Journal of Petroleum Science and Engineering 205 (2021) 108793

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

Fracturing technology with carbon dioxide: A review

Li Nianyin a, Yu Jiajie a, *, Wang Chao a, Zhang Suiwang b, Liu Xiangke c, Kang Jia a, Wang Yuan a,
Dai Yinhong a
a
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, China
b
Oil and Gas Technology Research Institute of PetroChina Changqing Oilfield Company, Xian, China
c
Engineering Technology Research Institute of Petrochina Southwest Oil and Gas Field Company, Chengdu, 610000, China

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

Keywords: As unconventional oil and gas have increasingly gained considerable attention, the application of water-free
Unconventional resources fracturing technology represented by carbon dioxide (CO2) fracturing technology in unconventional oil and
CO2 phase change gas resources development has broad prospects. The CO2 fracturing technology has several advantages, such as
CO2 fracturing
low damage and easy flowback. It is especially suitable for complex rock strata exhibiting low pressure, low
Fracture initiation and propagation
permeability, and strong water sensitivity. Moreover, this technology positively affects the reservoir with low
water content and experiencing serious pollution. In this paper, the related literature of the different CO2
fracturing technologies from the aspects of technical principle and technological process, technical character­
istics, fracturing fluid system, and field application is analyzed, the fracture initiation and propagation are
summarized as well. The results indicate that CO2 fracturing can stimulate unconventional reservoirs more
effectively than the conventional hydraulic fracturing, exhibits high technical feasibility, and can be applied in
the reservoir stimulation and reconstruction in the future. In this paper, how to further improve the viscosity of
fracturing fluid, enhance the sand-carrying capacity of fracturing fluid, and reduce the pipeline friction is
determined.

1. Introduction However, the traditional water-based fracturing fluid induces incom­

Economic construction and development are seriously restricted by
energy utilization. The conventional oil and gas resources cannot satisfy
people’s demand for energy resources. With the progress of oil and gas
field technology, the development of unconventional oil and gas re­
sources exhibiting low permeability has increasingly attracted consid­
erable attention (Holditch, 2013). The development and potential
application of unconventional oil and gas determine the pattern of
future energy market. Currently, there are great opportunities for such a
development; however, they are accompanied by multiple challenges.
The evaluation of tight oil and gas is becoming more and more mature.
Moreover, the contribution of tight oil and gas has become increasingly
important (Cui, 2019a, 2019b). In recent years, shale gas and tight oil
are the main unconventional fossil fuels in North America (ight
oil-producing, 2019). China’s shale gas in the Asia-Pacific region and
coalbed methane in Australia are adequate examples of success (Mauter
et al., 2014; Yuzhu, 2018). The unconventional oil and gas in Europe
have also made breakthroughs (Estrada and Bhamidimarri, 2016).
plete gel breaking and incomplete flowback, is significantly retained in
the formation, and causes serious damage to the formation. What is
more, the conventional hydraulic fracturing consumes a huge amount of
water resources, and its application in areas experiencing water shortage
is significantly restricted (Johnson and Frost, 2018). In addition, hy­
draulic fracturing poses a risk for environmental pollution (Bostrom
et al., 2014). The commonly used water-based fracturing fluid also has
several drawbacks, such as incomplete gel breaking, high residue con­
tent, clay swelling, and difficulty in flowback, which also affect the
development of fracturing technology (Wang et al., 2014). Even in some
countries, the application of hydraulic fracturing has been prohibited
(Scholtens, 2017). Thus, to produce unconventional oil and gas, the use
of a more suitable fracturing fluid needs to be considered. New anhy­
drous fracturing technologies, which are mainly employed for the
stimulation of unconventional reservoirs, have emerged one after
another (Fu and Liu, 2019; Zhang et al., 2019). Among them, CO2
fracturing is considered to be safer for the environment and enables
water resource conservation, oil and gas production improvement, and

* Corresponding author.
E-mail address: yujiajie_swpu@163.com (Y. Jiajie).

https://doi.org/10.1016/j.petrol.2021.108793
Received 16 November 2020; Received in revised form 24 February 2021; Accepted 7 April 2021
Available online 17 April 2021
0920-4105/© 2021 Elsevier B.V. All rights reserved.
L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

CO2 storage (Li et al., 2017a; Sun et al., 2014; Monjezi et al., 2020).
Moreover, CO2 fracturing has the potential for application in the stim­
ulation and development of unconventional oil and gas reservoirs
(KHSMS et al., 2017; Siqi, 2020; Yang et al., 2019). The mixture of sand
and liquid carbon dioxide (CO2) has been successfully used in fracturing
owing to its advantages (Lillies and King, 1982; Bennour et al., 2018; Li
et al., 2016). The strong self-supporting potential of reservoir rock, in
addition to the proppant effect of sand, is important to achieve suc­
cessful CO2 fracturing. Due to the low viscosity of fracturing fluid, the
bearing capacity of CO2 proppant is also low; this state is not conducive
to the placement of proppant, thus limiting the application of CO2
fracturing. The more complex and extensive fracture network produced
by CO2 fracturing overcomes the disadvantage of ultralow permeability
of unconventional reservoirs (Middleton et al., 2015). CO2 is also
environmentally friendly. When CO2 is injected into the formation, it
can indirectly reduce the greenhouse gases in the atmosphere and
relieving environmental pressure. Contrary to hydraulic fracturing, CO2
fracturing does not consume a significant amount of water resources,
and it induces only low damage and easy flowback during the fracturing
process. This process has been widely studied, and the results of labo­ Fig. 1. Compressibility under different CO2 partial pressures (Carbon dioxide:
ratory and field tests indicate that the CO2 fracturing technology ex­ temperatu, 2018) (a) Boyle curve (b) Vapor liquid two phase region (c) Vapor
hibits high technical feasibility and good input–output ratio. phase region (d) Liquid phase region.
Currently, the CO2 fracturing technology is mainly categorized into
CO2 foam fracturing technology, CO2 dry fracturing technology, super­ Fig. 1 shows the compressibility at different CO2 partial pressures.
critical CO2 fracturing technology, and some special CO2 fracturing
pV
technology (e.g., CO2 mixed fracturing technology, secondary atmo­ A=
p0 V0
spheric pressure sand-mixing quasi-dry fracturing technology, and CO2
phase change fracturing technology). And CO2 can also be used in foam where p, p0, V and V0 is the pressure and volume of real gas and ideal gas
acid fracturing (Karadkar et al., 2018). In this paper, the CO2 fracturing respectively. The compressibility factor Z can be obtained from the value
technology is introduced based on the aspects of technical principle, of A. Z = A(T/T0), where T and T0 represent the real temperature and
technological process, technical characteristics, fracturing fluid system, standard state temperature of the gas respectively. The compression
and field application. The laboratory experiment and numerical simu­ factor is related to the contrast pressure Pr and the contrast temperature
lation of fracture initiation and propagation are summarized. The Tr. the same compression factor should be obtained under the same
existing problems of CO2 fracturing are also analyzed, and we look contrast pressure and temperature.
forward to the future developmental direction.

2. Properties of CO2 2.2. Phase characteristics of CO2

2.1. PVT properties of CO2
Carbon dioxide is commonly known as carbonic acid gas. Under the
standard conditions, carbon dioxide is colorless, odorless, slightly acidic
gas, with a relative molecular weight of 44.01. It can not be burned and
is easy to be liquefied. Its relative density is about 1.53 times that of air.
The main physical properties are shown in Table 1.
Under ideal conditions, the equation of state of carbon dioxide can be
expressed as follows:
pV = nRT
When the temperature of carbon dioxide is lower than 31 ◦ C, carbon
dioxide can be liquefied, the density of fluid becomes larger and the
compression factor is lower. Compressibility factor is the ratio of actual
gas volume to ideal gas volume at the same pressure and temperature.
In Fig. 2, the phase characteristics of CO2 are presented. In addition
to the three phases (solid phase, gas phase and liquid phase) of CO2,
there is a supercritical state. The triple point of CO2 is − 56.56 ◦ C and
0.52 MPa, and a small change in temperature or pressure will cause CO2
to transform into a certain phase. Conversely, the critical point of CO2 is
31.1 ◦ C and 7.38 MPa; when the temperature and pressure of CO2 are
both greater than the critical point, the supercritical state is reached.
The density of supercritical CO2 fluid is relatively high, and it increases
with the increase in pressure. Supercritical CO2 fluid has both the partial
properties of gas and liquid.

Table 1
Physical properties of carbon dioxide.
Properties Value Properties Value

Molecular diameter 0.35–0.51 Surface tension (− 25 C),

◦
9.13
mN/m
Molar volume (0 C,0.101
◦
22.6 Sublimation heat, kJ/kg 573.6
MPa),L
Solid density, kg/m3 1562 Gaseous density, kg/m 3
2.814
Heat of fusion, kJ/kg 195.82 Gas viscosity(0 ◦ C,0.101 0.0138
MPa), mPa⋅s
Heat of vaporization(0 ◦ C), 235 Heat of formation(25 ◦ C), kJ/ 393.7
Fig. 2. The phase characteristic curve of carbon dioxide (Carbon dioxide:
kJ/kg mol
temperatu, 2018).

