Journal of Petroleum Science and Engineering 219 (2022) 111121

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Journal of Petroleum Science and Engineering

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

Hydrate-based CO2 sequestration technology: Feasibilities, mechanisms,

influencing factors, and applications
Xuewen Cao a, b, **, Hongchao Wang a, b, Kairan Yang a, b, Shichuan Wu a, b, Qian Chen c,
Jiang Bian a, b, *
a
College of Pipeline and Civil Engineering, China University of Petroleum (East China), Qingdao, 266580, China
b
Shandong Provincial Key Laboratory of Oil & Gas Sequestration and Transportation Safety, Qingdao, 266580, China
c
School of Petroleum Engineering, China University of Petroleum (East China), Qingdao, 266580, China

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

Keywords: CO2 is the primary contributor to greenhouse gas that causes rapid global warming. CO2 capture, utilization, and
CO2 hydrate storage (CCUS) is a crucial technology for CO2 reduction, typically, CO2 hydrates form at pressures and tem­
CH4 hydrate peratures greater than 3 MPa and lower than 10 ◦ C. These non-harsh environmental conditions determine the
Carbon sequestration
value of hydrate-based CO2 sequestration technology, which can be used as a potential effective sequestration
Marine sediments
measure. In addition, hydrates have the advantages of rapid formation kinetics, high stability, and a low
Hydrate cap
probability of gas leakage; therefore, they can be used to sequester CO2 in the near future. In this review, we
summarize the development status and existing problems of various hydrate-based CO2 sequestration methods
and analyze the mechanisms, influencing factors, and appropriate sequestration locations. The paper focuses on
the CO2 replacement reaction of CH4 hydrates technology. The feasibility of this method is discussed in terms of
thermodynamics and kinetics, the mechanism and influencing factors of the replacement process are analyzed,
and various methods to improve the replacement efficiency are illustrated, including the temperature and
pressure conditions, the injection phase state of CO2, the use of additives, and the assistance of other gases (N2
and H2). Next, the method of direct injection of CO2 into marine sediments to form hydrates for sequestration is
discussed. We also generalize appropriate sequestration locations and summarize experimental and simulation
studies on CO2 sequestration in marine sediments, including the technical feasibility, sequestration mechanism,
and influencing factors. In addition, the hydrate cap is also discussed. Finally, we briefly introduce a hydrate-
based CO2 sequestration method for reusing depleted deposits. This review paper can provide insights for
future research and may help accelerate the field application of the hydrate method for CO2 sequestration
technology.

1. Introduction Earth’s climate is caused by growth in CO2 gas levels (Dufresne et al.,
2020; Mikhaylov et al., 2020). In recent decades, global energy demand
Considering that fossil fuels have always been used as the main en­ has increased dramatically, and the search for low CO2 emission stra­
ergy source for economic development, the CO2 concentration in the tegies has been accompanied by the urgent need to deal with large
atmosphere has increased by approximately 30% since the industrial amounts of CO2 emissions. According to statistics, the global CO2
revolution owing to human activities (Vitousck et al., 1997). CO2 is emission exceeded 33.4 billion tons in 2017 (Company, 2018). Global
considered the main greenhouse gas contributing to global warming, warming will cause the melting of polar icebergs, which will conse­
and the rapid growth of industrial activities has increased the emissions quently lead to a series of catastrophic problems, such as sea level rise
of CO2. According to related studies, the combustion of fossil fuels ag­ and species extinction. Most CH4 hydrates exist mainly in permafrost
gravates the “greenhouse effect” by approximately 64%, and CO2 and marine sediments. Considering their significant gas storage capacity
treatment has become a global concern. The gradual alteration of the and abundant CH4 reserves, they may be considered a low-carbon

* Corresponding author. College of Pipeline and Civil Engineering, China University of Petroleum (East China), Qingdao, 266580, China.
** Corresponding author. College of Pipeline and Civil Engineering, China University of Petroleum (East China), Qingdao, 266580, China.
E-mail addresses: [email protected] (X. Cao), [email protected] (J. Bian).

https://doi.org/10.1016/j.petrol.2022.111121
Received 20 June 2022; Received in revised form 24 September 2022; Accepted 7 October 2022
Available online 13 October 2022
0920-4105/© 2022 Elsevier B.V. All rights reserved.
X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

energy source in the near future (J. Wang et al., 2021). However, from can lower the pH of seawater and harm marine ecosystems, resulting in
an environmental perspective, CH4 hydrate-bearing sediments play a an immeasurable impact on marine ecosystems. The cost of solving this
crucial role in the global carbon cycle, and the greenhouse effect of CH4 problem is high and technically demanding. Therefore, it is prohibited
is 20–30 times that of CO2 (Milich, 1999). With increasing temperature by international agreements, such as the Oslo/Paris Convention and the
and global warming, CH4 hydrates will move out of the stable temper­ London Convention. The oil and gas industries have demonstrated that it
ature range, resulting in decomposition. CH4 released by decomposition is economically feasible to sequester CO2 in deep formations under
eventually enters the atmosphere, leading to a vicious cycle reaction and specific conditions, such as depleted oil and gas reservoirs, deep brine
further accelerating global warming (Mestdagh et al., 2017; Yang et al., aquifers, and marine sediments (Li et al., 2018; Rochelle et al., 2009;
2019; Shakhova et al., 2010; Farahani et al., 2021a). Additionally, the Zaluski et al., 2016).
geomechanical stability of permafrost containing CH4 hydrates in the Gas hydrates have received increasing attention over the past few
Arctic is highly susceptible to global warming. At present, the Arctic is years (Liang et al., 2020). It is a non-stoichiometric, cage-shaped crys­
warming twice as fast as the rest of the planet, resulting in permafrost talline compound formed by gas and water molecules under certain
degradation (Pörtner et al., 2019). CH4 hydrates solidify sediment par­ conditions of higher pressure and lower temperature (Sharma and Dhir,
ticles by adhering to them and bearing the load between the sediment 2021). Specifically, water molecules act as host molecules and are linked
particles. Therefore, the physical properties of the host sediments may by hydrogen bonds to form a rigid cage lattice, whereas gas molecules
be completely affected by CH4 hydrate decomposition, particularly their (CH4 molecules, CO2 molecules, etc.) are sequestered in the cage lattice
geothermal and mechanical properties, resulting in severe geological as guest molecules. The three crystal structure types of hydrates are
disasters, such as sediments deformation and sliding at the continental depicted in detail in Fig. 1. The most common form of CO2 and CH4
margin and submarine slope failure (Milich, 1999; Yang et al., 2019; molecules is the structure I (sI) hydrate (Sloan, 2003). Currently, based
Farahani et al., 2021b). Nelson et al. (2002) also showed that in areas on the distinct characteristics of gas hydrates, hydrate-based application
under ice-rich permafrost, land subsidence caused by melting may technologies have shown great potential and have become a focus of
seriously damage infrastructure as climate changes. Paleoclimatic data attention. Important applications of gas hydrates in sustainable chemi­
show that the current global CO2 volume fraction (385 × 10− 6) is cal technologies include, but are not limited to, CH4/H2 storage and
already in a hazardous situation (Retallack and Conde, 2020). According transport, gas (especially CO2) separation and sequestration, seawater
to the Intergovernmental Panel on Climate Change, to limit global desalination, and cold energy storage (Xia et al., 2022; Hassanpour­
warming to no more than 1.5 ◦ C above pre-industrial levels, the quantity youzband et al., 2020; Manakov and Stoporev, 2021). H2 is the cleanest
of CO2 that would have to be captured and permanently sequestered by energy source for power generation, automobiles, and other energy
mid-century would be around 50–100 million tons per year. Therefore, sources; however, there is still a lack of suitable H2 storage media
mankind must actively seek long-term and effective solutions from all (Nadeem et al., 2019). Compared to conventional methods, such as
levels of technology, economy, policy, and law to accomplish interna­ compressed H2, liquefied H2, and metal hydrides, the hydrate-based H2
tional cooperation and ultimately reduce CO2 emissions (Li et al., 2020). storage method is fascinating because of its low cost, high safety, and
CCUS technology is considered the most effective way to reduce environmental friendliness (Profio et al., 2009). Hydrate-based storage
greenhouse gas, and its environmental and economic benefits have technology, known as solidified natural gas (SNG) technology, also
attracted much attention from all countries. CCUS technology refers to opens up a new direction for efficient natural gas storage (Kim et al.,
the capture and separation of CO2 emitted by industries, which is then 2015; Wang et al., 2013; Veluswamy et al., 2018). Mcturk and Waller
transported to oil and gas reservoirs or other sequestration sites to (1964) reported a method for continuously storing O3 in the form of a
enhance oil and gas recovery or sequestering permanently under the gas hydrate. Additionally, the slurry can be used to transfer CO2 (i.e., a
ground or subsea. The use of CO2 in global oil and gas reservoirs can mixture of CO2 hydrates and water). The main advantage of this concept
increase oil production by more than 35 billion tons and provide 70–100 is that CO2 hydrates can be made into particles and transported over
billion tons of CO2 sequestration potential (Kumar et al., 2010; Wei long distances by trucks or ships (Matsuo et al., 2017; Veluswamy et al.,
et al., 2011). The 21st century is a period of rapid development of CCUS 2018). The basic principle of hydrate-based gas separation is that
technology, with many countries, including the USA, Canada, Australia, different gases have different formation conditions. When a mixed gas
Italy, Norway, the UK, and Japan, carrying out research and practice on forms hydrates, the components that can easily form hydrates are
CO2 sequestration projects to varying degrees (White and Foxall, 2016; enriched in the hydrate phase, thus achieving gas separation. It is mainly
Jung et al., 2019; Osman et al., 2021). CCUS technology includes four applied to gas mixtures containing CO2, such as flue gas (N2/CO2),
main parts: capture, utilization, transportation, and sequestration. CO2 natural gas (CH4/CO2), coal-bed methane (CH4/CO2), syngas (H2/CO2),
sequestration is one of the most promising methods of reducing CO2 and other mixtures (Wang et al., 2017; Horii and Ohmura, 2018; Xu
emissions. Currently, sequestration technology primarily includes three et al., 2019). Laboratory studies have shown that compared with other
methods: geological sequestration, marine sequestration, and mineral conventional technologies, hydrate-based CO2 capture is an
carbonization (Voormeij and Simandl, 2004). Specific sequestration energy-saving, environmentally friendly, and simple process (P.F. Wang
technologies include injection into oil and gas reservoirs to improve et al., 2022; Xia et al., 2022; Cheng et al., 2022). As early as the 1940s,
recovery, coal seams to obtain coal bed methane, and nature gas hydrate Parker (1942) proposed the desalination of seawater using gas hydrate
reservoirs to obtain CH4. These methods exist the utilization and technology. When hydrate is formed, hydrate crystals can exclude dis­
sequestration of CO2 simultaneously; in addition, CO2 sequestration can solved ions from the aqueous phase, and fresh water can be obtained
also be achieved by injecting it into depleted hydrocarbon reservoirs and after hydrate decomposition (Babu et al., 2018; Lv et al., 2017). The
coal seams, deep brine aquifers, and marine sediments. In these pro­ advantage of hydrate-based cold storage technology is that it has a large
cesses, CO2 can be adsorbed on the pores of the reservoir structure, energy storage density and low operating temperature difference; thus,
dissolved in the ocean, mineralized into inorganic carbonates, or it is considered a promising cold storage method (Xie et al., 2010).
sequestered as liquid CO2 lakes or CO2 hydrates (Aminu et al., 2017; Hydrate-based CO2 sequestration methods have been widely studied
Gadikota et al., 2014). Mineral carbonation is the conversion of CO2 into in recent years because of their suitability for many geological and
solid inorganic carbonic acid through a chemical reaction. However, marine locations, as shown in Fig. 2. CO2 hydrates generally form under
owing to the high cost, environmental impact, and availability of rocks, low temperature and high-pressure conditions below 10 ◦ C and above 3
mineral carbonation has been excluded from large-scale implementation MPa. At the standard pressure and temperature, one cubic meter of CO2
(Muhammad et al., 2019). Dissolving CO2 in the ocean is not a suitable hydrate can emit 175 cubic meters of CO2 gas, which facilitates CO2
method (Chang et al., 2016) and may lead to unpredictable environ­ sequestration (Cai et al., 2020; Herri and Chassefiere, 2012). Under
mental problems. If a large amount of CO2 is injected into the ocean, it abundant water, appropriate pressure and temperature conditions, CO2

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

Fig. 1. Schematic diagram of three-unit crystal structures of gas hydrate (adapted from Wei et al., 2022) (CH4-methane, C2H6-ethane, CO2-carbon dioxide,
NG-natural gas, C3H8- propane, C4H10-isobutane, C6H14-neohexane, C7H14-cycloheptane).

