Journal of CO2 Utilization 72 (2023) 102479

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Journal of CO2 Utilization

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Review article

A review of the supercritical CO2 fluid applications for improved oil and gas
production and associated carbon storage
Siddhant Kumar Prasad a, Jitendra S. Sangwai b, Hun-Soo Byun a, *
a
Department of Chemical and Biomolecular Engineering, Chonnam National University, Yeosu, Jeonnam 59626, South Korea
b
Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600 036, India

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

Keywords: Supercritical fluids find use in various areas in oil and gas production operations due to their unique properties.
Sc-CO2 mobility control Supercritical CO2 (sc-CO2) with its reduced viscosity, increased diffusivity, and liquid like density, is attractive
CO2 storage for enhanced hydrocarbon recovery, shale gas fracturing and drilling (especially in underbalanced condition).
Enhanced oil recovery
Apart from enhanced hydrocarbon recovery CO2 injection is also desirable due to associated CO2 storage through
Fracturing
various trapping mechanisms. CO2-EOR/EGR and storage processes are affected by coupled geochemical, pet­
Supercritical fluids
rophysical and geomechanical alterations due interaction of sc-CO2 with reservoir rock/fluids Along with
diffusion/dispersion of sc-CO2 in the fluid filled pore spaces. CO2-monitoring combined with lifecycle analysis
can help to ensure safety and optimize the CO2-EOR/storage project, considering the environment. However,
many technical, financial and policy challenges need to be overcome to realize the success of the CO2-EOR/
storage project and achieve carbon neutrality. This review paper discusses such challenges, the current miti­
gation practice, gaps and future direction of research. This holistic review would help gain insights into the sc-
CO2-EOR/storage mechanisms, selection criteria, various limitations, mitigation and optimizations while
applying the method for unconventional reservoirs with heterogeneity and varying fluid properties.

1. Introduction
The oil and gas industry has a significantly influence on the global
economy. Fossil fuels are the world’s primary source of energy genera­
tion. The data on energy consumption suggests that the total global
energy consumption was 564.01 × 1018 J as of 2020, which increased to
595.15 × 1018 J in 2021 [1]. Out of the total energy consumption, fossil
fuels have contributed almost ~82% of the total demand during the
2020–2021. Crude oil and natural gas consumption stood at ~55% of
the world energy consumption or ~312.09 × 1018 J during this period.
Petroleum products are present in nearly everything that people require
in their daily lives. For example, electricity generation, feedstocks for
chemicals, plastics, heating, asphalt for the construction of roads, and
synthetic materials. Thus, rising energy demands have forced the oil and
gas industry to increase their production.
Initially, the primary production commences from the reservoir due
to its internal energy [2]. This internal energy consists of dissolved gas
and gas cap expansion, encroachment of the aquifer, gravity drainage or
a combination, and maintaining the reservoir pressure sufficiently high
enough for production [3]. The recovery is roughly up to < 30% of the
total oil in place (TOIP). After the decline in production due to insuffi­
cient pressure, secondary recovery methods are adopted, including
water and gas injection into the reservoir to augment production. During
the secondary recovery, ~< 60% of the TOIP is recovered. However,
some amount of oil is still left in the reservoir after the secondary re­
covery, which is the target of the tertiary or enhanced oil recovery (EOR)
method [3–6]. Depending on the method, the EOR increases the oil re­
covery by either targeting the sweep efficiency or displacement effi­
ciency, or both [3,6]. The polymer flooding method is a type of
chemical-enhanced oil recovery that targets the macroscopic sweep ef­
ficiency to increase the oil recovery [3,7,8]. CO2 flooding is mainly
implemented to target the miscible displacement, though it can also be
used for immiscible flooding for medium to heavy crude oil. Being
highly soluble in oil, CO2 swells the crude oil and reduces its viscosity
and density, which, combined with the miscibility effects, enhance
displacement efficiency and oil recovery [3]. CO2 can also be injected
into the reservoir in a supercritical state (above the critical point of P =
7.38 MPa and T = 304 K) for increasing oil and gas recovery. In its su­
percritical state, CO2 has a density comparable to liquid, low viscosity,
and higher diffusivity [9,10], resulting in easy penetration in the pore

* Corresponding author.
E-mail address: hsbyun@jnu.ac.kr (H.-S. Byun).

https://doi.org/10.1016/j.jcou.2023.102479
Received 10 January 2023; Received in revised form 12 March 2023; Accepted 15 April 2023
Available online 22 April 2023
2212-9820/© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S.K. Prasad et al.
spaces and enhanced oil recovery. Apart from tertiary oil recovery, CO2
also finds its use in well-stimulation techniques, specifically fracturing,
to recover shale gas from tight or low permeability reservoirs [11,12].
Although, using CO2 as a fracturing fluid increases the fracture
complexity and improves the oil recovery, it has a poor proppant car­
rying capacity due to lower viscosity which restricts its use [11,12].
Increased fossil fuel production by using EOR methods and well
stimulation has also contributed to increased levels of CO2 in the at­
mosphere due to exponential anthropogenic emissions. According to a
report by the International Energy Agency (IEA), the average annual
atmospheric CO2 concentration has increased to ~412.5 ppm in 2020
[13], which is attributed to CO2 emissions of up to ~31.5 billion tonnes,
with a growth rate of ~5% during 2021. Increased emissions of CO2 and
other greenhouse gases have led to an increase in global warming, and
the threshold of 1.5 ◦ C is about to be crossed before 2030. Even with
aggressive CO2 reduction measures, this dangerously increased global
temperature might take the next 80 years or more to limit to 1.5 ◦ C [14].
Thus, efforts are being made globally, to restrict carbon emissions,
which are being fuelled by a massive dependency on fossil fuels. sc-CO2
injection and fracturing are attractive ways to increase oil and gas
production (tertiary oil recovery) while simultaneously reducing CO2
levels in the atmosphere through sequestration. Fig. 1a shows the
number of publications regarding supercritical fluids used for EOR. The
data were obtained from Scopus using the keyword “supercritical fluids”
under “enhanced oil recovery” starting from 1981. Unrelated publica­
tions were filtered out from the obtained results. It is visible from the
figure that the research towards integrating supercritical fluids in
improving oil/gas production and carbon sequestration has increased
significantly over the years and is now being actively pursued. A glance
at Fig. 1b shows the categorization of these publications into various
Fig. 1. (a) Publications regarding sc-CO2 fluids in enhanced oil recovery; (b)
Publications in various areas in upstream oil and gas production involving sc-
CO2 fluids.
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Journal of CO2 Utilization 72 (2023) 102479
areas in upstream oil and gas production operations. EOR methods and
carbon dioxide sequestration have attracted a majority of research focus
compared to drilling and hydraulic fracturing. Vital CO2-EOR aspects,
including minimum miscibility pressure (MMP), reservoir rock and
crude oil interactions with supercritical fluid, and its association with
carbon sequestration, have been segregated to emphasize the research
focus of those publications. These, and other vital aspects such as CO2
mobility, and gravity segregation, need careful consideration while
injecting CO2 into the reservoir to displace the residual oil.
The MMP is an important criterion while designing the CO2 flooding
program. The CO2 miscible flooding is generally superior to immiscible
flooding for recovering light and medium crude oil. MMP needs to be
reduced if it is higher than the reservoir pressure or due to constraints in
the development technology and reservoir fluid properties [15]. MMP
also depends on the critical properties of the injected fluid and density
variation with reservoir temperature[16]. Depending on the reservoir
characteristics and fluid properties, various methods are used to lower
the MMP, including supercritical CO2 microemulsion, CO2-philic sur­
factants, and solvents. Higher mobility of the displacing fluid and
gravity differences with reservoir fluid will lead to early breakthroughs
and lower sweep efficiency. Thickeners can be used to increase the
sc-CO2 viscosity thereby reducing its mobility [17,18]. Many different
thickeners, such as polymers, oligomers, and surfactants (cationic,
anionic, non-ionic, zwitterionic, and tailor made) have been investi­
gated for this purpose. While developing a suitable thickener for sc-CO2,
reservoir and fluid properties (higher temperature and brine salinity),
economic and environmental aspects must also be kept in mind. Com­
puter simulation plays a vital role in investigating intermolecular forces
between the thickeners and sc-CO2 at molecular level, thereby selecting
an appropriate strategy for selecting and developing CO2 thickeners.
The supercritical fluid interaction with reservoir rocks and fluids
affect the geochemistry, petrophysics (porosity, permeability, and
wettability), and geomechanical properties (including fracture tough­
ness, Young’s modulus and compressive strength). Also, stress distri­
bution can occur during gas injection, due to temperature, pore pressure
changes apart from asphaltene precipitation (injectivity loss). Thus,
geochemical, petrophysical, and geochemical alterations are vital for
CO2-EOR and storage projects [19–28]. sc-CO2 exposure leads to min­
eral dissolution and precipitation in the porous media, altering petro­
physical properties and hydrocarbon recovery [29]. Other factors such
as saturation, injected fluid solubility, compressibility and gravity
segregation need to be accounted. Supercritical fluid exposure changes
the crude oil composition due to miscibility and dissolution of non-polar
and polar compounds. In addition, swelling and viscosity reduction
occurs, increasing the recovery efficiency. However, formation damage
might happen due to the compositional change and precipitation of
certain fractions of the crude oil (heavy and polar asphaltenes). Geo­
mechanical properties are affected by precipitation of minerals and
creation of flow channels, risking rock failure and CO2 leakage. Het­
erogeneity and anisotropy (especially for fractured carbonates) lead
storage sites to vary from one another. Typical timescales vary from few
decades for CO2 injection for both EOR and storage to few centuries or
near permanent for storage process. Injecting CO2 is also attractive to
develop shale gas reservoirs due to combined benefits of enhanced gas
recovery (EGR) and CO2 sequestration (higher CO2 adsorption
compared to CH4)[30]. Additionally, compared to hydraulic fracturing.
it avoids the clay swelling in shales, and enhances hydrocarbon recovery
due to complex sinuous fractures while reducing the risk of formation
fracture. Equally vital for CO2-EOR/storage and gas recovery are the
diffusion and dispersion mechanisms of CO2 upon injection [31–34]. For
low porosity and permeability tight formations such as fractured shales,
the diffusion of CO2 into the matrix (concentration gradient between oil
and CO2) is dominant mechanism whereas convection dominates for
higher permeability or conventional reservoirs[35]. CO2 diffusivity is
affected positively by the pressure, temperature, porosity, permeability,
and oil saturation whereas brine salinity affects it adversely [33,36].
S.K. Prasad et al.
Various mathematical and empirical models have been developed in this
regard. Further research is ongoing to reliably predict the diffusion co­
efficient of CO2 in the reservoir fluids as its dispersivity is highly scale
and heterogeneity dependent [16].
Field applications, monitoring technologies and life cycle analyses
play a very indispensable role in the feasibility, safety, and commercial
success any CO2-EOR/storage project. While monitoring techniques
such as 4D seismic provide information about CO2 migration, saturation
inside the reservoir with time, field application provide valuable infor­
mation about the hydrocarbon recovery and CO2 storage viability in a
real field conditions instead of lab-scale studies. Lastly, the economic
and environmental feasibility of any CO2-EOR/storage project can be
understood with the help of life cycle analysis. Sensitivity of any CO2-
EOR/storage project on various components in the process chain
including the CO2 source, emission, and crude oil price can be analyzed
and economically optimized keeping environment considerations in
mind. Additionally, there are numerous challenges in the successful
implementation of CO2-EOR/storage project. Technical challenges
include mobility control, recovery from unconventional and fractured
reservoir, CO2 storage performance and corrosion. Additionally, eco­
nomic and policy challenges also exist which have a vital impact on the
feasibility of project. These require careful analysis and mitigation in
order for the project to be a success.
This review discusses the literature on sc-CO2 fluid application for
improved oil and gas production operations and associated carbon
storage. Crucial CO2-EOR aspects including minimum miscibility pres­
sure, mobility control, CO2-EOR/storage in unconventional liquid
(tight), carbonates, and transgressive reservoirs along with field imple­
mentation is discussed. Factors such as geochemical, petrophysical and
geomechanical alterations resulting from CO2-rock-brine interactions
play a vital role in affecting the CO2-EOR/storage potential. Addition­
ally, life cycle analysis and CO2 monitoring technologies are vital to
optimize the CO2-EOR/storage. During injection for EOR/storage pur­
pose (typically at supercritical conditions), presence of water makes CO2
corrosive. Depending on operating conditions, water chemistry, CO2
impurity, H2S, corrosion can jeopardize the infrastructure if not miti­
gated. Current challenges and mitigation practices in current CO2-EOR/
storage technology have been discussed and future recommendations
are also provided. This holistic review would help gain insights into the
mechanisms, selection criteria, limitations, mitigation and optimiza­
tions when applying the sc-CO2-EOR/storage for unconventional reser­
voirs with heterogeneity and varying fluid properties.
Fig. 2. Schematic of the sc-CO2-crude oil interaction and EOR mechanisms in a conventional sandstone reservoir.
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Journal of CO2 Utilization 72 (2023) 102479
2. Improved oil and gas recovery with sc-CO2 fluid
2.1. Application of sc-CO2 in EOR methods
CO2 injection into the reservoir is widely seen as one of the promising
ways to increase the ultimate oil recovery from the reservoir while
simultaneously sequestering the atmospheric CO2 [37]. As stated earlier,
a reduction in crude oil viscosity, density and swelling (dissolution of
CO2) leads to an increased crude oil recovery due to increased mobility
and reduction in the mass of residual oil [3]. Various sc-CO2-crude oil
interaction mechanisms by which enhanced oil recovery takes place in a
conventional sandstone reservoir have been condensed into a schematic,
given in Fig. 2. Here, the crude oil-CO2 interaction is governed by
convective processes. For low permeability fractured shales and car­
bonates, it occurs through diffusion (discussed in Section 2.1.3.).
2.1.1. Minimum miscibility pressure (MMP)
CO2-EOR method is governed by MMP, the pressure at which the
injected gas attains dynamic miscibility at the reservoir temperature [3,
15,38,39]. The determination of this parameter is critical to the appli­
cation of CO2 injection. Numerous studies have developed empirical
correlations, while some have used neural network and genetic algo­
rithm based MMP determination methods [40–46]. A new method de­
termines the MMP using acoustically monitored separator, based on
disappearance of phase boundary between CO2-oil as the pressure is
increased at fixed temperature [47]. Authors studied CO2-crude oil
(39.6◦ API) MMP at 296.15 – 333.15 K. The process is fast, reliable, and
non-invasive, compared to other methods. Another technique uses rapid
pressure increase to investigate the phase behaviour of fluids and
determine the MMP [48]. The main principle behind this method relies
in the change of slope or critical ratio of pressure change to the reduced
volume of the measuring cell. Like the previous method, it is fast, cost
effective and reliable. In addition, this method can account for the
asphaltene precipitation.
If the reservoir pressure is below the MMP of the injected gas, then an
immiscible displacement ensues. For the reservoir pressure above MMP,
miscible displacement occurs through direct or multiple contact misci­
bility [3]. The miscible displacement occurs through three mechanisms:
first-contact, vaporizing and condensing gas drives [49]. In the first
contact miscibility, the injected gas mixes with the reservoir fluid in all
proportions, resulting in a single phase. Hydrocarbon gas mixtures are
first-contact miscible with crude oil. On the other hand, CO2, N2, and
flue gases are not first-contact miscible. Instead, they develop miscibility
upon multiple contacts (dynamic miscibility). The miscible displace­
ment has been observed to result in a greater oil recovery than the
S.K. Prasad et al.
immiscible process by about ~8–14% due to stronger CO2-oil in­
teractions [50]. When the reservoir pressure is above the MMP, dynamic
miscibility occurs in a transition zone where lighter and intermediate
crude oil fractions (C2-C6) are vaporized and mix with the injected gas
phase (natural and flue gas, N2, and CO2). Also, a part of the injected gas
dissolves into the reservoir fluid. Ungar et al. designed a microfluidic
chip based slim tube experiment consisting of medium and light crude
oils, two mixed hydrocarbon and CO2 gases at ~24–42 MPa and
~366–417 K [46]. The MMP for CO2-light crude oil system was deter­
mined to be ~16.4–30.6 MPa. In addition, flooding experiments were
carried out at pressures above and below MMP values. Author observed
a significant amount of residual oil left in the chip for injection pressures
less than MMP in contrast with no almost residual oil at higher injection
pressures.
The MMP depends on several factors, such as reservoir temperature,
permeability, composition and purity of the injected gas, and crude oil
[16,51–54]. Increasing temperature increases the MMP because higher
pressure is required for CO2 to be miscible with reservoir fluid due to
increased thermal energy. MMP also increases with the C1 and N2 con­
tent due to increased lighter fractions and molecules in the gas phase.
However, an increase in the intermediate molecules (C2-C6) leads to a
decrease in the MMP. For heavy oil reservoirs, the CO2-crude oil MMP is
much higher than the reservoir pressure, restricting the use of miscible
flooding [52]. Orr and Silva have concluded in their experiments that
hydrocarbon extraction from crude oil can be correlated to the differ­
ence in the molecular size of the injected gas and reservoir fluid [53].
Hawthorne et al. studied MMP of various injection fluids (CH4, C2H6,
C3H8, CO2, and produced gas with light crude oils (33.5–40.2◦ API) ob­
tained from Bakken and Cut Bank oilfield (USA) with varying reservoir
temperatures [16]. The crude oil with highest reservoir temperature had
highest MMP values for all injected fluid except produced gas. Addi­
tionally, all the studied crude oils had the highest CH4 MMP followed by
produced gas, CO2, C2H6, and C3H8. This reduced MMP for C3H8 is
dependent on its critical parameters (physical state) and density along
with reservoir temperature. Generally, fluids with a sharp density
change during transition between gas and liquid states exhibit a reduced
MMP. A lower fluid quantity was needed to achieve MMP at gas phase
compared to liquid and supercritical state, beneficial for low pressure
and low permeability reservoirs. Another EOR study has confirmed the
increased light crude oil (41◦ API) recoveries when hydrocarbon rich
gases were used for flooding (at 10.3–34.5 MPa, and 383.15 K)[54]. The
study pointed out considering the variations in the molar density of the
injected fluid with pressure for designing an efficient EOR project. Out of
all the fluid considered C3H8 had least narrow range of variation for
recovery of almost 80% of the hydrocarbons. Higher C2-C4 content in the
produced gas could yield even better recoveries compared to CO2. CH4
yield the least recovery of heavy hydrocarbon fractions, even at higher
pressure of 34.5 MPa compared to C2H6, C3H8, CO2, and produced gas.
As these gases recover mostly the lighter fractions, the remaining crude
oil will be richer in heavier hydrocarbons, which will become progres­
sively harder to recover.
High capillary pressure in shales and tight reservoirs impacts the
crude oil-gas phase behaviour through multicontact miscibility[55].
MMP doesn’t get affected by capillary pressure changes for binary sys­
tem as only MMP is through first contact miscibility. This first-contact
miscibility is dominant in ultralow permeability reservoirs (k < 200
nD) where diffusion dominates over advection. In contrast, capillary
pressure changes at larger scales (k > 200 nD), impact the multicontact
miscibility. Nano confined spaces (~10 nm) can change the phase
behaviour of the system due to high capillary pressures. However, as
confirmed in slim tube simulations and multiple mixing cells, this
change is very less (~5% of the MMP)[55]. This is possibly due to the
similarity between two phases at MMP, making the capillary pressure
effect insignificant, which is practically neglected. Similarly, Zheng et al.
(2021) in their investigations on the effect of nanopore confinement on
the CO2-hydrocarbons on tight reservoirs found out that pore
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Journal of CO2 Utilization 72 (2023) 102479
confinement has negligible effect on the bubble point pressure at pore
throat size greater than 100 nm[56]. For 5 nm pore throat, CO2-crude
oil MMP reduction by up to 16.2% was observed (~3.79 MPa differ­
ence). The reservoir heterogeneity along with miscibility also plays a
major role in oil recovery[57]. Two sandstone cores obtained from Berea
and Kirby formation with ~100 mD, φ = 18% and ~80 mD, φ = 23%
were used and the nC10 was used instead of crude oil. Immiscible
flooding was carried out in layered setup (MMP of CO2-C10 – 12.6 MPa
at 344 K). X-ray CT scanner was used to generate 3D tomography of
flooding. Authors observed a strong dependence of flow and oil recovery
on the heterogeneity of the core sample. Higher permeability layer
creates a channel for crossflow which resulted in a higher recovery
compared to case with no crossflow, probably due to increased dis­
placing fluid mobility and two-phase flow. But this was countered by
less contact between oil and CO2 due to same reason, leaving behind
crude oil in low permeability regions as confirmed by X-ray CT. In
addition, authors attributed the crossflow between layers to the capil­
lary forces leading to an incremental oil recovery by ~4.8%.
For accurate determination of the MMP of injected gas, contributions
from the abovementioned factors should be carefully evaluated. Neural
network based MMP determination methods are useful in situations with
limited data [38,58]. Table 1 lists selected literature regarding MMP
determination methods for CO2-EOR. From Table 1, it is evident that
neural network-based MMP models have performed better than corre­
lations with average absolute relative error (AARE) values < 4%
compared to ~3–16% for empirical correlations. As more and more
literature datasets are available to train and test the neural networks
model, the accuracy would increase compared to other estimating
methods. The above discussion shows that miscible displacement (above
MMP) is more efficient than immiscible. However, in some cases, the
MMP is greater than the reservoir pressure, preventing the use of
miscible flooding [15]. The H-block of X oilfield in southern Iraq is low
permeability and high-temperature reservoir located at ~6100–8200 ft
with a high salinity formation brine, far lower reservoir pressure than
CO2-crude oil MMP[59]. In other cases, even if the MMP is lower than
the reservoir pressure, miscible flooding cannot be implemented in the
reservoir due to constraints presented by the reservoir, fluid properties,
and techniques/equipments. In such cases, reducing the MMP is
required to increase the hydrocarbon recovery [15]. This reduction in
MMP of CO2-crude oil can be achieved through the use of surfactants
and miscible solvents. Further details on CO2-philic surfactants are given
in Section 3.1.
2.1.2. Miscible flooding and CO2-WAG method
Various authors have studied oil recovery through miscible
displacement in a lab-based setup. Multiple contact miscibility (MCM)
was observed to result in a nearly 100% recovery from a heterogeneous
etched-glass model using 1.5 pore volume (PV) of pure CO2 [60]. In the
presence of heterogeneity, an early breakthrough has been observed in
MCM flooding along with oil recovery in the range of 80–100% [60–63],
highlighting the efficiency of the process. Also, for MCM flooding,
soaking followed by water-alternating-gas (WAG) injection is preferred
for higher recovery due to enough time for increased oil-CO2 in­
teractions. However, the compositional changes in the oil after the
soaking in the MCM process may increase the oil’s viscosity, making it
harder to recover [50]. CO2 flooding uses various injection modes
depending on the crude oil and reservoir properties, such as continuous
CO2 gas with and without water and conventional and tapered WAG
injection. While a continuous gas injection scheme is suitable for light
and medium oils or water-wet reservoirs, water is injected to increase
the sweep efficiency in low permeability or with layered permeability
contrast reservoirs. A schematic of CO2 miscible flooding with WAG
injection is given in Fig. 3. WAG method is widely used in tertiary oil
recovery as it enhances the macroscopic and microscopic sweep effi­
ciency combined with the reduction in oil viscosity and breakthrough of
gas due to high mobility. A slug of gas is injected, followed by water
S.K. Prasad et al. Journal of CO2 Utilization 72 (2023) 102479

Table 1
Selected literature regarding the minimum miscibility pressure (MMP) for CO2 – EOR.
# MMP determination Valid prediction range Error (%) Remark
method
Injected fluid Tres (K) P (MPa) Crude oil composition