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L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

Comparing liquid CO2 and supercritical CO2, the former has surface
tension, whereas the latter has none. When the temperature is lower
than the critical temperature, there is gas-liquid interface in liquid
carbon dioxide, but not in supercritical carbon dioxide fluid. At the
critical temperature, the fluid molecules will escape from the liquid
surface to form a gas; thus, vaporization occurs.
The large difference in temperature and pressure between the
reservoir and the ground renders the CO2 phase change difficult during
the fracturing construction process. For different CO2 fracturing
methods, the CO2 phase characteristics are different during the con­
struction process. The processes during which the CO2 phase changes
occur are as follows.

(1) CO2 foam fracturing

In Fig. 3, the CO2 phase change during CO2 foam fracturing is pre­
sented. As can be seen from the figure, CO2 is stored in the liquid phase
in CO2 tankers (Point 1 in Fig. 3). After CO2 passes through the booster
pump (Point 2 in Fig. 3), it enters the fracturing pump truck and is then
pressurized to the fracturing construction pressure (Point 3 in Fig. 3).
Subsequently, CO2 mixes with the water-based fracturing fluid at the
wellhead (Point 4 in Fig. 3) during which it is in a liquid phase. Liquid
CO2 mixes with the water-based fracturing fluid and is pumped to the
bottom of the well. After entering the reservoir, the temperature grad­
ually rises. At this time, CO2 is in a supercritical state (Point 5 in Fig. 3).
After the construction is completed and the flowback starts (Point 6 in
Fig. 3), the supercritical fluidity of CO2 becomes similar to that of gas,
and fracturing fluid flows back to the surface from the bottom of the
well. During this process, the pressure gradually drops and finally flows
back to the surface in gaseous phase (Point 7 in Fig. 3). During the whole
construction process, the density and viscosity of CO2 foam fluid dras­
tically change as its temperature and pressure change.
(2) CO2 dry fracturing
In Fig. 4, the CO2 phase change during CO2 dry fracturing is pre­
sented. As can be seen from the figure, CO2 is first stored in the storage
vehicle as a liquid (Point 1 in Fig. 4). Then, after CO2 is pressurized by a
booster pump under certain temperature conditions, it is injected into
the high-pressure pump (Point 2 in Fig. 4). At the outlet of the high-
pressure pump, liquid CO2 reaches the pressure required for fracturing
(Point 3 in Fig. 4). Then, liquid CO2 is pumped to the bottom of the well,
during which its temperature and pressure further increase (Point 4 in
Fig. 4). After it enters the fracture in the reservoir, CO2 contacts with
reservoir, which manifests as a further increase in temperature and a
decrease in pressure. At this time, CO2 is in a supercritical state (Point 5
in Fig. 4). After the fracturing is completed and the backflow begins, the
CO2 pressure rapidly drops and flows back to the ground in a gaseous
Fig. 4. Phase change of CO2 in liquid CO2 fracturing.
phase (Point 6 in Fig. 4). It is worth noting that after CO2 is injected into
the reservoir, the CO2 pressure drops sharply, and the volume rapidly
expands, inducing the Joule–Thomson effect, which significantly re­
duces the reservoir temperature (Liu et al., 2014).
(3) Supercritical CO2 fracturing
In Fig. 5, the CO2 phase change during supercritical CO2 fracturing is
presented. As can be seen from the figure, differences in the phase
change exist between the supercritical CO2 fracturing and liquid CO2
fracturing processes. First, CO2 is stored in a storage tank in a liquid
phase. It is worth noting that in this stage, the temperature and pressure
of CO2 are higher than the initial point of the CO2 dry fracturing process
(Point 1 in Fig. 4); then, CO2 mixes with the proppant (Point 1 in Fig. 5).
Subsequently, the mixture is injected into the high-pressure pump for
pressurization (Point 2 in Fig. 5). For shallow wells where CO2 cannot be
converted to a supercritical state, CO2 needs to be heated on the surface
(Point 3 in Fig. 5). Then, liquid CO2 is pumped to the bottom of the well.
During this period, the temperature and pressure of CO2 further in­
crease, and CO2 is transformed into a supercritical state (Point 4 in
Fig. 5). After it enters the fracture in the reservoir, CO2 contacts with
reservoir, which manifests as a further increase in temperature and a
decrease in pressure, with CO2 still in a supercritical state (Point 5 in
Fig. 5). When the backflow starts, the CO2 pressure rapidly drops and
flows back to the ground in a gaseous phase (Point 6 in Fig. 5).

Fig. 3. CO2 phase change during foam fracturing. Fig. 5. Phase behavior change of CO2 in supercritical CO2 fracturing.

3
L. Nianyin et al.
3. CO2 fracturing technology
3.1. CO2 foam fracturing technology
3.1.1. CO2 foam fracturing technology principle and process flow
The CO2 foam fracturing technology uses the gas–liquid two-phase
foam fluid as a carrier and the mixed solution of liquid CO2 and
water-based fracturing fluid with a volume fraction >52% as a sand-
carrying fluid. The quality of CO2 foam is important in the CO2 foam
fracturing process. Generally, the process in which the foam quality is
52%–96% is called foam fracturing, whereas the process in which the
foam quality is less than 52% is called energized fracturing (Xiangzeng
et al., 2014). When the bubble mass is greater than 52%, the bubble
particles at the inner phase are small, exhibit good stability, and have
long half-lives. When the fluid is flowing, the bubble particles come into
contact with each other, thus making the viscosity of fracturing fluid is
increased and the sand carrying capacity is enhanced.
In Fig. 6, the CO2 foam fracturing process is presented. The specific
steps are as follows (Malik et al., 2015; Wanniarachchi et al., 2017).
First, the foam stabilizer, crosslinking agent, and other reagents are
prepared and then injected into the sand mixer through the pipeline.
Then, the solution and sand are evenly mixed in the sand mixer. After
the mixing is completed, the mixture is pumped into the wellhead by the
fracturing pump truck. CO2 stored in the CO2 tanker is injected into the
closed pump truck through the pipeline and then pumped to the well­
head. Liquid CO2 and the reagent mixed liquid are pumped out by the
two fracturing pump trucks at a controlled flow rate so that they can be
mixed evenly. Subsequently, the temperature of the mixed liquid grad­
ually increases during the downhole injection process, and CO2 begins to
transform into a gaseous phase to form a gas–liquid two-phase mixture,
wherein CO2 is in the gaseous phase and the additive solution in the
liquid phase. The gas–liquid two-phase fluid finally forms a CO2 foam
fracturing fluid before reaching the destination layer.
3.1.2. Technical characteristics of CO2 foam fracturing
Compared with the conventional hydraulic fracturing, the advan­
tages of CO2 foam fracturing are in the following. When liquid CO2
comes into contact with the formation water, weak carbonic acid is
generated, which reacts with clay minerals, thus inhibiting clay
expansion. At the same time, CO2 foam fracturing prevents the occur­
rence of hazards, such as the water blocking effect and rock wettability
reversal, maintains or improves the permeability of the formation, and
effectively protects the reservoir from damage. Moreover, due to the
reduced water consumption and residue generation, the formation
damage is also further reduced (Zheng et al., 2019). The large amount of
energy provided by CO2 in the gaseous phase under the conditions of
reservoir temperature and pressure can quickly remove the remaining
liquid from the fracturing fluid in the reservoir and achieve a rapid
flowback. In gas reservoirs, the loss of relative permeability near the
Fig. 6. Carbon dioxide foam fracturing process.
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Journal of Petroleum Science and Engineering 205 (2021) 108793
fracture surface is eliminated (Emrani et al., 2017). Liquid CO2 exhibits
low viscosity and easily enters into tiny cracks compared with the gel
fracturing fluid, thereby increasing the formation of fracture networks
(Jing et al., 2017). The cost of fracturing fluid flowback is much less than
that of the traditional fracturing fluid flowback. Thus, by employing the
former, water consumption during the fracturing operations can be
reduced without the need for well swabbing (Zhenyun et al., 2014).
Fig. 7(a) demonstrates that during hydraulic fracturing, only the prop­
pant is concentrated at the bottom of the fracture. The sand-carrying
capacity of the conventional hydraulic fracturing is not strong, and
only a small amount of the proppant reaches the top of the fracture.
When foam fracturing is employed, the proppant follows the flow of the
foam and is distributed throughout the fracture. The red dots in Fig. 7(b)
indicate the proppant dose carried more than conventional hydraulic
fracturing. From the figure, it can be clearly seen that the foam has a
strong sand-carrying capacity; thus, it can carry the proppant to the top
of the fracture and then play a significant role in supporting the fracture
(Wanniarachchi et al., 2017).
The disadvantages of CO2 foam fracturing are discussed as follows.
Due to the small amount of water-based fracturing fluid, increasing the
sand ratio during the fracturing construction is difficult. Moreover, the
construction pressure is higher than what is required for the closed sand
mixer. Furthermore, from the perspective of environmental safety, a
fully degradable foaming agent and foam stabilizer needs to be selected
for the construction. This is because non-degradable or partially
degradable surfactants may cause numerous environmental problems,
such as groundwater pollution, health hazards, and decline in agricul­
tural land productivity. After comparing the cost of different fracturing
methods (Table 2), another important issue is the high overall cost of the
foam fracturing process as it requires special equipment and high-
strength technology and logistics facilities (Burke et al., 2011; Liu
et al., 2010).
3.1.3. CO2 foam fracturing fluid system
The foam fracturing technology was first studied in the United States
in the 1970s and was formally developed in the 1980s (Phillips et al.,
1987). In the 1970s, it was roughly divided into four stages.
In the first stage, the foam fracturing technology was initially studied
and applied. At that time, the fracturing fluid system used was water +
foaming agent + nitrogen (first-generation fracturing fluid), and the
sand–liquid ratio was 120–240 kg/m3 (1–2 lb/gal), which is mainly
suitable for low-pressure gas wells. In the second stage, the rapid
development of the foam fracturing fluid promoted the popularization
and application of the foam fracturing technology. The fracturing fluid
system used was water + foaming agent + polymer (second-generation
fracturing fluid). Moreover, to increase viscosity and stability of frac­
turing fluid, nitrogen or CO2 was used, and the sand–liquid ratio was
480–600 kg/m3 (4–5 lb/gal), which is mainly applied in high-pressure
gas wells. In the third stage, the foam fracturing fluid was further
L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