Fig. 2. Hydrated-based CO2 geological and marine sequestration locations.

hydrate can form rapidly (Zhao et al., 2014). In addition, rapid hydrate Manakov and Stoporev, 2021; Bian et al., 2022), or are mostly limited to
formation kinetics make it unlikely for cracks to form, thereby realizing the discussion of one sequestration method. However, CO2 sequestration
self-containment to a certain extent. Moreover, various studies have is a rapidly growing field, and recent advances and developments must
shown that CO2 replacement of CH4 hydrate is thermodynamically and be reviewed and discussed. In view of this, this paper makes a
kinetically feasible (Qanbari et al., 2011; Pandey et al., 2021b; Metz comprehensive review of the existing literatures to understand the basic
et al., 2005; Blackford et al., 2009). The replacement reaction can pro­ knowledge of hydrate-based CO2 sequestration technology and discusses
ceed spontaneously, maintaining the stability of the CH4 hydrate res­ all available methods. In addition, it also reflects the development trend
ervoirs and improving the safety of the extraction process. This new and the latest frontier problems.
approach to exploit CH4 hydrate resources is unique, but low efficiency In this review, various hydrate-based CO2 sequestration technologies
limits its application. Considering the vast ocean areas and suitable are described in detail, including the CO2 sequestration process in
environment conditions, injecting CO2 directly into marine sediments to various formations, as well as the sequestration mechanisms, feasibility,
form CO2 hydrates for sequestration would be a good option. Further, influencing factors, and appropriate sequestration locations. The chal­
based on existing facilities, depleted oil and gas reservoirs, or even lenges that need to be overcome in the future development of CO2
depleted CH4 hydrate reservoirs after future commercial extraction, sequestration methods are identified, and various countermeasures are
would be promising regions for future CO2 sequestration. In conclusion, proposed based on the current research status. This review provides
hydrate-based CO2 sequestration is a sustainable technology that can theoretical and insightful guidance for improving the efficiency of the
sequester CO2 in geological and marine sediments. However, some CO2–CH4 hydrates replacement method with the aim of applying this
previous reviews have not covered sequestration mechanisms and lo­ method to the commercial extraction of CH4 in the future. It also pro­
cations in detail (Lee et al., 2012; Aminu et al., 2017; Shukla et al., 2010; vides theoretical support for the field application of hydrate-based CO2

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

sequestration technology and proposes the scope of future work. Table 1

Advantages and disadvantages of gas hydrate extraction methods.
2. CO2 sequestration by replacing CH4 hydrate Method Advantages Disadvantages

Depressurization Can be used in NGH reservoirs Causes land subsidence and

CH4 hydrates are a kind of sub-stable state mineral whose formation with low hydrate saturation, submarine landslides
and distribution are mainly controlled by hydrocarbon gas sources and high porosity, and low free gas Hydrate reforming occurs
certain temperature and pressure conditions. The formation tempera­ without extra energy input readily during
ture is usually lower than 10 ◦ C and the pressure is usually greater than depressurization
Thermal Rate of heat injection can be Low productivity
10 MPa (Sun et al., 2022). At present, CH4 hydrates are mainly Stimulation varied to control productivity High heat loss and high
distributed in two types of regions on the earth: one is the ocean with a cost
certain depth of 300–4000 m, where they are formed under Chemical Productivity can be improved in Recycling is difficult, easy
high-pressure conditions and mainly distributed on the muddy seabed Injection a short time to cause environmental
pollution
and stored in the loose sediments of 0–1500 m below the seabed; the
The high cost
other is the permafrost zone and part of the polar land region at a water Gas replacement Good strategy for CO2 capture Not suitable for low
depth of 100–250 m, where CH4 hydrates are formed mainly under and sequestration permeability gas hydrate
low-temperature conditions. The global locations of CH4 hydrate res­ reservoirs
ervoirs are shown in Fig. 3. In the cold permafrost region, the CH4 hy­ Production efficiency is
low
drates formation pressure is not too high because the temperature is
lower than 0 ◦ C. However, in marine sediments, the presence of
seawater increases the pressure, resulting in hydrate formation at higher economic standpoint, requiring not only the expense of CO2 capture,
temperature conditions, even up to 25 ◦ C. When the temperature and collection, and purification but also the purchase of ancillary equipment
pressure change greatly, the stable phase equilibrium condition will be (such as reservoir environmental parameter acquisition and fluid
disrupted, leading to the decomposition of CH4 hydrates (Ejike, 2019; J. leakage monitoring) to lower the sequestration risk. However, the rev­
Sun et al., 2015). In response to this property of CH4 hydrates, various enue from the extracted CH4 is sufficient to cover the CO2 treatment
extraction techniques of CH4 hydrates have been proposed, including costs and project investment during the replacement process (Zhao
depressurization, thermal stimulation, chemical injection, and CO2 et al., 2014; Lee et al., 2015).
replacement method (Sloan, 1990; Fan et al., 2000; Boswell et al., 2015; In addition, studies have shown that environmental conditions, such
Tang et al., 2015; Cai et al., 2020; Liu and Li, 2021). The main advan­ as temperature and pressure, and the locations of CH4 hydrates, are
tages and disadvantages of these methods are listed in Table 1. Tradi­ suitable for CO2 sequestration. The measurement of hydrate-liquid-
tional approaches have certain drawbacks and can easily cause vapor equilibria in the CH4–CO2–H2O system indicates that below
environmental pollution. However, the CO2 replacement method can 283 K, CO2 hydrates are more thermodynamically stable than CH4 hy­
realize the extraction of CH4 hydrates and sequestration of CO2 in the drates because the equilibrium pressure of CO2 hydrates is lower than
form of hydrates in the reservoirs (Herri and Chassefiere, 2012). Related that of CH4 hydrates (Anderson et al., 2003). Ohgaki et al. (1996)
mechanical tests also demonstrated that the replacement reaction is demonstrated that the distribution of CO2 in the hydrate phase is
conducive to the stability of the CH4 hydrate layer (Liu et al., 2016). different from that of CH4 by examining the distribution coefficient of
Furthermore, a plain CO2 sequestration project is costly from an CH4 and CO2 across the gas and hydrate phases at 280 K. The total global

Fig. 3. Locations of CH4 hydrate reservoirs around the world (Ejike, 2019).

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

CH4 hydrate resources are estimated to be approximately 20 trillion m3.

Among them, marine CH4 hydrate resources account for more than 90%
and are mainly distributed in submarine sediments with water depths of
300–4000 m (Lu, 2015). And towards sequestering CO2 in deep-sea
sediments, the formation of CO2 hydrates can lead to a
low-permeability secondary cap to prevent CO2 diffusion and leakage.
This is a relatively permanent and theoretically safe sequestration
technology (Chen et al., 2015; Kwon et al., 2008; Qanbari et al., 2011).
Hyodo et al. (2014b) investigated the geological properties of
hydrate-saturated sediments after CO2–CH4 replacement and found that
newly formed CO2 hydrates can help to maintain the mechanical sta­
bility of the marine sediment reservoirs. Therefore, CO2 replacement of
CH4 hydrates is considered a win-win technology that can simulta­
neously realize CH4 hydrate extraction, CO2 emissions reduction, and
CO2 sequestration, and is also a beneficial supplement to CCUS tech­
nology (Gebauer et al., 2003).

2.1. Feasibility study

With extensive research, it has been realized that CO2 replacement of

CH4 hydrates is thermodynamically and kinetically feasible. The field
Fig. 4. Phase equilibrium diagram of CH4 and CO2 hydrates (Sloan and
trial using this method is the Ignik Sikumi#1 well in the Prudhoe Bay
Koh, 2008).
field on Alaska’s north slope, a collaboration between Conoco Philips,
Japan Oil, Gas, and Metals National Corporation, and the United States
Department of Energy. The cumulative CH4 gas production reached equilibrium of the mixed gas:
more than 20,000 and lasted approximately 6 weeks (Schoderbek and 89009 1.1307 × 10
Boswell, 2011). ln(pcal ) = 175.3 −
T
+ 0.07392y +
T2
23.392y (2)
− 5 2
− + 3.9566 × 10 y
2.1.1. Thermodynamic feasibility T
Through molecular simulation, Yezdimer and Ota et al. (2005a) re­
ported that the Gibbs free energy for CO2 replacement reaction is where pcal is the phase equilibrium pressure of the gas mixture; T is the
negative, indicating that this process is thermodynamically feasible temperature; y is the molar percentage of CO2 in the mixed gas.
because the chemical reaction always proceeds in the direction of Goel (2006) conducted an experimental study on the CH4 and CO2
decreasing Gibbs free energy. The decomposition of CH4 hydrates is an hydrates formation process and found that CO2 hydrates exist stably in
endothermic reaction, whereas the formation of CO2 hydrates is an the temperature range of 260–270 K and pressure range of 0.6–1.7 MPa,
exothermic reaction. Rueff et al. (1988) found that the enthalpy change whereas CH4 hydrates are not easily formed. The phase-equilibrium
of CO2 hydrates formation is − 57.98 kJ/mol, and CH4 hydrates curves of different proportions of the mixed gas of CO2 and CH4 were
decomposition is +54.49 kJ/mol. Therefore, the enthalpy change in the plotted according to Eq. (2). It is found that the phase-equilibrium
replacement reaction is − 3.49 kJ/mol. It could be analyzed that the heat pressure of the mixed gas decreases with increasing CO2 content,
released from the formation of CO2 hydrates will promote the decom­ whereas the temperature increases with increasing CO2 content.
position of CH4 hydrates and reduce the input of external heat (Shaga­
pov et al., 2017). The equation for the replacement reaction can be 2.1.2. Kinetic feasibility
expressed as Uchida et al. (2010) conducted an experimental study of the mixed
gas hydrate formation process of CO2 and CH4 using gas chromatog­
CO2 + CH4 ⋅ nH2 O⇌CO2 ⋅ nH2 O + CH4 (n ≥ 5.75) (1) raphy and Raman spectrometry and obtained the expression of the
change in gas composition with respect to time in the displacement re­
where n is the hydration index, that is, the number of water molecules. action, as follows:
And n is related to the environmental pressure and temperature. ( )
Other experimental studies have found that CO2 molecules have a XCH4
=
XCH4
+ αlgt (3)
larger affinity potential than CH4 molecules, and react more readily with XCO2 XCO2 0
free water to form hydrates, facilitating the replacement reaction in the ( )
XCH4
positive direction (Ota et al., 2005a). Sloan and Koh (2008) plotted a where X is the gas phase composition; XCO2 represents the component
0
typical phase equilibrium diagram of the CH4–CO2–H2O system, as ratio when the initial test time was 0; t is the reaction time. α is a fitting
shown in Fig. 4. It can be seen that regions A and B lie above the phase parameter related to the rate of condensation of the CH4 molecules in the
equilibrium curve for water-hydrate-CO2 and below the phase equilib­ gas phase.
rium curve for water-hydrate-CH4, which is the region of coexistence of According to the analysis of Eq. (3), it can be seen that the CH4 gas in
CH4 gas and CO2 hydrates. The temperature and pressure conditions for the gas phase decreases at the beginning of the reaction, and gradually
the corresponding replacement reactions were also in regions A and B. increases after a period of reaction. This is because CH4 molecules
This shows that the formation pressure of CH4 hydrates is significantly occupy two cages (512 and 51262), while CO2 molecules only occupy the
higher than that of CO2 hydrates under the same temperature condi­ large cage (51262); hence more CH4 than CO2 is consumed in the early
tions, whereas the formation temperature of CH4 hydrates is lower than stage of the replacement reaction. The continuous formation of CO2
that of CO2 hydrates under the same pressure conditions. Akihiro (2005) hydrates hinders the formation of CH4 hydrates as the reaction con­
found the same law for determining the phase equilibrium temperature tinues, increasing the proportion of CH4 in the gas phase. Yang et al.
and pressure of CH4 and CO2 hydrates below the freezing point. The (2010) found that the consumption of CO2 is greater than that of CH4 in
mixed gas of CO2 and CH4 occurs during the replacement process, and the overall experimental process, but the consumption of CH4 is greater
Adisasmito et al. (1991) provided an equation to calculate the phase