Vol. Int. MW (g/

(mol (mol mol)
%) %) C5+ / C7+

1. GA-ANN algorithm Pure CO2 305.3–383.1 6.9–28.2 5.4 – 6.9 – 180.6 – AARE − 2.32% Reliable for limited field
(Dehghani et al.38) 53.4 35.6 240.7 / - information
2. Analytical correlation Pure CO2 294.8 – 7.6 – 2–54 3– 154 – 259 / AAE − 11.9% Correlation for impure CO2
(Yuan et al.40) 394.3 34.5 43.5 142 – 319.7 flood valid upto 40 mol% C1
CO2 +C1 313.7 – 1.3 – 10.5 – 23.6 – - / 206–240 MAE – 9%
(10 − 20 mol%) 331.5 1.8a 16.5 24.4
3. Extrapolated vapour Pure CO2 305.1 – 0 – 25.6 - 5.48b - - For dead oil, Tres< 322 K, and
pressure method 322.1 fixed composition, add
(Orr and Jensen41) 1.4–2.1 MPa for dissolved gas
4. Empirical correlation CO2 + C1-4 / N2 / 305–390 6.5–34 0.14 – 13.6c 169.2 – Pure CO2 error Limited to N2 < 8%, Tcrit for C2
(Alston et al.42) H2S 302.5 7.2 – 8.3% and H2S; Most accurate
6.9–17.2 MPa
5. Empirical correlation CO2 + C1/N2/ 311 – 344 6.9 – 17.03 23.6 - Avg error – 8% Accurate for up to 55 mol%
(Sebastian et al.43) C4/separator gas 20.7 impurities
6. Empirical correlation Pure CO2 308.1 – 7.6–16.2 23 20–40 201 – Major effect of GOR variation
(Yellig and Metcalfe44) 362.1 on CO2-oil MMP for saturated
oils, Minor effect of C7+
variation
7. Optically quantitative Pure CO2 366.1 16.3 ◦
API - 34.8 – 41.4, GOR – 58 (Sm3/ 6.2% deviation from Optically quantitative approach
microfluidic method Sm3) slim tube results for T ≤ 417.1 K, P ≤ 35 MPa
(Ungar et al.46)
8. Empirical correlation Pure CO2, CO2 301.5 – 6.8 – *Weighted C2+ parameter (F) – AAD – 4.4–11.7% Limited to oils with given F
(Orr and Silva53) + C1–4 / H2S 395.9 29.6 0.768 – 2.466 (Pure CO2); 6.4 –
7.2% (Impure CO2)
9. ANN algorithm Pure CO2, CO2 - - 83 Datasets; 70% for training and AARE – 3.9% (Pure MMP sensitive to change in Tres,
(Chen et al.58) + C1-4 / N2 / H2S 30% for testing. CO2), 4.4% (Impure Intermediates in oil and gas
CO2) stream decrease MMP.
( )
a MMPpure
;
MMPimpure
b
C mol%;
(5+ )
Volatile ∑
c
; Tres – reservoir temperature; *F = 37 th
2 ki wiC2+ (Representative of crude oil composition; wi – weight fraction of i carbon number in C2+ fraction of
Intermediate
crude oil; ki - weighting factor); AARE (average absolute relative error); AAE (average absolute error); AAD (average absolute deviaton); MAE (maximum average
error).

which acts as a chase fluid, and this cycle of alternate injection of water
and gas is carried. The injected CO2 dissolves in the crude oil, leading to
swelling and viscosity reduction. In addition, the lower interfacial en­
ergy between gas-oil compared to water-oil helps to displace more crude
oil from pores inaccessible to water. A three-phase mixing zone is
developed as a result of which a large region of the reservoir is swept by
the injection [64]. Gas entrapment has also been proposed as one of the
accompanying mechanisms in the WAG injection [65]. During the
imbibition of water in the gas-saturated regions, some of the gas is
trapped in the pores, leading to the mobilization of residual oil that was
Fig. 3. Schematic of the water-alternating-gas (WAG) injection scheme with
CO2 miscible flooding.
not mobile in the presence of water. In reservoirs with a permeability
contrast or highly heterogeneous, WAG is particularly advantageous
because gas and water are less affected by the reservoir heterogeneity in
the three-phase mixing zone, which helps to alleviate the
non-favourable mobility ratio effect. Hoare and Coll investigated the
effect of reservoir heterogeneity on the WAG injection efficiency
through simulations on inputs based on Hutton oilfield located in the
North Sea and observed an incremental oil recovery of upto 10% [66]. In
conclusion, the WAG injection scheme reduces the gas consumption and
decrease water, making it an attractive method for highly heterogeneous
reservoirs. However, CO2-WAG EOR process suffers from what is known
as injectivity loss (especially in reservoirs with permeability less than
10 mD). A Sharp decline is observed for water injectivity after initial and
first cycle along with further losses in the WAG cycle[67]. WAG injec­
tivity is affected by several factors including mobility ratio, relative
permeability hysteresis, Wettability, gas entrapment, reservoir hetero­
geneity and anisotropy[68–70]. Injectivity loss issue is discussed in
detail in Section 7.1.
CO2-EOR projects generally have a target depth higher than ~800 m
at which supercritical conditions are naturally reached in the subsur­
face, ensuring a denser state of CO2 and minimizing the buoyancy effects
in the reservoir (which reduce the recovery efficiency) [71]. As
mentioned earlier, the low surface tension and lower viscosity enable
supercritical CO2 to have good dissolving properties. However, extrac­
tion properties depend on the molecular structure and polarity of the
crude oil fractions, according to Roopa and Dawe [72]. In their

5
S.K. Prasad et al.
lab-based study on heavy oil and tar sands, the recovery efficiency using
CO2 around its critical conditions was observed to be around 15–30%
from the packed porous medium. Also, the soaking period was suggested
to improve the recovery of heavier crude oil fraction. The authors also
suggested the application of supercritical CO2 for reservoirs with depth
and pressure of about ~1500 m and 20 MPa, which are unsuitable for
steam injection due to heat loss in the overburden. For tight sandstones
(~0.8–1 mD and porosity of ~13–14%), sc-CO2 flooding led to an
asphaltenic crude oil recovery of 45% as opposed to the huff-n-puff
method with 22% [73]. Authors have also concluded a need for
higher injection pressure to enhance the oil recovery. Also, the oil pro­
duction through the huff-n-puff method was reduced in comparison,
likely due to asphaltene precipitation and permeability reduction, which
will be discussed later. computational fluid dynamics (CFD) simulations
have enabled the pore scale flow visualization and sc-CO2 – oil in­
teractions. CO2 efficiently displaces the oil phase due to its higher sol­
ubility at supercritical conditions [74]. However, some of the CO2 upon
flooding will inevitably get trapped in the pore spaces. This phenome­
non has been studied through CFD simulations in 2D randomly packed
medium [75]. The authors included representative light (nC4-nC9) and
heavy (nC13-nC16) oils in their study at supercritical conditions
(20–40 MPa and 323–353 K). They observed that supercritical miscible
flooding is more effective in recovering lighter oil than the heavier due
to a wider displacement front. However, the viscous fingering in tests
with heavy oil reduced upon increasing the temperature.
2.1.3. CO2-EOR for unconventional liquid reservoirs (ULRs), carbonate
formations and transgressive reservoirs
(a) Unconventional liquid reservoirs (ULRs) such as shales are
characterized by permeability less than conventional reservoirs
by 100–1000 times. Additionally, the mixed wettability in these
reservoirs make oil recovery difficult. One estimate has put pri­
mary recovery from ULRs to only less than 10% [35]. Using a low
viscosity and miscible fluid (sc-CO2 and other hydrocarbon gases)
is attractive for EOR in such reservoirs due to easy penetration of
pore spaces already discussed earlier. EOR mechanism in frac­
tured shale reservoir can be divided into 4 distinct stages: Injec­
tion, soaking, late soaking, and production. In the injection
phase, the high-pressure injected CO2 flows through the
matrix-fracture interface without permeating into the matrix
which occurs in the soaking phase. A pressure gradient is created
when the swelled oil moves through fracture in addition to
possible wettability shift from oil-wet to water-wet from CO2
exposure. During late soaking, a molecular diffusion occurs due
to concentration gradient between oil and CO2. This process is
slow in ultra-low permeability reservoirs. Oil swelling and vis­
cosity reduction continue to extract oil from pores to fractures.
During production phase, as the pressure decreases to below
bubble point in the high permeable fractures, solution gas drive
helps move the oil towards the well.
sc-CO2 is an ideal fluid of choice for EOR fluid in ULR compared
to other fluids such C2H6, CH4, N2, and H2O as its attributes have
positive effect on oil recovery, which has also been discussed in
previous section. At supercritical conditions, only CO2 and C2H6
can reach liquid like density, and retain a higher diffusivity
(lower viscosity) out of other fluids mentioned here. Also, both of
these fluids induce significant asphaltene precipitation. C2H6 at­
tains miscibility with crude oil at lower pressure than sc-CO2 and
unlike CO2, does not forms acid. Its only downside of being
costliest of all the EOR fluids, whereas CO2 is significantly
cheaper with added benefit of storage. Various lab scale CO2
flooding experiments have been performed of core samples with
low to extremely low permeability values (1 mD and below, up to
0.0001 mD). A range of recovery factors have been reported:
from ~11–46% for low permeability cores (1 – 0.1 mD) to ~54%
6
Journal of CO2 Utilization 72 (2023) 102479
for tight and very tight cores (0.1 – 0.01 mD), and ~56 – 87% for
extremely tight cores (0.001 – 0.0001 mD). While the continuous
and huff-n-puff method have been used in low to very tight cores,
huff-n-puff injection with immersed core was preferred mode for
extremely tight cores [76–80]. continuous CO2 and multi-well
cyclic injection are feasible due to slow diffusion of CO2 into
shale matrix and unrealistic expectation of injection one core end
and production from the other. Immersed core huff-n-puff modes
with unconfined and immersed core allows gas flow around the
core for maximum surface area contact, making it most efficient
method. Other factors such as injection pressure, soak time, and
lithology also play a vital role in oil extraction from ULRs. Oil
recovery has been found to increase for injection pressure above
MMP, the increase however varies significantly. Increasing the
soak increases the recovery upto a certain limit, beyond which a
financially diminishing returns are met. Inclusion of CO2-WAG
injection technique with 0.125 PV water slug has been observed
to yield an incremental recovery of 30% over continuous CO2
injection attributed to controlled mobility and reduced break­
through[81]. Microfluidic huff-n-puff experiments have been
carried out in a fractured glass model at 10 MPa and 323.15 K
with CO2, N2, water and nC10 as oil phase[82]. Connected frac­
tures yielded higher recovery than dead end fractures at 90% and
60%, respectively for CO2. Nanofluidic devices (10 µD perme­
ability and 14% porosity) have also been to simulate ULRs in CO2
huff-n-puff injection experiments[83]. Light crude oil was used
and flooding was done at 323 K at pressure upto 11 MPa. At low
injection pressures, gas solubility was reduced due to nano­
confinement. In contrast gas breakouts and oil recovery was
observed at faster depressurization. Simulation studies for un­
conventional reservoirs include fracture-matrix coupled flow
equations along with dual porosity models to better capture the
complexity[35].
The effect of CO2-rock-brine interaction with shales can have
complex effect on the permeability owing to mineralogy. In some
cases, permeability has been found to be increased due to disso­
lution, exaggerated in presence of water [29,84–86]. In other
cases, permeability reduction in shales has been observed due to
CO2 adsorption. Drastic permeability reductions have been
observed in vertical directions compared to minor (10%) re­
ductions in parallel bedding [87,88].
(b) Carbonates are characterized by strong heterogeneity, fractures
and poor pore connectivity, leading to gas breakthroughs and low
oil recovery during CO2-EOR[89]. The diffusion dominated
CO2-EOR in carbonates is similar to fractured low permeability
reservoirs due to presence of fractures and vugs can be divided
into major steps[89,90]: direct flow (fractures and vugs), flow
under pressure gradient and oil swelling, crude oil viscosity
reduction and expansion, and fracture-matrix hydrocarbon con­
centration equilibrium and production. Yu and Amro have pro­
posed a mechanism of oil recovery through dual porosity
carbonate reservoirs[91]. In the first stage the CO2 displaces
crude oil from macropore system (fractures) followed by
permeability governed diffusion into matrix in the second stage.
A higher permeability understandably reduces the diffusion. The
typically diffusion coefficients associated with carbonate reser­
voirs are similar to conventional oil reservoirs (9.4 ×10–10 to
9.4 ×10–7)[92,93]. During CO2 injection Minerals found in the
carbonate reservoirs such as dolomite (CaMg(CO3)2), calcite
(CaCO3), and anhydrite (CaSO4) react with CO2[94]. Interaction
with CO2 can lead to mineral dissolution and ultimately,
compaction, reducing porosity and permeability.
Khather et al. carried out sc-CO2 flooding of dolomite and
limestone core samples saturated with light crude oil (38◦ API,
0.0754 wt%) at 338.15 K and 14 MPa and an incremental re­
covery over water flooding was observed in the range of 11–45%
S.K. Prasad et al.
[94]. A reduction in porosity and permeability was observed by
up to ~58.3% and ~25.2%, respectively apart from the miner­
alogical changes. Asphaltene content in the recovered oil had also
decreased ~39% from initial content, indicating precipitation
during the flooding process. These alterations are more severe for
increased contact time. Apart from complex recovery mechanism
and asphaltene precipitation, CO2-EOR pose other issues in car­
bonates including viscous fingering, corrosion, injectivity loss.
These issues are discussed in Section 7.1.
(c) Transgressive sandstone-carbonate reservoirs present chal­
lenges especially to CO2/WAG injection due to their interbedded
nature with varying petrophysical properties[95]. An example is
S1A reservoir in upper Qishn formation in Yemen with reservoir
pay zone of 1.5–7.6, 18–28% porosity. AlRassas et al. developed a
geo-cellular model of S1A reservoir utilizing geophysical,
geological, and petrophysical data[95]. The static model had
initial reservoir temperature and pressure of 358.7 K and
12.8 MPa with 30% and 27% porosity and 999.9 and 948.5 mD
permeability for sandstone and carbonate layer respectively.
Authors included CO2-WAG injection scheme in the simulation
study to investigate their effect on the CO2-EOR coupled with the
CO2 storage. 21-year field production data were utilized for his­
tory matching and constraining of the reservoir model. The re­
sults confirmed the CO2 trapping mechanism of CO2-WAG
process to be much more than continuous CO2 injection. Also, a
WAG ratio of 2:1 with 43.8% residual trapping was observed to
yield higher recovery factor of 32% compared to the 1:1 WAG
ratio (29%). Reservoir anisotropy ratio (kv/kh) has a strong effect
on the CO2 storage capacity (solubility trapping and residual
trapping of over 12% and 14%, respectively). These findings
indeed provide valuable insights for improved oil recovery and
storage from a mixed lithology reservoir.
2.1.4. Other supercritical fluids in EOR
Besides CO2, water and N2 have also been used in a supercritical state
for enhanced oil recovery studies [96–98]. However, the recovery effi­
ciency with sc-N2 was observed to be lower than the sc-CO2 (8.7% and
15.8%, respectively) due to lower swelling and a significant increase in
the bubble point pressure, not suggested for EOR processes [98]. Su­
percritical water flooding (SCWF) is suited to reduce the viscosity of
heavy crude oil due. In addition, it overcomes the poor performance of
hot water flooding due to heat loss to overburden and surrounds porous
medium. The critical point of water is around 22.1 MPa, and 674.15 K.
Supercritical water has also been used in many chemical industry pro­
cesses such as solvent/catalyst/reactants. Also, it can fully dissolve the
non-polar crude oil fractions and maintain a higher solubility for polar
crude oil fractions or ionic compounds [96]. One advantage of super­
critical water is that it acts as a hydrogen donor, which has implications
for solvency (inhibition of coke formation) and heavy crude oil upgra­
dation [99]. An experiment study regarding the treatment of oil sand
bitumen by supercritical water concluded that the residue obtained after
the treatment had lower molecular weight distribution and related
structural parameters due to the degradation of the molecular structures
[100]. The authors also suggested using supercritical water to disperse
the heavy crude oil fractions. To demonstrate the feasibility of super­
critical water flooding (SCWF) for enhanced heavy oil recovery, a sand
pack was first saturated with extra heavy oil from the Tuha oilfield,
China [96]. The boundary conditions of the reactor were kept adiabatic
to minimize the heat unbalance. The oil recovery using SCWF had ~97%
efficiency with operating conditions of 25 MPa and 673.15 K, compared
to ~80% for steam and ~74% for hot water flooding. This recovery was
achieved with only 1.5 PV injection, suggesting the advantage of this
method. The slightly higher recovery for steam flooding at PV< 1.5 was
attributed due to the higher enthalpy of steam at 2 MPa and 623.15 K,
compared to SCWF at 25 MPa and 673.15 K. However, during the initial
stages, when there could be coke formation in the reservoir due to the
7
Journal of CO2 Utilization 72 (2023) 102479
low water-heavy oil ratio, the recovery cannot reach 100%.
A recent development uses a supercritical multithermal fluid
(SCMTF), composed of N2, H2O, and CO2, to develop deep offshore
heavy oil reservoirs [101]. SCMTF has been produced by gasification
and combustion of organic liquids comprised of sewage, diesel, and
natural gas in the air and SCW environment at ~647–973 K and
22.1–30 MPa [102]. Authors investigated the feasibility of SCMTF
flooding, and a mechanism of heavy oil (ρ of 977 kg/m3 and 3.52 wt%
asphaltene) recovery from a sand pack was also proposed. Three ex­
periments involving sc-CO2 and sc-N2 in a 1:5 molar ratio were carried
out at ~673–713 K and 23–25 MPa, respectively. The oil recovery was
observed to be ~85–94% of OOIP, incrementally over the steam flood­
ing alone by ~25–34%. The recovery was attributed to the combined
action of density, viscosity, and molecular weight reduction of crude
with enhanced swelling, reduced interfacial tension, dealkylation, and
extraction of lighter fractions. Injection at higher pressures was rec­
ommended to maximize the heavy oil recovery. However, higher tem­
perature injection should be carefully evaluated for coke deposition and
formation damage problems. In addition, a moderate amount of sc-CO2
and sc-N2 mixture in the SCMTF flooding leads to optimum recovery,
and an excess amount leads to quicker front advancement and break­
through. Another study has investigated the generation and feasibility of
SCMTF flooding in detail [103]. The authors conducted flooding at
~673–773 K and 23–25 MPa in a sand pack saturated with crude oil
(after reducing to irreversible water saturation). The crude oil
displacement efficiency of the SCMTF reached up to ~90%, with an
optimal oil-to-water ratio of 10% during the SCMTF generation. SCMTF
flooding has also been numerically modelled to investigate the effect of
injection parameters on the oil recovery at ~653 K and 23 MPa [104].
The average porosity and permeability were set at 24.44% and 1096 mD
in a grid size of 30 × 30 m and varying thickness from 0.25 to 2.19 m.
The SCMTF flooding showed a higher recovery than steam and SCWF
(up to 29.6% and 11.09%, respectively) throughout the range of injected
PV (0− 4). The oil and water content in the reactants during the SCMTF
generation plays a vital role in its composition and enthalpy, thereby
affecting its application for the flooding process [103]. Higher oil con­
tent in the reactant would generate higher gas in the process of SCMTF
generation, which would increase the cost of production and lead to a
lower recovery than the lower oil content case. Also, it should be noted
that lower oil content would lead to less gas generation and hence lower
the enthalpy of the SCMTF. A higher enthalpy SCMTF is desirable since
it has more energy. Thus, there should be an optimal composition of
SCMTF for the flooding results to be successful. Table 2 provides the
details of EOR experimental studies carried out with CO2 and other
supercritical fluids. Besides the above studies, supercritical fluids and
other methods have been explored to enhance oil recovery. These are
discussed below.
2.2. sc-CO2 for enhanced shale gas production (shale gas fracturing)
Shale gas is a cleaner energy source than coal and natural gas and
emits less than half of the CO2 emission of coal [105]. According to an
article by the US energy information administration, the technically
recoverable shale gas is ~7922 trillion cubic feet (tcf), making it an
attractive prospect for hydrocarbon extract to fulfil energy demands
[106]. Shale gas, along with shale oil, is an unconventional resource
found in the lower permeability reservoir (1 µD) [107]. Hydraulic
fracturing is used to improve the recovery from these tight reservoirs. A
high-pressure fluid composed of water and other chemicals is injected
into the formation resulting in fracture formation and increased con­
ductivity. The fracture stays open by the use of a proppant, generally
sand. Various fluids have been used, viz., liquid, foam, and gas based.
Liquid-based fracking fluids have added chemicals, some of which might
be toxic and need proper disposal to avoid contamination. sc-CO2, with
its liquid-like density, very low viscosity, and no surface tension and
capillary force, could be vital for its role in shale gas fracturing, which
S.K. Prasad et al. Journal of CO2 Utilization 72 (2023) 102479

Table 2
Selected literature of EOR experiments carried out using CO2 and other supercritical fluids.
# Lithology Crude oil EOR experimental details Ref
no
Type φ (%) /k (mD) ρo (g/cc) / µo Injected Oil- fluid Injection parameters Results
(cP) fluid MMP (MPa)

1. Sandstone core 12.03 / ~4.2 0.897a / 1.9 CO2 29.6 1.2 PVI, 381.7 K Miscible flooding, 5.4% incremental oil 15
(318.7 K) recovery over 3.58% for waterflooding
2. Low φ, low k 13.5–20.2 / CO2 25.1 – 36.2 ~6.5 – 30 MPa, Immiscible flooding, increased CO2 33
cores 8–985 (343.2 – 343.2 – 403.2 K diffusion with P, T, oil saturation
403.2 K)
3. Etched glass 1–15%b /- 0.813 / 3.3 CO2 ~8 Up to 1.5 PVI, 8.3 MPa, Miscible flooding, 80–100% oil recovery 60
surface (305.4 K) 298.2 K
4. Fractured 46 – 49% / nC10 Liq. CO2 5.4 2.2 – 12 PVI, 2–12 mL/ 79 – 100% oil recovery 61
chalk 2.7–2247 (293.2 K) min,
9 MPa, 293.2 K
5. Sandstone 17% / 176 nC10 CO2 14.24 2 PVI, ~11 – 15.9 MPa, 8.1 – 92% oil recovery 62
cores (353.2 K) 353.2 K
6. Glass bead 38 − 42 / IPA + water IPA - Up to 3.5 PVI, 0.3 – 6 mL/ FCM, vap/ condensing drive, 50 – 100% 63
pack 10–25 + C6H10 min oil recovery
7. Epoxy 26 – 35 / 0.862 / 4.2 CO2 23 0.68 – 2.52 PVI 5 – 95% oil recovery; 8.6 – 14% 64
cemented ~4.8 – 1247.9 (382.2 K) 0.5 mL/min, incremental for FCM over IM
cores (PC – 1 − 154) 15 – 30 MPa
8. Sandstone ~18 / 0.847–0.858 / CO2 16.9 0.05 – 0.1 PVI gas and 20% incremental oil recovery over 65
cores 25 – 300 1 (WAG) (328.2 K) water slug, 7.4 MPa, wateflooding
328.2 K
9. Tight 13.5 – 14.4 / 0.878 – 0.882 sc-CO2 - 1 PVI, 0.1 mL/min, 12 – Upto 20% oil recovery for 4 cycles 73
sandstone 0.832 – 1.034 / 32 MPa, 348.2 K
4.23–20
10. Sand pack 49.7 / 3360 0.977 / 50879 SCWF - So- 92.4%, 25 MPa, ~97.1% oil recovery, µo reduction 36.9% 96
673.2 K
11. Carbonate 16.9–17.3 / 31.2◦ API / sc-CO2 / - Soi- 67 – 70%, 14.6, 8.7% incremental oil recoveries for 98
2.45–7.18 0.74 sc-N2 12.7 MPa, 373.2 K sc-CO2, sc-N2 over 45–46.1%
(waterflooding)
12. Sand pack 54.4 – 56.2 / 0.977 / 6230 SCMTF - Soi- ~94 – 96%, 85.2 – 90.4% oil recovery for SCW:(sc- 102
4432–4519 23 – 25 MPa, CO2 + sc-N2) molar ratio - 5:1
673.2 – 713.2 K
a
ρC7+;
b
Area porosity; φ – Porosity; k- permeability; ρo, µo – crude oil density and viscosity; PV- pore volumes injected; IPA- Isopropyl alcohol; PC – Permeability contrast;
FCM -First contact miscible; IM- immiscible; SCWF – Supercritical water flooding; SCMTF – Supercritical multithermal fluid.

has been investigated by various authors [108–110]. A schematic for
shale gas fracturing using CO2 is given in Fig. 4a. sc-CO2 allows for
higher penetration and faster clean-up due to higher mobility, leaves the
proppant inside the fractures upon vaporization and does not lead to
clay swelling phenomenon, which is associated with the water-based
fluids [108]. sc-CO2 and water, with different physical properties, will
have different fracturing fluid properties. An experimental investigation
into the fracturing in granite with different fluids (sc-CO2, liquid CO2,
water and oil) concluded that the formation breakdown pressure
increased with the viscosity [110]. Also, the low viscosity of sc-CO2
(with the lowest breakdown pressure of ~9–10 MPa) was observed to
form three-dimensional sinuous fractures with secondary branches,
making it appropriate for shale gas recovery. Another study regarding
fracture propagation in shale using sc-CO2, liquid CO2 and water
observed a reduction in fracture initiation pressure by almost ~50%
compared to water with more complex networking (irregular cracks),
resulting in increased conductivity [111]. Liu et al. made a geo­
mechanical model for investigating rock and gas interaction during
sc-CO2-based fracturing in a shale specimen [112]. Authors observed a
wider and more complex fracture in the case of sc-CO2, probably due to
lower dynamic viscosity and higher adsorption, eventually leading to
more damage and higher cracks. The fracture initiation pressure,
propagation, and characteristics will, of course, depends on the bedding
or pay zone orientation, reservoir stress and temperature. An experiment
was conducted to investigate the effect of anisotropy of the shale core on
the hydraulic and sc-CO2 based fracturing [113]. The fracturing was
done through holes drilled at different angles from the horizontal plane
(0◦ to 90◦ ). Core was loaded at an axial load of 10 MPa and confining
pressure of 20 MPa. The fracture initiation pressure decreased with
increased orientation for freshwater and sc-CO2. However, the
breakdown pressure for later remained lower than fresh water
throughout the orientation range (a decrease from ~21–15 MPa from
0–90◦ ). On the other hand, the higher reservoir temperature reduces the
viscosity of sc-CO2, resulting in an enhanced fracturing [11]. Feng et al.
studied the mechanical characteristics and failure mechanisms of shale
upon exposure to sc-CO2 [114]. The splitting modulus (E) and adsorbed
energy (U) of the shale samples were reduced by 22% and 50% upon
exposure to sc-CO2 resulting in a tensile and shear failure. Upon XRD,
SRF, and SEM analysis it was pores and fissure were observed to have
been developed which gradually intensified with time due to increasing
adsorption of sc-CO2. This could increase the conductivity and lead to
enhanced recovery from shale. Another vital aspect of developing shale
gas reservoirs with CO2 which impacts the CO2 storage is CO2 and CH4
adsorption potential. This has been discussed in detail in Section 4.2.
However, certain limitations are involved in sc-CO2 as a fracturing
fluid, such as proppant carrying ability. Foam-based fracking fluids have
several benefits. They reduce water consumption significantly, have a
high proppant carrying and suspending capacity, and lead to reduced
fluid loss and formation damage. CO2 and N2 foams are generally used
for hydraulic fracturing [115]. N2 foam can be generated at a lower
pressure than CO2 foam but has the drawback of being more
energy-intensive due to higher surface pumping pressure [11]. As dis­
cussed earlier, adding chemicals to generate foam could have a potential
environmental impact, similar to the water-based fracturing fluid.
2.3. Application of sc-CO2 fluid in drilling operations
The feasibility of using supercritical fluids in drilling operations was
first investigated by Kolle [116]. sc-CO2 was explored for its use in
jet-assisted coiled tubing drilling of ultrashort lateral completions. A