Fig. 7. Hydraulic fracturing propping in water and foams.

surfactants become positively charged and can be easily adsorbed when

Table 2
they migrate in porous media, with large losses; however, their practical
Fracture treatment cost of Area 1 wells (Burke et al., 2011).
application in oil fields is limited. The nonionic foaming agent does not
Proppant Rate Liquid Injection Frac induce ionization in water, but it can be dissolved in water by forming
Mass (kg) (bpm) Volume Pressure Treatment
hydrogen bonds with water molecules. Thus, this foaming agent is
(m3) (MPa) Cost
relatively stable under acidic, alkaline, and high-salinity conditions.
Slick 907184 60 3439 55 $1299000 However, high temperature destroys the hydrogen bond between the
Water
Nitrified 907184 60 31398 61 $1448000
nonionic foaming agent and water molecules, thus causing the surfac­
Slick tant molecules to precipitate out of the water, affecting the foaming
Water performance. The amphoteric foaming agent exhibits good resistance to
CO2 Foam 839145 25 15803 46 $2024000 temperature and salt, but the adsorption loss in the formation is rela­
tively high.
How to continuously improve the foaming performance of the
developed, and the fracturing fluid system used was water + foaming
agent + polymer + crosslinking agent (third-generation fracturing foaming agent in the formation under high-temperature, high-pressure,
and high-salinity conditions is a hot research topic. Single-component
fluid). In this stage, nitrogen or CO2 foam was used as the fracturing
fluid system, and the sand–liquid ratio was 600 kg/m3 (5 lb/gal), which foaming agents often cannot meet the requirements of a complex stra­
tum environment. Thus, the current research direction is mainly the
is mainly used for large-scale fracturing of high-temperature and deep
gas wells. In the fourth stage, the constant-internal-phase technology application of compound surfactants. For example, Qu (Qu et al., 2019)
uses water, sodium α-alkenyl sulfonate, sodium dodecyl sulfate, and
was mainly used to increase the sand–liquid ratio to improve the frac­
turing effect. anionic–nonionic surfactant for the preparation of a foaming agent
solution.
The latest developments in the foam fracturing process include clean
fracturing fluid systems and nanoparticle-stabilized foams. Although the
(2) Foam stabilizer
conventional foam still accounts for a large proportion of water volume
(one-tenth to one-quarter), it may still damage the formation due to the
A thickener exhibits poor ability for foam stabilization in an aqueous
presence of water. Currently, an ultra-dry foam technology (the water
solution (its half-life is generally less than 15 min). Thus, it cannot meet
content of the ultra-dry foam is less than 5%) is being studied. Moreover,
the requirements of the fracturing construction. Improving fluid
the ultra-dry foam is being developed in the laboratory (Carpenter,
rheology, increasing viscosity, and increasing the strength of the film
2016; Xue et al., 2015; Johnston et al., 2016). However, no relevant field
between foams are the technical keys to enhance foam stability. The
tests have been conducted yet.
commonly used foam stabilizers can be categorized into three: natural
polymer foam stabilizers, artificial polymer foam stabilizers, viscoelastic
(1) Foaming agents
surfactant (VES), and nano-foam stabilizers.
The foam stabilizer utilized in the initial foam fracturing is the
Foaming agents are among the key additives of the foam fracturing
thickener (guar gum and its derivatives) commonly used for the prep­
fluid. Their performance directly influences the foaming ability and
aration of water-based fracturing fluids. However, the performance re­
stabilizing ability of the foam fracturing fluid. According to the types of
quirements of fracturing fluid are higher and higher, this gel foam
surfactants, these agents can be divided into four categories: anionic,
system has high residue content after the gel breaking process, and it
cationic, nonionic, and amphoteric.
easily damages the reservoir, so its research value is gradually declining
The anionic foaming agent is inexpensive exhibits excellent tem­
(Li et al., 2019). To overcome the drawbacks of the traditional foam
perature resistance, and is the most widely used agent. It effectively
stabilizers, scholars proposed a clean foam fracturing fluid system. Shen
reduces interfacial tension and exhibits good temperature resistance.
(Feng et al., 2016) developed a BCG-8 artificial polymer and determined
However, it has the disadvantage of poor resistance to salt, acid, and
a new formula for clean foam fracturing fluid by optimizing other ad­
alkali. It may react with Ca2+ ion, which seriously affects its foaming
ditives and used it in the development of high-temperature shale res­
performance (Qu et al., 2019). After being hydrolyzed, cationic
ervoirs. By conducting the fracturing fluid experiment, Chen (Li et al.,

5
L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

2017a) systematically investigate the rheological properties of the clean
fracturing fluid and CO2 mixed system. Due to its continuous break­
throughs in technology, the inorganic nanoparticle-reinforced foam
system gradually entered the field of researchers. In a research con­
ducted by Singh et al. (Singh and Mohanty, 2015; Pan et al., 2018; Li
et al., 2017b), it has been pointed out that the nanoparticle interface
adsorption layer can stabilize the liquid film, reduce gas diffusion,
inhibit the effect of bubble coalescence, and achieve the purpose of foam
stabilization. Espinosa (Espinosa et al., 2010) found that after the
addition of SiO2, the resistance factor of the nanoparticle CO2 foam in
porous media was 2–18 times that of the conventional foam. Khajehpour
(Khajehpour et al., 2016) utilized modified nanoparticles for the prep­
aration of steam foams. The results of the displacement experiments
indicate that under high-temperature and high-pressure conditions, the
particle-reinforced foam exhibits stronger generation and stability ca­
pabilities than the ordinary foams and can generate stronger flow
resistance in the core. On the basis of Khajehpour’s research (Kha­
jehpour et al., 2016), Lu (Qichao et al., 2020)utilized SiO2 nanoparticles
as a new intensifier of CO2 foam fracturing fluid. Although nano­
materials have unique advantages, they are too expensive, and their
performance is poor under harsh conditions. Therefore, selecting foam
stabilizers suitable for complex formation conditions is extremely
important.
(3) Cleanup additive
The cleanup additive has the ability to reduce the surface tension of
the fracturing fluid or the oil–water interfacial tension, increase the
contact angle with the rock, and reduce the capillary resistance during
the flowback of the fracturing fluid. Generally, the comparison of the
flowback rate of the fracturing fluid with and without the help of a
drainage agent is not possible. The determination of the drainage per­
formance of the cleanup additive is generally based on the Young–La­
place equation, which is used to calculate the capillary pressure, and
then refer to the three physical quantities of the drainage aid: the surface
tension, interfacial tension, and contact angle with the rock. Fluoro­
carbon surfactants are often used in gas wells owing to their greater
ability to reduce the surface tension of water and hydrochloric acid and
their better thermal stability than hydrocarbon surfactants. However,
the cleanup additive used in oil wells is often compounded due to the
mutual animosity between fluorocarbon chains, and the price of fluo­
rocarbon surfactants is much higher than that of hydrocarbon surfac­
tants; thus, hydrocarbon surfactants are widely used.
3.1.4. Field application of CO2 foam fracturing technology
In the 1980s, the United States and Canada conducted experimental
research on CO2 foam fracturing. In 1986, CO2 fracturing was success­
fully employed in the gas reservoir in Germany to increase its production
by nearly 12 times. The United States has attempted to use this tech­
nology in the Wasatch and Cotton Valley tight sandstone gas reservoirs.
It was found that CO2 fracturing exerted a better stimulation effect than
the conventional water-based fracturing. In 2000, American fracturing
company carried out test and application in the development process of
Ohio shale gas. Moreover, in 2002, the Burlington Company succeeded
in the application of CO2 foam fracturing in the Lewis shale reservoir
and had a major breakthrough. From 2008 to 2011, the Montney Shale
Gas in Canada employed hydraulic fracturing on 1364 wells (Burke
et al., 2011), of which 737 (54%) were energized and foamed, which
significantly reduced the pressure on local water resources (EG and LA,
2012).
Currently, the CO2 foam fracturing technology is relatively mature in
the United States (Downing, 2012), Canada (EG and LA, 2012; Downing,
2016), Saudi Arabia (Malik et al., 2015; Bernal et al., 2015), and China
(Changlin et al., 2016; Ting et al., 2018a; Xuxing et al., 2019). From the
field data presented in Table 3, it can be seen that after the CO2 con­
struction, the wells in each area have achieved good results, and the
backflow rate after compression is greater than 70%, which indicates the
superior performance characteristics of the CO2 foam fracturing fluid. It
is worth mentioning that Saudi Arabia has successfully employed CO2
energized fracturing in the acid fracturing process. When acid fracturing
was applied, the daily gas production reached 28.3 × 104 m3/d, which
indicates an increase of almost 50% (Malik et al., 2015).
As the foam fracturing technology has become more mature, the
performance requirements of the foam fracturing fluid have become
stricter in the field construction. Moreover, foam fracturing fluid has
some defects. How to ensure the foamability and stability of the foam
fracturing fluid and minimize the damage to the formation is the subject
of the current research.
3.2. CO2 dry fracturing technology
3.2.1. CO2 dry fracturing technology principle and process flow
The CO2 dry fracturing technology is categorized into CO2 dry
fracturing technology without sand and CO2 dry fracturing technology
with sand. The former uses liquid CO2 as the fracturing fluid, which is
injected at a large displacement into the high-pressure pump to frac­
turing the formation. Then, a dynamic fracture forms in the reservoir
based on the wall-building properties of liquid CO2. Such a fracture
closes after the construction is completed. As the wall of the crack is
destroyed by CO2, certain rock fragments are produced, which play a
significant role in supporting the crack, thereby providing a seepage
channel exhibiting higher permeability for the outflow of natural gas to

