this process represents an en-
with the experimental findings for Berea-1 core, which, upon vironmentally favorable CO2 sequestration mechanism, it im-
entering the miscible flooding stage, exhibited superior recov- pacts material balance calculations for CO2 flooding. From a
ery compared to other core samples. production standpoint, the material balance equation for CO2
 9

flooding must account for both produced gas and oil. To sim- can be determined from laboratory measurements of the crude
plify the reservoir’s physical model, irreducible water effects oil’s properties.
are neglected, and water-free production is assumed. Con- In Eq. (8), the right-hand side consists of four terms: crude
sequently, the equation considers: (a) the CO2 depletion in oil expansion, rock matrix expansion, injected gas volume,
the produced gas, and (b) the dissolved CO2 remaining in the and the expansion effect due to the pseudo-dissolution gas
crude oil. These characteristics are distinctive in the material drive formed by CO2 . N represents the total crude oil volume
balance formulation for CO2 flooding reservoirs. under surface conditions (original oil in place). Boi denotes
The reservoir material balance equation is essentially a the oil formation volume factor at the initial reservoir pres-
mass conservation equation. The following assumptions are sure pi , and N(Bo − Boi ) quantifies the oil expansion resulting
made for the reservoir model: from fluid production, corresponding to the first term on the
(1) The reservoir exhibits excellent homogeneity, with es- right-hand side of Eq. (8). As production time t progresses,
sentially uniform physical properties of both the rock matrix reservoir pressure decreases from the initial pressure pi to the
and contained fluids, satisfying isotropic conditions. final pressure p, with the pressure drop ∆p = pi − p being
(2) Stress transmission within the reservoir is instantaneous measurable. The model neglects the effects of initial gas caps
and sensitive. At any given time t, formation pressure remains and solution gas, so despite the pressure drop ∆p, there is no
consistent throughout the reservoir, with the model maintain- expansion of the gas cap or the rock matrix in the gas cap re-
ing stable mechanical equilibrium. gion. The model also ignores irreducible water and natural
(3) The entire reservoir development system is treated as an water influx, assuming a pure CO2 flooding process with no
isolated mass system with no mass exchange with external en- water injection, and thus no aqueous phase volume changes.
vironments. However, the system possesses ideal heat transfer In the absence of irreducible water, the pore volume is equal
characteristics, maintaining a constant background tempera- to the initial oil volume, Vp = NBoi . By incorporating measur-
ture T0 throughout development. able formation compressibility C f , the rock expansion vol-
(4) The following effects are neglected: influence of irre- ume is calculated as VpC f ∆p = NBoiC f ∆p, corresponding to
ducible water and water influx; gravitational effects during the second term on the right-hand side of Eq. (8). The cumu-
development; capillary pressure impacts on reservoir produc- lative injected CO2 volume is Gi Bg , where Gi is the surface-
tion; gas slippage effects; initial solution gas presence; and volume of CO2 , representing the third term on the right-hand
potential reservoir compaction during production. side of Eq. (8). The CO2 flooding process induces a pseudo-
(5) Oil production rates remain balanced across all reservoir dissolution gas drive effect, leading to oil expansion due to
regions during development. the CO2 retained in the reservoir. This expansion combines
Produced fluids are replaced by internal system expansion the oil and CO2 volumetric expansions for the drive mech-
and injected fluids; otherwise, a vacuum would form in the anism. It is important to note that formation-absorbed CO2
reservoir, which contradicts physical principles. In this study, contributes solely to storage. Therefore, the expansion term
total oil and gas production equals the expansion volume of becomes [(1 − α) Gi − N p (R p + β ) Bg ] (Bg − Bgi ), where α is
crude oil and rock, plus the volume of injected gas, yielding the CO2 absorption coefficient and Bgi is the CO2 formation
the CO2 flooding material balance equation volume factor at the initial pressure pi , representing the su-
N p Bo percritical CO2 volume factor under initial conditions. This
+ N p (R p + β ) Bg = N (Bo − Boi ) + NBoiC f ∆p + Gi Bg corresponds to the fourth term on the right-hand side of Eq.
γ (8).
+ [(1 − α) Gi − N p (R p + β ) Bg ] (Bg − Bgi ) . (8) From Eq. (8), the total crude oil volume N could be derived
as:
All the parameters in Eq. (8) will be illustrated in the fol-
lowing text. Eq. (8) shows that the left-hand side is composed (
of two terms, which represent oil production and gas produc- 1
N= N p Bo /γ + N p (R p + β ) Bg − Gi Bg
tion, respectively. Over a specified development period t, the Bo − Boi + BoiC f ∆p
production volume consists of the oil phase as N p and the gas )
phase as G p . The effect of irreducible water is neglected, as- − [(1 − α) Gi − N p (R p + β ) Bg ] (Bg − Bgi ) . (9)
suming no water production. The dissolution of CO2 in the N p
oil phase causes oil phase expansion, with the expansion coef-
ficient γ. At the current formation pressure p, the measurable All parameters on the right-hand side of Eq. (9) can be de-
volume factor Bo accounts for the volume differences of crude termined through laboratory analysis and field measurements.
oil under varying pressures. Thus, the cumulative volume of Additionally, Eq. (8) allows for cross-verification of the re-
N p oil production at pressure p is N p Bo /γ, corresponding to maining parameters by comparing them with estimated reser-
the first term on the left-hand side of Eq. (8). The overall voir reserves.
gas-oil ratio, defined as R p = G p /N p , is measurable. Under Based on the actual production data from Section II, the
the assumption of no initial dissolved gas, G p is considered CO2 flooding reservoir material balance equation is used to
to consist entirely of the displacing gas CO2 , which replaces calculate the modified production data. The traditional reser-
part of the dissolved gas. This contribution is represented by voir material balance equation is employed to calculate the-
the second term on the left-hand side of Eq. (8). Both the dis- oretical production data. A comparison is made between the
solution ratio β and the gas phase volume factor of CO2 , Bg , actual production, the modified production, and the theoreti-
 10