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

in the initial experimental process, which proved the theoretical accu­ particle size can modify flow properties and affect percolation charac­
racy of Uchida’s equation. Ota et al. (2005b) studied the displacement teristics by changing the size of pores and throat channels. Lei et al.
reaction under the condition of 3.6 MPa and 273.2 K, and the detailed (2019), in their experiments on the pore habit of CH4 hydrate and its
results are shown in Table 2. The results showed that the decomposition evolution in sediments, used phase-contrast micro-CT to find that CH4
rate of CH4 hydrates and the formation rate of CO2 hydrates are high at hydrates formation in excess gas systems can lead to partial cementa­
the beginning of the reaction. However, as the reaction proceeds, both tion, while hydrates in excess water systems act mainly as pore fillers.
decomposition and formation rates decrease to low values (Yang et al., Ullerich et al. (1987) proposed moving boundary ablation, which sug­
2010). gests that the water generated by hydrates decomposition is directly
Hirohama et al. (1996) proposed that the driving force of replace­ carried away from the solid surface by CH4. Gabitto and Tsouris (2006)
ment reaction with liquid CO2 is the difference in the chemical potential proposed the decomposition of the outer surface and the formation of
gradient. Bishnoi and Natarajan (1996) proposed a kinetic model for the the inner surface of the interface, and the aggregation and growth of
formation and decomposition of CH4 hydrates based on the difference unstable clusters were proposed by Sloan and Fleyfel (1991). Although
between the fugacity of CH4 gas and three-phase equilibrium. Ota et al. understanding the replacement mechanism is critical in the quest to
(2005b) concluded that the driving force is the fugacity difference be­ improve the efficiency of the replacement process, a complete conclu­
tween two molecules in the liquid and hydrate phases through the sion has not yet been reached (Ota et al., 2005b). considered that the
Raman experiment. He modified the model proposed by Bishnoi and displacement reaction mainly occurs in the hydrate phase, and the hy­
Natarajan (1996) and established a simple kinetic model of the drates will reform through surface reaction and CO2 diffusion using
replacement reaction based on their experimental data as follows: Raman spectroscopy. Based on the stoichiometric analysis of the
( ) 1 ( ) CO2-occupied large cages and the CH4-occupied small cages, Ota et al.
niCH4 ,H dx
− H
= KA fCH L
− fCH L
− KA fCO H
− fCO (4) (2005b) considered that the driving force of the replacement reaction is
100 dt 3 the fugacity difference between the components in the gas and hydrate
4 4 2 2

where x is the proportion of remaining CH4 in the hydrate phase; t is the phases. Li et al. (2008) reported that the decomposition of CH4 hydrates
reaction time; f is the fugacity; K and K′ are the total rate constants for may be controlled by the rearrangement of H2O molecules, and the
decomposition and formation, respectively; A is the surface area be­ formation of CO2 hydrates may be controlled by the diffusion of CO2
tween the liquid and hydrate phases. molecules from the experimental data of activation energy in the
displacement reaction.
Extraction of CH4 hydrates by injecting supercritical CO2 with heat
2.2. Mechanism of the replacement reaction generates complex multi-component, multiphase transport reactions
(Deusner et al., 2012). Highly dynamic processes, including hydrates
Since the 1990s, experimental and theoretical studies on the micro- decomposition, hydrates transformation, and pure or mixed hydrates
mechanisms of the replacement reaction have mainly focused on the reformation, can alter sediments parameters, such as overall thermal
exchange and occupation of guest molecules. Ohgaki et al. (1996) first behavior and geomechanical performance. Fig. 5 shows the associated
proposed the concept of CO2 sequestration by replacing the CH4 mole­ transports and reactions during the injection of heated CO2 into CH4
cules in CH4 hydrates, and Nakano et al. (1998) later extended it to hydrate-bearing sediments: (1) injection of heated CO2; (2) CH4 hy­
ethane hydrates. In terms of mechanistic studies of hydrates formation drates decompose rapidly under thermal stimulation; (3) heat conduc­
and decomposition, many scholars have used neutron diffraction, tion through sediment particles or non-flowing pore water to stimulate
Raman spectroscopy, nuclear magnetic resonance (NMR), and other and decompose distant CH4 hydrate particles in the distance; (4) mixing
visualization techniques to propose various explanations. Kuang et al. of CO2 and CH4; (5) formation of hydrates from CO2 with pore water; (6)
(2022) studied the microstructural evolution of CO2 hydrates in porous formation of mixed CO2–CH4 hydrates; (7) CO2 replacement of CH4
media using low-field NMR techniques and discussed the effect of hydrates is limited by the diffusion and transport of CH4 and CO2; (8)
different initial water/gas saturation and pressure on the hydrates for­ CO2 is rapidly converted to CO2 liquid after cooling; (9) formation of
mation rate. Farahani et al. (2021) used high-field NMR techniques to hydrates from CO2 with excess pore water may lead to pore space
compare the formation and decomposition of CH4 hydrates in synthetic blockage and substantial changes in porosity and permeability; (10)
and natural sediment samples under thermal stimulation. They investi­ production of fluids containing CH4, water, and CO2 in different states
gated the effect of thermal cycling on the induction time and found that and proportions; (11) decomposition of hydrate-bearing particles leads
natural sediment samples have a wider particle size distribution and to sediments settlement, which changes the integrity and geomechanical
greater micropore capillarity than synthetic sediment samples. Kossel stability of sediments; and (12) CH4 gas may be released into hydrau­
et al. (2021) conducted CO2 replacement experiments in gas-saturated lically isolated pores as non-producible gas.
aqueous solutions and porous media using Raman spectroscopy and Pandey et al. (2020, 2021a, 2021b, 2022a, 2022b) investigated the
observed that 50% of CO2 was involved in gas exchange while the rest effect of injected CO2 on the hydrate morphology evolution in CH4
was used to form new CO2 hydrates. Kumar et al. (2022) confirmed by hydrate-saturated pore space based on the pore-scale visualization and
X-ray diffractometer that the mixed gas of CO2 and CH4 will nucleate high-pressure micromodels. They observed that the injected liquid CO2
and grow as sI hydrate even in the presence of sH hydrate forming agent. invades the pore space through dissolving CH4 hydrates. The hydrate
Based on the analysis of CT data, Wang et al. (2016) demonstrated that film nearby transforms into crystalline hydrate, which indicates a pro­
cess of film thickening. Due to the hydrophilic and porosity of the hy­
Table 2 drate film, during the continuous injection of CO2, the hydrate film
Relationships between the amounts of CH4 hydrates decomposition and CO2 attracts water from the surrounding pores. A new hydrate formation
hydrates formation (Ota et al., 2005b). process begins, leading to continuous thickening of hydrate film and
Reaction time (h) Decomposition amount of CH4 Formation amount of CO2 growth of massive hydrates. At the end of the injection, the mixed
hydrate hydrate CH4/CO2 hydrates are obtained. They also used a slow stepwise pressure
mmol mmol/(cm2⋅h) mmol mmol/(cm2⋅h) drop for decomposition and observed that the hydrate film decomposes
43 34.5 0.02588 24.7 0.01853
first with the released gas being immobilized by solid hydrate blocks.
93 47.7 0.01655 38.8 0.01346 Then the decomposition front moves from one pore to the other and the
114 68.4 0.01935 42.8 0.01211 released gas flowed downstream. As the hydrate film decomposes, the
184 70.5 0.01236 71.2 0.01248 released gas starts to separate into two parts: one part is covered by the
307 66.2 0.00700 56.7 0.00610
reformed hydrates, whereas the rest flows freely without forming

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

pores (Y. Wang et al., 2022).

Demurov et al. (2002) proposed the microscopic mechanism of the
replacement reaction by investigating the dual action between the host
and the guest molecules, as well as between the guest molecules: (1)
motion of CO2 molecules causes vacancies in the hydrogen bonding
network of the CH4 hydrates, which allows CH4 molecules to jump and
diffuse; (2) CO2 molecules are first in the hydration shell and then
gradually move into the center of the amorphous inclusion; (3) CO2
molecules reach the CH4 hydrates decomposition front in which CO2
molecules compete with CH4 molecules. That is, the mechanism of
replacement reaction is dual and the vacancy assistance of host mole­
cules and the competition of two guest molecules, which is a natural
unification of the formation and decomposition processes. Based on the
above summaries and analysis, Lee et al. (2003) also argued that the
replacement process between CO2 and CH4 is a dual mechanism, which
is determined by cage occupation. As shown in Fig. 6, Bai et al. (2012)
studied the replacement process using the molecular dynamics (MD)
method. The simulation box is divided into several regions along the
z-direction according to the crystal unit length, which are represented
by regions A, B, C, and D. The regions A, B, and C are for 3 × 3 CH4
hydrate crystals, respectively, and region D is for 1656 H2O, 23 CH4, and
94 CO2 molecules. They demonstrated that the chemical potential
perturbation of the CO2 molecules leads to the CH4 hydrates decompo­
sition. It is concluded that the CH4 hydrates decompose first, and
amorphous CO2 hydrates form later. However, Tung et al. (2011a) also
used the MD method to investigate the replacement reaction with liquid
CO2, and concluded that CO2 can directly replace CH4 in the hydrates
without decomposition. Yohei et al. (2011) studied the
micro-mechanism of replacement reaction using the isobaric isothermal
MD method. The results showed that the binding effect of large cages on
CH4 molecules is much weaker than that of small cages; hence, it is
easier for CH4 molecules in large cages to escape during the replacement
reaction. It also shows that the replacement reaction occurs mainly in
the surface layer of the CH4 hydrate. Qi et al. (2011) studied the
Fig. 5. Reaction process of injecting hot CO2 into CH4 hydrate-bearing sedi­
microscopic replacement process using the potential method. According
ments (Deusner et al., 2012).
to the simulation results, the microscopic processes of the replacement
reaction are divided into the following two steps: first, the CH4 hydrate
hydrates. This interprets that the mixed gas of CH4 and CO2 released
cages opened and CH4 molecules escaped from the cages; then, CO2
from decomposition is separated into CO2-rich gas and CH4-rich gas. The
entered the empty cages and formed CO2 hydrates.
former can reform hydrates, while the latter cannot. The mechanism of
simultaneous reformation and decomposition of hydrates is believed to
arise from the different equilibrium pressures of CH4 and CO2 hydrates.
The mixed hydrates with different compositions of CH4 and CO2 are
decomposed under different pressures. The released CH4 gas cannot
react with water and convert to hydrates under these pressures, whereas
the released CO2 gas can because the pressures are still higher than the
equilibrium pressure of pure CO2 hydrates. Therefore, the effect of
gradual pressure reduction is to concentrate the amount of CO2 in the
hydrate phase and allow replacement reaction to propagate deeper into
the formation until CO2 eventually reacts with pore water and forms
hydrates. In summary, when CO2 is injected into one well and CH4 gas is
produced through gradual pressure reduction in another well, the re­
covery of CH4 gas can be substantially enhanced. Another benefit is CO2
sequestration through forming CO2 hydrates, which also helps maintain
the geomechanical stability of the formation. Y. Wang et al. (2021)
studied the replacement reaction by establishing a pore network model
and concluded that the reaction rate varies with the area of CH4 hydrates
in the pores. The replacement reaction starts at the edge of the hydrates
distribution area and proceeds inward. The CO2 hydrates formation rate
is similar to the CH4 gas production rate at first but lags behind, and is
slow in the interior of the CH4 hydrates distribution area. Finally, the
CO2 hydrates saturation in the interior is lower than the edge. In other
words, mixed hydrates also tend to form at the edges of the CH4 hydrates Fig. 6. (a) Initial (top) and (b) final configuration (bottom) for a typical
distribution area. The initial water tends to stay in the corners and edges simulation run (Bai et al., 2012) (magenta spheres represent CH4 molecules and
green spheres represent CO2 molecules). . (For interpretation of the references
of the pore channels without the CH4 hydrates distribution region,
to colour in this figure legend, the reader is referred to the Web version of
leading to the formation of large amounts of pure CO2 hydrates in the
this article.)