Table 3
CO2 foam construction data.
Well Well section m Construction displacement m3/ Sand CO2 consumption Reverse Remarks References
min ratio m3 rate
% %

x-3 2563–2607 3.2–5 17.5 240.5 – Haolong et al. (2018)

3 3366–3370 3.5–6 – 162 95 Yaoyao et al. (2017)
– 3520–3532 4–4.3 22.2 154.5 – Ting et al. (2018b)
Y2 3526–3530 5 18.2 145 84.2 Yagang et al. (2017)
Y508 2464–2469 5 17.5 – 88.1
Liu91- – 3.208 27 72.49 84 Ruilin and Xianwen
29 (2000)
Shan28 – 2.553 19.9 81.55 77.11
Shan156 – 27.95 20.83 89.81 81.14
Su6 – 2.515 22.8 70.6 89.26
Shan11 – 2.833 22.6 94 89.3
Su6 – 3.1 21.9 80.2 98.74
Shan217 – 2.842 24.7 80.08 71.22
Yu18 2563–2607 2.653 27.3 70.1 90.99
A 3657.6 2.39–6.3 – 143.6 – CO2 energized acid Malik et al. (2015)
fracturing

6
L. Nianyin et al.
increase the production. However, the application of CO2 dry fracturing
technology is mainly restricted by the closed sand mixer, wherein
addition of sand cannot be achieved. Nowadays, owing to its continuous
technological breakthroughs, the CO2 dry fracturing technology with
sand is a non-water fracturing technology in which CO2 replaces the
conventional hydraulic fracturing fluid (Liu et al., 2014).
The CO2 dry fracturing process is performed as follows (Pan et al.,
2018; Luk and Apshkrum, 1996): As shown in Fig. 8. (1) Connect several
CO2 storage tanks in parallel and then connect them sequentially to the
CO2 booster pump truck, closed sand-mixing truck, fracturing pump
truck, and wellhead equipment. Subsequently, connect the instrument
car to the abovementioned vehicles and monitor the working status. (2)
Inject the proppant into a closed sand-mixing tank followed by liquid
CO2 for pre-cooling. (3) Test the pumps for high-pressure pipelines and
wellheads and then the pressure for low-pressure liquid supply pipe­
lines. If the results of the pressure test meet the requirements, proceed to
the next steps; otherwise, check the pipeline. (4) Liquid CO2 is injected
into the formation at a temperature of − 25 ◦ C to − 15 ◦ C, fracturing the
formation and extending the fracture. Subsequently, open the closed
sand mixer to inject the proppant. Stop the pump until the proppant just
enters the formation completely. (5) After fracturing, shut in the well for
1.5–2.5 h (6) After the construction is completed, it is important to not
only control the flowback speed to prevent sand blasting but also to
make the best use of the CO2 energy to speed up the flowback. In this
stage, we can first use a small-caliber nozzle to control the discharge
speed and then gradually increase the diameter of the nozzle. In addi­
tion, a CO2 detector can be used to monitor the change in the CO2
concentration at the outlet.
3.2.2. Technical characteristics of CO2 dry fracturing
The technical characteristics of CO2 dry fracturing have the
following advantages: the absence of water phase, prevention of water
sensitivity, water locking damage to the reservoir, and rapid and
continuous flowback (Weidong et al., 2011; Jianwen et al., 2017). There
is no residue damage to the permeability of the reservoir and supporting
fractures (Middletona et al., 2014). Fracture networks can easily form
during the fracturing process, and CO2 in the liquid phase exhibits a
relatively low viscosity. Compared with the conventional hydraulic
fracturing fluids, CO2 can easily penetrate into micro-fractures (Fig. 9),
which can facilitate in the formation of more networked fractures
(Chengzheng et al., 2016; Wu et al., 2018). CO2 dry fracturing exerts a
good energy-enhancing effect. After the pressure is released, CO2 ex­
pands, and the pressure rapidly flows back.
The CO2 dry fracturing technology also has certain limitations.
Liquid CO2 is a Newtonian fluid and creates a large pipeline friction at
high flow rates. In addition, liquid CO2 exhibits low viscosity, large filter
loss, and poor sand-carrying capacity (Lei et al., 2015). The CO2 phase
changes with the change in the pressure and temperature. Although the
use of this fracturing technology can significantly improve the produc­
tion effect, the fracturing procedures and fracturing schemes are
different from those of the conventional fracturing. Generally, the re­
quirements for ground equipment are higher, and the fracturing design
is more complicated (Gandossi and Estorff, 2015). Liquid CO2 fracturing
Fig. 8. CO2 dry fracturing process.
7
Journal of Petroleum Science and Engineering 205 (2021) 108793
is limited by the scale of the sand addition and depth of the well.
Moreover, this technology requires a special closed sand mixer. There­
fore, the initial investment cost is high.
3.2.3. CO2 dry fracturing fluid system
The CO2 dry fracturing fluid system used is liquid CO2 added with a
thickener. Some scholars have proposed the addition of a resistance
reducing agent to reduce the system friction and injection pressure loss.
However, the resistance reducing agent is not suitable for liquid CO2 as
it is a Newtonian fluid. The current research on and development of
liquid CO2 resistance reducing agents is still a difficult problem. To
overcome the problem of low viscosity of liquid CO2, a thickener was
added to increase the system’s viscosity. Thickeners are the main ad­
ditives of fracturing fluids. Generally, thickeners can be categorized into
two: polymers and small molecular organics (Wan, 2017; Manxue and
Na, 2017). However, most of the reference on the application of thick­
ened CO2 is related to enhanced oil recovery (Olsen et al., 2011). There
are few related reference on the viscosity-increasing agent for CO2
fracturing fluid, so briefly refer to the CO2 viscosity-increasing agent in
EOR.
(1) High-molecule polymer thickener
Numerous scholars have attempted to identify polymers that can
effectively thicken CO2 at a certain temperature and pressure. Tapriyal
utilized vinyl acetate and benzene ring-containing monomers for copo­
lymerization to form polymer polyBOVA (Tapriyal et al., 2008). About
1%–2% of ployBOVA can increase the viscosity of liquid CO2 by 40%–
80%. However, the disadvantage is that a pressure of 64 MPa is required
to dissolve 0.5% of polyBOVA in liquid CO2 at 25 ◦ C. Although this type
of polymer can increase the viscosity of CO2, due to the complex site
conditions, the polymer dissolved under the best conditions cannot be
actually applied to the site; thus, the polymer dissolved under the best
conditions cannot be applied to the field. Enick used fluoroacrylate–­
styrene copolymers to increase the viscosity of liquid CO2 polymers
(Enick et al., 2001). Jyoti used 3-vinyl aniline and 2-perfluorooctyl ethyl
acrylate to synthesize a liquid CO2 thickener via free-radical polymeri­
zation (Jyoti et al., 2014). Although this polymer type has an obvious
viscosity-increasing effect, one disadvantage is that fluoropolymers are
relatively expensive and not environmentally friendly (fluoropolymers
are not easily degraded), thus limiting their large-scale application.
There are less tackifiers that can thicken CO2 (Xiaoyu et al., 2014). It
is worth mentioning that some scholars have employed the molecular
simulation technology to study the molecular structure of liquid CO2 and
the viscosity-increasing agent (Dai et al., 2018). The three synthetic CO2
thickeners (TNJ-1, TNJ-2, and TNJ-3) have been evaluated for the
viscosity-increasing effect of liquid CO2. In this study (Enick et al.,
2011), tackifier was used, and the formula of the liquid CO2 dry frac­
turing fluid was screened out. The results indicate that under the con­
ditions of 62◦ C–63 ◦ C and 15–20 MPa, the viscosity of the liquid CO2 dry
fracturing fluid can be increased to 5–10 mPa s by adding a thickener in
the range of 0.8%–5%. Such an increase is 240–490 times higher than
when CO2 is added. The average damage to the gas well core is 2.75%,
L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

Fig. 9. Schematic diagram of rock fractured by different fracturing fluids.