interactions between the formation and crude oil to enhance

formation permeability, collectively improving oil mobility
and displacement efficiency. This effectively mitigates some
challenges in conventional water flooding (e.g., poor mobi-
lization of residual oil) and surfactant-polymer (SP) flooding
(e.g., polymer-induced plugging in low-permeability zones).
(2) Superiority of miscible flooding: The experimental re-
sults demonstrate that under miscible conditions (24.00 MPa
in this study), the ultimate recovery reached 60.97%, 3.44%
higher than the maximum recovery of 57.53% achieved in im-
miscible flooding, while the differences in the other four core
samples did not even exceed 3%. The comparative analysis
between miscible and immiscible flooding reveals that misci-
ble displacement exhibits distinct advantages. The complete
dissolution of CO2 into crude oil under miscible conditions
creates a pseudo-single phase flow, eliminating interfacial ten-
sion and enabling more efficient displacement of both light
and heavy oil components. Moreover, CO2 flooding technol-
ogy is not limited by chemical agent failure and can achieve a
higher recovery rate than the theoretical limit during the dis-
FIG. 8. Relationship between recovery factor and reservoir pressure placement process. Therefore, CO2 flooding technology is
drop.
more suitable for light oil reservoirs with low miscible pres-
sure and no reliance on chemical agents to reduce viscosity
than medium-heavy oil reservoirs. In practical applications,
cal production, and a relationship curve between the recovery priority should be given to achieving miscible displacement
factor and the reservoir pressure drop is plotted in Fig. 8. by increasing the injection pressure to maximize the oil re-
From Fig. 8, it is evident that for the same pressure drop covery effect.
∆p, the actual production is lower than the theoretical produc- (3) Optimization of injection parameters: The PV-
tion of the reservoir. The modified production, however, lies dependent recovery behavior provides critical insights for
between the actual and theoretical production, indicating that field application strategies. The experimental data show that:
the CO2 flooding reservoir material balance equation serves to Initial rapid production can be achieved with small PV injec-
adjust the material balance of the reservoir. The CO2 flooding tions (0.2 PV yielding 47.40% recovery in miscible case);
reservoir material balance equation is therefore more applica- Sustained production requires larger PV injections (2.0 PV in-
ble to reservoirs under CO2 flooding development. creasing recovery to 60.97%); The marginal recovery gain de-
The modified production matches the theoretical produc- creases with increasing PV, suggesting an economic optimum
tion calculated using the traditional material balance equation for field operations.
in the early stages of the displacement process. As the dis- (4) Diffusion-enhanced displacement mechanism: The de-
placement progresses, and the reservoir pressure decreases, veloped convection-diffusion model quantitatively describes
the pressure drop ∆p increases, causing the modified produc- the important role of molecular diffusion in CO2 flooding.
tion to deviate more significantly from the theoretical produc- Numerical solutions of the dimensionless transport equation
tion. This suggests that the CO2 flooding reservoir material reveal that: Diffusion significantly extends the CO2 pene-
balance equation is more accurate for reservoirs with higher tration depth beyond the displacement front; The diffusion-
production in CO2 flooding development, compared to the tra- dominated mass transfer accelerates the establishment of mis-
ditional reservoir material balance equation. cible conditions; The time-dependent concentration profiles
enable more accurate prediction of gas breakthrough.
(5) Improved material balance approach: The modified ma-
V. Conclusions and Discussions terial balance equation incorporating CO2 -crude oil interac-
tions and diffusion effects shows superior predictive capabil-
This study systematically investigated the mechanisms ity compared to conventional models. Key improvements in-
and efficiency of CO2 flooding in low-permeability reser- clude: Explicit accounting for CO2 dissolution in oil (through
voirs through comprehensive core experiments and theoretical parameter β ); Consideration of CO2 sequestration in rock ma-
modeling. The main findings are summarized as follows: trix (parameter α); Better alignment with experimental data,
(1) Enhanced recovery performance of CO2 flooding: The particularly at higher recovery factors.
experimental results demonstrate that CO2 flooding is partic- In summary, CO2 flooding is a highly effective method for
ularly effective for low-permeability, ultra-low permeability, developing low-permeability light oil reservoirs, where misci-
and tight reservoirs. CO2 interacts with crude oil through mul- ble displacement and large-PV-number injection serve as key
tiple mechanisms including viscosity reduction, oil swelling, strategies for enhancing oil recovery. Future research should
and extraction of light components, modifing the solid-liquid further investigate the dynamic behavior of CO2 flooding un-
 11