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

2.3. Influence factors of the replacement reaction the overall replacement rate is significant, and also concluded that the
mass transfer limitation is the main factor preventing the replacement
It has been confirmed that the replacement reaction follows a two- process from proceeding. Bai et al. (2012) found that as the displace­
stage pattern: (1) initial rapid surface reaction: CO2-rich mixed gas ment reaction proceeded, the formed CO2 hydrates cowered the unde­
forms hydrates on the surface of particles without obvious generation of composed CH4 hydrates, thus slowing down the subsequent replacement
free water; (2) later slow diffusion-controlled replacement reaction: CO2 reaction rate. Simultaneously, the chemical potential of the guest mol­
molecules and CH4 molecules slowly diffuse through the surface of ecules, mass transfer, and memory effect of the hydrates can affect the
mixed gas hydrates for gas molecules exchange (Zhou et al., 2017; overall replacement reaction. Fig. 7 shows the flow chart of the exper­
Falenty et al., 2016a). The replacement rate and efficiency are mainly imental device for high-pressure CO2 gas replacing CH4 hydrates, which
determined by the environmental conditions (temperature, pressure, is commonly used in replacement reaction experiments (Li et al., 2014).
CO2 phase state, reaction time, multiphase fluid transfer, etc) and CH4
hydrates properties (hydrate particle size, occurrence state,
2.4. Methods to improve efficiency
gas-liquid-hydrate three-phase saturation, etc). These external factors
can influence the diffusion rate of the guest molecules in the hydrate
The replacement ratio is a value that characterizes the efficiency and
crystal structure and the gas-liquid-hydrate three-phase fugacity, thus
assesses the effect of the replacement reaction. Although the CO2
controlling the rate and efficiency of the replacement reaction (Babu
replacement method has obvious environmental-friendly advantages, its
et al., 2014). Lee et al. (2003) argued that the replacement process is
relatively low efficiency is an inevitable problem due to the “armor ef­
controlled by a combination of the chemical potential of guest mole­
fect” and shielding effect during replacement reaction. Consequently,
cules, water memory, and mass transfer. The phenomenon that CO2
researchers are working to find suitable methods to enhance the
molecules mainly occupy the large cages and CH4 molecules released
replacement efficiency in terms of external temperature and pressure,
from decomposition reoccupy the small cages can be observed through
the phase state of CO2, and the additives (Acosta et al., 2011; Kakati
Raman experiments and theoretical models (Li et al., 2008). In terms of
et al., 2015; Azizi et al., 2016; Mwa and Hc, 2020).
replacement efficiency, Lee et al. (2003) suggested that the replacement
rate is slightly affected by pressure changes above the CO2 hydrate
2.4.1. Temperature and pressure conditions
formation pressure using NMR.
According to a detailed analysis of the replacement reaction, the
Temperature and pressure have a significant effect on the reaction
coexistence state of mixed gas hydrates is different under different
rate. Li et al. (2007) conducted experiments on the replacement reaction
temperature and pressure conditions, thus the replacement efficiency is
and showed that increasing the temperature facilitates the replacement
greatly influenced by them (Zhou and Yu, 2015). The relevant experi­
reaction, which is consistent with the conclusion reached by Qi and
ments showed that the replacement efficiency gradually increased with
Zhang (2010). It also was observed that the diffusion process played a
increasing temperature for a certain pressure, which also showed the
dominant role in the NMR results. Ersland et al. (2010) synthesized CH4
same trend with increasing pressure for a certain temperature. However,
hydrate samples with different initial saturations and observed the
the effect of increasing the temperature is more significant (Song et al.,
microscopic replacement reaction of liquid CO2 using Raman spectros­
2016). The replacement reaction proceeds through two stages: a fast and
copy. The observations showed that the number of CH4 molecules in the
a slow reaction, which are controlled by the decomposition of surface
small and large cages of CH4 hydrates gradually decreased as the reac­
CH4 hydrates and the diffusion of CO2 molecules, respectively, whereas
tion proceeded, but the reduction rates of the two cages were quite
temperature and pressure mainly affect the latter (S. Sun et al., 2015).
different. The CH4 molecules in the large cages eventually approached 0,
When the temperature rises, the molecular movement is intense, the
whereas the reduction rate in the small cages remained essentially
stability of CH4 hydrate decreases, hydrates decomposition and gas
constant. This is because the Van der Waals diameter of the CO2 mole­
molecules diffusion accelerate, and the free water generated from
cule is 0.512 nm, which makes it difficult to stabilize in small cages. The
decomposition promotes the formation of CO2 hydrates, resulting in a
CH4 molecules released from decomposition also reoccupy the small
higher replacement efficiency. Numerous replacement experiments
cages; hence, it is more difficult for CO2 molecules to replace the CH4
under different temperature and pressure conditions are conducted, as
molecules in the small cages than in the large cages. Lee et al. (2003)
shown in Table 3. It shows that increasing temperature and pressure
examined the composition of the guest molecules in the large and small
within a particular range can improve displacement efficiency.
cages of the sI hydrate using NMR. Assuming that CO2 molecules
completely occupy the large cages, the CO2/CH4 ratio in the hydrate
2.4.2. Effects of additives
phase is 1.8; therefore, the theoretical recovery rate of CH4 hydrates is
Acosta et al. (2011) experimentally studied the effect of tetrabuty­
64%. In addition, they observed that the effect of hydrate particle size on
lammonium bromide (TBAB) on the phase equilibrium of CO2+CH4

Fig. 7. Simple diagram of CO2 replacement experimental device (adapted from Li et al., 2014).

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

Table 3 formation of CO2 hydrates. Kinetic promoters such as SDS and SDBS
Summary of the CH4 recovery efficiency of CO2 replacement reaction under mainly enhance the formation rate of CO2 hydrates and reduce their self-
different temperature and pressure conditions. protection ability. In addition, the hydrates formed in the additives so­
T (K) P (MPa) Method CH4 recovery References lution system are granular and easier for gas molecules to diffuse into
efficiency (%) free water. The surface tension of the gas-water system is effectively
268.15 2.67 GC 68 Lee et al. (2013) improved, which enhances heat and mass transfer, therefore acceler­
272.2 3.6–4.5 GC 8.63–13.2 Zhang et al. ating the decomposition of CH4 hydrates and increasing the replacement
(2018a) efficiency.
273 3.36 Roman 20.3 Ota et al.
(2005b)
274 4.5 25–35 Ryou et al. 2.4.3. Phase state of CO2
(2021) Mcgrail et al. (2004) first proposed a new replacement method using
274.15 3.5 Roman 64 Park et al. CO2 emulsions, which were prepared with water as the continuous
(2006) phase and liquid CO2 as the dispersed phase. This method takes the
274.2–281.2 3.4 GC 18.9–46.6 Fan et al. (2017)
274.7 2.96–3.18 GC 3–27 Yuan et al.
advantages of multiphase flow, mass transfer, and heat transfer pro­
(2012) cesses in porous sediment media to enhance the replacement reaction.
275 3.3 GC 3.4 Li et al. (2009a) The replacement efficiency can reach 35% using liquid CO2 under
275–280 3.6–6 Roman 2.66–11.4 Falenty et al. suitable hydrate saturation conditions, which is significant compared to
(2016b)
the injection of gaseous CO2 (Yuan et al., 2013). The results of the
276 2.0 GC/ >80 Komai et al.
Roman (2000) replacement experiments using CO2 emulsions with different CO2/H2O
276.15 3.7 NMR 67 Lee et al. (2013) mass ratios are shown in Fig. 8 (Zhou et al., 2013). The replacement
278.3–281.1 3.18–3.4 GC 36.7–75.3 Rossi et al. efficiency increases with increasing water content in the emulsion
(2019) within 35 h and showed the opposite trend after 35 h. The reactions in
these two stages are controlled by the diffusion and permeation of CO2,
mixed gas hydrates. They found that TBAB molecules can form a respectively. The higher the H2O content, the more CO2 hydrates are
half-cage structure with CO2 molecules, significantly reducing the CO2 generated, and more heat is released to decompose CH4 hydrates and
hydrates formation pressure at a given temperature. Similarly, promote CH4 molecules escape. After diffusion is basically complete, the
Mohammadi et al. (2013) analyzed the effect of TBAB on the phase permeation of CO2 molecules in the hydrates plays a dominant role, and
equilibrium of CO2+H2+CH4 mixed gas hydrates using the constant as the CO2 hydrate film becomes thicker, the permeation effect becomes
volume pressure search method, which is consistent with Acosta et al. worse, leading to a decrease in the replacement rate. However, the
(2011). Sodium dodecyl sulfate (SDS) and tetrahydrofuran (THF) solu­ overall replacement efficiency is still significantly improved. The phase
tions can increase the mixed gas separation efficiency by promoting the state of injected CO2 has a significant impact on the efficiency of the
dissolution of CO2 gas in the solution and optimizing the formation overall replacement process; the relationship of displacement efficiency
conditions for CO2 hydrate (Tang et al., 2013). The effect of the TBAB between different states is emulsion CO2 > liquid CO2 > gaseous CO2.
solution on the CO2 capture process is systematically analyzed by However, for the preparation of gaseous CO2 into liquid or emulsion too,
measuring the gas solubility and observing the formation of cage the initial preparation cost and the complexity of the process are issues
structure (Babu et al., 2014). It shows that TBAB promotes CO2 hydrates that need to be addressed.
formation for two main reasons: TBAB prolongs the induction time of
hydrates nucleation and increases the solubility of CO2 gas. From the 2.4.4. Injection of mixed gas
promoting effects of various additives on the hydrate-based CO2 cap­ Since CO2 molecules can only replace CH4 molecules in the large
ture, it can be concluded that many additives have a facilitating effect on cages of hydrates and CO2 needs to be purified at a high cost, flue gas,
CO2 hydrate formation (Ricaurte et al., 2014). The promoting effects of CO2+H2, and other mixed gases are recommended to replace CH4 hy­
various kinetic additives are: SDS > sodium dodecyl benzene sulfonate drates. The phase equilibrium characteristics of CO2+N2 mixed gas
(SDBS) ≫ dodecyl trimethyl ammonium chloride (DTAC); thermody­ hydrate have been widely studied. Belandria et al. (2011) determined
namic additives are: THF > cyclopentane (CP) > dioxane (DIOX) ≫ the phase equilibrium conditions of CH4+CO2 hydrates and CO2+N2
m-THF. Partoon et al. (2016) experimentally measured the phase equi­
librium curve of CO2+CH4 mixed hydrate in a THF solution. The results
showed that the presence of THF shifts the phase equilibrium curve
towards high temperature and low pressure, expanding the stable exis­
tence area of the mixed hydrates (Wang et al., 2014). They also inves­
tigated the effects of various additives, such as SDS, THF, and TBAB, on
the replacement reaction under simulated subsea environment condi­
tions. The replacement efficiencies of the different groups are shown in
Table 4, where the relationship of displacement efficiency between them
is TBAB > SDS > pure water > THF.
In summary, THF can increase the decomposition temperature and
reduce the decomposition pressure of CH4 hydrates; however, it can also
reduce the rate of hydrates formation, which weakens the replacement
effect. Thermodynamic promoters such as THF and TBAB mainly shift
the phase equilibrium curve towards a direction favorable for the

Table 4
Replacement efficiency of CO2 replacement reaction (Wang et al., 2014).
pure water THF-0.05% TBAB-0.05% SDS-0.03% SDS-0.05%
Fig. 8. Replacement efficiency in various states of injected CO2 (data collected
6.05 4.08 40.52 24.35 30.33
from Zhou et al., 2013).