whereas that to the oil well core is 0.98%. in the entire San Juan Basin. Although this process has been widely used,
the early field application of CO2 dry fracturing has been limited to a
(2) Small molecule thickener maximum depth of 1000–1200 m. The use of the CO2 dry fracturing
technology in China started late. According to incomplete statistics, in
The use of small molecules to form large molecular structures to Changqing, Jilin and Yanchang oilfields of China, about 50 wells have
thicken CO2 has been explored by scholars (Enick et al., 2011). Among been operated with liquid CO2 fracturing (Manxue and Na, 2017).
the small molecules, only a few with less polarity can be dissolved Although CO2 dry fracturing can effectively develop unconventional
(Jianwen et al., 2017), such as methyl methacrylate, styrene, acryloni­ reservoirs, it has several disadvantages, such as low fracturing fluid
trile, and octene. Molecules with higher polarity, such as methacrylic viscosity, low sand ratio (Table 4), and poor performance of fluid loss
acid and acrylic acid, cannot be dissolved. Ideally, molecules should reduction. Compared with hydraulic fracturing, CO2 dry fracturing ex­
have a hydrophobic segment to promote CO2 dissolution and a hydro­ hibits better performance. Unfortunately, because the research on
philic segment to form a structure with adjacent molecules. Unfortu­ thickeners, which can be utilized in CO2 fracturing fluid, lags far behind
nately, many difficulties have been encountered when this type of the field application and the construction equipment is expensive, the
thickener was used during the development process. Scholars have application of the CO2 dry fracturing technology has been restricted.
tested several compounds, such as aluminum hydroxide (Eastoe et al.,
2003; Enick, 1991), semi-floral alkanes (Iezzi et al., 1989), small organic
3.3. Supercritical CO2 fracturing technology
compounds and gels (Gullapalli et al., 1995; Lancaster et al., 1987), and
copolymer (Liave et al., 1990), but none of them achieved better eco­
3.3.1. Principle and technology of supercritical CO2 fracturing technology
nomic benefits. In addition, Trickett (Trickett et al., 2010) injected
Supercritical CO2 fracturing is a special form of CO2 dry fracturing.
surfactants into liquid CO2, which thickened the CO2 through the mi­
Its technical principle is similar to that of CO2 dry fracturing. The main
celles. However, even if the fluorinated surfactant content added to CO2
difference between the two processes is that CO2 has reached the su­
is as high as 10%, only a 90% increase in viscosity can be achieved.
percritical state before reaching the fracture zone. Ensuring that the CO2
Although small-molecule compounds can dissolve and slightly thicken
at the bottom of the well is in a supercritical state is important (Car­
CO2, such compounds are too expensive and need to exhibit high con­
penter, 2016). Generally, when the working layer is shallow, the tem­
centrations (2%–10%) (Enick et al., 2011); thus, no field test data has
perature gradient is small, and the injection displacement is large. Thus,
been found.
it is important to equip the ground with a heating device or use the waste
heat generated by the ground fracturing equipment to heat CO2. This is
3.2.4. Field test of CO2 dry fracturing technology
performed to ensure that CO2 is in a supercritical state during the con­
In the earliest CO2 dry fracturing process, sand and CO2 were
struction process. If the working layer is buried deep and the downhole
injected into the reservoir without any additives to increase the viscosity
temperature is sufficiently high, no additional equipment is needed for
of the fracturing fluid. The CO2 process, which was developed by Frac­
heating. As CO2 can be directly heated by the formation, it can reach the
master, has achieved widespread commercial success in Canada (Sinal
supercritical state through the displacement control (Haizhu et al.,
and Lancaster, 1987). Subsequently, the technology completed the
2018, 2020).
fracturing process in numerous wells in tight unconventional gas res­
Supercritical CO2 fracturing technology is introduced as an example
ervoirs. Moreover, Canada had successfully applied this process in more
of coiled tubing jet fracturing (Dawei et al., 2018). Before the con­
than 350 wells before 2003 (Gupta, 2003). Fracmaster introduced the
struction process, a sufficient CO2 gas source should be prepared, and
technology to the US market after 1980s and subsequently applied it in
the CO2 storage tank should be equipped with a refrigeration unit to
the Devonian shale reservoirs in Western Pennsylvania, Texas, and
achieve suitability of the temperature and pressure and to ensure that
Colorado (Harris et al., 1998). Field tests sponsored by the US Depart­
the CO2 entering the sand mixer is in a liquid phase. The subsequent
ment of Energy and Devonian shale reservoir operators have proven the
process can be divided into two: supercritical CO2 sandblasting and
commercial viability of the CO2 dry fracturing technology (Yost et al.,
perforation and supercritical CO2 fracturing (Fig. 10). First, liquid CO2 is
1993, 1994). In 1999, the Burlington Company in Mexico selected 16
fully mixed with the abrasive using a closed sand-mixing truck and then
wells to test the feasibility of the liquid CO2 sand fracturing technology
transported to the fracturing truck through a high-pressure pipeline. The
in the entire San Juan Basin (Campbell et al., 2000). The results revealed
mixed fluid is pumped by the fracturing unit into the wellbore through
that this technology can safely and effectively stimulate the Lewis shale
coiled tubing. Under the formation conditions, if the displacement is

8
L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

Table 4
CO2 dry fracturing construction data.
Well Lithology Construction displacement m3/min Sand ratio CO2 consumption m3 References
%

xx-22 Sandstone 2–4 3.5 254 Zhenyun et al. (2014)

YY-x Shale with sandstone 4 Maximum 10 100 Juntao et al. (2018)
YY-1 Shale 2–3 0 – Xiangzeng et al. (2014)
53PING9-3 Sandstone 8 Maximum 14 696 Lei et al. (2015)

Fig. 10. The principle of supercritical CO2 coiled tubing jet fracturing.

moderate, CO2 can reach the supercritical state after the well depth
exceeds 750 m. Conversely, in a shallow formation under extremely
special conditions, such as very shallow well sections or
low-temperature formations, a CO2 heating device can be installed at the
wellhead to help CO2 reach the supercritical state. Subsequently, the
mixed fluid gradually descends. When it reaches the jet fracturing de­
vice, a high-speed supercritical CO2 abrasive jet is produced, which
penetrates into the casing and reservoir rock to form jet channels.
3.3.2. Technical characteristics and adaptability of supercritical CO2
fracturing
As a new type of fracturing fluid, supercritical CO2 fluid exhibits
some characteristics that conventional fracturing fluids do not (Yuxiong
et al., 2013). For example, in hydraulic fracturing, the water in the
water-based fracturing fluid inevitably causes clay swelling in the
reservoir and blocks the reservoir pores. This situation is serious espe­
cially in water-sensitive reservoirs, such as shale and coal seams. Su­
percritical CO2 fluid does not contain water, thus preventing the

Fig. 11. The surface structure of shale before and after supercritical CO2 (Haizhu et al., 2018).