8
S.K. Prasad et al.
Fig. 4. A schematic of (a) sc-CO2 based shale gas fracturing; and (b) sc-CO2
based underbalanced drilling operations.
CO2 model was used to provide various drilling-related parameters. The
author observed that the threshold pressure of erosion in granite and
shale using sc-CO2 was reduced by almost ~33% and 56% compared to
water, respectively. The specific energy of erosion (SE) also showed an
even more significant reduction of ~58% and 97%, respectively. The
reduced threshold pressure for erosion for sc-CO2 is probably due to
different physical properties than water, such as lower viscosity and
higher adsorption. Upon observing the encouraging results from this
study, it was decided to conduct a feasibility study for the sc-CO2
application in deep underbalanced drilling operations through compu­
tational modelling to predict the pressure, density and viscosity in the
annulus with depth [117]. Simulation results concluded that a higher
density of sc-CO2 helped maintain the necessary torque for the down­
hole motor for the drilling to continue. Also, the sc-CO2 gets converted
into the gaseous phase, maintaining an underbalanced condition. It was
ultimately concluded that the sc-CO2 can be helpful in underbalanced
situations and turbulent annular flow. A schematic of sc-CO2 based
underbalanced drilling is given in Fig. 4b. Numerous other studies have
concluded the advantage of using sc-CO2 over water for drilling. The
findings include the maintenance of underbalanced conditions and
higher depth at the same pressure compared to water [118,119]. For
situations like turbulent flow, increased borehole inclination and cutting
size, transporting cuttings by sc-CO2 alone would be difficult, requiring
additives to improve its viscosity (see Section 3).
3. Mobility control of sc-CO2 fluid
Gas-based methods for enhanced oil recovery have the disadvantage
9
Journal of CO2 Utilization 72 (2023) 102479
of gravity override and high mobility, which lower the oil recovery ef­
ficiency. For supercritical CO2, higher gravity differences with reservoir
fluids will lead to undesirable segregation of the injected gas and
reservoir fluid. Increased mobility of the injected gas will lead to
fingering effects and breakthroughs, reducing the recovery. This section
discusses the methods and chemicals used to control injected fluid
mobility, increasing sweep efficiency and hydrocarbon recovery.
3.1. sc-CO2 mobility control through the use of entrainers, surfactants,
and nanoparticles
Mobility control of supercritical fluids by co-solvents has been
explored by Llave et al. [120]. An entrainer or a co-solvent addition
increases the solubility of crude oil components in a CO2 gas phase,
increasing its density and viscosity in addition to improving its hydro­
carbon extraction capabilities. Authors selected higher molecular
weight 2-ethylhexanol, n-decanol, a long chain ethoxylated alcohol, and
isooctane. Experiments were performed at ~313–323 K and
~5.5–22.1 MPa. Results showed a limited sc-CO2 viscosity increase and
minor density improvements due to low solubility in alcohols and higher
molecular weight hydrocarbon. For 2-Ethylhexanol, although a signifi­
cant increase in viscosity was achieved (up to ~1565 cP) at ~0.44 mol
fraction, a limited density increase was observed. These results indicate
a requirement for a higher concentration of entrainers, making en­
trainers economically unfeasible.
Foam flooding can overcome the mobility issues associated with CO2
and considerably increase sweep efficiency [121]. Foam means a gas
dispersed in a liquid medium. It is characterized by foam quality which
essentially means gas content (% (v/v)). Foam with quality exceeding
90% is known as dry foam. Nanoparticle-assisted CO2 foam flooding has
been investigated for enhanced oil recovery from etched glass micro­
fluidic setup [122]. Crude oils with API gravities ranging from 14◦ to 37◦
were used, and commercially available silica-coated nanoparticles were
used to stabilize the foam. The generated foam displayed excellent sta­
bility in the microporous media for the duration of flooding. It resulted
in an additional 15% oil recovery compared to only CO2 flooding,
possibly aided by the wettability alterations in the presence of nano­
particles. Strong foam generation is a prerequisite for foam flooding as it
is thermodynamically unstable and would break down in reservoir
conditions. Various chemicals can be added to generate the foam, such
as polymers (e.g., PAM, HAPAM) and nanoparticles. Some researchers
have also considered the usage of N2 and CO2 mixture foam in their
lab-scale studies for enhanced oil recovery [123]. Authors proposed that
supercritical CO2 is unable to generate strong foam probably due to less
gas available at supercritical conditions since the density is close to
liquid at these conditions, reducing the foam strength. Studies have
attributed the weakening CO2 foam to high mobility compared to N2
foam due to degradation at increased pressures, leading to poor sweep
efficiency [123,124]. The addition of N2 creates more gas phase in the
system since its density is almost one-fourth that of supercritical CO2
(~10 MPa and 323 K), thus enabling foam generation. According to Du
et al.[125], this difference in the behaviour of CO2 and N2 foams is
attributed to the higher solubility of CO2 in water. An experimental
study to investigate the performance of CO2/N2 mixed foam flooding in
a Barea sandstone core at ~12.4 MPa and 363 K observed a 62.5% in­
crease in the intermediate crude oil normalized recovery over pure CO2
foam [121]. The apparent viscosity of the CO2/N2 mixed foam is higher,
as indicated by the higher nominal pressure drop, compared to CO2
foam, thus aiding the sweep efficiency.
Various surfactants used to control the mobility of sc-CO2 are
condensed into a schematic form in Fig. 5 and listed in Table 3. These
range from common ionic to custom surfactants discussed below. The
various ionic surfactants can be anionic, cationic, zwitterion, and non-
ionic [126–131]. The first effort to find a suitable surfactant was made
by Bernard and Holm [132]. However, as sc-CO2 dissolves surfactants
poorly due to low dielectric constant, a lot of effort has been put into
S.K. Prasad et al. Journal of CO2 Utilization 72 (2023) 102479

phenyl ethoxylated alcohols (SURFONIC® L12–6, TDA-9, and N-100,

respectively. See Table 3)[139]. These surfactants have a solubility of
~1 wt% in CO2 at ~13.8 – 34.5 MPa for 298.15–373.15 K). Authors
observed an incremental oil recovery of 1–4% with branched alkyl
ethoxylate over 71% for pure CO2 owing to wettability alteration (in­
termediate to water-wet) rather than minor change in CO2-crude oil IFT.
A similar study observed a 75% oil recovery for branched phenol
ethoxylate SURFONIC® N-100[140]. The use of foaming agents controls
the mobility of CO2 in supercritical conditions, but they have limitations
and disadvantages in certain conditions. The requirement of a high
quantity of foam (up to ~80% of the HC pore volume in place) and
controlling its propagation inside the reservoir over long distances are
some of the significant challenges [18,141]. For high temperatures and
extreme salinity conditions such as those found in the reservoir in the
Middle East (~120 ◦ C and up to 220,000 ppm salinity), the surfactant
should have a high cloud point (the temperature above which the
generated foam is stable) [142].
Apart from the above, various authors have also used custom-made
surfactants in CO2 solubility and viscosity enhancement studies. These
include fluorinated (fluoroalkyl AOT analogs, double tail hybrid,),
structurally modified AOT analogs, siloxanes, and hydrocarbon surfac­
Fig. 5. Various surfactant categories used for sc-CO2 mobility control in
enhanced oil recovery operations.
tants [143–148]. The functional analogs of alkyl anionic and non-ionic
surfactants generated by silicone and CO2 phobic chains were found to
be miscible with CO2 at ~27.6–41.4 MPa and ~338 K in a study con­
selecting surfactants suitable for this role [126]. Typically, anionic
ducted by Fink and Beckman [149]. The increased solubility and vis­
surfactants are used in CO2 foam flooding for sandstone formations due
cosity depend on the shape of micelles, including rod-shaped and
to the negatively charged nature of the sandstone surface, leading to less
spherical. Both siloxane and fluoro-based surfactants suffer from envi­
adsorption [130]. CO2 - brine emulsion is more stable in the presence of
ronmental effects and high costs. Hydrocarbon surfactants promise to
water-soluble non-ionic alkylphenol ethoxylates than alkyl ethoxylates,
overcome these disadvantages. In addition, these have also been studied
probably due to π- π interactions of the benzene rings, enhancing the
in combination with short-chain alcohols including 1-pentanol as a
stacking at the CO2 – brine interface resulting in the foam stability
co-solvent [150]. Eastoe et al. used structurally modified AOT analogs
[133]. For carbonate formations, cationic or non-ionic surfactants are
with vinyl acetate, carbonyl, and tert-butyl functional groups based on
suitable for CO2 foam generation in due to minimized adsorption owing
enhanced solubility as exhibited by simulation studies showing strong
to electrostatic interactions as carbonates have positively charged sur­
aggregation, compared to typical surfactants [144].
face [134,135]. In addition, ethoxylated amines are beneficial because
of the flexibility of high cloud point and interfacial activity at high
3.2. Oligomers, polymers, and in-situ polymerization for sc-CO2
pressure, temp, and salinity conditions (up to ~393 K, ~182 g/L of
thickening
NaCl, and 22.7 MPa) as well as the non-ionic form for the surfactant
injection process. These surfactants are switchable and non-ionic in the
In-situ polymerization is another way to increase CO2 viscosity. It
dry state to cationic in the aqueous phase [136]. They do so by the
utilizes free radical polymerization, which can be done at typical
protonation from the carbonic acid due to the dissolution of CO2 in the
reservoir conditions and does not require water or other additives. Terry
formation brine. Some commercially available anionic and amphoteric
et al. used three olefin monomers (1-octene, ethylene, and 1-decene)
surfactants have been examined in a high temperature and saline envi­
based on CO2 solubility and conducted the experiments at pressures
ronment (393 K, 1.89 M monovalent NaCl, 0.32 M divalent CaCl2 and
upto ~13 MPa and ~342–350 K [151]. Though authors observed the
MgCl2) [137]. The generated foam is viscous and stabilized by strong
polymerization for ethylene and octane, the viscosity increase was not
solvation of the surfactant head and tail by the brine and CO2, respec­
observed, the reason being low solubility due to the absence of side
tively, which reduces the interfacial tension. At higher temperatures, the
chains to support the suspension. CO2-soluble organic titanates, poly­
foam stability reduces due to the surfactant becoming less CO2-philic. In
merized with an organic substrate, have produced satisfactory results
addition, alcohol can also be used to dissolve surfactants in sc-CO2
upon field trials with a 300% increase in gas production. The concen­
owing to arranging between the surfactant tails and reducing the micelle
tration of this organic fluid was 2%, and the viscosity at ambient tem­
interactions and the interfacial tension [126,138]. Ethanol has been
perature was observed to be around 18 cP [152]. Numerous authors
used to enhance the dielectric constant and the polarizability of sc-CO2,
have used thickeners to increase the injected gas-phase viscosity [18].
hence the dissolution of sodium bis(2-ethylhexyl) sulfosuccinate (AOT),
These, in low concentrations, could increase the viscosity of the injected
an anionic surfactant. Also additionally, the increased pressure has been
gas phase to almost that of the crude oil, improving the sweep efficiency
found to improve the dissolution for surfactants though limited. This
considerably. An increase in the displacing fluid viscosity leads to
increased dissolution of AOT in sc-CO2 could be useful for foam flooding
delayed breakthrough, increased sweep efficiency, and reduced gas-oil
in tight (low permeability) reservoirs. Zwitterionic surfactant such as
ratio (GOR). This observation is supported by the results of a simula­
alkyl betaines with low adsorption on the surface could be used for
tion study in CSM-GEM software involving heterogeneous formation by
sandstone and carbonate formation, depending on their molecular
Hinai et al. [153], where an increase in the viscosity of CO2 by 0.1, 0.16,
structure. The critical areas to focus on while applying the supercritical
and 0.25 cP enhanced the ultimate oil recoveries by ~4.4%, 6.5%, and
CO2 foam flooding include the foam pressure gradient, the flow
9%, respectively for 20 years. In addition, an increased recovery of up to
behaviour, especially in tight reservoirs, and the injection plan [130].
4% was observed for natural gas, compared to pure CO2. However, the
Commercially available non-ionic surfactants have been used in
dissolution of light hydrocarbon gases (C2-C4) produced higher oil re­
CO2-EOR studies involving shale cores[139,140]. Burrows et al. per­
coveries due to more significant swelling and viscosity reduction.
formed huff-n-puff sc-CO2 flooding through Eagle Ford and Mancos
A look at the literature reveals various classes of polymers and
shale cores, with and without linear/branched alkyl and branched
oligomers being studied for CO2 viscosity enhancements, including

10
S.K. Prasad et al. Journal of CO2 Utilization 72 (2023) 102479

Table 3
Selected list of surfactants commonly used for sc-CO2 mobility control.
# Surfactants Molecular weight Experimental parameters Results

Concentration Pressure (MPa) and

Temperature (K)

Anionic surfactants (suitable for sandstone formations)

1. Sodium bis(2-ethylhexyl) sulfosuccinate 444.46 g/mol 0.5–3.5 wt% 20 MPa and 313.15 K Increased CO2 foam viscosity upto 0.35 cP for 1.5 wt%
(AOT)126 AOT + 20 wt% ethanol; in situ foam generation by
dissolved AOT
2. α-olefin sufonates131 324 g/mol 0.5 wt% 323.15 K, ΔPdrop upto Increased foam half-life (5–8 times) with Si
100 psi nanoparticles (0.5–1 wt%), stable foam with 1 wt%
NaCl, oil recovery up to ~49% with nanoparticles
Cationic surfactants (suitable for carbonate formations and high temperatures and salinity)
3. Quaternary ammonium surfactants134 ~220–320 g/mol Upto 1 wt% Up to 23 MPa and 393 K CO2 foam stable at high salinity (22 wt%), increased
foam viscosity up to 10 cP at 0.6 wt%
4. Duomeen TTM (C16‑18 N(CH3)C3N(CH3)2 - 0.05–1 wt% 23.4 MPa and 393.5 K Increased CO2 foam viscosity (~45 cP) at 1 wt% in a
(TTM))130 limestone core flood (4 ft/day)
Non-ionic surfactants (suitable for carbonate and shale formations)
5. Ethoxylated surfactant (C12− 14 E22)128 - 0.05–0.2 wt% 0.1 MPa and 353.15 K Less adsorption at carbonate surface.
6. Linear/branched alkylphenol and alkyl - Up to 0.1 wt% ~9 MPa and 298.15 K Stabilized CO2-brine emulsion (5 wt% NaCl)
ethoxylates133
7. Linear/branched alkyl and branched ~428, 463 Upto 1 wt% ~13.8 – 34.5 MPa for Enhanced solubility, ~1–4% incremental recovery of sc-
phenyl ethoxylated alcohols139,140 298.15–373.15 K CO2 Flooding (27.6 MPa and 353.15 K.
Zwitterionic surfactants (suitable for both sandstones and carbonate formations)
8. Cetyl betaine129 328.3 g/mol 0.1–2 wt% Up to 423.15 K and Thermally stable at 408.15 K for 30 days, increased
23.4 MPa foam viscosity up to > 15 cP at ~22 wt% salinity and
TDS at 423.15 K
Switchable surfactants (suitable for carbonate formations with high temperatures and salinity)
9. Ethoxylated cocoamine surfactants136 - 0.2–1 wt% 23.4 MPa and 393.15 K Stabilized CO2 foam at 182 g/L salinity, increased foam
viscosity up to ~15 cP at 393.15 K for 1 wt%
10. N-erucamidopropyl-N,N- - 12 mM Ambient/room conditions Switchable CO2 foam at room temperature without any
dimethylammonium bicarbonate stabilizers
(UC22AMPM.H+)127
Fluorinated/semifluorinated surfactants
11. Fluoroalkyl AOT analog –(bis - 0.01–0.05 wt% 313.15 K Solubility in sc-CO2 at moderate pressures
(dodecafluoroheptyl)sodium
sulfofumarate)146
12. Hybrid fluorinated surfactants (F7H4)147 - 4.4 wt% 38 MPa and 313.15 K Enhanced solubility and sc-CO2 viscosity upto ~2 times
Siloxane based surfactants
13. PDMS based block copolymers148 ~5100–20700 g/ 1 wt% 6.9–34.5 MPa Stable water in CO2 emulsions for 24 h and no
mol 293.15–343.15 K coalescence for 7 days, reduced flocculation for 20%
nC6
14. Amphiphilic trisiloxane surfactants143 - 1 wt% 5.9 MPa and 283 K Stabilized dilute (1 wt% water) and CO2 emulsions for
> 2 h at 298 K and 30 MPa, minimal flocculation
Hydrocarbon surfactants
15. Methylated branched hydrocarbon ~335–694 g/mol 1 wt% 298.15–348.15 K Stabilized dilute (1.1 wt% water) and CO2 emulsion at
surfactants145 > 2.4 MPa and 308.15–338.15 K
16. AOT surfactant150 444.56 g/mol 25 MPa and 313.15 K Solubilization in AOT modified sc-CO2 with 10 mol% n-
pentanol due to polar core.
17. Structurally modified AOT (vinyl acetate, - 6.2–50 mmol/ 50 MPa and 318.15 K Improved CO2-philicity for stabilized emulsions.
carbonyl, and tert-butyl functional dm3 (AOK) / 298.15 K (AOVac)
groups)144

temperature (298.15–333.15 K) and pressure (~20 – 56 MPa). A subtle

Fig. 6. Polymer types used for controlling the mobility of sc-CO2 in enhanced
oil recovery.
siloxanes, fluoro, vinyl, hydrocarbon, and copolymers (given as a
schematic in Fig. 6). These have also been listed in Table 4. A significant
obstacle to using polymers and sc-CO2 is the low solubility of the high
molecular weight polymers and oligomers [154]. Siloxane-based poly­
mers have an affinity to CO2, making it attractive to investigate them for
thickening sc-CO2. Low molecular weight, functionalized poly­
dimethylsiloxanes oligomers have been investigated to enhance the
viscosity of sc-CO2 [154]. The experiment was performed at a range of
change in the number of repeating units led to a noticeable reduction in
the viscosity-increasing capability. An increase in the viscosity of
nC6-sc-CO2 mixture up to 3–20 times was observed during the experi­
ments at 298.15–333.15 K and ~21–57 MPa). O’Neil et al. studied the
solubility of various oligomers and polymers, including polyether, pol­
yacrylate, polysiloxane and commercially available block copolymers in
CO2 at 298.15–338.15 K and 6.89–41.37 MPa, correlating it to weak
solute-solute interactions [155]. It was concluded that lower interfacial
tension reduces the cohesive energy density and makes an additive more
soluble in CO2. In contrast, molecular weight is governing factor for less
CO2-philic polymers. Functionalization of polymer side chains can
enhance the polymer solubility in CO2, which is indicated by a reduction
in the cloud point of the CO2-polymer system. Fink et al. carried out
cloud point measurements in systems containing CO2 and propyl acetate
functionalized dimethylsiloxane (DMS) and hydromethylsiloxane
(HMS) [156]. The authors observed a cloud point pressure reduction of
~17.23 MPa at ~295.15 K, indicating considerably increased solubility.
Interestingly, functionalizing with alkane side chains raised the cloud
point indicating reduced solubility. CO2 is a weakly dielectric which

11
S.K. Prasad et al. Journal of CO2 Utilization 72 (2023) 102479

Table 4
Selected literature regarding the polymers and oligomers used for mobility control of sc-CO2 in enhanced oil recovery.
# Polymer Molecular weight Experimental parameters Results Oil recovery (%)

Concentration Pressure (MPa) and

Temperature (K)

Siloxane based polymers

1. Amide-terminated Polydimethyl x = upto ~50 10–16.6 wt% 20.7–56.5 MPa Miscible with sc-CO2 + nC6 at 1 wt -
siloxane (PDMS) oligomers154 298.15–333.15 K %; viscosity increase up to > 20
times
2. Polysiloxane homo and Up to 75000 g/mol Up to 4 wt% ~6.9–41.4 MPa Homopolymer solubility - 4 wt%, -
copolymers155 298.15–338.15 K 20.7 MPa, 308.15 K
Copolymer solubility – up to 1 wt%,
27.6 MPa, 308.15 K
3. Side chain functionalized x=5 ~0.4–3.5 wt% Up to ~40 MPa, Increasing solubility with side chains -
PDMS156 295.15 K (decrease in cloud point up to
17.2 MPa)
4. PDMS157 ~197,000 g/mol 2–6 wt% ~17.23 MPa and Increased cloud point pressure with ~25% increase from neat
327.59 K increase in temperature, ~90-fold CO2; reduced
viscosity increase for 6 wt% breakthrough
5. PDMS158 x = ~200–2000 ~5 wt% 298.15 K Cloud point of 20–30 MPa for -
x = ~200–2000
6. PDMS159 - 4 wt% 20 MPa and 327.15 K Viscosity increase up to ~13 times -
Fluoropolymers
7. Fluorinated polymers and ~85000–530000 g/ 5 wt% 300 MPa and Increased solubility of polymers in -
copolymers160 mol 543.15 K presence of fluorinated groups
8. Perfluoropolyethers161 ~8165–29252 g/ ~1–28 wt% 298.15 K Deceasing solubility with mol. wt.; -
mol complete miscibility with optimal
mol. wt.
9. Trialkyltin fluorides and < 50,000 g/mol < 5 wt% 297 K Dissolution without cosolvent; -
fluorinated telechelic increased viscosity (2–3 times) for
Ionomers162 2–4 wt%
10. Styrene-fluoroacrylate - 1–5 wt% 6.7–48.28 MPa, 295 K Enhanced CO2 viscosity by -
copolymers163 5–400 times, decreased solubility
with styrene content
11. Styrene/heptadecafluorodecyl - 0.5–5 wt% 308.2 K Increased viscosity by 352 times for -
acrylate (St–HFDA) 5 wt% with 0.299 molar ratio of
copolymers164 styrene
Hydrocarbon polymers
12. Poly(butene)165 ~500–2500 g/mol 1.5–20 g/L 298.15 K, 11.7 MPa Increased CO2 viscosity by up to 1.09 -
times
13. Poly (vinyl ethyl ether) (PVEE) 3800 and 910 g/mol 0.005–0.01 mf 329.15 K Increased CO2 viscosity by 13–14 Incremental 2.2–82%
and poly(1-decene) (P-1-D)166 times at 14.6–20.1 MPa and over pure CO2, delayed
329.15 K breakthrough
14. Poly (vinyl acetate-co-vinyl - Up to 2.35 wt 308 K Increased viscosity -
ether) (PVAEE)167 %
15. PVEE and Poly (iso-butyl vinyl 3800 and 4000 g/ 0.081–3 wt% 329 − 377 K Completely soluble in CO2 at -
ether) (Piso-BVE)141 mol 55 MPa, negligible viscosity increase
for Piso-BVE, 43% for PVEE

x – repeating units; mf- mol fraction

means it does exhibit a polar interaction, leading to increased solubility perfluoropolyethers (NMR molecular weight range of ~8160 to 29,252)
of polymers with a polar functional group is increased as opposed to have been shown to exhibit increased CO2 solubility due to the presence
non-polar. Polydimethyl siloxane combined with co-solvent toluene of fluorine groups [161]. Both CO2-philic and CO2 phobic groups can be
increased the CO2 viscosity by 90 times and lowered the pore volume of incorporated into the polymers, increasing the solubility and viscosity in
injection fluid required for ultimate recovery for viscous CO2, compared CO2, respectively, as shown in Fig. 7. CO2-philic groups increase the
to neat CO2 or CO2-toluene [157]. Polydimethylsiloxane (PDMS) has solubility due to increase affinity towards CO2 whereas CO2-phobic
been investigated for sc-CO2 viscosity enhancement by several authors
in concentrations ranging from ~1–5 wt%, along with various
co-solvents involving toluene, nC7, CHCl3, and tetrahydrofuran (THF)
[154,158,159].
Another class of polymers with a fluoride group, fluoropolymers,
have also been found to increase sc-CO2 viscosity. Non-polar polymers
or copolymers can be more soluble in CO2 by incorporating fluorine or
polar groups. Rindfleisch et al. conducted cloud point tests to determine
the solubility of fluorinated (poly(tetrafluoroethylene-co-hexa­
fluoropropylene), poly(vinylidene-cohexafluoropropylene)) and non-
fluorinated (polyacrylate, poly(ethylene-co-methyl acrylate)) polymers
in sc-CO2 at ~543 K and 300 MPa [160]. Authors found the increased
solubility of fluorinated and partially fluorinated polymers, compared to
the non-fluorinated counterparts. Teflon AF (fluorinated copolymer)
with polar groups was found to be soluble at pressures and temperatures
as low as ~60 MPa and 343 K. Similarly, high molecular weight Fig. 7. Functionalization with various CO2-philic and CO2-phobic groups for
increased polymer solubility and CO2 viscosity.