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

hydrates using a pressure search method. They also compared the promising option for CO2 geological sequestration due to the significant
measured experimental data with the CSMGem (a software for pre­ reduction in CO2 separation costs. Hassanpouryouzband et al. (2018,
dicting CH4 hydrates formation conditions) model, which did not differ 2019a) also suggested the direct injection of flue gas from coal-fired
significantly. Lee et al. (2012) observed the phase equilibrium behavior power plants into CH4 hydrate reservoirs is a potential way to reduce
of CH4+CO2+N2 mixed gas hydrates and found that with the increase of CCS costs by eliminating the major cost of CO2 capture. It was found that
N2 content in the mixed gas, the phase equilibrium pressure increases at this method could produce up to 70% of CH4-rich gas in the mixed gas
the same temperature. Kakati et al. (2015) also studied the phase and store up to 80% of the CO2 present in the flue gas (Hassanpour­
equilibrium conditions of CH4+CO2+N2 mixed gas hydrates in different youzband et al., 2019b). Compared to pure supercritical CO2, the pres­
concentrations of NaCl or CaCl2 solutions and found that either NaCl or ence of N2 in the feed gas facilitates gas movement and reduces
CaCl2 could inhibit hydrates formation. Sun et al. (2016) measured the corrosion of the facility. Under certain conditions, the stable sequestered
phase equilibrium data of CO2, CO2+CH4, CO2+N2, and CH4+CO2+N2 CO2 is greater than 92%, which meets the technical requirements of
using a stirred high-pressure reactor, and the difference between the typical industrial-scale geological CO2 sequestration reported in the
measured data differed very little from the predicted value of the literature (Hassanpouryouzband et al., 2019b, 2019c). Temperature rise
CSMGem software. Zang and Liang (2018a, 2018b) suggested that the first leads to N2 release while CO2 is retained in the hydrates, which
cage occupancy characteristic is also a key parameter associated with provides a safety indicator for the sequestered CO2 in the case of a
phase equilibrium. Sum et al. (1997) carried out an in-situ Raman sudden temperature increase. They also found that the solubility of the
spectroscopy study of CH4+CO2 hydrates and analyzed the cage occu­ flue gas increases with increasing pressure, decreasing temperature, or
pancy characteristics of CH4 and CO2 molecules, inferring that the large increasing molar fraction of gas components in the gas phase. The sol­
cages were almost entirely occupied by CH4 and CO2 molecules but not ubility of CO2+N2 decreased with the increasing NaCl concentration in
100%, while most of the small cages were occupied by CH4 molecules. the water phase due to the brine effect. This has a certain guiding effect
Nakano and Ohgaki (2000) determined the composition and cage oc­ for CO2 sequestration in brine aquifers.
cupancy of CH4+CO2 mixed hydrates using Raman spectroscopy and Similar to the mechanism of CO2+N2 mixed gas, CO2+H2 mixed gas
found that CO2 molecules would be captured in large cages before can also be applied to the extraction of CH4 hydrates. The separation of
occupying small cages compared to CH4 molecules. Lim et al. (2017) CH4+N2 is relatively difficult using conventional methods due to their
investigated the cage occupancy characteristics of CH4+CO2+N2 mixed similar physical properties. Currently, deep cooling separation offers
gas hydrates and found that CO2 was more likely to occupy large cages significant advantages in producing high-purity gas; however, the
and N2 was more likely to occupy small cages. equipment has a large footprint and high energy consumption. Consid­
To improve the replacement efficiency of the CH4 hydrates in the ering that the flue gas can save CO2 capture costs, the cost of separating
small cages, Park et al. (2006) first proposed the use of a CO2+N2 mixed and recovering CH4 gas in the later stage may be higher. Therefore, Rice
gas to replace sI CH4 hydrates and found that N2 molecules can quickly (2006) proposed a scheme for H2 production from CH4 hydrates via CH4
attack CH4 molecules and occupy small cages; the CO2 molecules pref­ and H2O reforming, where the end product was clean energy H2 with no
erentially replaced CH4 molecules in the large cages, as shown in Fig. 9. atmospheric CO2 emissions. The main steps of this scheme are as fol­
Based on the complementary synergistic effect of CO2+N2 in the lows: (1) CH4 produced from the hydrates is sent to a water vapor
replacement process, it is experimentally demonstrated that the reformer, where it is converted to H2 and CO2; (2) CO2+H2 mixed gas is
replacement efficiency could be increased from 64% for pure CO2 to separated to recover H2; and (3) CO2 is injected into the undeveloped
85% for binary CO2+N2 mixed gas. Koh et al. (2012) also used 20% hydrate reservoirs for cyclic extraction. Recently, to improve the overall
CO2+80% N2 mixed gas to replace CH4 hydrates and found that the efficiency through an integrated system approach, Azizi et al. (2016)
replacement efficiency obtained was consistent with Park et al. (2006). proposed a method that integrates three processes: CH4 hydrates
Koh used X-ray diffraction (XRD) and 13C NMR spectroscopy to observe extraction; CH4 and H2O vapor reforming; and syngas conversion to
the replacement reaction of CO2+N2, and the XRD results showed no electricity via solid fuel cells. Wang et al. (2017) also proposed a new
significant change in the hydrate structure during the replacement method for CO2+H2 injection a combination of steam reforming reac­
process. However, the 13C NMR results showed a faster replacement tion of produced CH4, the principle of which is shown in Fig. 10. CH4
rate in the small cages than in the large cages of the sI hydrate, sug­ obtained from hydrate-bearing sediments is reformed with steam on the
gesting that N2 molecules diffused faster than CO2 molecules. platform to produce CO2+H2 mixed gas (Mwa and Hc, 2020). The mixed
In addition, direct injection of flue gas or the mixed gas of CO2+N2 gas is then partially separated to produce pure H2 as a single product,
into CH4 hydrate reservoirs or water/ice sediments is considered a and the rest CO2-rich mixed gas is reinjected into the hydrate sediments
for cyclic production. This method has the following advantages: (1) the
hydrate decomposition rate is high, and the injection of CO2+H2 mixed
gas can reduce the CH4 partial pressure and break the phase equilibrium
of the CH4 hydrates; (2) CO2 is reinjected into the CH4 hydrates to
replace CH4 and maintain the stability of the formation, which also re­
duces the emission of greenhouse gas; (3) CO2+H2 mixed gas produced
from steam reforming is easier to separate than the CH4+N2 mixed gas;
(4) CH4 steam reforming is carried out on the platform, and the pressure
of the CO2+H2 mixed gas is approximately 2–7 MPa, which is more
suitable for high-pressure injection. Therefore, compared to the use of
flue gas, it can significantly reduce gas pressurization and transportation
costs.

2.5. CH4 hydrate reservoirs stability

It is important to study the stability of the sediments during and after

CH4 hydrates extraction because the presence of CH4 hydrates has a
great cementation strength to the sediments (Lee et al., 2020). Changes
Fig. 9. Schematic diagram of CO2+N2 mixed gas to improve CH4 recovery in the pore pressure and overburden pressure of the sediments can lead
(Park et al., 2006). to changes in effective stress, destruction of the sediment skeletal

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

Fig. 10. Gas production diagram of CO2+H2 cycle continuous injection production hydrate mode (Wang and Sun, 2017).

structure or brittle damage, or even reservoir deformation. More seri­ increases with increasing strain rate and decreasing local temperature
ously, CH4 hydrates decomposition may cause serious geological haz­ and porosity (B. Liu et al., 2013). Luo et al. (2013) through triaxial ex­
ards. The increase of seawater temperature due to global warming and periments further concluded that the strength of CO2 hydrates deposi­
warming currents or decrease of pressure due to sea level changes will tion is 15% higher than that of CH4 hydrates deposition. On the other
lead to CH4 hydrates decomposition. This decomposition leads to excess hand, Li et al. (2016) confirmed that the failure strength and elastic
pore pressure (overpressure) and may trigger subsequent seafloor modulus of CH4 hydrates are slightly lower compared to CO2 hydrates,
deformation or movements, such as positive landforms (mud volcano, which is consistent with the view of Luo et al. (2017). Since the
gas peak, dome), negative landforms (subsidence, pockmark), and sea­ replacement reaction is a dynamic process, Espinoza and Santamarina
floor landslides (Andreassen et al., 2017; Liu and Jiang, 2019; Serie (2011) monitored the stiffness change of the sediments. The tests
et al., 2012; Zhu et al., 2019). In addition, during large submarine showed that the stiffness between the granular media will not disappear
landslides, CH4 is released as gas plumes or abruptly released into the throughout the replacement process, which indicated that the sedi­
water or even the atmosphere, which may lead to ocean acidification mentary layer can maintain its mechanical stability during and after CH4
and global climate change (Solomon et al., 2009). hydrates extraction. Therefore, the stability strength of the sediments
One of the purposes of injecting CO2 into reservoirs to replace CH4 is does not change and the mechanical stability is further restored after the
to maintain the mechanical strength and integrity of hydrate reservoirs replacement process. However, Wang et al. (2015) pointed out that the
(Lee et al., 2018). Therefore, CO2 plays a crucial role in recovering CH4 elastic modulus of hydrate sediments decreases with the decomposition
and avoiding potential geohazards. Fig. 11 compares the failure of CH4 hydrates and the formation of CO2 hydrates, and the stiffness of
strengths before and after CO2 injection. When CH4+CO2 gas exchange the sediment skeleton decreases during the replacement process. How­
occurs in a relatively short time in an environment with uniform dis­ ever, the stiffness fluctuates only within a very limited range and the
tribution of pore space, the newly formed CO2 hydrates can maintain the overall stiffness of the sediments can be maintained. W. Liu et al. (2013)
mechanical properties of the reservoirs (Hyodo et al., 2014b). The used CO2 and CO2+N2 for replacement and concluded that the sedi­
strength of CO2 hydrates is higher than that of CH4 hydrates and ments experience stiffness loss during the replacement process, espe­
cially when the mixed gas is used. Therefore, it is recommended to
conduct experimental studies on the mechanical properties of CH4 hy­
drates sediments that have actually undergone the in-situ replacement
process and to evaluate the mechanical stability of the displacement
method comprehensively and systematically, which will be the focus of
future research.

3. Marine sequestration of CO2 by direct injection

Due to the appropriate pressure and temperature conditions in the

ocean and the self-sealing and self-protective properties of hydrates,
hydrate-based CO2 sequestration technology is well-suitable for marine
sequestration. Even if a small amount of CO2 seeps out of the seabed,
most of it will disperse and dissolve into the seawater; hence, it is safer to
treat CO2 under the seabed than in inland aquifers (Aminu et al., 2017).
The sequestration of large amounts of CO2 can be almost complete
through the isolation of the deep seabed. Using imaging technology, CO2
hydrates grow significantly when liquid CO2 is injected into sandstones
filled with unsaturated water, suggesting that CO2 hydrates can seal
Fig. 11. Comparison of failure strengths before and after CO2 injection (Lee systems (Almenningen et al., 2018, 2019). Fig. 12 shows a schematic
et al., 2020).

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

Fig. 12. Schematic diagram of hydrate-based carbon sequestration in deep-sea sediments (Teng and Zhang, 2018).

diagram of the process of sequestering CO2 into deep-sea sediments. The

captured CO2 is transported to the platform by a ship and then injected
into marine sediments to form CO2 hydrates in the hydrate stable zones
(HSZ) (Teng and Zhang, 2018).