9
L. Nianyin et al.
occurrence of water-sensitive damage (Songze et al., 2020). Contrarily,
after supercritical CO2 penetrates into the reservoir, it can further
improve the effect of increasing production owing to its unique prop­
erties. From the comparative scan before and after shale treatment
(Fig. 11), it can be seen that the surface morphology of shale has un­
dergone significant changes after the supercritical CO2 treatment. The
primary pores of shale are corroded, and some minerals are dissolved.
This effectively increases permeability and is also beneficial to the
production of oil and gas (Haizhu et al., 2020). In general, supercritical
CO2 fracturing has the following advantages: (1) The supercritical CO2
fracturing fluid does not contain water; thus, it does not cause clay
swelling in the reservoir, but it dehydrates the tight clay sand, open the
sand pores, dredge the flow channel between the reservoir and wellbore,
and reduce the skin coefficient in the near-well zone. (2) Compared with
the conventional fracturing fluids, supercritical CO2 fracturing fluids
exhibit low viscosity and strong diffusion ability. Its surface tension is
close to zero, indicating very strong permeability. Moreover, it can
easily penetrate into the pores and micro-fractures in the reservoir,
which results in the generation of a large number of micro-fracture
networks (Yan et al., 2019a; Chen et al., 2019; Dawei and Guangqing,
2020). (3) Supercritical CO2 has the ability to dissolve heavy oil com­
ponents and other organic matter in the near-well zone, reduce the skin
coefficient, reduce the flow resistance of oil and gas in the near-well
zone, and further improve the fracturing and stimulation effect. (4)
Supercritical CO2 also exhibits strong permeability and can penetrate
into crude oil, which expands the volume of crude oil and reduces vis­
cosity. Consequently, the fluidity of crude oil and the energy of the
reservoir are increased, which is beneficial to crude oil displacement in
the reservoir. (5) CO2 can be adsorbed by adsorption reservoirs, such as
coal seams and shale layers. Also, the adsorption capacity of CO2 and
reservoirs is stronger than that of CH4 and reservoirs (Pathak, 2015).
Therefore, when the supercritical CO2 fracturing technology is
employed to transform shale gas and coalbed methane reservoirs, a
competitive adsorption relationship between the injected CO2 and CH4
emerges, which significantly improves the recovery efficiency of the gas
reservoir.
The potential drawbacks are categorized into economic factors and
equipment factors: increased cost of capturing, pressurizing, and trans­
porting CO2 and increased budget allocation for CO2 emissions and
storage. Separating hydrocarbons and formation water from the
returning CO2 and recovering the returning CO2 incur addition costs.
The pipeline used to transport CO2 under supercritical pressure needs to
exhibit a certain degree of strength. Thus, in most cases, the trans­
portation of CO2 to the destination zone incurs additional costs. During
the flowback, after the fracturing is completed, a mixture of CO2 and
natural gas is produced. Gas separation is important to satisfy the market
requirements for natural gas. However, this incurs additional costs.
Moreover, the water present in the formation also tends to dissolve in
supercritical CO2. If a portion of the pure water of high-concentration
formation water is dissolved in supercritical CO2, the remaining brine
may be supersaturated by the dissolved salt and precipitate. Blockage of
fine pores and throats may occur due to the precipitation of mineral
salts, thus resulting in the decrease in reservoir permeability (Middleton
et al., 2015).
3.3.3. Supercritical CO2 fracturing fluid system
The fracturing characteristics and advantages of supercritical CO2
fluids have only been discovered in recent decades. When CO2 fluid is in
a supercritical state, CO2 exhibits a low viscosity. In the same way as dry
fracturing, the viscosity of fracturing fluid needs to be increased by
adding viscosity increasing agent.
Similar to dry fracturing thickeners, CO2 thickeners, which are
currently being studied, mainly include small-molecule thickeners,
small-molecule surfactants, and polymer thickeners (Wenchao et al.,
2019; Baojiang and Wenchao, 2015). Among them, small-molecule
tackifiers include 12-hydroxystearic acid, trialkyltin semifluoride,
10
Journal of Petroleum Science and Engineering 205 (2021) 108793
fluoroether diurea, 2-ethylhexanol, and the like. Small-molecule sur­
factants include perfluoropolyether ammonium carbonate, di-HCF4,
F7H4, AOK, Dynol-604, and Ls-36, and Ls-45. Their viscosity-increasing
effect in supercritical or liquid CO2 is not ideal, even if their mass
fraction reaches several percentage points. It can only increase the vis­
cosity of CO2 by three to five times at most (Enick et al., 2011). It is
worth mentioning that silicone polymers and fluoropolymers exhibit
relatively good viscosity-increasing effects. The viscosity of supercritical
CO2 can be increased by 90 times using 6% polydimethylsiloxane, with
the addition of 20% toluene as a co-solvent (Bae and Irani, 1993; Wil­
liams et al., 2004). Xu Liu synthesized polymethylsilsesquioxane
(PMSQ) and polymethylsilsesquioxane-vinyl acetate (PMSQ-VAc) bi­
nary copolymer thickeners (Liu et al., 2020a). Their results indicate that
PMSQ-VAc is relatively good and increases the viscosity to 3.892 mPa s.
Moreover, fluorinated acrylate–styrene can increase the viscosity of CO2
by two orders of magnitude without a cosolvent, and its mass fraction of
5% can increase the viscosity of liquid CO2 by 400 times (X, 2003;
Huang et al., 2000; Xu et al., 2003). Subsequently, Xu further introduced
the synthesis and thickening mechanism of fluorinated acrylate–styrene
as a tackifier (Chuanqi et al., 2020). However, because of cost and
environmental issues, fluorine-containing and silicone polymer tacki­
fiers are only a proof of concept and have no application value. Unfor­
tunately, low-cost and environmentally friendly hydrocarbon polymers
exhibit poor solubility in CO2 (ER et al., 2004). Even the most soluble
hydrocarbon polymer in CO2–polyvinyl acetate (PVAc), which has a
mass fraction of 5%, and the pressure required to dissolve in liquid CO2
exceeds 60 MPa, which does not have sufficient Pro-CO2 (JM. et al.,
1992).
Currently, the development of supercritical CO2 tackifier is still in
the experimental stage. To successfully increase the viscosity of CO2, the
addition of a large amount of co-solvent or the use of highly fluorinated
CO2 affinity molecules is sufficient. Fluorine-containing compounds are
often expensive, and fluoride poses harm to the environment. Tackifiers
that have economic value and are environmentally friendly have not yet
been produced. Generally, research on the viscosity-increasing effect
and molecular design methods of supercritical CO2 thickeners has not
kept up with the pace of engineering applications.
3.3.4. Field test of supercritical CO2 fracturing technology
Currently, with regard to the supercritical CO2 fracturing technol­
ogy, numerous scholars have conducted research on the rock-breaking
mechanism of different lithological reservoirs, such as shale (Zhang
et al., 2016), granite (Isaka et al., 2019), and coal rock (Lei and Weiguo,
2019). At present, the technology as a whole is still in the basic research
stage (Isakaa and Ranjith, 2020; Rod et al., 2020), with only a small
number of field tests which are all concentrated in China.
In 2017, China conducted a supercritical CO2 fracturing field test in
the Yan’an X area (Haizhu et al., 2020). This field experiment was
conducted mainly to confirm the feasibility of supercritical CO2 frac­
turing. In the test, the depth of the well was 2940 m, and the total CO2
injected was 386 m3; low-density ceramsite with a bulk density of 1.45
g/cm3 was used, and its volume fraction in the sand-carrying liquid was
about 3%. In the process of fracturing, the frictional resistance was high,
which was mainly reflected in the nozzle-spraying process. Moreover,
due to the low density and low viscosity of supercritical CO2, sand
plugging frequently occurred at the ends of the fractures; thus, the
conventional fracturing fluids were utilized to carry the sand. The results
of the microseismic fracture monitoring revealed that the supercritical
CO2 fracture initiation signal was densely and uniformly distributed in
all directions around the well. However, the fracture initiation signal of
the conventional hydraulic fracturing was only distributed along the
direction of the maximum horizontal principal stress (Fig. 12). It was
further confirmed that supercritical CO2 fracturing can effectively pro­
mote the generation of complex fracture networks. In addition, the
technical test confirmed the feasibility of supercritical CO2 and its
development prospects, thus laying the foundation for future on-site
L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

Fig. 12. Comparison of microseismic crack detection (Haizhu et al., 2020).

construction. of liquid CO2 in the high-pressure manifold tee at the wellhead. The
mixed liquid CO2 rapidly thickens and carries sand. This process realizes
the integrated application of drag reduction and sand carrying. The at­
3.4. Other CO2 fracturing technology
mospheric pressure sand-mixing quasi-dry fracturing technology has the
following advantages: (1) No special airtight sand-mixing equipment is
3.4.1. CO2 composite fracturing technology
required, and sand-mixing can be performed under a normal pressure;
The technical principle of the CO2 mixed fracturing technology is as
moreover, the scale of sand addition is not restricted by the airtight
follows: the liquid CO2 itself easily breaks the rock, and its excellent
equipment. (2) This technology can prepare drag reducing fluid and
ability for fracture creation is used to apply pure CO2 fracturing. Sub­
sand carrying fluid at the same time. The water–sand ratio is as high as
sequently, the water-based sand-carrying hydraulic fracture propagated
80%–100%, and the overall sand ratio can reach 40% after mixing with
and supported the fracture. The advantages of this technology are that it
liquid CO2. (3) The fracturing fluid exhibits good viscoelasticity and
can effectively solve the technical problems of CO2 energized fracturing,
excellent temperature and shear resistance. (4) A small amount of water-
simplify the construction process, and reduce the construction cost.
based sand-carrying liquid is prepared, which exhibits an excellent
Moreover, pre-CO2 fracturing can effectively open micro-fractures and
yield-increasing effect and high cost performance and also causes low or
increase the expansion orientation and complexity of artificial fractures.
no damage at all.
The water-based sand-carrying hydraulic fracture can also further
The atmospheric pressure sand-mixing quasi-dry fracturing tech­
extend and effectively support the fracture, as well as realize the energy
nology has been successfully applied in unconventional ultralow
enhancement, volume transformation, and large-scale transformation of
permeability gas wells for two consecutive times. The natural gas flow
the reservoir.
rates obtained from the field test conducted on the two wells exceeded
The Dongsheng Gas Field in China has conducted a pilot test on
30,000 m3/d. The adjacent wells that underwent conventional frac­
composite dry fracturing using supercritical CO2 as a prefluid and mixed
turing hardly produced gas. The specific field application conditions of
composite fluid of liquid CO2/bipolar fracturing fluid as a sand-carrying
the two wells are presented in Table 5.
fluid (Guangliang, 2018). The well was fractured with a total of 580.23
m3 of CO2, 490.0 m3 of bipolar fracturing fluid, and 60.07 m3 of sand.
3.4.3. CO2 phase change fracturing technology
The Xiasiwan Shale Gas Demonstration Base of China’s Yanchang oil
The phase change fracturing technology was proposed by Cardox
field has applied the compound fracturing technology in six wells
technology. This technology heats liquid CO2. Liquid CO2 rapidly ex­
(Xiangzeng et al., 2014). The injection volume of liquid CO2 was
pands during heating to produce high-pressure gas, which ruptures the
40–120 m3, the volume of slippery water carrying sand–liquid was
coal or rock formations. The phase change fracturing technology is a
800–1600 m3, the sand volume was 40–80 m3, and the displacement was
non-explosive blasting technology, and its technical principle is to place
8–12 m3/min. After fracturing, the rate of assisting drainage was 35%
a fracturing device in the drilled gas borehole in advance. The heating
higher than that of the conventional fracturing; the drainage cycle was
element of the cracker is activated by switching on the device. Under the
shortened by 20 days, and the transformation effect was very obvious.
action of the heating element, the liquid CO2 in the tube is converted
The Jilin oil field in China successfully conducted a composite fracturing
into a high-pressure gas within 20–40 ms. At this time, the CO2 pressure
process (pre-CO2 fracturing fluid and gel fracturing fluid) in the
can reach 120–280 MPa. Under high-pressure conditions, the shear
Chengshen 131 well (Manxue and Na, 2017). The total liquid volume
blades at a constant pressure are broken, and the high-pressure CO2 is
was 616 m3, the volume of liquid CO2 was 582 m3, and the sand volume
ejected from the jet valve and acts on the coal seam, thus destroying the
was 77 m3. The construction pressure was 23–47 MPa, the flowback rate
coal seam, increasing the permeability of the coal seam, and providing a
was 50%, and the daily gas production was 1.5 × 104 m3.