12
S.K. Prasad et al.
groups lead to molecular association leading to increased viscosity.
Semi-fluorinated trialkyltin fluorides and fluorinated telechelic ion­
omers were synthesized and investigated for CO2 viscosity increase
[162]. These polymers were able to dissolve in CO2 without the use of a
co-solvent and increase the CO2 viscosity by 2–3 times at a concentration
of 2–4 wt% at 297 K. Huang et al. [163] investigated the effect of
styrene/fluoroacrylate copolymers on the viscosity of CO2 at 295 K and
6.7–48.28 MPa. They observed a considerable increase in the viscosity
for 1–5 wt% concentration possibly due to phenyl groups stacking in the
CO2-copolymer solutions. Similarly, the molecular dynamic simulation
of styrene-heptadecafluorodecyl acrylate (St-HFDA) interaction
revealed that the π-π stacking of styrene groups had a crucial role in
increasing the CO2 viscosity [164]. The results are desirable for use in
enhanced oil recovery operations, but use is restricted due to the cost
and environmental concerns related to fluorinated chemicals.
The search for environmentally benign polymers efficient in CO2
viscosity enhancement at typical reservoir conditions leads to hydro­
carbon polymers. Examples include poly(propylene), poly(1-decene) (P-
1-D), and poly(butene) which have an aliphatic side chain, improving
their solubility in CO2 [165]. The presence of aromaticity seems to
negatively impact the solubility of these hydrocarbon polymers with
some exceptions, such as poly(acenaphthalene) and poly (1-vinyl
naphthalene). The authors of the above study have shown that func­
tionalization with carbonate, amide, ester, aldehyde, halogens, hy­
droxyl, and benzene rings system with unsaturation decrease the
polymer solubility in CO2. Despite enhanced solubility for some poly­
mers, the viscosity increased by only upto < 1.3 times against a required
range of 20–30 times. Based on the results of the above study, Zhang
et al. selected two lower molecular weight polymers, namely P-1-D,
polyvinyl ethyl ether (PVEE), and polyvinyl acetate (PVA), in their
studies regarding enhanced oil recovery (14.6–20 MPa and 329.15 K)
[166]. Results displayed an adequate CO2 solubility for both polymers,
although higher for PVEE, compared to P-1-D at the same cloud point
pressure. Both polymers led to an appreciable rise in the viscosity of pure
CO2 (13–14 times at 14.6–20.1 MPa and 329.15 K). The flooding ex­
periments at ~15.2–16.2 MPa and 329.15 K with thickened CO2
exhibited an incremental oil recovery from 2.2–82% over pure CO2,
depending on the petrophysical properties and fluid saturations. The
molecular dynamic simulations carried out to study the CO2-poly (vinyl
acetate-co-vinyl ether) (PVAEE) interactions give more microscopic in­
sights into the viscosity increase mechanism [167]. The interaction of
CO2 with polymer depends on the mesh structure of the polymer, which
constrains its movement, giving it more time to interact. Ideally, the
non-fluorous polymers should have a monomer with the weakest
solute-solute interactions and another monomer with a Lewis base to
interact with CO2, a weak Lewis acid [168]. Increasing the viscosity of
the CO2 is easy compared to the natural and associated gas due to less
concentration of polymers required to enhance CO2 viscosity. For
example, it was observed that 3 wt% of P-1-D polymer in sc-CO2 in­
creases the viscosity up to 0.13 cP compared to 5 wt% for associated gas
for the same value [169]. But, the application of thickeners for sc-CO2 is
trickier at higher temperatures due to decreasing density (lower disso­
lution) and lower mixture viscosity [170,171]. A majority of studies
from the literature have investigated the polymers at a temperature
lower than many of the reservoirs around the world. A recent study
investigated 26 polymers (including high and low molecular weight) at
higher temperatures and high pressure (329 – 377 K and 50–55 MPa)
[141]. Cloud point pressure measurements were taken at different
temperatures. Also, the polymers showing lower cloud point pressures
were studied for their effect on the viscosity of sc-CO2 using a viscom­
eter. It was observed that changes in the alkyl arm and the steric effect of
the polymer greatly affected their solubility in the sc-CO2 but were
ineffective in changing the viscosity. For example, Piso-BVE polymer is
more soluble in the sc-CO2 than PVEE at higher temperatures but has a
negligible rise in the viscosity for same concentration and temperature,
compared to 43% in the case of PVEE at 377 K. Also, the P-1-D polymer
13
Journal of CO2 Utilization 72 (2023) 102479
was found to be most effective in increasing the sc-CO2 viscosity by
~1.2–2.8 times over a concentration range of 0.81–5 wt%.
Small associating compounds can also thicken CO2. Like copolymers,
they also require functionalization with CO2-phobic and CO2-philic
groups to increase viscosity and solubility, respectively. A close look at
the literature reveals many small associating molecules based on the
above properties. The CO2-philic group majority studied include fluo­
rinated and silicon-based groups, which have environmental and cost
concerns, as already discussed earlier. Ester side chain functionalization
increases the solubility in CO2 by side chain carbonyl-CO2 interactions
due to the presence of carbonyl oxygen [156]. As observed by many
studies, the presence of acetate side chains enhances solubility. Also, the
alkyl group functionalization can affect solubility [141]. CO2 phobic
groups generally have a high molecular weight, leading to unfavourable
interaction due to the disparity between molecular weights. On the other
hand, much less molecular weight also leads to the CO2 phobic group
dominating the free energy of mixing, making it insoluble in CO2 [172].
Also, π-π stacking and hydrogen bonding contribute to more CO2-phobic
characteristics.
In conclusion, there are various categories of additives for sc-CO2
mobility control. The performance (solubility in CO2 and viscosity
enhancement) depends on various factors, including operational pres­
sure and temperature, concentrations, functionalization, molecular
structure and weight. This is indicated by a schematic diagram. (Fig. 8).
As visible from this figure, various factors such as pressure temperature,
concentration and thickener type, molecular weight and structure in­
fluence the solubility of thickeners in sc-CO2 and the viscosity of the
resulting solution which are vital along with developing cost-effective
and environment-friendly additives for sc-CO2. The goal is to reduce
the challenges associated with high mobility, breakthrough, and gravity
segregation and increase the sweep efficiency and hydrocarbon recovery
from the reservoir.
4. CO2 EOR and associated CO2 storage
4.1. Associated CO2 storage
A part of injected CO2 for EOR becomes trapped in the reservoir
which is known as associated CO2 storage [173]. The different trapping
mechanisms by which CO2 storage typically takes place in a saline
aquifer as discussed by various authors are given below [21,174,175].
a. Solubility trapping: The dissolution of CO2 in the formation brine in
pores spaces.
b. Mineral trapping: Chemical reaction between CO2 and minerals
present in brine.
Fig. 8. Factors affecting CO2 thickener performance (increased solubility and
CO2 viscosity).
S.K. Prasad et al.
c. Structural trapping (stratigraphic or hydrodynamic): Trapping of
CO2 in formation below an impermeable seal or under the influence
of an aquifer.
d. Residual (capillary) trapping: CO2 due to capillary forces and relative
permeability effects.
Various subsurface features preferred for CO2 storage are deep saline
aquifers, basalt structures, depleted reservoirs and coal seams[21,
176–178]. CO2 is generally injected into subsurface geological forma­
tions under supercritical conditions for permanent storage[21].
4.2. Adsorption capacity of CO2 and CH4
Developing the shale prospects with CO2 and CH4 has implications
for CO2 storage which has been investigated by various researchers
[179–185]. Apart from the above-mentioned CO2 storage mechanisms
for saline aquifers, shale reservoirs also trap CO2 through adsorption
[184,185]. A schematic regarding the same has been provided in Fig. 9.
While hydrodynamic, adsorption, and residual trapping occur in a
shorter timescale (compared to injection time), solubility and mineral
trapping act on long term or permanent[184]. High-pressure adsorption
studies were done on coal and shale samples from a Brazilian basin
involving CH4 and CO2 up to 17 and 25 MPa, respectively, at ~308,
318 K. Results were fitted with Langmuir isotherm [180]. Authors
observed increased CO2 adsorption on shale up to 6.9 times that of CH4
for the coal and carbonaceous shales. A similar adsorption study on the
shale samples from Barnet, Eagle Ford, Marcellus, and Montney reser­
voirs in the US (at 313 K) concluded CO2 to have an adsorptive capacity
up to ~2–3 times that of CH4 in the shale samples [181]. The influence
of shale composition and pore structure on the selective adsorption of
CO2 over CH4 has been studied by Gu et al. [186]. The authors
concluded that the saturated vapour pressure of CO2 is lower than CH4,
resulting in multilayer adsorption. The shale samples had a high total
organic carbon (TOC) with higher heterogeneity in pore size, favourable
for the CO2 movement. As the CO2 molecule is slightly smaller than CH4
(kinetic diameter of 0.33 nm compared to 0.38 for CH4), it has a higher
surface area and can penetrate the pore spaces in the shale formation.
Also, the adsorption capacity of CO2 has been observed to increase from
3 to 10 MPa, in contrast with CH4 [187]. Also, the authors observed a
lower adsorption capacity of CO2 compared to liquid CO2. sc-CO2
adsorption studies on shale have been done by various authors [114,
188]. Zhou et al. exposed crushed shale samples from various oilfields in
China to sc-CO2 at ~308 K and different pressures of 8, 12, and 16 MPa
[188]. CO2 and CH4 adsorption were done before the exposure to
sc-CO2. Authors observed that sc-CO2 exposure decreased the adsorption
of gases owing to pore structure change and surface chemistry. The
average pore size was observed to increase while the silicate, carbonate,
Fig. 9. A schematic of CO2-storage in shale reservoirs through various trap­
ping mechanisms.
14
Journal of CO2 Utilization 72 (2023) 102479
and aromatic hydrocarbon content of the shale samples decreased after
sc-CO2 exposure. Thus, developing shale prospects with sc-CO2 benefits
from increasing fracture conductivity while the higher preferential
adsorption of CO2 on shale over CH4 leads to simultaneous increased gas
production and CO2 sequestration.
4.3. Factors affecting CO2-EOR / CO2 storage potential
Processes such as geochemical interactions of CO2 with reservoir
fluids can change mechanical, petrophysical properties significantly
[19,20,23,189]. It is therefore important to study effects of interaction
of CO2 with reservoir rocks and geochemical, petrophysical and geo­
mechanical alterations. Also, diffusion and dispersion of CO2 have
crucial impact on the EOR/storage as well as gas recovery. These
mechanisms are shown in a schematic in Fig. 10 and discussed below.
4.3.1. Interaction of sc-CO2 with reservoir rock and brine - geochemical,
petrophysical, geomechanical changes
In a study carried out to study the sandstone surface properties after
sc-CO2 exposure at 348.15 K and 32 MPa, authors observed that
chemical interactions led to the dissolution of certain minerals from
sandstone formation (K-feldspar, albite, ankerite). Combined with the
kaolinite formation and mineral surface corrosion, this resulted in a
wettability change to more water-wet [29]. A recent study has investi­
gated the effects of CO2-brine-rock interaction on the porosity and
permeability of the shale samples at ~353 K for 24 h [190]. The porosity
of the samples had increased by ~2–3.4% while permeability increased
by ~7 times after 24 h. To determine the changes in the mineral
composition and fluid chemistry, the authors carried out XRD and
SEM-EDS analyses of the exposed samples. It was deduced from the
study that sc-CO2 exposure had dissolved dolomite, K-feldspar, albite,
and calcite. Also, kaolinite precipitation resulted in an increased clay
percentage in the sample after the exposure. Apart from the above
analysis, tensile strength and surface friction coefficient had reduced
noticeably in 24 h (up to 9.8%). The increased permeability observation
is also supported by the works of other authors [191,192]. As a result,
there is more adsorption and, thus, consumption of CO2, which has
implications for CO2 sequestration. However, some studies have also
observed a decrease in permeability due to free particle formation due to
mineral dissolution, making it necessary to inject dry CO2 to successfully
implement carbon storage [193]. A lab-scale study involved low-field
NMR and XRD analyses to quantify the alterations of porosity, perme­
ability, and geochemistry of a synthetic core with pure minerals (calcite,
feldspar, illite, and kaolinite) after exposure to CO2 at 20 MPa and
343.15 K [19]. Interplanar spacing of the sample had increased by the
interactions with sc-CO2, and it was concluded that the injection of
saturated CO2 could further expand pore size. In another study, cores
obtained from a tight sandstone reservoir in Lucaogou formation
(China) were exposed to brine (~29800 ppm salinity) and subcritical to
sc-CO2 environments (348.15 K and 2.6–32.8 MPa)[29]. The miner­
alogy of core samples was studied through SEM-EDS, XRD and ion
concentrations were studied through ICP-AES. Authors observed a 0.3%
decrease in the mas of the core samples due to mineral dissolution at
acidic sc-CO2 environment. This resulted in a dissolution of K-feldspar,
albite, and ankerite. Iron minerals and kaolinite precipitate were
observed in the core samples from SEM-EDS analysis. These mineral­
ogical changes altered the rock surface to a more water-wet. A higher
water wet surface can help desorb oil from rock surface, enabling
imbibition and ultimately, oil recovery. These changes are crucial for
improved pore connectivity in tight reservoir which would enable both
CO2-EOR and sequestration.
Shale lithologies present challenges to properly understand the
various parameters related to CO2 mobility and storage including
diffusion, dissolution, and displacement. Clay rich shales have exhibited
a decreased pore connectivity in contrast to increase for carbonates upon
CO2-brine exposure for 45 days[194]. Zhang et al. have observed a
S.K. Prasad et al.
Fig. 10. A schematic of interactions sc-CO2 reservoir rocks and fluids (crude oil and water) relevant for CO2-EOR/storage operations.
decrease in the Ca content in the shale upon exposure to sc-CO2[195].
The dissolution of minerals affects the CO2 diffusion in addition to
mechanical properties such as ductility and brittleness. Production and
EOR process related to shale reservoirs need to significantly alter the
reservoir properties in form of fracturing, and other stimulation tech­
niques as they are extremely tight (low permeability). Typically, shale is
composed of kaolinite, illite, smectite, montmorillonite, biochemical
carbonates in form of dolomite and calcite, and some iron minerals[22].
Reservoir petrophysical and mechanical properties could change due to
CO2 storage due to reaction with the rock as discussed above, leading to
possible formation of new flow paths and leakage[24,196]. In one of the
studies for investigating mechanical properties of shale rock sample
upon exposure CO2-brine system, fracture toughness has been observed
to increase by about 0.5 MPa owing to calcite cementation[25]. Lami­
nated zones are more prone to CO2 permeation as they are weaker than
other lithofacies[197]. Rock failure can happen due to reduced stress
compliance owing to microfractures initiations and expansion following
the porosity and permeability alterations[195]. This reduced strength in
shales has been observed to reduce the Young’s modulus and brittleness,
depending on the saturation time. It has also been reported that faults or
fractures can be reactivated due to increased pore pressures upon CO2
flooding, possibly risking CO2 leakage[25]. Commonly used parameters
to evaluate formation susceptibility to failure are UTS (ultimate
compressive strength) and Young’s modulus (E)[23]. In an experiment
to evaluate mechanical properties of shale samples exposed to sc-CO2,
UTM and E were observed to decrease by ~34%[23]. Similarly, another
study has concluded UCS, E, and brittleness index to decrease time upon
exposure to sc-CO2[198], however the magnitude of decrease is
dependent on the orientation of bedding (more reduction for vertical
bedding compared to parallel), and more for UCS compared to E after
sometime. Stress redistributions can happen during CO2 injection due to
temperature and pore pressure changes, or asphaltene precipitation (loss
of CO2 injectivity), changing the rock geomechanics[27,28]. Pore
pressure fluctuations alter the effective stress leading to deformations
and permeability alterations[27], impacting hydrocarbon recovery and
CO2/storage. Temperature effects on the CO2 diffusivity and dispersion
and asphaltene precipitation due to CO2 and are discussed in 4.3.2 and
4.3.3. CO2 storage is feasible in fractured shales but the storage sites as
well as geochemical and mechanical impacts always vary from one
15
Journal of CO2 Utilization 72 (2023) 102479
another due to heterogeneity and anisotropy. An ideal the CO2 storage
site should have following attributes[24]:
a. Sufficient injectivity and capable of resisting buoyancy driven flow
of CO2 over an appreciable timescale without leak and migration.
b. Caprock: should have sufficient fracture and fault resistance. Ideal
characteristics are non-(porous, permeable, fracture and reactive)
layer, undisturbed by surrounding chemistry and tectonics[22].
According to Ozotta et al., there has been an increased push for CO2
storage in recent years to combat the climate change. More efforts have
been put into CO2 storage in shales than in carbonates which are more
prone to dissolution and failure upon CO2 exposure[21]. CO2 storage
form a part of strategy to achieve carbon neutrality, the other part
concerns with the reduction of CO2 emissions[199]. As already dis­
cussed in previous sections, CO2- comes with the advantage of associ­
ated carbon storage potential. Two important viewpoints have been put
forth by Jiang et al. in regard to the economic viability carbon seques­
tration methods. In first part, CO2-EOR is economically encouraging
compared to other methods. The costs associated with CO2-EOR (pur­
chasing, processing facilities, transportation, injection, and monitoring
infrastructure can be recovered, depending on the prevailing crude oil
prices. In contrast to the first viewpoint, CO2-EOR contribution to car­
bon sequestration could be questioned, especially since CO2 is put back
into the atmosphere upon consumption of fossil fuels. According to
Ghiat and Al-Ansari, approximately 0.75–1.5 tonnes of CO2 are stored
for emission of 1 tonne of CO2[200]. This is however, a very conserva­
tive estimate as numerous factors affect the net CO2 savings. The CO2
source, thus becomes vital for realizing carbon negative status. Various
carbon sources such as direct air capture, biomass conversion, and
ethanol plant are potential candidate for this purpose[201,202]. For
example, using ethanol plant as the CO2 source, 1–2.5 tonnes of CO2 can
be stored per tonne of CO2 emitted[202].
4.3.2. Diffusion and dispersion of CO2 in reservoir fluids
CO2 diffusion and dispersion mechanism impact the CO2-EOR/stor­
age projects and gas recovery. Rezk and Foroozesh carried out a
compositional simulation study coupled with fine tuned EoS model to
understand the effect of porosity, permeability, injection rate and soak
S.K. Prasad et al.
time on oil recovery and storage for varying CO2 diffusion coefficient
[34]. The reservoir conditions were kept above the sc-CO2 conditions
(17.2 MPa and 368.7 K), homogeneous porosity and permeability and
light crude oil (0.813 g/cc and 2.21 cP). For all the cases, an increase in
the diffusion coefficient increased the recovery factors and tapping ef­
ficiency. High permeability had least impact of variation in diffusion
coefficient while decreased injection rate and increased soak time led to
increased incremental recovery factor and solubility trapping. For
enhanced gas recovery (EGR) process, dispersion of CO2 in CH4 is
important[31]. Temperature, residual water, salinity, and impurities in
CO2 play a major role in affecting the dispersion and ultimately on the
recovery and CO2 storage. There is scarcity of field data on EGR oper­
ations using CO2, warranting the need of complex geological, petro­
physical, and fluid properties in simulation studies.
4.3.3. sc-CO2 induced compositional changes in crude oil and precipitation
of heavy crude oil fractions
Nielsen et al. studied the effects of temperature and pressure on the
asphaltene precipitation from crude oils ranging from asphaltenic to tar
sand bitumen diluted by nC5 [203]. The authors concluded that aggre­
gate mean size increased slightly with pressure (0–5.6 MPa) while
decreasing with temperature (273–423 K). The core flooding experi­
ments performed at ~332–336 K and 16 MPa by Srivastava et al. have
concluded an increased asphaltene flocculation (up to 3.48 wt%)
accompanied by the saturation pressure, gas-oil-ratio alterations due to
an increase in CO2 concentration from ~0.7–75 mol% [204]. Similarly,
other studies have shown that higher CO2 concentrations in the system
can lead to increased asphaltene precipitation, which reduces upon
increasing pressure and decreasing temperature [205–207].
A molecular dynamics simulation study investigated the sc-CO2-
induced asphaltene aggregation, with and without the presence of in­
hibitor Limonene [208]. Simulations carried out at 350 K and 15 MPa
have exhibited aggregation for all the molecular configurations
considered. Liu et al. observed in their simulation study that asphaltene
molecules exhibited a strong aggregation tendency compared to nC7 and
toluene. [209]. CO2-induced asphaltene precipitation through multiple
contact miscibility was studied in a high-pressure high, temperature
(HPHT) cell (~344 K and 21 MPa) [210]. The authors observed a
decrease in the asphaltene content in the crude oil (with 3.75 wt% C60+
and 34◦ API) with an increase in CO2 concentration, indicating their
precipitation. FTIR analyses of the precipitates obtained from the
exposure to CO2 had shorter alkyl chains than those obtained using
paraffins. Also, apart from asphaltenes, other fractions such as saturates,
aromatics, and resins have been found in the precipitate. Such changes
in the crude oil composition also affect the flow properties of the crude
oil, affecting the oil recovery when using supercritical CO2. A study
investigated the flow properties of a waxy crude oil (18.6% wax) treated
with sc-CO2 at 25 MPa and 353.15 K (similar to reservoir conditions)
[211]. The treated waxy crude oil had a higher content of C24+ hydro­
carbons. The rheological test revealed that the treated waxy oil was
harder to flow due to its increased yield stress and apparent viscosity.
The increased heavier hydrocarbons led to a more stable emulsion after
sc-CO2 exposure. Apart from sc-CO2, injection of sc-H2O could also lead
to changes in the composition and physicochemical properties of the
crude oil. Using sc-H2O leads to viscosity and density reduction due to
the cracking of higher molecular weight hydrocarbons. Unlike sc-CO2,
where there is a higher chance of coke formation, sc-H2O leads to less
coke formation and upgradation of heavy crude.
Like conventional reservoirs, CO2 EOR in ULRs suffer from asphal­
tene deposition. A study investigated the asphaltene plugging during
CO2 injection at 298.15 K in a confined shale core samples with pore
sizes 3 and 50 nm. Asphaltene particles with size ranging from 30 to
200 nm were found to have deposited on a nanomembranes, indicating
increased plugging potential[212]. Increased cycles of CO2 soaking were
observed to reduce the pore size and permeability (one third of original
permeability)[213].
16
Journal of CO2 Utilization 72 (2023) 102479
5. Role of field applications, CO2 monitoring, and life cycle
analyses for development, safety, and optimization of CO2-EOR/
storage project
Field applications and CO2 monitoring are valuable for ensure safety
and integrity of any CO2-EOR/storage project. Life cycle analysis on the
other hand is indispensable for the optimization of any EOR/storage
project and considers its environmental as well as economic impact.
5.1. Successful CO2-EOR/storage field case studies
A successful field implementation of any EOR/EGR process has many
different stages namely the pre-implementation and implementation
stages, the evaluation of recovery response and the commissioning and
related startup activities[214]. For example, after the peak oil produc­
tion of ~31700 barrels of oil per day from Wasson field in the Texas,
USA in 1975, field and plant studies were carried out and CO2 miscible
flooding was opted for implementation in 1984. The pay zone is dolo­
mite with an average depth of ~5100 ft and areal extent of ~41-acre.
The MMP was determined from the black oil model to be ~1315 psi
(9.07 MPa) and CO2 was injected at ~1800 psi (12.4 MPa). Field facil­
ities for CO2 injection, production, gas collection and excess water
handling including the transmission pipelines were designed as per the
requirements. The Oil production rate had increase from
mid-1986–1988 (15700 BOPD, 108800 BWPD for Jan 1988) in response
to CO2 injection, beyond the projected decline value for secondary
flooding, indicating success. Additionally, excess CO2 removal facility
had been commissioned in 1987. Some of the wells were shut or excess
CO2 was reinjected.
The impurity of the reinjected gas affects CO2-EOR and the associ­
ated CO2 storage performance[173]. The impurities consist primarily of
CH4 and lighter components such as N2 and C2 (up to 99.6%). Presence
of lighter fraction that is CH4 increase the CO2-MMP which has a direct
impact on the oil recovery as the displacement mechanism changes from
more efficient miscible to a less efficient immiscible. For example, a
WAG injection scheme has been implemented in the Northeastern
Powder River basin in Wyoming, USA. The reservoir temperature is
315 K. Using the vanishing interfacial tension (VIT) method the CO2-oil
MMP range was determined to be 9.72–28.13 MPa for CH4 content
0–100 mol%. The miscible flooding was realised for upto 30 mol% CH4
for a pressure of 17.23 MPa and above. The hydrocarbon pore volume
injected (HCPVI) increased with impurity content due to the less
compressible CH4 (compared to CO2) at reservoir conditions. Incre­
mental oil recovery increased upto 20 mol% before decreasing for
higher CH4 content due to increased MMP as discussed above. The
associated CO2 storage on the other hand decreased with impurity in the
reinjected gas. Increased CH4 content shifted the phase envelope to
higher pressures and reduced the gas mixture density, negatively
impacting the reservoir CO2 storage potential.
Relative permeability hysteresis and various trapping mechanism
play an important role in the CO2 storage potential by affecting residual
trapping of CO2 (changing wettability and capillary pressure just after
CO2 injection)[215–217]. The Bell Creek oil field, Montana, USA has
seen CO2-EOR implementation in 2013. Core plugs with 26% porosity
and 1052 mD permeability were collected from a depth of 4533 ft and
relative permeability tests were carried out at reservoir conditions of
16.20 MPa and 315.37 K. The increased irreducible gas saturation
during imbibition of 0.19 compared to 0.07 for drainage process indi­
cated a significant trapping of CO2 during the cycle. The swelling tests
indicated an enhanced dissolution of CO2 in the crude oil (up to
0.48 mol fraction at 10.38 MPa) and increased swelling up to 23%. A
reservoir simulation study concluded that the oil recovery and associ­
ated CO2 storage had increased by 1.21% and 20%, respectively, for
permeability hysteresis and a residual CO2 saturation of 0.3.
S.K. Prasad et al.
5.2. Field monitoring technologies and CO2-EOR/storage safety
Once CO2 is injected into the reservoir, understanding its behaviour
and spatial distribution is crucial to develop and optimize the EOR and
CO2 capture projects. Time lapse seismic monitoring or 4D seismic
technique is frequently used for this purpose. 4D seismic monitoring
essentially measures the P and S wave velocity data over the same area
at different times. This is useful to monitor changes in the dynamic
properties such as saturation and pressure. Static properties including
mineralogy and porosity do not change during a 4D survey. Two sets of
data are acquired for CO2-EOR data monitoring: before and after the
injection. The measured compressional wave velocities change when the
insitu fluid is replaced with the one having different density and elastic
moduli[218]. The P-wave can travel through both rock and fluid
whereas S-wave can travel only through solids. Therefore, the P and S
wave velocities changes when seismic wave travels through fluid filled
pore spaces in the formation. This change in P-S velocity ratio combined
with seismic inversion and rock physics can be helpful to detect stored
CO2 along with fluid and pressure distributions over time[219]. Saline
water aquifers and depleted oil and gas reservoirs offer a great potential
for CO2 storage[220–222]. Most of the CO2 is heterogeneously stored in
the reservoirs in a supercritical state. Properties of sc-CO2 changes with
varying conditions of reservoir pressure and temperatures. In addition,
the compressibility of formation brine also changes when interacting
with sc-CO which in turn, affect the P-wave velocity[222]. For depleted
oil and gas reservoirs, the physical properties of residual oil changes
with time upon contact with sc-CO2. Depleted reservoirs with less GOR
(gas oil ratio) are favourable for monitoring CO2. GOR affects the
seismic response by altering the density, bulk modulus and velocity. In
addition, unconsolidated rocks are favoured for monitoring CO2 due to
large P-wave velocity decreases. In the same way, compacted formations
are not suitable for seismic CO2 monitoring.
The CO2 itself reacts with rock surface in the pore scale (discussed in
section rock interaction) and alters the rock matrix which could have
significant changes in the seismic response and making it difficult to
segregates the effects of CO2. Another issue is the presence of CO2
patches in relative to the seismic wavelength, which change the rock
compressibility, thus changing the response at higher and lower fre­
quencies of measurement. Thus, calibrating compressibility saturation is
vital to design a CO2 monitoring project and predict the stored CO2 in
the reservoir through image processing and seismic inversion. Also,
improving the signal-to-noise ratio and anomaly detection in 4-D seismic
survey will play a vital role in further enhancing the accuracy. Salako
et al. have combined 4-D seismic technique with pulsed-neutron log data
for predicting pore volume as well as dynamic reservoir property
changes with 69% accuracy for Bell Creek oilfield[223]. The matured
sandstone reservoir (payzone depth of 1310–1372 m and thickness of
6–9 m) has been subjected to CO2-EOR using WAG and continuous CO2
injection scheme (CCI). Another CO2 monitoring and storage related
studies have been carried out by White at the Weyburn-Midale field in
Canada[224]. Oil reserves lie at ~1450 m depth with a fractured
dolomite thickness of < 30 m. Passive time lapse seismic monitoring
studies revealed a P and S wave velocity change by ~8% and 1.5%,
respectively, when the reservoir brine was replaced by CO2. The over­
lying formation has higher porosity and the change is reflected in
seismic response when CO2 is injected. This technique is sensitive to low
CO2 saturation of 5–10%, making P wave time lapse image accurate to
detect CO2 presence. In addition, the above technique combined with
saturation estimates from reservoir flow simulation can be used for ac­
curate volume predictions, relevant for associated CO2 storage.
Apart from 4-D seismic imaging, other CO2 monitoring techniques
have also been used which can monitor a host of parameters related to
CO2-EOR/storage. These are listed below:
17
Journal of CO2 Utilization 72 (2023) 102479
a. Ground deformation due to CO2 injection – Interferometric synthetic
aperture radar (InSAR)[225] and global positioning system (GPS)
[226]
b. Oil displacement and CO2 trapping in pores - Nuclear magnetic
resonance (NMR)[227]
c. CO2 saturation- Thermal neutron detection (TND)[228]
5.3. Life-cycle analysis and optimization of CO2-EOR/storage project
Life cycle analysis helps us to make economic decision while eval­
uate environmental consequences. CO2 is initially injected into reservoir
in EOR project causing increased oil production and CO2 storage. At the
surface, CO2 and water are separated from oil and CO2 is reinjected into
the reservoir. Additionally, some CO2 is purchased during this process.
During this cycle, CO2 emissions take place from compressors, pumps
and other facilities to which emissions from refinery and combustion of
oil products add up. For example, for Weyburn CO2-EOR project a net
storage of 18.6 million tonnes of CO2 has been estimated to be stored out
of 23 million tonnes recycled for a period of 25 years. According to
NRCan (Natural Resources Canada), CO2 emissions from usage of 130
million barrels of oil is estimated to be ~61 million tonnes. Thus, it is
easy to infer from above involved statistics that making economic de­
cisions in developing EOR project could have huge environmental
impact. An optimization methodology known as GLP (gray linear pro­
gramming) has been used to optimize the objective function consisting
delivered, recycled, and stored CO2 based on CO2 purity, supply, and
emitted along with expected oil recovered from EOR. According to the
optimized model, 20 million tonnes of has been purchased for Weyburn
project and incremental oil recovery has been estimated to be around
~133–142 million barrels for 25 years period. More details can be
accessed from the reference[229]. From the sensitivity analysis, the
Weyburn project has been found to be economical success and could be
further extended upon increased oil prices.
6. Corrosion and its impact on CO2-EOR/storage process chain
Corrosion is a challenging issue associated with CO2-EOR process
chain which can be divided into carbon capture, CO2 storage, trans­
portation, injection and oil production. During the process of EOR, CO2
is transported preferably in a single phase such as supercritical or gas
phase at 5–20 MPa due to since energy consumption, while temperature
varies from 293.15 to 323.15 K. Typical wellhead pressure involved in
CO2-EOR is ~10 MPa[230]. Depending on the injection rate and well­
head pressure depth, the pressure encountered in the bottomhole could
be higher than 30 MPa. During production, the conditions generally
vary from supercritical conditions for CO2 to around ~303.15 K,
< 1 MPa (wellhead). In CO2-EOR production, the CO2 content can be as
high as 70% (v/v) after continuous production for months[231]. The oil
and gas gathering transportation lines operate at relatively less pressure
than well at 0.3–2 MPa. Corrosion happens in CO2-EOR/process chain in
the presence of trace amount of water in the injected CO2 due to car­
bonic acid formation. Some of the major factors affecting the corrosion
in a CO2-EOR project are listed below and their effects are listed below.
1. Water-wetting: can accelerate the corrosion rate. As a rule of thumb,
corrosion rates are drastically reduced under 30% water cut. The
maximum recommendation concentration for CO2 transportation is
500 ppm [10].
2. Partial pressure of CO2: leads to formation of more carbonic acid and
carbonate ion to carry forward the corrosion.
3. Temperature: Increase in temperature above dew point precludes the
condensation of water, thereby reducing the corrosion rate
4. pH value: reduces the corrosion rate due to ions precipitation. An
increase from pH value 5–6 decreases the solubility of ions in water
by 100 times.
S.K. Prasad et al. Journal of CO2 Utilization 72 (2023) 102479