3.1. Suitable sequestration location

CO2 hydrates are generally formed under the conditions of low

temperature and high pressure below 10 ◦ C and above 3 MPa. Therefore,
it is mainly distributed in the offshore area of the continental margin
with high pressure, low temperature, and water depth greater than 300
m, as well as in the sediments 0–300 m below the seabed. Therefore,
deep-water areas (depth >300 m) with high sequestration safety and
cost-effectiveness can be used as ideal areas for CO2 sequestration. The
sequestration of CO2 in deep-sea sediments was first proposed by Teng
and Zhang (2018), who considered that the CO2-clay-ash mixed solution
could be sequestered in the ocean sediment for tens of meters; they
theoretically analyzed and identified three seafloor depth models for
sequestering CO2: “shallow seafloor” (<300 m), “deep seafloor”
(300–3700 m) and “ultra-deep seafloor” (>3700 m). They concluded
that the greater the depth and density of the seawater, the better the
sequestration safety, the lower the impact on the seabed ecosystem, and Fig. 13. Stable area of submarine hydrate formation (adapted from Manakov
the higher the cost of the technology. However, they only studied the and Stoporev, 2021).
effect of CO2 sequestration in the seafloor sediment layer at different
water depths (i.e., under different pressure conditions) without consid­ decrease in sea water depth owing to the influence of the hydrothermal
ering the effect of thermal gradients in the seafloor sediment layer. The gradient. Thus, the thickness of the HSZ is controlled by the geothermal
specific depth of the sediment zone below the seafloor suitable for CO2 gradient; hence, it is relatively thin when the geothermal gradient is
hydrate formation and sequestration is also uncertain. high and thick when it is not. On the seafloor sediments, the thickness of
As shown in Fig. 13, different CO2 HSZ are formed with varying the HSZ is directly related to water depth, with the HSZ being thicker
depths of the seafloor and the effects of geothermal and hydrothermal when the water is deep, while, thinner when the water is shallow.
gradients (Camps, 2008). And the seafloor temperature is assumed to be Rochelle et al. (2009) also conducted theoretical studies on the scope of
2.5 ◦ C for different seafloor depths of 800, 1000, and 1200 m. Taking the the CO2 HSZ and used it to estimate the stability zones of CO2 hydrates in
depth of 1000 m as an example, the geothermal gradient is 0.03 ◦ C/m, offshore sediments of western Europe, as shown in Fig. 14. The algo­
and the temperature gradually increases from the seabed level to the rithm uses the empirical relationship between pure CH4 and pure water
lower sediments When it is 250 m below the seabed, the temperature as its basis, and the equilibrium relationship is described by the
reaches approximately 10 ◦ C. When it exceeds this depth, the temper­ following equation:
ature further increases, and the hydrate does not easily form. In the sea ln p = A − B/T (5)
water area above the seabed, the temperature gradually increases with a

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

Fig. 15. Potential CO2 hydrate sequestration sites in the United States (House
et al., 2006).

3.2.1. Feasibility study

The thermodynamics and kinetics of CO2 hydrate formation and
decomposition in porous media are fundamental indicators of the po­
tential sequestration capacity of CO2. Kinetic studies can help under­
Fig. 14. Plot of the predicted thickness of CO2 hydrate stability zone in seafloor stand the time-dependent behavior of hydrate formation and
sediments offshore Western Europe (Rochelle et al., 2009).
decomposition in porous media. Thermodynamic studies provided
relevant information on the appropriate conditions conducive to the
where p denotes the pressure. A and B are constants determined from sequestration of CO2 in the form of hydrates. The phase boundary con­
experimental data on hydrate stability. t is the temperature. ditions for CO2 hydrates can be used as indicators to assess CO2
Using this relationship, an algorithm was developed to calculate CO2 sequestration capacity and hydrate stability. Table 5 summarizes the
and CH4 HSZ. For each location, the program can perform the calcula­ effects of the physical and chemical properties of H2, CH4, and CO2 on
tion by inputting information such as the water depth (i.e., pressure), sequestration. The net heating value, which is incombustible gas, does
bottom water temperature, and geothermal gradient. Various types of not apply to CO2 sequestration. Molecular weight and dynamic viscosity
data are collected from a variety of sources, including the International were the most unfavorable for H2 sequestration, favorable for CH4
Council for Exploration of the Sea, the British Oceanographic Data sequestration, and very favorable for CO2 sequestration. The feasibility
Centre, and the Coriolis Data Service. Water depth is relatively well of CO2 sequestration has been indirectly proven by analyzing the gas
constrained in the model, and is also based on high-resolution, detailed characteristics that affect sequestration (Tarkowski et al., 2021).
datasets. The resolution of the geothermal gradient data has the largest The dynamic process of hydrate decomposition occurs simulta­
uncertainty, where values of 30 ◦ C/km are used in the model owing to neously as hydrate formation in the sediment layer, owing to changes in
the limited information available. However, some areas, particularly at mass and heat transfer at the gas-liquid interface. This combined effect
local scales, may have higher or lower geothermal gradients, affecting of hydrate formation and decomposition determines the sequestration
the predictions. For example, higher geothermal gradients can lead to properties of the hydrates. Wendland et al. (1999) obtained the tem­
thinning of the hydrate stability zone, which is consistent with the re­ perature and pressure data for a three-phase line, four-phase point, and
sults of Lei et al. (2012). critical point of the CO2-water binary system using a high-pressure vi­
The sequestration of CO2 in the form of hydrates in marine and sual reactor, and the experimental temperature and pressure range were
permafrost sediments has received increasing attention. In addition, 270–305 K and 1.0–7.4 MPa, respectively. The phase equilibrium
numerous CO2 hydrate sequestration sites have been investigated and properties of CO2 hydrates are important factors in hydrate-based CO2
proposed worldwide. The Geological Survey of Canada (2010) demon­ sequestration. Nakano et al. (1998) used an in-situ Raman probe to
strated that the pressure and temperature conditions of sedimentary measure the three-phase coexistence curves of CO2 hydrate-water-liquid
rocks in some areas of Alberta in western Canada are suitable for CO2 at high pressure. Miller and Smythe (1970) studied the phase
forming CO2 hydrates. The thickness of the CO2 hydrate stability zone equilibrium conditions of CO2 hydrates at low temperatures and sug­
beneath Lake Superior was estimated to be 200–1000 m, with a potential gested that CO2 hydrates may be present in the Martian atmosphere. The
capacity of 256 Gt CO2. House et al. (2006) suggested that the US coastal equilibrium of CO2 hydrates with and without NaCl has been studied
200-mile economic zone has a sufficient area of more than 1.3 × 1012 m2 experimentally, and the results show that the temperature and pressure
to sequester CO2, as shown in Fig. 15. When liquid CO2 is injected into on the seabed can satisfy the conditions for CO2 formation (Circone
the sediments in the above areas, CO2 may enter the hydrate stability et al., 2003; Henning et al., 2003; Song et al., 2013; Yang et al., 2014a).
zone and form a CO2 hydrate cap to prevent leakage, which allows
long-term sequestration. Therefore, studies on CO2 hydrate formation
properties are essential to realizing the long-term sequestration of CO2. Table 5
Impact of physico-chemical properties of H2, CH4, and CO2 on their underground
sequestration (adapted from Tarkowski et al., 2021).
3.2. Experimental and simulation study of the direct injection method
Properties H2 CH4 CO2
Most hydrate-based CO2 sequestration sites are composed of sedi­ Molecular weight (g/mol) * ** ***
ments or porous media; therefore, a detailed understanding of the Dynamic viscosity in 20 ◦ C (10− 5 Pa) * ** ***
mechanisms and influencing factors for CO2 hydrate formation in porous Compressibility factor *** ** *
Air-diffusion coefficient in excess of air at NTP (cm2/s) ** *** ***
media systems is required. Numerous studies have been conducted using Critical density (kg/m3) *** ** *
various porous media to simulate real sediment. Solubility in water (g/100 g) *** ** *
Net heating value (MJ/kg) *** ** N

*** - very favorable, ** - favorable, * - not favorable, N - not applicable.

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

Løken and Austvik (1993) proposed a method for depositing CO2 on the aquifers flow through the capillary tube, and hydrate film forms on the
seabed and conducted experiments at a hydrate formation pressure water surface in this reactor. It has also been found that reducing the
(4.0–4.2 MPa) and low pressure (ambient pressure). They found that CO2 flow rate or increasing the water flow rate changes the buoyancy of
gaseous CO2 could form hydrates more readily than liquid CO2 under the hydrate. The above studies analyzed the kinetics of CO2 hydrate
high-pressure conditions. The addition of N2 to CO2 can also promote formation under different conditions and demonstrated the feasibility of
hydrate formation, as confirmed by a laboratory study by Zhou et al. hydrate-based CO2 sequestration.
(2018a). Hassanpouryouzband et al. (2019c) used well-characterized
silica sand from Fife, Scotland as a porous medium. They concluded 3.2.2. CO2 sequestration mechanism of the direct injection method
that more than 92% of the CO2 is sequestered in the sediment when flue Gas hydrate formation in porous media occurs in two stages, nucle­
gas is injected into the water-ice sediments. ation and growth. The dissolution of gas in porous media is key to
The use of additives can also enhance hydrate formation behavior determining the behavior of hydrate formation. Sloan (1990, 2003)
thermodynamically or kinetically. The thermodynamic hydrate addi­ introduced a clear concept of nucleation: the formation of a stable
tives used for CO2 hydrate formation in porous media were CP, THF, and crystal nucleation process with a critical size in gas supersaturated so­
TBAB. These additives typically expand the hydrate formation boundary lutions. Nucleation can occur when a solution is in a supercooled or
region by reducing the pressure and temperature conditions required for supersaturated state. The cluster nucleation model subsequently pro­
CO2 hydrate formation. For example, the presence of THF (Yang et al., posed suggests that clusters of molecules can grow together until they
2013) can extend the phase boundary curves of all gas-hydrate systems. reach a critical size. The hydrate morphology remains stable as long as
However, THF can also form hydrates, which may affect the amount of the temperature and pressure conditions are maintained (Sloan and
CO2 sequestered in the hydrate phase. Therefore, when THF is used to Fleyfel, 1991). Christiansen and Sloan (1994) extended this model and
aid CO2 hydrate sequestration, an optimal THF concentration is required provided a complete description of hydrate formation in terms of hy­
to achieve the best sequestration effect. The mechanism of action of drate kinetics and molecular mechanics. The formation kinetic mecha­
TBAB is similar to that of THF. In addition, studies have shown that THF nism of hydrates mainly includes two parts: first, water molecules form
has a significant synergistic effect with TBAB (Hassan et al., 2020). clusters around non-polar molecules; second, the combination of these
Methyl cyclopentenolone (MCP) is another chemical additive that en­ clusters forms the nucleus of the hydrate. Kutergin et al. (1994) studied
hances hydrate phase equilibrium conditions and can form a complex the formation mechanism of gas hydrates and proposed a hydrate
hydrate with CO2. The combination of MCP and CO2 changes the crystal interface nucleation model, which suggested that hydrate nucleation
structure of the hydrate and improves its stability by obtaining different occurs at the gas-phase side interface. The Chen–Guo model, with
thermodynamic stability states. The newly formed hydrates are more further consideration of the local stability and kinetic mechanism, was
stable than the pure CO2 hydrates (Zheng and Yang, 2019). And the proposed (Chen and Guo, 1996) and was based on the VDW-P model
additives are mainly used to change the liquid surface tension and (Van der Waals and Platteeuw, 1959). The determination of the hydrate
reduce the formation conditions of CO2 hydrates. Table 6 summarizes number and the prediction of multicomponent mixed gas hydrate for­
the methods used by many scholars to promote CO2 hydrates formation mation conditions were further improved. Hydrate nucleation is carried
through physical principles. These physical methods mainly enhance out in two processes: standard chemical reaction kinetics and adsorption
gas-liquid contact area, heat and mass transfer rate by perturbation to kinetics.
promote CO2 hydrates formation. A kinetic model for hydrate growth based on the two-film and
Lz et al. (2020) studied the kinetics of CO2 hydrate formation in crystallization theories was proposed by Englezos et al. (1987). This
quartz and found that a kinetic surfactant accelerated the CO2 gas cap­ suggests that the process of hydrate formation involves the diffusion of
ture in the pore space. Hirai et al. (1997, 2000)investigated the effect of gas from the gas phase to the liquid film layer at the interface between
a hydrate film on the dissolution of liquid CO2 in water and showed that the crystal and water, and then the gas molecules and water molecules
the formed hydrate film tends to strongly inhibit the diffusion of CO2. combine to form crystals through adsorption. Chun and Lee (1996)
The kinetics of CO2 hydrate formation has also been studied using carried out experiments on the consumption of CO2 gas during hydrate
magnetic resonance imaging (MRI). It was determined that at 10 MPa formation under different pressure and temperature conditions, the re­
and 277.2 K, 40 μm water droplets could be converted to hydrates sults of which are in good agreement with the predicted curve of the
within 40 s. Therefore, a method of injecting small water droplets into consumption rate calculated by Englezos’s kinetics model (Englezos
liquid CO2 to form dense hydrate particles is proposed, which makes the et al., 1987). The nucleation and growth of CO2 hydrates in seabed
CO2 sequestration state more stable. Gabitto et al. (2005) designed a reservoirs were successively calculated and simulated using the
coaxial cylindrical reactor consisting of a capillary tube located at the multi-scale methods of phase theory, MD, Monte Carlo, and cellular
center of the outer tube. CO2 flows through the outer ring, fresh or brine automata models. It can be considered that CO2 gas diffusion is a con­
trolling factor in hydrate growth (Buanes et al., 2006, 2009). The growth
mechanism of CO2 hydrates is very similar to that of CH4 hydrates based
Table 6 on MD method (Tung et al., 2011b). Kang et al. (2004) developed a
Physical methods for promoting CO2 hydrate formation.
Boltzmann model to simulate hydrate crystal growth in supersaturated
Method The influence on hydrate formation References solutions and found that hydrate formation undergoes a process from
Stirring method CO2 gas consumption increased by 0.07 mol Li et al. (2017) diffusion to surface reaction and from clusters to corals to a compacted
Bubbling Induction period is shortened by 2/3 Zhou et al. ring shape. Liu and Flemings (2007) established a multiphase and
method (2005) multi-component fluid flow model for hydrate formation in a submarine
Spray method Hydrate formation time is reduced by 20min An et al.
sediment layer. The model explored the effects of salinity, temperature,
(2016)
Ultrasonic CO2 gas consumption increased by 4 times Park and Kin pressure, and hydraulic properties on the kinetics of hydrate formation
method (2013) and also obtained a mathematical relationship for the effects of hydrate
Ultrasonic Induction time is reduced by 20min Sun and Liu formation and growth on the variation of porosity, permeability, and
method (2006) capillary pressure in the submarine sediment layer. CO2 hydrate for­
Supergravity Hydrate reactor heat utilization efficiency up Bai et al.
method to 87.39%, resulting in faster CO2 hydrate (2010)
mation in seabed sediments is essentially a multiphase,
formation multi-component crystallization kinetic process accompanied by phase
Microwave Supercooling degree is reduced by Liang et al., transformation in porous media. The hydrate nucleation kinetics,
method approximately 3 ◦ C, and the induction time is 2009 growth kinetics, and hydration driving force are all involved in the
reduced by 3.2 h
studies, and the typical kinetic models of CO2 hydrate are summarized in