3.4.2. Atmospheric mixed sand quasi-dry fracturing technology Table 5

The atmospheric pressure sand-mixing quasi-dry fracturing tech­ A Yanchang field well application of normal pressure sand mixing quasi-dry
fracturing technology (Zheng et al., 2019).
nology was proposed by the Aipu Polymer Technology in China. This
technology uses conventional sand mixers to add water-based thickener Well Porosity Permeability Water CO2 Reverse Gas
deep % % m3 m3 rate production
APFR-6, CO2 thickener APFR-2, proppant, and gel breaker. In this pro­
m % m3/d
cess, a water-based fracturing fluid with high viscosity and high sand
ratio is formed (the water-based fracturing fluid accounts for 10%–40% 3122 7.8 0.64 160 320 58.5 3500–3700
3322 8.3 0.92 160 240 55.3 3200–3400
of total fracturing fluid). The water-based part is mixed with 60%–90%

11
L. Nianyin et al.
channel for gas migration. China introduced this technology in the
1990s and successfully tested it at the beginning of the 21st century. It
was found that the phase change fracturing technology has a good effect
in gas control. After numerous researches, the phase change fracturing
technology has been widely used in several applications, such as pres­
sure relief gas extraction, rapid coal road excavation, and early roof
caving in fully mechanized mining faces (Siqi, 2020; Fei et al., 2020;
Jiuyuan and Lizhou, 2015).
4. Fracture initiation and propagation in carbon dioxide
fracturing
It is very important to study on fracture initiation and propagation in
CO2 fracturing process for the development of unconventional oil and
gas reservoirs. The research results will provide guidance for the design
of CO2 fracturing procedures and help to control the morphology of
shale fracture network. In this paper, the fracture initiation and propa­
gation are studied and discussed from two aspects of laboratory exper­
iments and numerical simulation.
4.1. Laboratory experiment
Many scholars have conducted comparative experiments on hy­
draulic fracturing and CO2 fracturing for different lithology to study the
initiation and propagation of fractures under different conditions
(Zhang et al., 2017; Deng et al., 2018; Zhou et al., 2018; Zhao et al.,
2018). Table 6 summarizes the rock breakdown pressure under different
experimental conditions. In previous studies, researchers often used a
triaxial test system to analyze CO2 fracturing. For example, Zhang et al.
(2017) used the triaxial test system in the laboratory to simulate the
SC-CO2 fracturing of shale outcrops, and compared it with the fracturing
test using hydraulic fracturing fluid under the same conditions. The
initial pressure of shale SC-CO2 fracturing is about 50% smaller than that
of hydraulic fracturing. Moreover, the initial pressure of SC-CO2 frac­
turing is also lower than that of L-CO2 fracturing.
In fact, the viscosity of SC-CO2 is about 5% of that of water. The SC-
CO2 with lower viscosity tends to break rock samples under lower
breakdown pressure. And CO2 easily penetrates pores and micro­
fractures in the reservoir, resulting in a large number of microfracture
networks, as shown in Fig. 13. Li et al. (2015) showed through labora­
tory tests that, compared with other fracturing fluids, the fractures
produced by CO2 fracturing are more complex and have the largest
apparent local damage. Zhou et al. (2018) divided the CO2 fracture
propagation process into 4 stages based on the research of Li et al.:
damage zone evolution, fracture breakdown, post-instability and frac­
ture arrest, divided the SC-CO2 rupture mode into 3 types，and proved
to produce fracture zones or networks。Deng et al. (2018) believed that
the shear mechanism affects the propagation of fractures through two
methods. Shear stress limits the extension of inclined fractures perpen­
dicular to the direction of minimum principal stress. The direction and
length of propagating fractures are closely related to the stress state and
Table 6
Rock breakdown pressure under different experimental conditions.
Number Triaxial stress (MPa)σY/σX/σZ Fluid injection rate (ml/min)
1 12/10/8 30
2 12/10/8 30
3 12/10/8 30
4 25/10/5 60
5 25/10/5 60
6 28/18/8 120
7 28/18/8 120
8 23/21/19 – Water + guar gum
9 23/21/19 – SC-CO2
10 Confining pressure 5 MPa 50
11 50
Journal of Petroleum Science and Engineering 205 (2021) 108793
pore pressure of oblique fractures. Shear slip requires a higher hori­
zontal stress difference (shear stress), which is roughly the same as the
conclusion obtained by Ye Liang et al. (2018). Therefore, CO2 fracturing
is an important technical means to increase the complexity of fractures
in natural fractures and reservoirs with underdeveloped bedding.
4.2. Numerical simulation
Recently, with the increasing attention to CO2 fracturing, many
scholars have begun to study the theoretical model and numerical
simulation of CO2 fracturing. Table 7 summarizes the characteristics of
the numerical simulation of CO2 fracturing fracture propagation. Un­
fortunately, due to the special properties of the CO2 fluid and the
complexity of the fracturing process, the research progress in this area is
not smooth. At present, the numerical simulation of CO2 fracturing
mostly adopts the computational fluid dynamics method. For example,
Chen et al. (Liqiang et al., 2015) constructed the pressurization rate
model and fracture initiation pressure model of SC-CO2 fluid in fractured
wells, and compared the initiation pressure of hydraulic fracturing and
liquid CO2 fracturing with that of SC-CO2. Based on fluid flow, heat
conduction and solid mechanics equations, Zhang Jian et al. (2018)
established a Thermo-hydro-mechanical coupling model to study the
fracture propagation law of CO2 fracturing. The study shows that the
viscosity of CO2, injection displacement, and thermal stress have a
certain relationship with fracturing. Hao Yan et al. (2019b) used the
extended finite element method to establish a fluid-solid coupling model
to study the SC-CO2 fracturing process of coal. The study shows that the
coal seam fractures initiate and expand in the initial stage of SC-CO2
fracturing, and then produce new fractures in the stage of CO2 phase
transition-induced fracturing. Liu et al. (2020b) developed a coupling
model with a new unsteady two-phase flow model and a solid model to
simulate SC-CO2 and water-based fracturing. It is believed that the low
viscosity of SC-CO2 is helpful to enhance permeability compared with
water. During fracturing, low viscosity and low capillary force of CO2
will bring higher pore pressure in larger areas, thus increasing the
possibility of shear and mixed failure. Mollalali et al. (Mollaali et al.,
2019) set CO2 as compressible fluid and used the phase-field method to
model fracturing in porous media under isothermal conditions. The in­
fluence of natural fracture is considered. Similarly, the CO2 fracturing
model established by Zhao et al. (2021) also takes CO2 as compressible
fluid, taking into account the variation of CO2, including density and
viscosity, and the interaction between hydraulic fracturing and natural
fractures. At present, the theoretical research on fracture initiation and
propagation of CO2 fracturing is still in the preliminary stage.
Scholars have done many kinds of research on the filtration effect,
heat transfer, CO2 physical parameters and permeability change of CO2
fracturing. However, as a new fracturing medium, there are few sys­
tematic studies on the fracture initiation pressure, fracture propagation
law and complex fracture network formation mechanisms during CO2
fracturing. It is worth mentioning that due to the complex influence of
temperature on CO2, the actual reservoir temperature is variable, so the
Fracturing fluid Specimen type Breakdown pressure (MPa) References
Water Shale 31.79 Zhang et al. (2017)
L-CO2 Shale 17.30
SC-CO2 Shale 15.16
L-CO2 Shale 20.39 Deng et al. (2018)
Water Shale 29.54
L-CO2 Coal 12.50
Water Coal 13.20
Portland About 21 Zhou et al. (2018)
Cement and Sand About 17
SC-CO2 Shale 11.76 Zhao et al. (2018)
Water Shale 12.58
12
L. Nianyin et al.
Fig. 13. Comparison of fracture propagation under different fracturing methods (Zhou et al., 2018).
fracturing process is always assumed to be the constant temperature in
the simulation, and the influence of temperature change on CO2 frac­
turing is not considered, which is also the difficulty of simulation
research.
5. Discussion and summary
In this paper, different CO2 fracturing processes have been intro­
duced. Table 8 compares these processes with the conventional hy­
draulic fracturing. It can be seen from the table that during the
fracturing process, neither the water-based fracturing fluid nor the CO2
fracturing fluid is environmentally friendly, as both require the addition
of chemical reagents, especially fluorine-containing compounds. Such
an addition poses risk for environmental pollution. Due to the low vis­
cosity and strong diffusion capacity of CO2, fluids are more likely to
penetrate into the microcracks. Therefore, CO2 fracturing is more
capable of forming complex fracture networks than the conventional
hydraulic fracturing; however, the ability of supercritical CO2 fracturing
to form fracture networks is the best. The CO2 foam fracturing fluid is a
mixture of liquid CO2 and water-based fracturing fluid; thus, its sand-
carrying capacity is stronger than that of dry fracturing fluids and su­
percritical fracturing fluids, which do not contain water. However, the
sand-carrying capacity of the water-based fracturing fluid is stronger
than those of the three previously mentioned fluids. One of the unique
advantages of CO2 fracturing is its strong reverse drainage ability after
fracturing. Compared with the conventional hydraulic fracturing, the
reverse drainage rate of wells with better CO2 fracturing treatment can
even reach 100%. However, while CO2 fracturing exerts a better pro­
duction increase effect, the additional cost of equipment, such as airtight
sand mixers, as well as pipelines with better materials cannot be
ignored, as these increase the initial investment. The results of the field
tests revealed that CO2 has a high return on investment and can effec­
tively expand the economic benefits of oil fields.
The common advantage of the different CO2 fracturing processes in
the treatment of formations is that CO2 generates weakly acidic carbonic
acid when it comes into contact with the formation water and possibly
reacts with clay minerals to inhibit clay expansion, significantly reduce
water consumption, and effectively prevent water sensitivity, water
locking damage, and other phenomena. The gas expands after frac­
turing, which can then promote a rapid flowback. In addition, one of the
advantages of CO2 fracturing technology is to inject CO2 underground,
13
Journal of Petroleum Science and Engineering 205 (2021) 108793
which is a technically feasible and socially acceptable means of CO2
reduction. The concept of CCS（Carbon Capture and Storage）was
introduced in 1977 (Marchetti, 1977)，then CCS has attracted
increasing worldwide attention, particularly in countries where elec­
tricity generation and export earnings are heavily dependent on fossil
fuels, such as China, Western Europe, Australia, Canada and the United
States (Raza et al., 2019). Assuming that shale is eventually pressurized
to 15 MPa by CO2, up to 9.43 cubic meters of CO2 can be adsorbed per
tonne of shale. Therefore, the fractured reservoir based on CO2 frac­
turing has great potential in storing CO2. After the completion of oil and
gas field production, the fractured reservoir can also be used as a CO2
storage site, which can achieve additional CO2 sequestration and has
great potential in CO2 emission reduction (Rubin et al., 2015)。
The characteristics and adaptability of the different CO2 fracturing
processes are also different. Foam fracturing fluid is a mixture of water-
based fracturing fluid and CO2. Contrary to this fluid, the conventional
guar gum fracturing fluid is used in small amounts, which can effectively
reduce damage to oil and gas fields with low permeability. It also solves
the problems of large polymer residues, serious water sensitivity, and
difficulty in draining liquid in the conventional hydraulic fracturing.
However, due to the small amount of the water-based fracturing fluid,
achieving a high sand ratio is difficult, and the construction pressure
poses stricter requirements for the equipment. Therefore, CO2 foam
fracturing is suitable for the reconstruction of oil and gas reservoirs with
low permeability, low pressure, and water-sensitive formations, as well
as low-temperature or water locking reservoirs. The CO2 foam fracturing
technology exerts a significant effect on the reconstruction of the
reservoir affected by serious oil layer pollution and with low moisture
content. According to the public reports, due to the limitation of high
temperature crosslinking agents, CO2 foam fracturing construction
generally has a depth of about 2400–4000 m, and the maximum sand
ratio is between 15 and 25%. Well Y2 and well y508 in Yanchang oilfield
(Yagang et al., 2017) and well 3 in Sulige gas field (Yaoyao et al., 2017)
can be referred.
Compared with CO2 foam fracturing, CO2 dry fracturing is
completely water-free. It uses pure liquid CO2 to replace the conven­
tional hydraulic fracturing. As CO2 fracturing does not use water, the
CO2 dry fracturing technology has obvious technical advantages in
improving the productivity of water-sensitive/water locking reservoirs
and adsorptive gas reservoirs (shale gas, coalbed methane, etc.). How­
ever, liquid CO2 exhibits low viscosity, poor sand-carrying capacity,
L. Nianyin et al. Journal of Petroleum Science and Engineering 205 (2021) 108793