5. Flow regime and velocity: As the flow regime changes from laminar Table 5
to turbulent flow, this protective layer near pipeline wall is removed, Challenges encountered in CO2-EOR/storage process and their mitigation
exposing the surface to corrosion. measures.
6. Presence of H2S: Aside from cracking, sulphide scales protect the # Challenges Description Mitigation measures
steel from further corrosion and lead to a reduced rate than sweet Technical challenges
corrosion. When the ratio of CO2/H2S is < 20, sour corrosion ensues 1. Injectivity loss in CO2- Average injectivity • Decreasing the WAG
while for higher ratios, sweet corrosion occurs. (recommended WAG scheme: loss of 20% in CO2- ratio to increase CO2
maximum concentration of 200 ppm)[10]. WAG injection mobility.
scheme; dependent on • Increase injection
wettability, pressure or additional
Every CO2-EOR project is different from another and require several heterogeneity, injection wells.
parameters that need to be evaluated for successful corrosion mitigation anisotropy, trapped • Increased lab and field
and asset integrity, especially in case of CO2 breakthrough. Some of gas scale studies for
these parameters include CO2 purity and water chemistry, injection and optimized injectivity
and oil recovery
design parameters, service life, production data and simulation inputs. depending on each
The equipments and field infrastructure related to CO2-EOR can be case
divided into different categories: CO2 injection system, down-hole 2. CO2 mobility control Higher mobility of CO2 • Reduce the CO2
equipments, pipelines, and existing equipment. Corrosion assessment – Viscous fingering, mobility with
breakthrough and additives (surfactants,
and mitigation measures are important for effective corrosion control.
reduction in oil polymers, cosolvents,
Corrosion allowance, corrosion resistant alloys (Super 13 Cr, Alloy 28 or recovery efficiency nanoparticles)
825) can be used during the design phase. CO2 recovery plant could be • WAG injection
used to remove excess CO2. scheme
Laumb et al. have selected a CO2/water injector and an oil producer 3. Understanding CO2- Diverse for rock and • Integration of
oil and CO2-rock-brine fluid properties, geomechanics with
well from Weyburn CO2-EOR and storage project[232]. The selection of
interaction pressure and geochemistry with
corrosion case studies is subject to availability of sufficient data during temperature, governs petrophysics
pre, active and post CO2 injection phases. Corrosion in a well is typically the mechanism of oil
evaluated through the casing and cement integrity assessment by using recovery
4. CO2-EOR performance Low to extremely low • Reinjection of CO2
cement bond logs (CBL), vertilogs, imaging and sector bond tools (SBT),
in ULR permeability and and produced gas
and calliper logs. The CO2/water injector well had multiple perforations (Unconventional mixed wettability, (rich in intermediates)
above the production perforations as detected by vertilogs. During the liquid reservoirs) leading to low oil • Oil production by huff
year 1987–2002, casing wall loss severity increased upto ~70–80% at recovery (slow diffusion of CO2
~1350 m depth causing the injection well to be abandoned in 2010. The into matrix) and puff
(expansion and
producer well had ~80–93% loss in pipeline at ~485–875 due to severe
production).
pitting corrosion as determined by CIT (casing imaging tool) along with • Using field core at
URS (ultrasonic radial scanner) and MSC (mechanical side wall coring). reservoir conditions
for reliable lab data
• Numerical simulation
7. Current challenges and mitigation practices and gaps
for qualitative
analysis
CO2-EOR has been established its potential for enhanced hydrocar­ 5. CO2-EOR performance Poor oil recovery due • Using CO2 volume
bon recovery coupled with CO2 storage. Increasing efforts are being in carbonate to strong swell technology (low
made for achieving carbon neutrality / negative status around the world reservoirs heterogeneity, mixed fluidity fluid
wettability, fractures, injection)
to reduce atmospheric CO2 levels. However, there are several challenges
vugs, poor pore • WAG injection, CO2
in the implementation of CO2-EOR which include technical, economical connectivity, mobility control
and policy support from government. Technical challenges are reactivity with CO2 • Intelligent CO2
numerous, ranging from surface facilities, transportation and corrosion, (geochemical, and monitoring
petrophysical (optimized injection
reservoir heterogeneity and CO2 mobility control, to CO2 interaction
changes), and production for
with rock, brine and oil. Economic challenges include crude oil price maximum recovery)
volatility and CO2 source cost while policy hurdles lie in encouraging 6. Corrosion (Sweet – Presence of trace • Assessment of CO2,
stakeholders towards CO2-EOR storage process in efforts towards CO2; Sour- H2S water in injected CO2- water chemistry,
achieving carbon neutral or negative status. These hurdles impact the severe corrosion of injection parameters,
downhole equipments, monitoring and
proper implementation of CO2-EOR and ultimately, the oil recovery and
injection system, inspection.
sequestration. These challenges along with mitigation measures are reduced service life. • CRA (Corrosion
provided in (Table 5) and have been discussed below. resistant alloys)
-Super 13, alloy 28
/825 and corrosion
7.1. Challenges and mitigation practices
allowance in the
design, carbon steel
i. Injectivity loss: WAG injection scheme oil increases the oil re­ with inhibitors
covery and overcomes the problem associated with CO2-EOR by • CO2 recovery plant to
increasing the macroscopic sweep efficiency in addition to remove excess CO2
• ICD (Inflow control
microscopic displacement of oil through CO2. However, WAG device to control the
scheme suffers from a phenomenon known as the injectivity loss flow rate of producing
[67,68]. A Sharp decline is observed for water injectivity after wells
initial and first cycle along with further losses in the WAG cycle. 7. CO2 source for CO2- Contaminated CO2 • CO2 from large
EOR and storage impacts oil recovery industrial sources as
The post waterflood injectivity decline is due to relative perme­
negatively (less relatively pure
ability hysteresis[69]. Water and gas are competing for same pore concern for storage)
space. Wettability, gas entrapment, reservoir heterogeneity and (continued on next page)
anisotropy have a complex influence on the WAG injectivity[70].

18
S.K. Prasad et al. Journal of CO2 Utilization 72 (2023) 102479

Table 5 (continued ) followed by expansion[35]. The possible pressurization first oc­

# Challenges Description Mitigation measures curs followed by the fracturing phase. In the next phase (huff)
CO2 diffuses into matrix followed by expansion in puff phase. Oil
(ethanol, fertilizers,
hydrogen plants)
is expelled from tight pores through a combination of several
8. CO2 storage site Diverse and dependent • Integration of factors including swelling, viscosity and IFT reduction, wetta­
selection on geomechanics with bility alteration, and relative permeability hysteresis. Therefore,
CO2-rock-brine petrophysical, and huff and puff method (described above) and utilizing fractures
interactions geochemical
and increasing the pressure to above MMP can result in increased
(dependent on rock alterations
type, mineral, brine • Utilization of well oil recovery through above mentioned mechanisms. In addition,
composition, logging, rock physics reinjecting CO2 and produced gases rich in intermediates increase
petrophysical and model, and 4D seismic the miscible effects and hence, oil recovery.
mechanical monitoring. For carbonate reservoirs, WAG injection scheme followed by
properties)
Economic challenges
controlled mobility of CO2 should be preferred for tackling high
9. Crude oil price and Feasibility of CO2- • Life cycle analysis - permeable and conductive zones. Intelligent CO2 monitoring in­
CO2 source cost EOR/ storage project – Sensitivity analysis tegrated with injection and production profiles can help optimize
based on economics and economic the oil recovery in CO2-EOR.
and point of optimization under
iv. Corrosion control: Corrosion associated with CO2-EOR/storage
diminishing returns different price and
operating scenarios. process chain, poses a serious threat to asset integrity and deign
• Cheaper CO2 source to life, jeopardizing the production and leading to premature
reduce the overall abandonment. Dry CO2 does not pose an issue but the presence of
economic burden on trace amounts of water aggravates the corrosion depending on
CO2-EOR and storage
project.
pH, flow regime, temperature, water wetting, H2S and CO2 con­
Policy support centration. In addition, the presence of H2S leads to sour corro­
10. Achieving carbon Sensitization and Policy towards sion. Several factors need careful evaluation for corrosion
neutrality willingness to partake incentives, deployment mitigation including injected CO2 purity and water chemistry,
in accelerated and growth of CO2-EOR/
injection and operating parameters, service life and design, and
activities towards storage research and
achieving carbon activities, and field scale monitoring and inspection. Injection and production well
neutrality through tests downhole infrastructure and gathering stations are usually design
coupled CO2-EOR/ with CRA (Corrosion resistant alloys) -Super 13, alloy 28 /825. In
storage addition, corrosion allowance to the design based on anticipated
corrosion rate and service life. Pipelines may be design using
In an oil-wet or mixed wet rock, gas enters the permeable zones carbon steel with inhibitors or alloy 825. Excess CO2 in the pro­
and reduces the water relative permeability and injection rate. It duction stream can be removed by CO2 recovery plant. Lastly CO2
has been estimated that injectivity losses of approximately 20% ICD (Inflow control device to control the flow rate of producing
will happen in the WAG process[68]. Some techniques to mitigate wells are beneficial for varying permeability zones. All this is of
this issue include tapered WAG, decreasing WAG ratio increases course dependent on techno-economical evaluation. Monitoring
injection pressure, additional injection wells. In a tapered WAG, pipeline for corrosion in case CO2 ingress in production stream
the gas injection decreases progressively from longer to shorter from a nearby CO2-EOR/storage project depends on case-to-case
cycles. This technique reduces the response time with more in­ basis.
cremental oil recovery for less gas[233]. Also, with reduced gas v. CO2 source for EOR/storage and site selection for CO2 storage:
injection cycles, the water injectivity losses are also mitigated. Contaminated CO2 impacts oil recovery negatively. CO2 should
Optimal WAG ratio on the other hand is governed by the wetta­ be sourced from large industrial sources as relatively pure
bility of rock. WAG ratio is simply the ratio of volumes of injected (ethanol, fertilizers, hydrogen plants). These are cheaper than
water to gas. In a water-wet reservoir, higher WAG ratio results in other sources. Life cycle analysis and economic optimization can
a reduced oil recovery due to bypassing of oil whereas in a mixed be helpful for selecting CO2 source with least burden on the
wet rock, effect of WAG ratio is much smaller probably due to oil feasibility of CO2-EOR/storage project. Ideally, CO2 storage site
coated pore surfaces, improving the contact between oil and should have sufficient injectivity while resisting CO2 leakage
solvent. Thus, decreased WAG ratio in a water wet reservoir re­ along with sufficient fracture and fault resistant caprock. In real
duces this elimination of bypassed oil[234]. Reducing the WAG field conditions, every CO2 storage site is different from each
ratio will reduce the mobility control thereby facilitating other, depending on geochemical interaction of CO2 with reser­
increased injectivity, reduced loss of reservoir pressure, misci­ voir rocks and resulting petrophysical and geomechanical alter­
bility and oil recovery[70]. ations. Timescales vary from few decades for CO2 injection for
ii. CO2 mobility control: As discussed in Section 3, the higher both EOR/storage to centuries for storage. Thus, detecting
mobility of sc-CO2 leads to viscous fingering, gravity segregation leakage and subtle changes with high accuracy is difficult and
and breakthrough which reduces the oil recovery efficiency. significant post injection monitoring techniques and activities
Some methods to control the mobility of the injected CO2 is to use required. Integration of geomechanics with geochemistry and
WAG injection and use of mobility control additives to increase petrophysics along with CO2 monitoring technique, rock physics
sweep efficiency (Please refer to Section 3, Tables 3 and 4). model and well logging would ensure selection of appropriate
iii. CO2-EOR performance in ULRs and carbonate reservoirs: Un­ CO2 storage site (unique for each case)
conventional liquid reservoirs and carbonate formations are vi. Economic and policy support challenges: The feasibility of any
characterized by extremely low permeability, mixed wettability CO2-EOR/storage project depends on the economics and point of
and heterogeneity, which lead to low oil recovery efficiency. The diminishing returns. Cost of CO2 source and crude oil price have a
mechanism of oil recovery from ULR such as fractured shale differ major impact on the economics. Higher crude oil prices justify
from that of conventional reservoirs due to extremely low spending on CO2-EOR infrastructure and extend the oilfield life­
permeability and governed by diffusion through the matrix time. Life-cycle analysis using sensitivity analysis and economic
optimization is vital for understanding the economic impact of