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

Table 7 kaolinite and bentonite. Under the pressure and temperature conditions
Typical hydrate kinetic models. of 4.8 MPa and 279.2 K, the conversion of water to hydrate was 77.8%
Model CO2 CO2 water method Hydration and the uptake of CO2 was 0.336 mol for the bentonite clay material; the
gas liquid driving force conversion of water was 75.6% and the uptake of CO2 was 0.448 mol for
Van der Waals ✓ – ✓ molecular theory Δμ the kaolinite material. In addition, it can be concluded that the equi­
and librium pressure of CO2 hydrate in the bentonite clay was higher than
Platteeuw that of water through a comparative analysis. Palodkar et al. (2016)
(1959) model demonstrates the influence of the effective surface area of porous
Englezos et al. two-film theory Δf
media on the growth of CO2 hydrate. The flexural activity of the particle
✓ – ✓
(1987)
Chun and Lee ✓ – ✓ crystallization Δμ facilitates the formation of hydrate due to the increased surface area,
(1996) theory & two-film thus increasing the sequestration capacity of CO2 hydrate. And the
theory sequestration capacity of hydrate increases with the increase of
Chen and Guo molecular theory
✓ – ✓ Δμ
permeability (Zhang et al., 2018b). In addition to the permeability of
(1996)
Davie and ✓ – ✓ mathematical Δc CO2 hydrate, capillary pressure plays an important role in CO2 seques­
Buffett description tration and may affect sequestration capacity. Capillary pressure in
(2001) porous media is a function of pore radius and throat radius, hence it
Kvamme et al. – ✓ ✓ phase field theory & Δg controls the permeability of CO2 and water during hydrate formation.
(2004) nuclear magnetic
resonance
However, sufficient surface area and capillary properties are required to
Kang et al. ✓ – ✓ Lattice-Boltzmann Δc enhance the tortuous behavior or movement of CO2 and water molecules
(2004) method in the sediment to obtain a high CO2 sequestration capacity. Uchida
Tegze et al. – ✓ ✓ phase field theory & Δg et al. (1999) experimentally found that the stability conditions of hy­
(2006) molecular dynamics
drate are different with different pore sizes. Comparing CO2 hydrate
Buanes et al. – ✓ ✓ cellular automata & Δg
(2006) Monte Carlo equilibrium in glass beads and silica of different diameters, the increase
method in pore size reduces CO2 hydrate equilibrium pressure and facilitates
Uddin et al. ✓ – ✓ CMG STARS Δf hydrate formation (Yang et al., 2012). Zhang and Lee (2009) studied
(2008) numerical CO2 hydrate formation and growth at different pressures and tempera­
simulation
tures and concluded that CO2 hydrate sequestration and growth rate are
Tung et al. – ✓ ✓ molecular dynamics ΔT
(2011) closely related to pressure and temperature differences. The
high-pressure difference or low-temperature difference at the gas-liquid
interface can increase the hydrate formation and growth rate. NaCl
Table 7. would inhibit the mass transfer process by reducing the dissolved
Babu et al. (2013) first presented the mechanism of CO2 hydrate amount of CO2, hence reducing the formation of CO2 hydrate. It was
formation in porous silica sand media. They concluded that hydrate found that the decrease of CO2 hydrate equilibrium temperature by 1.1
formation occurs at the water-gas interface within the sand bed and the K is mainly caused by Cl− (Sun et al., 2013; Holzammer et al., 2017;
interstitial space between the sand grains. The gas diffuses into the water Holzammer et al., 2016). It is noteworthy that hydrate formation is
in the interstitial space by capillary action and finds a suitable location faster in salt solutions than in deionized water, even at lower hydrate
for hydrate formation within the pore space. In addition, the gas saturation. The above results indicate that the kinetic promotion and
permeability can be affected by the particle size of the silica sand. Camps inhibition of NaCl in different CO2 hydrate systems are different (Yang
(2008) compared the behavior of CO2 hydrate formation and distribu­ et al., 2014b).
tion in different porous media such as coarse quartz-rich sand and
medium-sized quartz-rich sand. In a CO2-rich environment, hydrates 3.3. CO2 hydrate cap
always form around sand grains and stick them together. In a water-rich
environment, hydrates exist in the form of pore-filling cement to prevent In the marine sequestration method, in addition to directly injecting
the further entry of CO2. Buffett and Zatsepina (2000, 2002) simulated a CO2 into sediments to sequester in the hydrated state, CO2 can also be
real marine environment; no mixing equipment was used in the exper­ injected into brine aquifers to sequester in a gaseous, liquid, or super­
iment, and the gas entered the pore fluid entirely by diffusion. The critical state. Deep sequestration of CO2 is injected into rocks at least
experiment showed that the sediment layer has an important influence 800 m, it is always possible that part of CO2 will migrate upward at some
on hydrate formation, as sediments can conduct heat and provide space time on unknown small faults/fractures lower than the resolution of
for hydrate nucleation and growth. It was concluded that hydrates can geophysical imaging, or boreholes with poor sealing. And CO2 hydrate
nucleate and grow in the fluid migrating upward from the seafloor has been used in many studies as the primary containment mechanism to
sediments. The difference in the resistivity during hydrate formation sequester CO2 and prevent its leakage (Koide et al., 1997; Sasaki and
reflects the various stages of hydrate nucleation and growth. When hy­ Akibayashi, 2000). Thermodynamic calculations show that the CO2
drate formation begins, the solubility of CO2 progressively decreases as hydrate is stable under relatively low pressure at typical seabed tem­
the temperature in the hydrate stability region decreases, and the peratures. Thus, it is expected that injected CO2 into appropriate seabed
amount of hydrate formation is limited by the dissolution capacity of formations will form hydrates, providing a secondary seal for any po­
CO2 in water. tential CO2 leakage from some sequestration sites such as depleted res­
ervoirs and brine aquifers, as shown in Fig. 16.
3.2.3. Influence factors of the direct injection method When CO2 is sequestered in the deep brine aquifers of the seafloor, a
Different types of porous media exhibit different properties, all of large amount of CO2 with low density will accumulate under the rock
which have significant effects on hydrate formation and sequestration cover, which forms a trap space to sequester CO2 due to the density
processes. The practical mineral composition, permeability, particle size difference. If submarine geological disasters or crustal movements lead
distribution, and ion species of seawater sediments are more complex to cracks in the caprock, CO2 will leak locally. And CO2 will migrate
than those obtained under laboratory conditions. upward through the cracks into the CO2 hydrate formation stable area
Bhattacharjee et al. (2015) first pointed out that different sediment under the action of density difference, whose fluid seepage and transport
materials have different effects on the sequestration process of CO2. process are in accordance with Darcy’s law. The solubility of the gas in
Zhang et al. (2017) studied the formation behavior of CO2 hydrate in the water decreases due to temperature reduction, hence that the

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

et al., 2019; Gauteplass et al., 2018). The process of gas migration to

form hydrate is a kinetics shift in the phase equilibrium curve and CO2
hydrate can form as long as the transition layer of the gas-liquid inter­
face reaches saturation (Guan et al., 2010). The formation and decom­
position of hydrate will cause stress-strain and deformation of the solid
skeleton of the porous media in the submarine sediment layer. Lee et al.
(2010) experimentally investigated the volume change of the porous
sediment layer in the presence and absence of hydrate and concluded
that the volume strain scale of the hydrate-bearing sediment layer is
closely related to the compressibility of the sediment layer and the hy­
drate saturation. Fig. 18 shows the mass distribution of CO2 in different
stages during long-term sequestration, which exists in the liquid CO2
phase, hydrate phase, or water phase. CO2 hydrate and liquid CO2
gradually disappear by diffusion and continuous dissolution into the
water as time goes by. It also shows that the hydrate does capture CO2,
but the mass fraction of CO2 in the hydrate phase is less than 10% during
Fig. 16. Scheme of CO2 injection and hydrates formation (Rochelle the whole process. This means that hydrates mainly act as a cap.
et al., 2015). Under in-situ pressure and temperature conditions, the interaction of
CO2 with seawater will favor the formation of CO2 hydrate, whether as
seepage of the gas-containing water presents a supersaturated state after skin or upper cap around the CO2 or directly forming as a solid hydrate.
Although CO2 hydrate will eventually dissipate through equilibration
the leaked CO2 enters the porous medium of the hydrate stability zone.
The favorable space and environment conditions for the formation of with seawater, CO2 may be locked up as a hydrate phase within a
measurable timescale for at least hundreds of years due to the slow re­
CO2 hydrate are formed in the sediment layers between the deep sea­
floor and the brine aquifers, so this area becomes a beneficial place for action rate and turnover in the deep ocean (Wilson, 1992).
the formation of CO2 hydrate. The formation and continuous growth of
hydrate would cause the decrease of the permeability and porosity of the
3.4. Risk analysis for CO2 marine sequestration
sediment layer, forming an impermeable or ultra-low permeability hy­
drate cap, which will close the leakage channel of CO2 and block the
CO2 marine sequestration is the most promising and feasible disposal
further upward transport of leaked CO2, as shown in Fig. 17. If some CO2
method for large-scale carbon sequestration, but safety is a crucial
still penetrates through the sediment layer without being blocked by the
consideration. The main concern of CO2 sequestration is its potential
formed hydrate secondary cap and continues to transport upwards to
leakage and the associated damage caused by the leakage of concen­
diffuse into the ocean, it will form a marine dissolved sequestration of
trated CO2 streams into the environment. The annual leakage rate re­
CO2. Therefore, this sequestration method is safer.
ported in the literature ranges from 0.00001% to 1%, depending on the
Tohidi et al. (2010) simulated the CO2 leakage from the sequestra­
geological structure and the permeability of its faults or defects (Metz
tion area in the seabed formation environment, and it showed that the
et al., 2005). Currently, the models of CO2 sequestration sites, natural
formation of CO2 hydrate reduced its diffusion rate by at least three
systems, atmospheric environments, and process systems have been
orders of magnitude. The leaked CO2 would form a hydrate layer in the
observed and analyzed. It is believed that 99% of the sequestered CO2
hydrate stability zone, which limited the further upward migration of
can remain stable for 100 or 1000 years without leakage accidents as
CO2 just like the rock caprock with ultra-low permeability. Therefore,
long as the regulations are strictly followed. The analysis also shows that
the formation of CO2 hydrate around the pipeline and seabed will also
if the sequestration site is reasonable and the sequestration method is
prevent the leakage of CO2 when liquid CO2 is injected into the seabed.
designed properly, the sequestered CO2 can be safely stored for millions
As the CO2 is solidified in the pores as hydrate, it exponentially reduces
of years. However, we must analyze the security of CCUS technology to
the permeability of the sediment, creating an artificial CO2 hydrate cap
prevent accidents before they occur.
that acts as a barrier to the overlying seawater and underlying CO2. The
The most common risk of CO2 sequestration comes from migration
reduction of rock permeability indicates that CO2 hydrate will always
through CO2 injection wells, cement and geologic formations, or
form an effective and solid barrier in sandstone aquifers even under the
through incomplete areas of non-cemented material or cement rein­
condition of low initial water saturation of 36% (Abe et al., 2013; Sun
forcement in the borehole. In the presence of water, CO2 becomes acidic
through chemical reactions, which can corrode the cement and