Table 8

Yan et al. (2019b)

Zhao et al. (2021)

Fang et al. (2014)
Comparison of CO2 fracturing technologies.

Liu et al. (2020b)

Jian et al. (2018)

Mollaali et al.
Consideration CO2 CO2 Supercritical Water
foam Lquid CO2 Based

Reference

(2019)
Environmentally N N N N
friendly
Environmental risk **** **** **** ***
Fluid recycling ? ? ? Y

● The model can simulate two-phase flow with viscosity and capillary force in pore scale
● SC-CO2 fracturing process is divided into SC-CO2 fracturing stage and CO2 phase change
Chemicals used Y Y Y Y
Reservoir compatibility Y Y Y ?
Fracture creation *** **** ***** ***

● The phase field model is applied for the first time and CO2 is compressible
Proppant carrying *** ** ** ****
Reverse discharging **** ***** ***** **
Fluid left in formation ** * * ***
Frac geometry N N N N

● It is helpful for CO2 fracturing of naturally fractured reservoir.

predictability
Frac cost **** ***** ***** ***
● Thermo-hydro-mechanical coupling in fracturing process

● The compressibility and viscosity of CO2 are considered;

Return on investment **** **** **** ***

● Model can compare slippery water, water and SC-CO2

*- Very low, **-Low, ***- General, ****- High, *****- Very high.
Y-yes, N-no.

large filter loss, and high friction; thus, it is not suitable for medium-to
large-scale sand fracturing. Referring to the existing data of YY-1 well
and Yunye-x well in Yanchang Oilfield (Xiangzeng et al., 2014; Juntao
et al., 2018), dry carbon dioxide fracturing can be applied to shallower
reservoir depth than foam fracturing, generally between 1100 and 3000
induced fracturing stage

m, and the maximum sand ratio can reach 14%. This is because almost
all of the fracturing fluid is composed of CO2, and the viscosity of the
fracturing fluid is greatly affected by temperature. It is also due to the
lack of an effective high-temperature resistant thickener.
Advantage

Supercritical CO2 fracturing is a special form of CO2 dry fracturing.

Both have similar technical principles. The main difference is that in
supercritical CO2 fracturing, CO2 has reached the supercritical state
before reaching the fractured zone. The supercritical CO2 fracturing
technology has become the development trend of the CO2 dry fracturing
The improved pore-scale network method and finite

technology owing to its better production increase effect and low con­
The simplified three-dimensional displacement-

struction pressure. However, there are only a few field applications, and
most of the research is concentrated in the theoretical research stage.
The advantages of supercritical CO2 fracturing are that it easily forms a
complex fracture network in the reservoir, and it does not require water
Universal Distinct Element Code

in the fluid, thus preventing the expansion of the reservoir clay.

Therefore, compared with foam fracturing and dry sand fracturing, this
technology is considered to be more suitable for low permeability and
Extended finite element

discontinuity-method
Phase field approach

water-sensitive formations, especially for tight gas reservoirs, such as

Solution method

shale. Similar to dry fracturing, the application depth of supercritical

element method
Summary of numerical simulation of fracture propagation in CO2 fracturing.

Finite element

CO2 fracturing is also shallow, and the key reason is that the develop­
ment of thickeners hinders the advancement of technology, which can
be referred to Yan-A well in Yanchang Oilfield (Haizhu et al., 2020). In
future research, if a breakthrough can be made in the development of
thickeners, CO2 fracturing technology will be hoping to be applied to the
development of deep wells or even ultra-deep wells.
Natural fractured
Tight sandstone
Reservoir type

6. Concluding remarks and future extended work

reservoir

1) Compared with the conventional hydraulic fracturing, CO2 frac­

Shale

Shale
Coal

turing has the ability to stimulate unconventional reservoirs more

–

effectively and exhibits high technical feasibility and good applica­

Whether to consider natural

tion prospects in future reservoir stimulation and reconstruction.

And during the fracturing, CO2 will be injected underground, which
is an effective means of CO2 reduction.
2) CO2 fracturing increases the cost of capturing, pressurizing and
transporting carbon dioxide, and requires special equipment and
high-strength pipelines to transport CO2 to the target layer, which
cracks

further leads to higher construction costs. How to reduce operating

Yes

Yes
No
No

No

No

costs is the focus of further research.

3) In the research direction of the CO2 foam fracturing technology for
Table 7

CO2

CO2

CO2
L-CO2
Fluid

CO2

CO2

unconventional reservoirs, the performance of CO2 foam fracturing

SC-

SC-

SC-

14
L. Nianyin et al.
fluid should be well understood, and a method to experimentally
evaluate the adaptability of unconventional reservoirs and CO2 foam
fracturing fluid should be established. Moreover, by improving the
construction equipment and process design methods, the CO2 foam
fracturing technology can be integrated into the current “factory”
fracturing of unconventional reservoirs.
4) The CO2 dry fracturing technology and supercritical CO2 fracturing
technology are completely water-free and do not cause damage to
water-sensitive formations. Both of these technologies can effectively
reduce the viscosity of the crude oil in the reservoir, improve the
percolation capacity of the crude oil, and increase the recovery ef­
ficiency of the reservoir. However, the development of CO2 frac­
turing fluid thickener is still difficult. Fluorine-containing and
organosilicon polymer thickeners may become a breakthrough in the
next study.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The work in this paper is supported by the grant from the National
Natural Science Foundation of China (No. U1762107) and Science and
technology program of Sichuan Province (No. 2019YJ0425). And
acknowledge the free and professional help from anonymous reviewers.
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