19
S.K. Prasad et al.
CO2 storage on different components in chain from cost consid­
eration and CO2 source selection to incremental oil recovery and
environment.
Cooperation from various stakeholder such as companies and govt is
essential in realizing the goal of carbon neutral/negative status. Gov­
ernment can encourage provide policies towards incentivizing the
deployment and growth of CO2¬EOR/ storage research and activities
[235]. Tax reduction crude oil recovered form CO2-EOR is an example of
such an incentive to companies. This along with stricter emission stan­
dards with help in achieving the goal of carbon neutrality.
7.2. Current gap and improvement scope
CO2-EOR/storage technologies have matured and many researches
have been done involving geochemistry, petrophysics, and geo­
mechanics. However, some gaps still remain which are listed below.
• Cheaper and environment friendly polymers/surfactants for suffi­
cient CO2 mobility control.
• Reduction in CO2-crude oil MMP and injectivity losses in WAG in­
jection scheme.
• Proper understanding of CO2-crude oil and CO2-rock-brine in­
teractions and oil recovery mechanisms for tight and fractured car­
bonate reservoirs.
• Fast and accurate real-time CO2 leak detection for storage projects
and safe CO2 storage over extended timescale (centuries).
• Cheap and abundant CO2 source for reduction in overall cost
8. Conclusion and future of research involving sc-CO2
This review discusses the literature on sc-CO2 fluid applications for
improved oil and gas production operations and associated carbon
storage. Crucial CO2-EOR aspects such as minimum miscibility pressure,
mobility control and CO2-EOR/storage mechanisms along with field
implementation are discussed. Geochemical, petrophysical and geo­
mechanical alterations resulting from CO2-rock-brine interactions, and
CO2 diffusion/dispersion in reservoir fluids play a vital role in affecting
the CO2-EOR/storage potential. Also, life cycle analysis and CO2 moni­
toring technologies are vital to optimize the CO2-EOR/storage. Major
challenges during CO2-EOR/storage process such as injectivity loss,
corrosion, EOR/storage performance, storage site selection, and current
mitigation practices are discussed along with gaps. This holistic review
would help gain insights into mechanisms and selection criteria, limi­
tations, mitigation/optimizations, and gaps when applying sc-CO2-EOR/
storage for unconventional reservoirs with heterogeneity and varying
fluid properties.
1. sc-CO2 mobility control for improved oil and gas production
sc-CO2 with less viscosity, high diffusivity and liquid like density is
attractive for EOR/EGR operations and underbalanced drilling. How­
ever, viscous fingering, early breakthrough, and gravity override reduce
the sweep efficiency. Also, the proppant transport and cuttings carrying
capacity are affected in shale gas fracturing and in underbalanced dril­
ling, respectively.
a. To overcome high mobility-related issues in EOR, polymers, co-
solvents, surfactants and nanoparticles can be used. Polymers are
functionalized with CO2-philic and CO2-phobic groups for enhanced
CO2 solubility and viscosity. Majorly studied fluorinated and
siloxane- polymers have environmental and cost concerns, leading to
research for environment-friendly hydrocarbon polymers and
surfactants.
b. Rigorous lab scale studies should be carried out to examine reservoir
and fluid compatibility, solubility and viscosity enhancement.
20
Journal of CO2 Utilization 72 (2023) 102479
Mobility ratio, injectivity, recovery efficiency and environment
compatibility should be evaluated before field scale deployment.
c. Future research should involve environment friendly, high-
temperature and salinity compatible polymers/surfactants with
favourable CO2 mobility. Increased injection pressure, number of
wells, and lower WAG ratio in CO2-WAG method can help reduce the
injectivity losses.
2. Other supercritical fluids for EOR
sc-N2 sc-H2O have also been used in EOR studies. sc-N2 leads to lower
oil recovery due to less swelling than sc-CO2. sc-N2 combined with sc-
CO2, yields a higher recovery than steam flooding. sc-H2O reduces the
oil density and viscosity due to thermal effects and dissolution of heavier
crude oil fractions, reducing coke formation, compared to sc-CO2. Su­
percritical multithermal fluid (SCMTF), a new concept which combines
N2, CO2, H2O, has shown promising results in the initial investigations.
3. CO2-EOR/storage performance
Geochemical, petrophysical, and geomechanical alterations due to
interactions of CO2-with reservoir rock and fluids impact the EOR/
storage potential. Coupling geomechanics with geochemistry and pet­
rophysics in lab scale experimental and simulation studies would lead to
more accurate results. Also, the diffusion and dispersion of CO2 in
reservoir fluids have vital effect on EOR/EGR as well as storage which
cannot be discounted.
a. There is a need to reliably predict the diffusion coefficient and
dispersion of CO2 in the reservoir fluids as its dispersivity is highly
scale and heterogeneity dependent.
b. Every CO2 storage site has different characteristics. CO2 monitoring
techniques, rock physics modelling and well logging would ensure
selection of appropriate CO2 storage site. Fast, real-time and accurate
CO2 monitoring technology is needed for leakage detection and
ensuring safe storage for extended timescale (centuries).
c. CO2 source and purity affect the EOR/storage potential and process
economics. CO2 can be sourced from large industrial processes
(ethanol, fertilizers, hydrogen plants) with least burden on the
feasibility of CO2-EOR/storage project, based on the life-cycle
analysis.
4. CO2-EOR for carbonates and unconventional liquid reservoirs
(ULRs)
Fractured shales present a challenge to oil recovery in form of
extremely low permeability and mixed wetting characteristics. Car­
bonate reservoirs on the other hand are heterogenous (fractures, vugs,
and poor pore connectivity) and react with CO2, leading to geochemical
and petrophysical alterations.
a. For URLs: CO2 huff-n-puff method and reinjecting CO2 and produced
gas rich in intermediate fractions can help achieve miscibility and
increased oil recovery. Field cores at reservoir conditions and
modelling can be helpful in optimizing oil recovery from URLs.
b. For carbonates: Some of the EOR strategy can be low fluidity fluid
injection, CO2 mobility control, and WAG injection scheme. CO2
monitoring technologies can help optimize oil recovery by adjusting
injection and production profile
5. Corrosion control in CO2-EOR/storage
Presence of water makes CO2 corrosive which can jeopardize the
infrastructure depending on various parameters including pressure,
temperature, pH, H2S content. Assessment and monitoring play a crucial
role in decide the action plan.
S.K. Prasad et al.
a. Corrosion resistant alloys or inhibitors can be used along with design
allowance.
b. Flow rate of producing wells can be controlled by ICD (inflow control
device) For removal of excess CO2, a recovery plant can be used.
CRediT authorship contribution statement
Siddhant Kumar Prasad: Conceptualization, Methodology, Writing
– original draft. Jitendra S. Sangwai: Supervision, Methodology,
Writing – review & editing. Hun-Soo Byun: Supervision, Methodology,
Writing – review & editing.
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.
Data Availability
No data was used for the research described in the article.
Acknowledgements
This work was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea government (MSIT) (No.
2021R1A2C2006888).
References
[1] British Petroleum. Statistical Review of World Energy 2022, 71st ed.
〈https://www.bp.com/content/dam/bp/business-sites/en/global/corporate/
pdfs/energy-economics/statistical-review/bp-stats-review-2022-full-report.pdf〉,
(accessed 13 March 2023).
[2] D.W. Green, G.P. Willhite. Enhanced Oil Recovery, second ed., Society of
Petroleum Engineers, Richardson, TX, 2018.
[3] A. Carcoana, Applied Enhanced Oil Recovery, Prentice-Hall, Inc, Englewood
Cliffs, New Jersey, 1992.
[4] E.C. Donaldson, G.V. Chilingarian, T.U. Yen, Enhanced Oil Recovery, I
Fundamentals and Analyses 17 A, in: Developments in Petroleum Science,
Elsevier, Amsterdam, 1985.
[5] S.M.F. Ali, J.A. Jones, R.F. Meldau, Practical Heavy Oil Recovery, 1997. https://
www.scribd.com/document/437903171/Farouq-Ali-Practical-Heavy-Oil-
Recovery-1-pdf.
[6] V. Vishnyakov, B. Suleimanov, A. Salmanov, E. Zeynalov, Oil recovery stages and
methods, in: Primer on Enhanced Oil Recovery, Gulf Professional Publishing,
Elsevier, Cambridge, MA, USA, 2020, https://doi.org/10.1016/B978-0-12-
817632-0.00007-4.
[7] A. Gbadamosi, S. Patil, M.S. Kamal, A.A. Adewunmi, A.S. Yusuff, A. Agi, J. Oseh,
Application of polymers for chemical enhanced oil recovery: a review, Polymers
14 (2022) 1433, https://doi.org/10.3390/polym14071433.
[8] S. Mahajan, H. Yadav, S. Rellegadla, A. Agrawal, Polymers for enhanced oil
recovery: fundamentals and selection criteria revisited, Appl. Microbiol.
Biotechnol. 105 (2021) 8073–8090, https://doi.org/10.1007/s00253-021-
11618-y.
[9] Y. Feng, D. Meier, Comparison of supercritical CO2, liquid CO2, and solvent
extraction of chemicals from a commercial slow pyrolysis liquid of beech wood,
Biomass Bioenergy 85 (2016) 346–354, https://doi.org/10.1016/j.
biombioe.2015.12.027.
[10] P.L. Pavlova, A.V. Minakov, D.V. Platonov, V.A. Zhigarev, D.V. Guzei,
Supercritical fluid application in the oil and gas industry: a comprehensive
review, Sustainability 14 (2022) 698, https://doi.org/10.3390/su14020698.
[11] Q. Lyu, J. Tan, L. Li, Y. Ju, A. Busch, D.A. Wood, P.G. Ranjith, R. Middleton,
B. Shu, C. Hu, Z. Wang, R. Hu, The role of supercritical carbon dioxide for
recovery of shale gas and sequestration in gas shale reservoirs, Energy Environ.
Sci. 14 (2021) 4203–4227, https://doi.org/10.1039/D0EE03648J.
[12] H. Chen, Y. Hu, Y. Kang, X. Wang, F. Liu, Y. Liu, Advantages of supercritical CO2
compound fracturing in shale on fracture geometry, complexity and width, J. Nat.
Gas. Sci. Eng. 93 (2021), 104033, https://doi.org/10.1016/j.jngse.2021.104033.
[13] I. Energy Agency, Review 2021 Assessing the effects of economic recoveries on
global energy demand and CO2 emissions in 2021, Glob. Energy (2021). 〈www.
iea.org/t&c/〉. accessed 12 November 2022.
[14] IPCC, Global warming of 1.5 ◦ C, Cambridge University Press, Cambridge, UK and
New York, NY, USA, 2019, p. 616, https://doi.org/10.1017/9781009157940.
[15] Y. Zhao, G. Fan, K. Song, Y. Li, H. Chen, H. Sun, The experimental research for
reducing the minimum miscibility pressure of carbon dioxide miscible flooding,
21
Journal of CO2 Utilization 72 (2023) 102479
Renew. Sustain. Energy Rev. 145 (2021), 111091, https://doi.org/10.1016/j.
rser.2021.111091.
[16] S.B. Hawthorne, D.J. Miller, C.B. Grabanski, L. Jin, Experimental determinations
of minimum miscibility pressures using hydrocarbon gases and CO2 for crude oils
from the Bakken and Cut Bank oil reservoirs, Energy Fuels 34 (2020) 6148–6157,
https://doi.org/10.1021/acs.energyfuels.0c00570.
[17] N. Pal, X. Zhang, M. Ali, A. Mandal, H. Hoteit, Carbon dioxide thickening: A
review of technological aspects, advances and challenges for oilfield application,
Fuel 315 (2022), 122947, https://doi.org/10.1016/j.fuel.2021.122947.
[18] R.M. Enick, D. Olsen, J. Ammer, W. Schuller, Mobility and conformance control
for CO2 EOR via thickeners, foams, and gels - a literature review of 40 years of
research and pilot tests, 18th SPE Improved Oil Recovery Symposium, Society of
Petroleum Engineers, Tulsa, Oklahoma, USA, 2012, https://doi.org/10.2118/
154122-MS.
[19] Y. Zhang, L. Shi, Z. Ye, L. Chen, N. Yuan, Y. Chen, H. Yang, Experimental
investigation of supercritical CO2 –Rock–Water interactions in a tight formation
with the pore scale during CO2–EOR and sequestration, ACS Omega 7 (2022)
27291–27299, https://doi.org/10.1021/acsomega.2c02246.
[20] N. Müller, Supercritical CO2-Brine relative permeability experiments in reservoir
rocks—Literature review and recommendations, Transp. Porous Media 87 (2011)
367–383, https://doi.org/10.1007/s11242-010-9689-2.
[21] O. Ozotta, M. Ostadhassan, K. Liu, B. Liu, O. Kolawole, F. Hadavimoghaddam,
Reassessment of CO2 sequestration in tight reservoirs and associated formations,
J. Pet. Sci. Eng. 206 (2021), 109071, https://doi.org/10.1016/j.
petrol.2021.109071.
[22] M.H. Bhuiyan, N. Agofack, K.M. Gawel, P.R. Cerasi, Micro- and macroscale
consequences of interactions between CO2 and shale rocks, Energies 13 (2020)
1167, https://doi.org/10.3390/en13051167.
[23] H. Yin, J. Zhou, X. Xian, Y. Jiang, Z. Lu, J. Tan, G. Liu, Experimental study of the
effects of sub- and super-critical CO2 saturation on the mechanical characteristics
of organic-rich shales, Energy 132 (2017) 84–95, https://doi.org/10.1016/j.
energy.2017.05.064.
[24] I.O. Ojala, The effect of CO2 on the mechanical properties of reservoir and cap
rock, Energy Procedia 4 (2011) 5392–5397, https://doi.org/10.1016/j.
egypro.2011.02.523.
[25] J.R. Major, P. Eichhubl, T.A. Dewers, J.E. Olson, Effect of CO2–brine–rock
interaction on fracture mechanical properties of CO2 reservoirs and seals, Earth
Planet. Sci. Lett. 499 (2018) 37–47, https://doi.org/10.1016/j.epsl.2018.07.013.
[26] S.A. Carroll, W.W. McNab, Z. Dai, S.C. Torres, Reactivity of Mount Simon
sandstone and the Eau Claire shale under CO2 storage conditions, Environ. Sci.
Technol. 47 (2013) 252–261, https://doi.org/10.1021/es301269k.
[27] T.W. Teklu, W. Alameri, R.M. Graves, A.N. Tutuncu, H. Kazemi, A.M. Alsumaiti,
Geomechanics considerations in enhanced oil recovery, SPE Canadian
Unconventional Resources Conference, Society of Petroleum Engineers, Calgary,
Alberta, Canada, 2012, https://doi.org/10.2118/162701-MS.
[28] P.D. Patel, P.G. Christman, J.W. Gardner, Investigation of unexpectedly low field-
observed fluid mobilities during some CO2 tertiary floods, SPE Reserv. Eng. 2
(1987) 507–513, https://doi.org/10.2118/14308-PA.
[29] X. Zhang, B. Wei, J. Shang, K. Gao, W. Pu, X. Xu, C. Wood, L. Sun, Alterations of
geochemical properties of a tight sandstone reservoir caused by supercritical CO2-
brine-rock interactions in CO2-EOR and geosequestration, J. CO2 Util. 28 (2018)
408–418, https://doi.org/10.1016/j.jcou.2018.11.002.
[30] J. Zhou, N. Hu, X. Xian, L. Zhou, J. Tang, Y. Kang, H. Wang, Supercritical CO2
fracking for enhanced shale gas recovery and CO2 sequestration: results, status
and future challenges, Adv. Geo-Energy Res. 3 (2019) 207–224, https://doi.org/
10.26804/ager.2019.02.10.
[31] S. Liu, L. Yuan, C. Zhao, Y. Zhang, Y. Song, A review of research on the dispersion
process and CO2 enhanced natural gas recovery in depleted gas reservoir, J. Pet.
Sci. Eng. 208 (2022), 109682, https://doi.org/10.1016/j.petrol.2021.109682.
[32] M.G. Rezk, J. Foroozesh, A. Abdulrahman, J. Gholinezhad, CO2 diffusion and
dispersion in porous media: review of advances in experimental measurements
and mathematical Models, Energy Fuels 36 (2022) 133–155, https://doi.org/
10.1021/acs.energyfuels.1c03552.
[33] S. Li, Z. Li, Q. Dong, Diffusion coefficients of supercritical CO2 in oil-saturated
cores under low permeability reservoir conditions, J. CO2 Util. 14 (2016) 47–60,
https://doi.org/10.1016/j.jcou.2016.02.002.
[34] M. Gamal Rezk, J. Foroozesh, Uncertainty effect of CO2 molecular diffusion on oil
recovery and gas storage in underground formations, Fuel 324 (2022), 124770,
https://doi.org/10.1016/j.fuel.2022.124770.
[35] L.C. Burrows, F. Haeri, P. Cvetic, S. Sanguinito, F. Shi, D. Tapriyal, A. Goodman,
R.M. Enick, A literature review of CO2, natural gas, and water-based fluids for
enhanced oil recovery in unconventional reservoirs, Energy Fuels 34 (2020)
5331–5380, https://doi.org/10.1021/acs.energyfuels.9b03658.
[36] S. Omrani, M. Ghasemi, S. Mahmoodpour, A. Shafiei, B. Rostami, Insights from
molecular dynamics on CO2 diffusion coefficient in saline water over a wide range
of temperatures, pressures, and salinity: CO2 geological storage implications,
J. Mol. Liq. 345 (2022), 117868, https://doi.org/10.1016/j.molliq.2021.117868.
[37] M. Al-Shargabi, S. Davoodi, D.A. Wood, V.S. Rukavishnikov, K.M. Minaev,
Carbon dioxide applications for enhanced oil recovery assisted by nanoparticles:
Recent developments, ACS Omega 7 (2022) 9984–9994, https://doi.org/
10.1021/acsomega.1c07123.
[38] S.A.M. Dehghani, M.V. Sefti, A. Ameri, N.S. Kaveh, Minimum miscibility pressure
prediction based on a hybrid neural genetic algorithm, Chem. Eng. Res. Des. 86
(2008) 173–185, https://doi.org/10.1016/j.cherd.2007.10.011.
S.K. Prasad et al.
[39] A.N. El-hoshoudy, S. Desouky, CO2 miscible flooding for enhanced oil recovery,
in: R.K. Agarwal (Ed.), Carbon Capture, Utilization and Sequestration, InTech, St.
Louis, USA, 2018, pp. 79–93, https://doi.org/10.5772/intechopen.79082.
[40] H. Yuan, R.T. Johns, A.M. Egwuenu, B. Dindoruk, Improved MMP correlations for
CO2 floods using analytical gasflooding theory, SPE Reserv. Eval. Eng. 8 (2005)
418–425, https://doi.org/10.2118/89359-PA.
[41] F.M. Orr, C.M. Jensen, Interpretation of pressure-composition phase diagrams for
CO2/crude-oil systems, Soc. Pet. Eng. J. 24 (1984) 485–497, https://doi.org/
10.2118/11125-PA.
[42] R.B. Alston, G.P. Kokolis, C.F. James, CO2 Minimum miscibility pressure: a
correlation for impure CO2 streams and live oil systems, Soc. Pet. Eng. J. 25
(1985) 268–274, https://doi.org/10.2118/11959-PA.
[43] H.M. Sebastian, R.S. Wenger, T.A. Renner, Correlation of minimum miscibility
pressure for impure CO2 streams, J. Pet. Technol. 37 (1985) 2076–2082, https://
doi.org/10.2118/12648-PA.
[44] W.F. Yellig, R.S. Metcalfe, Determination and prediction of CO2 minimum
miscibility pressures (includes associated paper 8876), J. Pet. Technol. 32 (1980)
160–168, https://doi.org/10.2118/7477-PA.
[45] C. Cronquist, Carbon dioxide dynamic miscibility with light reservoir oils. 4th U.
S. Dep. Energy Annu. Symp. Tulsa, U.S. Dep. Energy, Oklahoma, USA, 1978,
pp. 28–30.
[46] F. Ungar, S. Ahitan, S. Worthing, A. Abedini, K. Uleberg, T. Yang, A new fluidics
method to determine minimum miscibility pressure, J. Pet. Sci. Eng. 208 (2022),
109415, https://doi.org/10.1016/j.petrol.2021.109415.
[47] R. Czarnota, D. Janiga, J. Stopa, P. Wojnarowski, Determination of minimum
miscibility pressure for CO 2 and oil system using acoustically monitored
separator, J. CO2 Util. 17 (2017) 32–36, https://doi.org/10.1016/j.
jcou.2016.11.004.
[48] R. Czarnota, D. Janiga, J. Stopa, P. Wojnarowski, P. Kosowski, Minimum
miscibility pressure measurement for CO2 and oil using rapid pressure increase
method, J. CO2 Util. 21 (2017) 156–161, https://doi.org/10.1016/j.
jcou.2017.07.007.
[49] M.K. Verma, Fundamentals of carbon dioxide-enhanced oil recovery (CO2-EOR):
a supporting document of the assessment methodology for hydrocarbon recovery
using CO2-EOR associated with carbon sequestration, U. S. Geol. Surv. (2015),
https://doi.org/10.3133/ofr20151071.
[50] M. Ding, F. Yuan, Y. Wang, X. Xia, W. Chen, D. Liu, Oil recovery from a CO2
injection in heterogeneous reservoirs: The influence of permeability
heterogeneity, CO2-oil miscibility and injection pattern, J. Nat. Gas. Sci. Eng. 44
(2017) 140–149, https://doi.org/10.1016/j.jngse.2017.04.015.
[51] T. Ahmed, Equations of State and PVT Analysis, Elsevier, 2007, https://doi.org/
10.1016/C2013-0-15511-0.
[52] E. Shilov, A. Cheremisin, Huff-n-Puff test for minimum miscibility pressure
determination for heavy oil, Fifth CO2 Geological Storage Workshop, European
Association of Geoscientists & Engineers, Utrecht, The Netherlands, 2018,
https://doi.org/10.3997/2214-4609.201802977.
[53] F.M. Orr, M.K. Silva, Effect of oil composition on minimum miscibility
pressure—part 2: correlation, SPE Reserv. Eng. 2 (1987) 479–491, https://doi.
org/10.2118/14150-PA.
[54] S.B. Hawthorne, C.B. Grabanski, L. Jin, N.W. Bosshart, D.J. Miller, Comparison of
CO2 and produced gas hydrocarbons to recover crude oil from Williston basin
shale and Mudrock cores at 10.3, 17.2, and 34.5 MPa and 110 ◦ C, Energy Fuels 35
(2021) 6658–6672, https://doi.org/10.1021/acs.energyfuels.1c00412.
[55] K. Zhang, B. Nojabaei, K. Ahmadi, R.T. Johns, Effect of gas/oil capillary pressure
on minimum miscibility pressure for tight reservoirs, SPE J. 25 (2020) 820–831,
https://doi.org/10.2118/199354-PA.
[56] Z. Zheng, Y. Di, Y.-S. Wu, Nanopore confinement effect on the phase behavior of
CO2/hydrocarbons in tight oil reservoirs considering capillary pressure, Fluid-
Wall Interaction, and Molecule Adsorption, Geofluids 2021 (2021) 1–18, https://
doi.org/10.1155/2021/2435930.
[57] D. Al-Bayati, A. Saeedi, M. Myers, C. White, Q. Xie, insights into immiscible
supercritical CO2 EOR: an XCT scanner assisted flow behaviour in layered
sandstone porous media, J. CO2 Util. 32 (2019) 187–195, https://doi.org/
10.1016/j.jcou.2019.04.002.
[58] G. Chen, X. Wang, Z. Liang, R. Gao, T. Sema, P. Luo, F. Zeng,
P. Tontiwachwuthikul, Simulation of CO2-oil minimum miscibility pressure
(MMP) for CO2 enhanced oil recovery (EOR) using neural networks, Energy
Procedia 37 (2013) 6877–6884, https://doi.org/10.1016/J.
EGYPRO.2013.06.620.
[59] J. Liu, L. Sun, Z. Li, X. Wu, Experimental study on reducing CO2–oil minimum
miscibility pressure with hydrocarbon agents, Energies 12 (2019) 1975, https://
doi.org/10.3390/en12101975.
[60] I. Bahralolom, R.E. Bretz, F.M. Orr, Experimental investigation of the interaction
of phase behavior with microscopic heterogeneity in a CO2 flood, SPE Reserv.
Eng. 3 (1988) 662–672, https://doi.org/10.2118/14147-PA.
[61] M.A. Fernø, M. Steinsbø, Ø. Eide, A. Ahmed, K. Ahmed, A. Graue, Parametric
study of oil recovery during CO2 injections in fractured chalk: Influence of
fracture permeability, diffusion length and water saturation, J. Nat. Gas. Sci. Eng.