der extreme conditions, coupled with numerical simulation to Sg gas saturation, dimensionless
optimize field application schemes, thereby enabling more ef- φ porosity, dimensionless
ficient and economical hydrocarbon development. A cross-sectional area, m2
The primary challenge in CO2 flooding is that reser- q volumetric injection rate, m3 /s
voir heterogeneity causes CO2 to break through along high- c component concentration, %
permeability zones, leaving crude oil in low-permeability ar- v Darcy velocity, m/s
eas poorly displaced. Research efforts must focus on expand- D diffusion coefficient, m2 /s
ing CO2 sweep efficiency, such as using water-alternating-gas L total investigated depth of the zone, m
(WAG) injection, viscosity-enhancing agents, or nanoparti- K normalization parameter, dimensionless
cles to increase CO2 viscosity, combined with foam flood- N p production volume of the oil phase, m3
ing and other techniques to block high-permeability chan-
G p production volume of the gas phase, m3
nels and improve sweep volume. Additionally, to address
the issue of gas channeling during CO2 flooding, the devel- γ expansion coefficient, dimensionless
opment of multi-media composite conformance control sys- Bo factor accounts for the volume differences of oil under
tems is essential. This includes acid-resistant gel systems, in- varying pressures, dimensionless
situ emulsion-based conformance control systems, and self- R p overall gas-oil ratio, dimensionless
adaptive viscosity-enhanced conformance control systems. β dissolution ratio, dimensionless
Further advancements should focus on deep diversion systems Bg factor accounts for the volume differences of CO2 un-
with controllable migration and low-cost large-channel block- der varying pressures, dimensionless
age systems to enhance CO2 flooding regulation. Synergistic N original oil in place, m3
integration with emerging conformance control technologies pi initial reservoir pressure, MPa
should also be prioritized. Research on multi-media compos- Boi factor accounts for the volume differences of oil under
ite conformance control systems and novel conformance con- initial reservoir pressure, dimensionless
trol agents—such as combining CO2 miscibility with surfac- ∆p pressure drop, N/m2
tant mobility control—should be evaluated on a case-by-case C f formation compressibility, MPa−1
basis. From an engineering perspective, optimization of in- Gi initial surface-volume of CO2 , m3
jection and production processes, along with advancements α CO2 absorption coefficient, dimensionless
in monitoring technologies, is crucial. A surface-subsurface Bgi factor accounts for the volume differences of CO2 un-
integrated collaborative flooding system should be estab- der initial reservoir pressure, dimensionless
lished to achieve full-process optimization—from CO2 cap-
ture, transportation, and injection to production—maximizing
overall efficiency. References

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