27 (2015) 1063–1073, https://doi.org/10.1016/j.jngse.2015.09.052.
[62] M. Khosravi, A. Bahramian, M. Emadi, B. Rostami, E. Roayaie, Mechanistic
investigation of bypassed-oil recovery during CO2 injection in matrix and
fracture, Fuel 117 (2014) 43–49, https://doi.org/10.1016/j.fuel.2013.09.082.
[63] Y.M. Al Wahaibi, A.K.Al Hadhrami, First-contact-miscible, vaporizing- and
condensing-gas drive processes in a channeling heterogeneity system. SPE Middle
East Oil and Gas Show and Conference, Society of Petroleum Engineers, Manama,
Bahrain, 2011, https://doi.org/10.2118/138350-MS.
22
Journal of CO2 Utilization 72 (2023) 102479
[64] M. Namani, J. Kleppe, Investigation of the effect of some parameters in miscible
wag process using black-oil and compositional simulators. SPE Enhanced Oil
Recovery Conference, Society of Petroleum Engineers, Kuala Lumpur, Malaysia,
2011, https://doi.org/10.2118/143297-MS.
[65] E.F. Righi, J. Royo, P. Gentil, R. Castelo, A. Del Monte, S. Bosco, Experimental
study of tertiary immiscible wag injection. 2004 SPE/DOE Fourteenth
Symposium on Improved Oil Recovery, Society of Petroleum Engineers, Tulsa,
Oklahoma, USA, 2004, https://doi.org/10.2118/89360-MS.
[66] G. Hoare, C. Coll, Effect of Small/Medium Scale Reservoir Heterogeneity on the
Effectiveness of Water, Gas and Water Alternating Gas WAG Injection, 80th EAGE
Conference and Exhibition, Society of Petroleum Engineers, Copenhagen,
Denmark, 2018, https://doi.org/10.2118/190855-MS.
[67] A. Fager, B. Crouse, G. Sun, R. Xu, D. Freed, Evaluation of Directly Simulated
WAG Hysteresis at Pore Scale and its Effect on Injectivity Index. SPE Offshore
Europe Conference and Exhibition, Society of Petroleum Engineers, Aberdeen,
UK, 2019, https://doi.org/10.2118/195734-MS.
[68] R.E. Hadlow, Update of industry experience with CO2 injection, 7th Annual
Technical Conference and Exhibition, Society of Petroleum Engineers,
Washington, DC, USA, 1992, https://doi.org/10.2118/24928-MS.
[69] P.M. Jarrell, F. Charles, M. Stein, S. Webb, Practical Aspects of CO2 Flooding,
Society of Petroleum Engineers, 2002.
[70] J.D. Rogers, R.B. Grigg, A literature analysis of the WAG injectivity abnormalities
in the CO2 process, SPE Reserv. Eval. Eng. 4 (2001) 375–386, https://doi.org/
10.2118/73830-PA.
[71] S. Whittaker, E. Perkins, Technical aspects of CO2 EOR and associated carbon
storage, Global CCS Institute, 2013. 〈https://www.globalccsinstitute.com/archi
ve/hub/publications/118946/technical-aspects-co2-enhanced-oil-recovery-and-a
ssociated-carbon-sto.pdf〉.
[72] I. Roopa, R.A. Dawe, A laboratory study of recovery with carbon dioxide around
critical conditions of Trinidad’s heavy oil and tar sands, Pet. Sci. Technol. 28
(2010) 1544–1554, https://doi.org/10.1080/10916460903117578.
[73] B. Wei, X. Zhang, J. Liu, R. Wu, H. Xiang, X. Xu, Supercritical CO2-EOR in an
asphaltenic tight sandstone formation and the changes of rock petrophysical
properties induced by asphaltene precipitation, J. Pet. Sci. Eng. 184 (2020),
106515, https://doi.org/10.1016/j.petrol.2019.106515.
[74] S. Iglauer, A. Paluszny, T. Rahman, Y. Zhang, W. Wülling, M. Lebedev, Residual
trapping of CO2 in an oil-filled, oil-wet sandstone core: results of three-phase
pore-scale imaging, Geophys. Res. Lett. 46 (2019) 11146–11154, https://doi.org/
10.1029/2019GL083401.
[75] S. Chowdhury, M. Rakesh, S. Medhi, J. Trivedi, J.S. Sangwai, Pore-scale flow
simulation of supercritical CO2 and oil flow for simultaneous CO2 geo-
sequestration and enhanced oil recovery, Environ. Sci. Pollut. Res. 29 (2022)
76003–76025, https://doi.org/10.1007/s11356-022-21217-7.
[76] A.R. Kovscek, G.Q. Tang, B. Vega, Experimental investigation of oil recovery from
siliceous shale by CO2 injection (SPE Annual Technical Conference and
Exhibition), Society of Petroleum Engineers, Denver, Colorado, USA, 2008,
https://doi.org/10.2118/115679-MS.
[77] K. Zhang, Experimental and numerical investigation of oil recovery from Bakken
formation by miscible CO2 injection, SPE Annual Technical Conference and
Exhibition. Dubai, UAE: Society of Petroleum Engineers, (2016). https://doi.org/
10.2118/184486-STU.
[78] L. Li, J.J. Sheng, Y. Su, S. Zhan, Further investigation of effects of injection
pressure and imbibition water on CO2 huff-n-puff performance in liquid-rich shale
reservoirs, Energy Fuels 32 (2018) 5789–5798, https://doi.org/10.1021/acs.
energyfuels.8b00536.
[79] H. Wang, Z. Lun, C. Lv, D. Lang, M. Luo, Q. Zhao, C. Zhao, Nuclear magnetic
resonance study on oil mobilization in the shale exposed to CO2 (SPE Improved
Oil Recovery Conference), Society of Petroleum Engineers, Tulsa, Oklahoma,
USA, 2018, https://doi.org/10.2118/190185-MS.
[80] L. Li, Y. Su, Y. Hao, S. Zhan, Y. Lv, Q. Zhao, H. Wang, A comparative study of CO2
and N2 huff-n-puff EOR performance in shale oil production, J. Pet. Sci. Eng. 181
(2019), 106174, https://doi.org/10.1016/j.petrol.2019.06.038.
[81] L. Han, Y. Gu, Optimization of miscible CO2 water-alternating-gas injection in the
bakken formation, Energy Fuels 28 (2014) 6811–6819, https://doi.org/10.1021/
ef501547x.
[82] P. Nguyen, J.W. Carey, H.S. Viswanathan, M. Porter, Effectiveness of
supercritical-CO2 and N2 huff-and-puff methods of enhanced oil recovery in shale
fracture networks using microfluidic experiments, Appl. Energy 230 (2018)
160–174, https://doi.org/10.1016/j.apenergy.2018.08.098.
[83] J. Zhong, A. Abedini, L. Xu, Y. Xu, Z. Qi, F. Mostowfi, D. Sinton, Nanomodel
visualization of fluid injections in tight formations, Nanoscale 10 (2018)
21994–22002, https://doi.org/10.1039/C8NR06937A.
[84] H.Y. Zhu, L. Tao, Q.Y. Liu, Z.D. Lei, Multiscale change characteristics of Chinese
Wufeng shale under supercritical carbon dioxide (SPE Annual Technical
Conference and Exhibition), Society of Petroleum Engineers, Dubai, UAE, 2016,
https://doi.org/10.2118/181369-MS.
[85] J. Lu, J.-P. Nicot, P.J. Mickler, L.H. Ribeiro, R. Darvari, Alteration of Bakken
reservoir rock during CO2-based fracturing—an autoclave reaction experiment,
J. Unconv. Oil Gas. Resour. 14 (2016) 72–85, https://doi.org/10.1016/j.
juogr.2016.03.002.
[86] A. Goodman, S. Sanguinito, M. Tkach, S. Natesakhawat, B. Kutchko, J. Fazio,
P. Cvetic, Investigating the role of water on CO2-Utica shale interactions for
carbon storage and shale gas extraction activities – evidence for pore scale
alterations, Fuel 242 (2019) 744–755, https://doi.org/10.1016/j.
fuel.2019.01.091.
S.K. Prasad et al.
[87] M. Al Ismail, M. Zoback, CO2-based technologies in unconventional resources:
impact of rock mineralogy on adsorption (SPE Kingdom of Saudi Arabia Annual
Technical Symposium and Exhibition), Society of Petroleum Engineers,
Dammam, Saudi Arabia, 2017, https://doi.org/10.2118/188168-MS.
[88] M. Al Ismail, J.S. Reece, S. Hol, M. Zoback, The Effect of CO2 adsorption on
permeability anisotropy in the eagle ford shale (Unconventional Resources
Technology Conference), Unconventional Resources Technology Conference,
Tulsa, OK, USA, 2014, https://doi.org/10.15530/urtec-2014-1921520.
[89] Y. Tan, Q. Li, L. Xu, A. Ghaffar, X. Zhou, P. Li, A critical review of carbon dioxide
enhanced oil recovery in carbonate reservoirs, Fuel 328 (2022), 125256, https://
doi.org/10.1016/j.fuel.2022.125256.
[90] Z. Song, Y. Song, Y. Li, B. Bai, K. Song, J. Hou, A critical review of CO2 enhanced
oil recovery in tight oil reservoirs of North America and China, Fuel 276 (2020),
118006, https://doi.org/10.1016/j.fuel.2020.118006.
[91] Y. Yibing, M.A. Moh’d, Response of CO2 diffusion to macro- and microporosity in
carbonate reservoirs, SPE Kuwait Oil & Gas Show and Conference, Society of
Petroleum Engineers, Mishref, Kuwait, 2015, https://doi.org/10.2118/175296-
MS.
[92] S.H. Lie, Diffusion as an Oil Recovery Mechanism During CO2 Injection in
Fractured Reservoirs, University of Bergen, 2013.
[93] M. Ghasemi, W. Astutik, S. Alavian, C.H. Whitson, L. Sigalas, D. Olsen, V.
S. Suicmez, High pressure tertiary-CO2 flooding in a fractured chalk reservoir
(SPE Annual Technical Conference and Exhibition), Society of Petroleum
Engineers, San Antonio, Texas, USA, 2017, https://doi.org/10.2118/187349-MS.
[94] M. Khather, A. Saeedi, M.B. Myers, M. Verrall, An experimental study for
carbonate reservoirs on the impact of CO2-EOR on petrophysics and oil recovery,
Fuel 235 (2019) 1019–1038, https://doi.org/10.1016/j.fuel.2018.08.094.
[95] A.M. AlRassas, H. Vo Thanh, S. Ren, R. Sun, N.M. Al-Areeq, O. Kolawole, M.
H. Hakimi, CO2 sequestration and enhanced oil recovery via the water alternating
gas scheme in a mixed transgressive sandstone-carbonate reservoir: Case study of
a large Middle East oilfield, Energy Fuels 36 (2022) 10299–10314, https://doi.
org/10.1021/acs.energyfuels.2c02185.
[96] Q. Zhao, L. Guo, Z. Huang, L. Chen, H. Jin, Y. Wang, Experimental investigation
on enhanced oil recovery of extra heavy oil by supercritical water flooding,
Energy Fuels 32 (2018) 1685–1692, https://doi.org/10.1021/acs.
energyfuels.7b03839.
[97] Q. Zhao, L. Guo, Y. Wang, H. Jin, L. Chen, Z. Huang, Enhanced oil recovery and in
situ upgrading of heavy oil by supercritical water injection, Energy Fuels 34
(2020) 360–367, https://doi.org/10.1021/acs.energyfuels.9b03946.
[98] M. Lashkarbolooki, A. Vaezian, A.Z. Hezave, S. Ayatollahi, M. Riazi, Experimental
investigation of the influence of supercritical carbon dioxide and supercritical
nitrogen injection on tertiary live-oil recovery, J. Supercrit. Fluids 117 (2016)
260–269, https://doi.org/10.1016/j.supflu.2016.07.004.
[99] M. Watanabe, S. Kato, S. Ishizeki, H. Inomata, R.L. Smith, Heavy oil upgrading in
the presence of high density water: basic study, J. Supercrit. Fluids 53 (2010)
48–52, https://doi.org/10.1016/j.supflu.2009.11.013.
[100] M. Morimoto, Y. Sugimoto, Y. Saotome, S. Sato, T. Takanohashi, Effect of
supercritical water on upgrading reaction of oil sand bitumen, J. Supercrit. Fluids
55 (2010) 223–231, https://doi.org/10.1016/j.supflu.2010.08.002.
[101] Z. Shouwei, L. Qingping, L. Xin, F. Qiang, L. Yongfei, Supercritical multisource
multielement thermal fluid injection-production system and injection-production
method, CN106640008A, 2016.
[102] X. Sun, J. Cai, X. Li, W. Zheng, T. Wang, Y. Zhang, Experimental investigation of a
novel method for heavy oil recovery using supercritical multithermal fluid
flooding, Appl. Therm. Eng. 185 (2021), 116330, https://doi.org/10.1016/j.
applthermaleng.2020.116330.
[103] X. Tang, Z. Hua, J. Zhang, Q. Fu, J. Tian, A study on generation and feasibility of
supercritical multi-thermal fluid, Energies 15 (2022) 8027, https://doi.org/
10.3390/en15218027.
[104] X. Tan, W. Zheng, T. Wang, G. Zhu, X. Sun, X. Li, The supercritical multithermal
fluid flooding investigation: experiments and numerical simulation for deep
offshore heavy oil reservoirs, Geofluids 2021 (2021) 1–17, https://doi.org/
10.1155/2021/5589543.
[105] R.A. Kerr, Natural gas from shale bursts onto the scene, Science 328 (2010)
1624–1626, https://doi.org/10.1126/science.328.5986.1624.
[106] U.S. Energy Information Administration, U.S. Energy Information Administration
- EIA - Independent Statistics and Analysis, (n.d.). 〈https://www.eia.gov/today
inenergy/detail.php?id=11611〉 (accessed 23 November 2022).
[107] W.A.M. Wanniarachchi, P.G. Ranjith, M.S.A. Perera, Shale gas fracturing using
foam-based fracturing fluid: a review, Environ. Earth Sci. 76 (2017) 91, https://
doi.org/10.1007/s12665-017-6399-x.
[108] P. Pei, K. Ling, J. He, Z. Liu, Shale gas reservoir treatment by a CO2-based
technology, J. Nat. Gas. Sci. Eng. 26 (2015) 1595–1606, https://doi.org/
10.1016/j.jngse.2015.03.026.
[109] P. Peng, Y. Ju, Y. Wang, S. Wang, F. Gao, Numerical analysis of the effect of
natural microcracks on the supercritical CO2 fracturing crack network of shale
rock based on bonded particle models, Int. J. Numer. Anal. Methods Geomech. 41
(2017) 1992–2013, https://doi.org/10.1002/nag.2712.
[110] T. Ishida, Y. Chen, Z. Bennour, H. Yamashita, S. Inui, Y. Nagaya, M. Naoi,
Q. Chen, Y. Nakayama, Y. Nagano, Features of CO2 fracturing deduced from
acoustic emission and microscopy in laboratory experiments, J. Geophys. Res.
Solid Earth 121 (2016) 8080–8098, https://doi.org/10.1002/2016JB013365.
[111] X. Zhang, Y. Lu, J. Tang, Z. Zhou, Y. Liao, Experimental study on fracture
initiation and propagation in shale using supercritical carbon dioxide fracturing,
Fuel 190 (2017) 370–378, https://doi.org/10.1016/j.fuel.2016.10.120.
23
Journal of CO2 Utilization 72 (2023) 102479
[112] L. Liu, W. Zhu, C. Wei, D. Elsworth, J. Wang, Microcrack-based geomechanical
modeling of rock-gas interaction during supercritical CO2 fracturing, J. Pet. Sci.
Eng. 164 (2018) 91–102, https://doi.org/10.1016/j.petrol.2018.01.049.
[113] J. He, L. Afolagboye, C. Lin, X. Wan, An experimental investigation of hydraulic
fracturing in shale considering anisotropy and using freshwater and supercritical
CO2, Energies 11 (2018) 557, https://doi.org/10.3390/en11030557.
[114] G. Feng, Y. Kang, Z. Sun, X. Wang, Y. Hu, Effects of supercritical CO2 adsorption
on the mechanical characteristics and failure mechanisms of shale, Energy 173
(2019) 870–882, https://doi.org/10.1016/j.energy.2019.02.069.
[115] M.M. Reynolds, R.C. Bachman, W.E. Peters, A Comparison of the effectiveness of
various fracture fluid systems used in multi-stage fractured horizontal wells:
montney formation, unconventional gas (SPE Technology Conference), Society of
Petroleum Engineers, The Woodlands, Texas, USA, 2014, https://doi.org/
10.2118/168632-MS.
[116] J.J. Kolle, Coiled-tubing drilling with supercritical carbon dioxide (SPE/CIM
International Conference on Horizontal Well Technology), Society of Petroleum
Engineers, Calgary, Alberta, Canada, 2000, https://doi.org/10.2118/65534-MS.
[117] A.P. Gupta, A. Gupta, J. Langlinais, Feasibility of supercritical carbon dioxide as a
drilling fluid for deep underbalanced drilling operations, 2005 SPE Annual
Technical Conference and Exhibition, Society of Petroleum Engineers, Dallas,
Texas, USA, 2005, https://doi.org/10.2118/96992-MS.
[118] F. Al-Adwani, J. Langlinais, R. Hughes, Modeling of an underbalanced-drilling
operation using supercritical carbon dioxide, SPE Drill. Complet. 24 (2009)
599–610, https://doi.org/10.2118/114050-PA.
[119] Y. Du, R. Wang, H. Ni, M. Li, W. Song, H. Song, Determination of rock-breaking
performance of high-pressure supercritical carbon dioxide Jet, J. Hydrodyn. 24
(2012) 554–560, https://doi.org/10.1016/S1001-6058(11)60277-1.
[120] F.M. Llave, F.T.-H. Chung, T.E. Burchfield, Use off entrainers in improving
mobility control of supercritical CO2, SPE Reserv. Eng. 5 (1990) 47–51, https://
doi.org/10.2118/17344-PA.
[121] A. Abdelaal, R. Gajbhiye, D. Al-Shehri, Mixed CO2/N2 foam for EOR as a novel
solution for supercritical CO2 foam challenges in sandstone reservoirs, ACS
Omega 5 (2020) 33140–33150, https://doi.org/10.1021/acsomega.0c04801.
[122] P. Nguyen, H. Fadaei, D. Sinton, Pore-scale assessment of nanoparticle-stabilized
CO2 foam for enhanced oil recovery, Energy Fuels 28 (2014) 6221–6227, https://
doi.org/10.1021/ef5011995.
[123] M.A.Q. Siddiqui, R.N. Gajbhiye, Stability and texture of CO2/N2 foam in
sandstone, Colloids Surf., A 534 (2017) 26–37, https://doi.org/10.1016/j.
colsurfa.2017.04.049.
[124] R. Farajzadeh, A. Andrianov, H. Bruining, P.L.J. Zitha, Comparative study of CO2
and N2 foams in porous media at low and high pressure− temperatures, Ind. Eng.
Chem. Res. 48 (2009) 4542–4552, https://doi.org/10.1021/ie801760u.
[125] D.-X. Du, A.N. Beni, R. Farajzadeh, P.L.J. Zitha, Effect of water solubility on
carbon dioxide foam flow in porous media: an X-ray computed tomography study,
Ind. Eng. Chem. Res. 47 (2008) 6298–6306, https://doi.org/10.1021/ie701688j.
[126] C. Zhang, Z. Li, S. Li, Q. Lv, P. Wang, J. Liu, J. Liu, Enhancing Sodium Bis(2-
ethylhexyl) Sulfosuccinate Injectivity for CO2 foam formation in low-permeability
cores: dissolving in CO2 with ethanol, Energy Fuels 32 (2018) 5846–5856,
https://doi.org/10.1021/acs.energyfuels.8b00741.
[127] J. Wang, M. Liang, Q. Tian, Y. Feng, H. Yin, G. Lu, CO2-switchable foams
stabilized by a long-chain viscoelastic surfactant, J. Colloid Interface Sci. 523
(2018) 65–74, https://doi.org/10.1016/j.jcis.2018.03.090.
[128] G. Jian, M.C. Puerto, A. Wehowsky, P. Dong, K.P. Johnston, G.J. Hirasaki, S.
L. Biswal, Static adsorption of an ethoxylated nonionic surfactant on carbonate
minerals, Langmuir 32 (2016) 10244–10252, https://doi.org/10.1021/acs.
langmuir.6b01975.
[129] C. Da, S. Alzobaidi, G. Jian, L. Zhang, S.L. Biswal, G.J. Hirasaki, K.P. Johnston,
Carbon dioxide/water foams stabilized with a zwitterionic surfactant at
temperatures up to 150 ◦ C in high salinity brine, J. Pet. Sci. Eng. 166 (2018)
880–890, https://doi.org/10.1016/j.petrol.2018.03.071.
[130] G. Jian, L. Zhang, C. Da, M. Puerto, K.P. Johnston, S.L. Biswal, G.J. Hirasaki,
Evaluating the transport behavior of CO2 foam in the presence of crude oil under
high-temperature and high-salinity conditions for carbonate reservoirs, Energy
Fuels 33 (2019) 6038–6047, https://doi.org/10.1021/acs.energyfuels.9b00667.
[131] Z. AlYousef, M. Almobarky, D. Schechter, Enhancing the stability of foam by the
use of nanoparticles, Energy Fuels 31 (2017) 10620–10627, https://doi.org/
10.1021/acs.energyfuels.7b01697.
[132] G.G. Bernard, L.R.W. Holm, Method for recovering oil from subterranean
formations, US3342256A, 1964.
[133] D. Xing, B. Wei, K. Trickett, A. Mohamed, J. Eastoe, Y. Soong, R. Enick, CO2-
soluble surfactants for improved mobility control (SPE Improved Oil Recovery
Symposium), Society of Petroleum Engineers, Tulsa, Oklahoma, USA, 2010,
https://doi.org/10.2118/129907-MS.
[134] Y. Chen, A.S. Elhag, A.J. Worthen, P.P. Reddy, A.M. Ou, G.J. Hirasaki, Q.
P. Nguyen, S.L. Biswal, K.P. Johnston, High temperature CO2 -in-water foams
stabilized with cationic quaternary ammonium surfactants, J. Chem. Eng. Data 61
(2016) 2761–2770, https://doi.org/10.1021/acs.jced.6b00135.
[135] Y. Chen, A.S. Elhag, L. Cui, A.J. Worthen, P.P. Reddy, J.A. Noguera, A.M. Ou,
K. Ma, M. Puerto, G.J. Hirasaki, Q.P. Nguyen, S.L. Biswal, K.P. Johnston, CO2 -in-
water foam at elevated temperature and salinity stabilized with a nonionic
surfactant with a high degree of ethoxylation, Ind. Eng. Chem. Res. 54 (2015)
4252–4263, https://doi.org/10.1021/ie503674m.
[136] Y. Chen, A.S. Elhag, B.M. Poon, L. Cui, K. Ma, S.Y. Liao, P.P. Reddy, A.J. Worthen,
G.J. Hirasaki, Q.P. Nguyen, S.L. Biswal, K.P. Johnston, switchable nonionic to
cationic ethoxylated amine surfactants for CO2 enhanced oil recovery in high-
S.K. Prasad et al.
temperature, high-salinity carbonate reservoirs, SPE J. 19 (2014) 249–259,
https://doi.org/10.2118/154222-PA.
[137] Z. Xue, K. Panthi, Y. Fei, K.P. Johnston, K.K. Mohanty, CO2-soluble ionic
surfactants and CO2 foams for high-temperature and high-salinity sandstone
reservoirs, Energy Fuels 29 (2015) 5750–5760, https://doi.org/10.1021/acs.
energyfuels.5b01568.
[138] N. Chennamsetty, H. Bock, L.F. Scanu, F.R. Siperstein, K.E. Gubbins, Cosurfactant
and cosolvent effects on surfactant self-assembly in supercritical carbon dioxide,
J. Chem. Phys. 122 (2005), 094710, https://doi.org/10.1063/1.1855291.
[139] L.C. Burrows, F. Haeri, D. Tapriyal, P. Lemaire, P.G. Shah, A. Alenzi, R.M. Enick,
D.M. Crandall, A. Goodman, CO2-soluble surfactants for enhanced oil recovery
from shale, 9th Unconv. Resour. Technol. Conf, American Association of
Petroleum Geologists, Tulsa, OK, USA, 2021, https://doi.org/10.15530/urtec-
2021-5233.
[140] F. Haeri, L. Burrows, P. Lemaire, P.G. Shah, D. Tapriyal, R.M. Enick, D.
M. Crandall, A. Goodman, Improving CO2-EOR in shale reservoirs using dilute
concentrations of wettability-altering CO2-soluble nonionic surfactants, 8th
Unconv. Resour. Technol. Conf., American Association of Petroleum Geologists,
Tulsa, OK, USA, 2020, https://doi.org/10.15530/urtec-2020-2774.
[141] N.M. Al Hinai, A. Saeedi, C.D. Wood, M. Myers, R. Valdez, A.K. Sooud, A. Sari,
Experimental evaluations of polymeric solubility and thickeners for supercritical
co2 at high temperatures for enhanced oil recovery, Energy Fuels 32 (2018)
1600–1611, https://doi.org/10.1021/acs.energyfuels.7b03733.
[142] A. Al Sumaiti, A.R. Shaik, E.S. Mathew, W. Al Ameri, Tuning foam parameters for
mobility control using co2 foam: field application to maximize oil recovery from a
high temperature high salinity layered carbonate reservoir, Energy Fuels 31
(2017) 4637–4654, https://doi.org/10.1021/acs.energyfuels.6b02595.
[143] S.R.P. da Rocha, J. Dickson, D. Cho, P.J. Rossky, K.P. Johnston, Stubby
surfactants for stabilization of water and CO2 emulsions: trisiloxanes, Langmuir
19 (2003) 3114–3120, https://doi.org/10.1021/la026608y.
[144] J. Eastoe, S. Gold, S. Rogers, P. Wyatt, D.C. Steytler, A. Gurgel, R.K. Heenan,
X. Fan, E.J. Beckman, R.M. Enick, Designed CO2-philes stabilize water-in-carbon
dioxide microemulsions, Angew. Chem. Int. Ed. 45 (2006) 3675–3677, https://
doi.org/10.1002/anie.200600397.
[145] W. Ryoo, S.E. Webber, K.P. Johnston, Water-in-carbon dioxide microemulsions
with methylated branched hydrocarbon surfactants, Ind. Eng. Chem. Res. 42
(2003) 6348–6358, https://doi.org/10.1021/ie0300427.
[146] T.A. Hoefling, R.M. Enick, E.J. Beckman, Microemulsions in near-critical and
supercritical carbon dioxide, J. Phys. Chem. 95 (1991) 7127–7129, https://doi.
org/10.1021/j100172a006.
[147] S. Cummings, D. Xing, R. Enick, S. Rogers, R. Heenan, I. Grillo, J. Eastoe, Design
principles for supercritical CO2 viscosifiers, Soft Matter 8 (2012) 7044, https://
doi.org/10.1039/c2sm25735a.
[148] P.A. Psathas, S.R.P. da Rocha, C.T. Lee, K.P. Johnston, K.T. Lim, S. Webber,
Water-in-carbon dioxide emulsions with Poly(dimethylsiloxane)-based block
copolymer ionomers, Ind. Eng. Chem. Res. 39 (2000) 2655–2664, https://doi.
org/10.1021/ie990779p.
[149] R. Fink, E.J. Beckman, Phase behavior of siloxane-based amphiphiles in
supercritical carbon dioxide, J. Supercrit. Fluids 18 (2000) 101–110, https://doi.
org/10.1016/S0896-8446(00)00052-8.
[150] B.H. Hutton, J.M. Perera, F. Grieser, G.W. Stevens, AOT reverse microemulsions
in sc-CO2—a further investigation, Colloids Surf., A 189 (2001) 177–181, https://
doi.org/10.1016/S0927-7757(01)00474-5.
[151] R.E. Terry, A. Zaid, C. Angelos, D.L. Whitman, Polymerization in supercritical CO2
to improve CO2/oil mobility ratios (SPE International Symposium on Oilfield
Chemistry), Society of Petroleum Engineers, San Antonio, Texas, USA, 1987,
https://doi.org/10.2118/16270-MS.
[152] G.W. Lancaster, C. Barrianios, E. Li, R.C. Greenhorn, High phase volume liquid
CO2 fracturing fluids, 38th Annual Technical Meeting, Petroleum Society of CIM,
Calgary, Canada, 1987, https://doi.org/10.2118/87-38-71.
[153] N.M. Hinai, A. Saeedi, C.D. Wood, R. Valdez, A numerical study of using polymers
to improve the gas flooding in the Harweel cluster (SPE Reservoir
Characterisation and Simulation Conference and Exhibition), Society of
Petroleum Engineers, Abu Dhabi, UAE, 2017, https://doi.org/10.2118/185999-
MS.
[154] M.J. O’Brien, R.J. Perry, M.D. Doherty, J.J. Lee, A. Dhuwe, E.J. Beckman, R.
M. Enick, Anthraquinone siloxanes as thickening agents for supercritical CO2,
Energy Fuels 30 (2016) 5990–5998, https://doi.org/10.1021/acs.
energyfuels.6b00946.
[155] M.L. O’Neill, Q. Cao, M. Fang, K.P. Johnston, S.P. Wilkinson, C.D. Smith, J.
L. Kerschner, S.H. Jureller, Solubility of homopolymers and copolymers in carbon
dioxide, Ind. Eng. Chem. Res. 37 (1998) 3067–3079, https://doi.org/10.1021/
ie980010x.
[156] R. Fink, D. Hancu, R. Valentine, E.J. Beckman, Toward the Development of “CO2-
philic” hydrocarbons. 1. Use of side-chain functionalization to lower the
miscibility pressure of polydimethylsiloxanes in CO2, J. Phys. Chem. B. 103
(1999) 6441–6444, https://doi.org/10.1021/jp990333m.
[157] J.H. Bae, C.A. Irani, A laboratory investigation of viscosified CO2 Process, SPE
Adv. Technol. Ser. 1 (1993) 166–171, https://doi.org/10.2118/20467-PA.
[158] Z. Shen, M. McHugh, J. Xu, J. Belardi, S. Kilic, A. Mesiano, S. Bane, C. Karnikas,
E. Beckman, R. Enick, CO2-solubility of oligomers and polymers that contain the
carbonyl group, Polym. (Guildf. ) 44 (2003) 1491–1498, https://doi.org/
10.1016/S0032-3861(03)00020-X.
[159] D. Rousseau, S. Renard, B. Prempain, C. Féjean, S. Betoulle, CO2 Mobility control
with dissolved polymers: a core-scale investigation of polymer-rock and polymer-
oil interactions, 18th SPE Improved Oil Recovery Symposium, Society of
24
Journal of CO2 Utilization 72 (2023) 102479
Petroleum Engineers, Tulsa, Oklahoma, USA, 2012, https://doi.org/10.2118/
154055-MS.
[160] F. Rindfleisch, T.P. DiNoia, M.A. McHugh, Solubility of polymers and copolymers
in supercritical CO2, J. Phys. Chem. 100 (1996) 15581–15587, https://doi.org/
10.1021/jp9615823.
[161] R. Enick, E. Beckman, A. Yazdi, V. Krukonis, H. Schonemann, J. Howell, Phase
behavior of CO2–perfluoropolyether oil mixtures and CO2–perfluoropolyether
chelating agent mixtures, J. Supercrit. Fluids 13 (1998) 121–126, https://doi.org/
10.1016/S0896-8446(98)00043-6.
[162] C. Shi, Z. Huang, E.J. Beckman, R.M. Enick, S.Y. Kim, D.P. Curran, Semi-
fluorinated trialkyltin fluorides and fluorinated telechelic ionomers as viscosity-
enhancing agents for carbon dioxide, Ind. Eng. Chem. Res. 40 (2001) 908–913,
https://doi.org/10.1021/ie0001321.
[163] Z. Huang, C. Shi, J. Xu, S. Kilic, R.M. Enick, E.J. Beckman, Enhancement of the
viscosity of carbon dioxide using styrene/fluoroacrylate copolymers,
Macromolecules 33 (2000) 5437–5442, https://doi.org/10.1021/ma992043+.
[164] W. Sun, B. Sun, Y. Li, H. Fan, Y. Gao, H. Sun, G. Li, Microcosmic understanding on
thickening capability of copolymers in supercritical carbon dioxide: the key role
of π–π stacking, RSC Adv. 7 (2017) 34567–34573, https://doi.org/10.1039/
C7RA06041F.
[165] J.P. Heller, D.K. Dandge, R.J. Card, L.G. Donaruma, Direct thickeners for mobility
control of CO2 floods, Soc. Pet. Eng. J. 25 (1985) 679–686, https://doi.org/
10.2118/11789-PA.
[166] S. Zhang, Y. She, Y. Gu, Evaluation of polymers as direct thickeners for CO2
enhanced oil recovery, J. Chem. Eng. Data 56 (2011) 1069–1079, https://doi.
org/10.1021/je1010449.
[167] P. Xue, J. Shi, X. Cao, S. Yuan, Molecular dynamics simulation of thickening
mechanism of supercritical CO2 thickener, Chem. Phys. Lett. 706 (2018)
658–664, https://doi.org/10.1016/j.cplett.2018.07.006.
[168] T. Ragunathan, H. Husin, C.D. Wood, Wax formation mechanisms, wax chemical
inhibitors and factors affecting chemical inhibition, Appl. Sci. 10 (2020) 479,
https://doi.org/10.3390/app10020479.
[169] N.M. Al Hinai, A. Saeedi, C.D. Wood, R. Valdez, L. Esteban, Experimental study of
miscible thickened natural gas injection for enhanced oil recovery, Energy Fuels
31 (2017) 4951–4965, https://doi.org/10.1021/acs.energyfuels.7b00314.
[170] T. Kraska, K.O. Leonhard, D. Tuma, G.M. Schneider, Correlation of the solubility
of low-volatile organic compounds in near- and supercritical fluids. Part I:
Applications to adamantane and β-carotene, J. Supercrit. Fluids 23 (2002)
209–224, https://doi.org/10.1016/S0896-8446(02)00003-7.
[171] C.J. Seeton, Viscosity–temperature correlation for liquids, Tribol. Lett. 22 (2006)
67–78, https://doi.org/10.1007/s11249-006-9071-2.
[172] J.J. Lee, S.D. Cummings, E.J. Beckman, R.M. Enick, W.A. Burgess, M.D. Doherty,
M.J. O’Brien, R.J. Perry, The solubility of low molecular weight Poly(Dimethyl
siloxane) in dense CO2 and its use as a CO2-philic segment, J. Supercrit. Fluids
119 (2017) 17–25, https://doi.org/10.1016/j.supflu.2016.08.003.
[173] L. Jin, L.J. Pekot, S.B. Hawthorne, O. Salako, K.J. Peterson, N.W. Bosshart,
T. Jiang, J.A. Hamling, C.D. Gorecki, Evaluation of recycle gas injection on CO2
enhanced oil recovery and associated storage performance, Int. J. Greenh. Gas.
Control. 75 (2018) 151–161, https://doi.org/10.1016/j.ijggc.2018.06.001.
[174] S. Kumar, J. Foroozesh, K. Edlmann, M.G. Rezk, C.Y. Lim, A comprehensive
review of value-added CO2 sequestration in subsurface saline aquifers, J. Nat.
Gas. Sci. Eng. 81 (2020), 103437, https://doi.org/10.1016/j.jngse.2020.103437.
[175] H. Emami-Meybodi, H. Hassanzadeh, C.P. Green, J. Ennis-King, Convective
dissolution of CO2 in saline aquifers: progress in modeling and experiments, Int. J.
Greenh. Gas. Control 40 (2015) 238–266, https://doi.org/10.1016/j.
ijggc.2015.04.003.
[176] S.S.H. Boosari, U. Aybar, M.O. Eshkalak, Carbon dioxide storage and
sequestration in unconventional shale reservoirs, J. Geosci. Environ. Prot. 03
(2015) 7–15, https://doi.org/10.4236/gep.2015.31002.
[177] S. Bachu, D. Bonijoly, J. Bradshaw, R. Burruss, S. Holloway, N.P. Christensen, O.
M. Mathiassen, CO2 storage capacity estimation: methodology and gaps, Int. J.
Greenh. Gas. Control. 1 (2007) 430–443, https://doi.org/10.1016/S1750-5836
(07)00086-2.
[178] R. Khosrokhavar, S. Griffiths, K.-H. Wolf, Shale gas formations and their potential
for carbon storage: Opportunities and outlook, Environ. Process. 1 (2014)
595–611, https://doi.org/10.1007/s40710-014-0036-4.
[179] A. Busch, S. Alles, Y. Gensterblum, D. Prinz, D.N. Dewhurst, M.D. Raven,
H. Stanjek, B.M. Krooss, Carbon dioxide storage potential of shales, Int. J. Greenh.
Gas. Control 2 (2008) 297–308, https://doi.org/10.1016/j.ijggc.2008.03.003.
[180] P. Weniger, W. Kalkreuth, A. Busch, B.M. Krooss, High-pressure methane and
carbon dioxide sorption on coal and shale samples from the Paraná Basin, Brazil,
Int. J. Coal Geol. 84 (2010) 190–205, https://doi.org/10.1016/j.
coal.2010.08.003.
[181] R. Heller, M. Zoback, Adsorption of methane and carbon dioxide on gas shale and
pure mineral samples, J. Unconv. Oil Gas. Resour. 8 (2014) 14–24, https://doi.
org/10.1016/j.juogr.2014.06.001.
[182] S.M. Kang, E. Fathi, R.J. Ambrose, I.Y. Akkutlu, R.F. Sigal, Carbon dioxide storage
capacity of organic-rich shales (SPE Annual Technical Conference and
Exhibition), Society of Petroleum Engineers,, Florence, Italy, 2010, https://doi.
org/10.2118/134583-MS.
[183] Y. Liu, J. Wilcox, Molecular simulation studies of CO2 adsorption by carbon model
compounds for carbon capture and sequestration applications, Environ. Sci.
Technol. 47 (2013) 95–101, https://doi.org/10.1021/es3012029.
[184] D. Liu, Y. Li, R. Agarwal, Evaluation of CO2 storage in a shale gas reservoir
compared to a deep saline aquifer in the Ordos basin of China, Energies 13 (2020)
3397, https://doi.org/10.3390/en13133397.
S.K. Prasad et al.
[185] D. Liu, Y. Li, R.K. Agarwal, Numerical simulation of long-term storage of CO2 in
Yanchang shale reservoir of the Ordos basin in China, Chem. Geol. 440 (2016)
288–305, https://doi.org/10.1016/j.chemgeo.2016.08.002.
[186] M. Gu, X. Xian, S. Duan, X. Du, Influences of the composition and pore structure
of a shale on its selective adsorption of CO2 over CH4, J. Nat. Gas. Sci. Eng. 46
(2017) 296–306, https://doi.org/10.1016/j.jngse.2017.07.011.
[187] J. Liu, L. Xie, D. Elsworth, Q. Gan, CO2 /CH4 Competitive adsorption in shale:
implications for enhancement in gas production and reduction in carbon
emissions, Environ. Sci. Technol. 53 (2019) 9328–9336, https://doi.org/
10.1021/acs.est.9b02432.
[188] J. Zhou, S. Xie, Y. Jiang, X. Xian, Q. Liu, Z. Lu, Q. Lyu, Influence of supercritical
CO2 exposure on CH4 and CO2 adsorption behaviors of shale: Implications for CO2
Sequestration, Energy Fuels 32 (2018) 6073–6089, https://doi.org/10.1021/acs.
energyfuels.8b00551.
[189] H. Ott, K. de Kloe, M. van Bakel, F. Vos, A. van Pelt, P. Legerstee, A. Bauer,
K. Eide, A. van der Linden, S. Berg, A. Makurat, Core-flood experiment for
transport of reactive fluids in rocks, Rev. Sci. Instrum. 83 (2012), 084501,
https://doi.org/10.1063/1.4746997.
[190] Y. Zou, S. Li, X. Ma, S. Zhang, N. Li, M. Chen, Effects of CO2 –brine–rock
interaction on porosity/permeability and mechanical properties during
supercritical-CO2 fracturing in shale reservoirs, J. Nat. Gas. Sci. Eng. 49 (2018)
157–168, https://doi.org/10.1016/j.jngse.2017.11.004.
[191] B. Wei, X. Zhang, J. Liu, X. Xu, W. Pu, M. Bai, Adsorptive behaviors of
supercritical CO2 in tight porous media and triggered chemical reactions with
rock minerals during CO2-EOR and sequestration, Chem. Eng. J. 381 (2020),
122577, https://doi.org/10.1016/j.cej.2019.122577.
[192] Y. Zhang, Z. Zhang, M. Arif, M. Lebedev, A. Busch, M. Sarmadivaleh, S. Iglauer,
Carbonate rock mechanical response to CO2 flooding evaluated by a combined X-
ray computed tomography–DEM method, J. Nat. Gas. Sci. Eng. 84 (2020),
103675, https://doi.org/10.1016/j.jngse.2020.103675.
[193] Y. Tang, S. Hu, Y. He, Y. Wang, X. Wan, S. Cui, K. Long, Experiment on CO2-brine-
rock interaction during CO2 injection and storage in gas reservoirs with aquifer,
Chem. Eng. J. 413 (2021), 127567, https://doi.org/10.1016/j.cej.2020.127567.
[194] K.M. Mouzakis, A.K. Navarre-Sitchler, G. Rother, J.L. Bañuelos, X. Wang, J.
P. Kaszuba, J.E. Heath, Q.R.S. Miller, V. Alvarado, J.E. McCray, Experimental
study of porosity changes in shale caprocks exposed to CO2-saturated Brines I:
evolution of mineralogy, pore connectivity, pore size distribution, and surface
area, Environ. Eng. Sci. 33 (2016) 725–735, https://doi.org/10.1089/
ees.2015.0588.
[195] S. Zhang, X. Xian, J. Zhou, L. Zhang, mechanical behaviour of Longmaxi black
shale saturated with different fluids: an experimental study, RSC Adv. 7 (2017)
42946–42955, https://doi.org/10.1039/C7RA07179E.
[196] G.W. Kling, M.A. Clark, G.N. Wagner, H.R. Compton, A.M. Humphrey, J.
D. Devine, W.C. Evans, J.P. Lockwood, M.L. Tuttle, E.J. Koenigsberg, The 1986
Lake Nyos Gas Disaster in Cameroon, West Africa, Science 236 (1987) 169–175,
https://doi.org/10.1126/science.236.4798.169.
[197] J.A. Sorensen, J.R. Braunberger, G. Liu, S.A. Smith, R.C.L. Klenner, E.
N. Steadman, J.A. Harju, CO2 storage and utilization in tight hydrocarbon-bearing
formations: a case study of the Bakken formation in the Williston basin, Energy
Procedia 63 (2014) 7852–7860, https://doi.org/10.1016/j.egypro.2014.11.820.
[198] Q. Lyu, P. Ranjith, X. Long, B. Ji, Experimental investigation of mechanical
properties of black shales after CO2-water-rock interaction, Materials 9 (2016)
663, https://doi.org/10.3390/ma9080663.
[199] S. Jiang, Y. Li, F. Wang, H. Sun, H. Wang, Z. Yao, A state-of-the-art review of CO2
enhanced oil recovery as a promising technology to achieve carbon neutrality in
China, Environ. Res. 210 (2022), 112986, https://doi.org/10.1016/j.
envres.2022.112986.
[200] I. Ghiat, T. Al-Ansari, A review of carbon capture and utilisation as a CO2
abatement opportunity within the EWF nexus, J. CO2 Util. 45 (2021), 101432,
https://doi.org/10.1016/j.jcou.2020.101432.
[201] V. Núñez-López, E. Moskal, Potential of CO2-EOR for near-term decarbonization,
Front. Clim. 1 (2019), https://doi.org/10.3389/fclim.2019.00005.
[202] K.Y. Hornafius, J.S. Hornafius, Carbon negative oil: a pathway for CO2 emission
reduction goals, Int. J. Greenh. Gas. Control. 37 (2015) 492–503, https://doi.org/
10.1016/j.ijggc.2015.04.007.
[203] B.B. Nielsen, W.Y. Svrcek, A.K. Mehrotra, Effects of temperature and pressure on
asphaltene particle size distributions in crude oils diluted with n-Pentane, Ind.
Eng. Chem. Res. 33 (1994) 1324–1330, https://doi.org/10.1021/ie00029a031.
[204] R.K. Srivastava, S.S. Huang, Asphaltene deposition during CO2 flooding: a
laboratory assessment. SPE Production Operations Symposium, Society of
Petroleum Engineers,, Oklahoma, USA, 1997, https://doi.org/10.2118/37468-
MS.
[205] S. Takahashi, Y. Hayashi, S. Takahashi, N. Yazawa, H. Sarma, Characteristics and
impact of asphaltene precipitation during CO2 injection in sandstone and
carbonate cores: An investigative analysis through laboratory tests and
compositional simulation. SPE International Improved Oil Recovery Conference
in Asia Pacific, Society of Petroleum Engineers,, Kuala Lumpur, Malaysia, 2003,
https://doi.org/10.2118/84895-MS.
[206] S. Verdier, H. Carrier, S.I. Andersen, J.-L. Daridon, Study of pressure and
temperature effects on asphaltene stability in presence of CO2, Energy Fuels 20
(2006) 1584–1590, https://doi.org/10.1021/ef050430g.
[207] P. Zanganeh, S. Ayatollahi, A. Alamdari, A. Zolghadr, H. Dashti, S. Kord,
Asphaltene deposition during CO2 injection and pressure depletion: a visual
study, Energy Fuels 26 (2012) 1412–1419, https://doi.org/10.1021/ef2012744.
25
Journal of CO2 Utilization 72 (2023) 102479
[208] T.F. Headen, E.S. Boek, Molecular dynamics simulations of asphaltene
aggregation in supercritical carbon dioxide with and without limonene, Energy
Fuels 25 (2011) 503–508, https://doi.org/10.1021/ef1010397.
[209] B. Liu, J. Li, C. Qi, X. Li, T. Mai, J. Zhang, Mechanism of asphaltene aggregation
induced by supercritical CO2: Insights from molecular dynamics simulation, RSC
Adv. 7 (2017) 50786–50793, https://doi.org/10.1039/C7RA09736K.
[210] M. Deo, M. Parra, Characterization of carbon-dioxide-induced asphaltene
precipitation, Energy Fuels 26 (2012) 2672–2679, https://doi.org/10.1021/
ef201402v.
[211] G. Sun, C. Li, S. Yang, F. Yang, Y. Chen, Experimental investigation of the
rheological properties of a typical waxy crude oil treated with supercritical CO2
and the stability change in its emulsion, Energy Fuels 33 (2019) 4731–4739,
https://doi.org/10.1021/acs.energyfuels.8b04176.
[212] Z. Shen, J.J. Sheng, Experimental study of asphaltene aggregation during CO2 and
CH4 injection in shale oil reservoirs (SPE Improved Oil Recovery Conference),
Society of Petroleum Engineers, Tulsa, Oklahoma, USA, 2016, https://doi.org/
10.2118/179675-MS.
[213] Z. Shen, J.J. Sheng, Experimental and numerical study of permeability reduction
caused by asphaltene precipitation and deposition during CO2 huff and puff
injection in Eagle Ford shale, Fuel 211 (2018) 432–445, https://doi.org/10.1016/
j.fuel.2017.09.047.
[214] G.W. Bullock, T.B. Wood, M.L. Konecki, A brief history of the Wasson EOR
project, SPE Prod. Eng. 5 (1990) 338–344, https://doi.org/10.2118/17754-PA.
[215] L. Jin, L.J. Pekot, S.A. Smith, O. Salako, K.J. Peterson, N.W. Bosshart, J.
A. Hamling, B.A.F. Mibeck, J.P. Hurley, C.J. Beddoe, C.D. Gorecki, Effects of gas
relative permeability hysteresis and solubility on associated CO2 storage
performance, Int. J. Greenh. Gas. Control. 75 (2018) 140–150, https://doi.org/
10.1016/j.ijggc.2018.06.002.
[216] E.A. Al-Khdheeawi, S. Vialle, A. Barifcani, M. Sarmadivaleh, S. Iglauer, Effect of
wettability heterogeneity and reservoir temperature on CO2 storage efficiency in
deep saline aquifers, Int. J. Greenh. Gas. Control. 68 (2018) 216–229, https://doi.
org/10.1016/j.ijggc.2017.11.016.
[217] A. Raza, R. Rezaee, C.H. Bing, R. Gholami, M.A. Hamid, R. Nagarajan, Carbon
dioxide storage in subsurface geologic medium: a review on capillary trapping
mechanism, Egypt. J. Pet. 25 (2016) 367–373, https://doi.org/10.1016/j.
ejpe.2015.08.002.
[218] A. Mur, C. Barajas-Olalde, D.C. Adams, L. Jin, J. He, J.A. Hamling, C.D. Gorecki,
Integrated simulation to seismic and seismic reservoir characterization in a CO2
EOR monitoring application, Lead. Edge 39 (2020) 668–678, https://doi.org/
10.1190/tle39090668.1.
[219] C. Barajas-Olalde, A. Mur, D.C. Adams, L. Jin, J. He, J.A. Hamling, C.D. Gorecki,
Joint impedance and facies inversion of time-lapse seismic data for improving
monitoring of CO2 incidentally stored from CO2 EOR, Int. J. Greenh. Gas. Control.
112 (2021), 103501, https://doi.org/10.1016/j.ijggc.2021.103501.
[220] V. de Lima, S. Einloft, J.M. Ketzer, M. Jullien, O. Bildstein, J.-C. Petronin, CO2
Geological storage in saline aquifers: Paraná Basin caprock and reservoir chemical
reactivity, Energy Procedia 4 (2011) 5377–5384, https://doi.org/10.1016/j.
egypro.2011.02.521.
[221] Z. Li, M. Dong, S. Li, S. Huang, CO2 sequestration in depleted oil and gas
reservoirs—caprock characterization and storage capacity, Energy Convers.
Manag 47 (2006) 1372–1382, https://doi.org/10.1016/j.
enconman.2005.08.023.
[222] S. Nakagawa, T.J. Kneafsey, T.M. Daley, B.M. Freifeld, E.V. Rees, Laboratory
seismic monitoring of supercritical CO2 flooding in sandstone cores using the split
Hopkinson resonant bar technique with concurrent X-ray computed tomography
imaging, Geophys. Prospect 61 (2013) 254–269, https://doi.org/10.1111/1365-
2478.12027.
[223] O. Salako, L. Jin, C. Barajas-Olalde, J.A. Hamling, C.D. Gorecki, Implementing
adaptive scaling and dynamic well-tie for quantitative 4-D seismic evaluation of a
reservoir subjected to CO2 enhanced oil recovery and associated storage, Int. J.
Greenh. Gas. Control. 78 (2018) 306–326, https://doi.org/10.1016/j.
ijggc.2018.08.015.
[224] D. White, Monitoring CO2 storage during EOR at the Weyburn-midale Field, Lead.
Edge 28 (2009) 838–842, https://doi.org/10.1190/1.3167786.
[225] Q. Yang, W. Zhao, T.H. Dixon, F. Amelung, W.S. Han, P. Li, InSAR monitoring of
ground deformation due to CO2 injection at an enhanced oil recovery site, West
Texas, Int. J. Greenh. Gas. Control. 41 (2015) 20–28, https://doi.org/10.1016/j.
ijggc.2015.06.016.
[226] M.A. Karegar, T.H. Dixon, R. Malservisi, Q. Yang, S.A. Hossaini, S.D. Hovorka,
GPS-based monitoring of surface deformation associated with CO2 injection at an
enhanced oil recovery site, Int. J. Greenh. Gas. Control. 41 (2015) 116–126,
https://doi.org/10.1016/j.ijggc.2015.07.006.
[227] M. Cai, Y. Su, Y. Hao, Y. Guo, D. Elsworth, L. Li, D. Li, X. Li, Monitoring oil
displacement and CO2 trapping in low-permeability media using NMR: a
comparison of miscible and immiscible flooding, Fuel 305 (2021), 121606,
https://doi.org/10.1016/j.fuel.2021.121606.
[228] F. Zhang, Q. Zhang, R.P. Gardner, J. Liu, X. Zhang, F. Qiu, Q. Chen, L. Tian,
Y. Wang, Quantitative monitoring of CO2 sequestration using thermal neutron
detection technique in heavy oil reservoirs, Int. J. Greenh. Gas. Control. 79 (2018)
154–164, https://doi.org/10.1016/j.ijggc.2018.10.003.
[229] J. Suebsiri, M. Wilson, P. Tontiwachwuthikul, Life-cycle analysis of CO2 EOR on
EOR and geological storage through economic optimization and sensitivity
analysis using the Weyburn unit as a case study, Ind. Eng. Chem. Res. 45 (2006)
2483–2488, https://doi.org/10.1021/ie050909w.
S.K. Prasad et al.
[230] M. Wang, G.L. Song, An analytical model for the corrosion risk of water
alternating gas injection wells in CO2 enhanced oil recovery, Adv. Theory Simul. 1
(2018) 1800041, https://doi.org/10.1002/adts.201800041.
[231] Z.M. Wang, X.T. Liu, X. Han, J. Zhang, Managing internal corrosion of mild steel
pipelines in CO2-enhanced oil recovery multiphase flow conditions, Energy
Technol. 3 (2015) 225–233, https://doi.org/10.1002/ente.201402159.
[232] J.D. Laumb, K.A. Glazewski, J.A. Hamling, A. Azenkeng, T.L. Watson, Wellbore
corrosion and failure assessment for CO2 EOR and storage: two case studies in the
Weyburn field, Int. J. Greenh. Gas. Control. 54 (2016) 479–489, https://doi.org/
10.1016/j.ijggc.2016.08.031.
[233] M.Y. Khan, A. Kohata, H. Patel, F.I. Syed, A.K.Al Sowaidi, Water alternating gas
wag optimization using tapered wag technique for a giant offshore middle east oil
26
Journal of CO2 Utilization 72 (2023) 102479
field. Abu Dhabi International Petroleum Exhibition & Exhibition, Society of
Petroleum Engineers, Abu Dhabi, UAE, 2016, https://doi.org/10.2118/183181-
MS.
[234] D. Stern, Effects of pore-level fluid distribution, 66th Annual Technical
Conference and Exhibition, Society of Petroleum Engineers, Dallas, Texas, USA,
1991, https://doi.org/10.2118/22652-MS.
[235] Z. Dai, H. Viswanathan, R. Middleton, F. Pan, W. Ampomah, C. Yang, W. Jia,
T. Xiao, S.-Y. Lee, B. McPherson, R. Balch, R. Grigg, M. White, CO2 accounting
and risk analysis for CO2 sequestration at enhanced oil recovery sites, Environ.
Sci. Technol. 50 (2016) 7546–7554, https://doi.org/10.1021/acs.est.6b01744.