Fig. 17. Physical model of CO2 hydrate sequestration within the subsea for­ Fig. 18. Time evolution of the mass distribution of the CO2 component in
mation (adapted from Li et al., 2009b). different stages (Teng and Zhang, 2018).

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X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

compromise its integrity. Although some types of cement can also gas reservoirs often have some infrastructure, such as injection wells and
chemically react to form a protective layer of carbonate to prevent pipelines, and these facilities can be used for CO2 sequestration (Metz
further acidification of the cement, there is still a risk of CO2 leakage. et al., 2005). The sequestration of CO2 in depleted reservoirs requires a
There is also the risk of leakage of sequestered CO2 through rock faults re-evaluation of the type of deposition, depth, thickness, and
due to the change in geological formations. The injection of CO2 into the three-dimensional geometry and integrity of the reservoir, as well as the
crevices of rock increases the pressure of the formation; if the pressure physical and inhomogeneous nature of the reservoir, building on pre­
exceeds the formation pressure itself, it will possibly lead to fracture of vious research efforts of hydrocarbon exploration and development.
the formation and movement of the fault. The risk is reflected in two Field projects in Australia and Europe have demonstrated that
aspects: first, the fracture zone caused by the high pressure and the geological sequestration of CO2 in depleted reservoirs is a strategy with
microearthquake associated or acting with it will increase the perme­ significant potential to mitigate climate change caused by CO2 emissions
ability of the fracture zone and provide a channel for the leakage of CO2; from fossil fuel combustion (Bickle and Mike, 2009; Haszeldine, 2009).
second, fault activity or movement caused by high pressure will, in The Otway Basin CO2 sequestration project with an advanced U-tube
principle, induce earthquakes and cause disasters. Leakage mechanisms downhole sampling system for geochemical monitoring demonstrated
may include rapid flow events such as pipeline failures, transmissive long-term sequestration of CO2 in the gas reservoirs, as shown in Fig. 19.
faults or fractures in the cap, and infiltration through porous geological Three U-tube samplers are located in different formations of the reser­
structures (Blackford et al., 2008, 2009; Israelsson et al., 2010; Armitage voir for the water and gas partition. U-tube sampler 1 is located in the
et al., 2013). Although largely dependent on the extent and duration of CH4 gas cap area, U-tube sampler 2 is located at the water-gas interface,
exposure, experimental investigations and modeling studies have shown and U-tube sampler 3 is located in the groundwater area of the reservoir.
that CO2 leakage into sediments and the deep sea can lead to localized And the downhole sampling analysis of the reservoir was performed
decreases in pH and a cascade of biogeochemical changes with delete­ continuously during the sequestration process. It is estimated that the
rious effects on benthic organisms, communities, and ecosystems (Bibby CO2 sequestration potential of depleted oil and gas reservoirs in the
et al., 2008; Blackford et al., 2008, 2009; Ardelan et al., 2009). There­ world is 400–900 Gt (Jenkins et al., 2012; Gunter et al., 1998; Shukla
fore, before implementation, there is a fundamental need to identify, et al., 2010).
quantify and predict the potential environmental impacts of activities CO2 hydrate formation is very slow in depleted hydrocarbon reser­
associated with geological sequestration of CO2 on the seafloor (Wild­ voirs. Massah et al. (2018) used a silica sand layer with a porosity of 0.35
enborg et al., 2009; Widdicombe and Spicer, 2008). and water saturation of 0.22 to perform experiments to sequester CO2.
The success of CO2 sequestration depends on the characterization of The sequestration density of 126.6 kg m− 3 was obtained after 24 h at 3.2
the sequestration site, including the necessary injection, capacity, and MPa. However, at a pressure of 2.2 MPa, the induction time was quite
integrity of the sequestration and the challenge is to identify geological long, up to 137.5 h. Liu et al. (2018) investigated the CO2 sequestration
formations suitable for long-term CO2 sequestration. And relevant in the reservoir after CH4 extraction. It was found that the injection rate
exploration work must be done well, and the geological structure of the of CO2 must be slow, as the high CO2 injection rate induced the channel
sequestration area must be well understood to facilitate future moni­ and residual water to remain near the pipe wall, which has a negative
toring. For example, the site should be located far from the active plate, impact on sequestration.
and the stable basin is the best location for sequestration, and CO2 in­ In northeastern Alberta, at least 62 depleted gas reservoirs meet the
jection and post-injection conditions can be predicted using CO2 simu­ conditions for CO2 hydrate formation and can sequester 300 Mt CO2. In
lation models and it is very important to ensure the sequestration addition, the Mackenzie-Beaufort area also has significant CO2 seques­
quality. Modeling and simulation play important roles in deciding the tration potential. Sun and Englezos (2016) investigated the injection of
address and monitoring after injection. As sequestration and monitoring CO2 into a partially water-saturated silica sand layer under pressure and
techniques are improved, the evaluation and selection of sequestration temperature conditions similar to those typical of depleted gas reser­
sites to ensure quality is increasingly playing an active role, and large- voirs in northern Alberta. The gas-top mode and spiral pipe mode were
scale demonstration projects can also provide valuable information used to inject CO2 into the simulated reservoir and the results showed
and experience in this regard. that the hydrate rate of the gas cap mode injection experiment is
39–47%, and that of the spiral tube mode injection experiment is
4. Hydrated-based geological sequestration of CO2 using 51–55%. Under the same pressure-temperature conditions, the
depleted reservoirs

CO2 can form hydrate rapidly under conditions of abundant

groundwater and appropriate pressure and temperature (Herzog et al.,
1996; Circone et al., 2003). In addition, the rapid formation kinetics of
the hydrate can likewise assist in the formation of a hydrate cap, thereby
achieving a degree of self-sealing. The formation of CO2 hydrate is
suitable for geological and marine sequestration. However, since hy­
drate is only stable at temperature below 10 ◦ C and higher pressure,
their applicability for geological sequestration is limited to a few envi­
ronments, including shallower sediments beneath cold water and
neighboring sediments under deep permafrost (Camps, 2008).

4.1. Depleted oil and gas reservoirs

Depleted oil and gas reservoirs are generally defined as those that
have lost the economic recovery benefits after triple recovery and are
prime candidates for the geological sequestration of CO2. Firstly, the oil
and gas in the reservoir have not leaked from the reservoir before
exploitation, which proves the integrity and safety of the reservoir.
Secondly, the geological structure and physical properties of most oil Fig. 19. Fluctuation of CO2 content with time in the U-tube sampler systems
and gas reservoirs have been well studied. And finally, depleted oil and (Boreham et al., 2008).

17
X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

sequestration of CO2 in the hydrate form can be 100% higher than that reduced following the decomposition of CH4 hydrates in the reservoirs,
in the gaseous form. Zatsepina and Pooladi-Darvish (2012) also inves­ but CO2 hydrate can strengthen the formation structure again (Koh
tigated CO2 sequestration in depleted CH4 gas reservoirs. They found et al., 2016; Takeya et al., 2000; Hyodo et al., 2014a; Li et al., 2014). The
that when considering individual blocks and ignoring the temperature glass sand with diameters of 0.105–0.125 mm has been used to form CH4
rise caused by hydrate formation, the pressure decreases with increasing and CO2 hydrates as the simulated porous medium (Song et al., 2018;
CO2 injection. This is because the equilibrium pressure of hydrate for­ Wang et al., 2018). The experiment on CH4 hydrate formation and
mation decreases with increasing CO2 fraction in the steam. And it decomposition was carried out first, and then it was set to simulate the
suggested that water availability is the limiting factor for hydrate for­ depleted CH4 hydrate reservoir. CO2 was injected into the glass sand
mation. In contrast, when considering the heat of hydrate formation, the containing excess water after the decomposition of CH4 hydrate, the
total amount of hydrate formed is greatly reduced compared to the results are summarized in Table 8. It is concluded that flow pressure is
previous case due to the influence of temperature. Furthermore, hydrate the key control factor for CO2 hydrate formation during the flow of CO2
formation near the wellbore can be avoided and thus the blockage can in water-saturated reservoirs. The pore water saturation and gas flow
be avoided by controlling the temperature of the injected CO2. The rate have less influence on CO2 hydrate formation and the contact time
associated simulations show that hydrate usually forms at the bottom between CO2 and water is the key to improving the sequestration
and top, and that the heat of hydrate formation dissipates to bedrock and capacity.
cap layers at the bottom and top. where p is the flow pressure of CO2. SWS is the pore-water saturation
after CH4 hydrate decomposition. V is the CO2 injection rate. SCH is the
4.2. Depleted CH4 hydrate reservoirs saturation of CO2 hydrate after the flow process. nCO2inj is the amount of
injected CO2. nCO2 is the amount of sequestered CO2. r is the ratio of CO2
Regarding the sequestration of CO2 in CH4 hydrate reservoirs, most sequestration mount to injection.
of the current studies have been achieved by the replacement method. Considering that the higher purity of CO2 is expensive to obtain, the
However, the implementation period of this method is lengthy and the process of sequestration of CO2-dominated gas mixture has also been
efficiency of CH4 hydrate extraction is low, thus many aspects need to be studied. Herri et al. (2011) investigated the phase equilibrium condi­
optimized further. In contrast, the depressurization method is currently tions of hydrates with CO2+N2, and CO2+CH4 gas mixtures and opti­
the most widely researched and applied method for CH4 hydrate mized the parameters of the thermodynamic model. In addition to the
extraction and is also the most promising method for commercial above studies of phase equilibrium conditions for multivariate hydrates,
extraction of CH4 hydrate in the future. In view of the current research Lee et al. (2014) studied the structure and decomposition heat of
and development status, the commercial exploitation of CH4 hydrate CO2+N2 hydrates in the context of hydrate-based CO2 capture and
reservoirs is imminent and the disposal of depleted CH4 hydrate reser­ separation. Using X-ray diffractometry and Raman spectroscopy, the
voirs should be on the agenda. In addition, CH4 hydrate reservoirs are structural changes during mixture hydrate formation are determined,
considered the ideal address for CO2 sequestration. Song et al. (2018) and the results demonstrate that the hydrate structure created from the
proposed CO2 sequestration in depleted CH4 hydrate reservoirs as a CO2+N2 mixture is sI hydrate and does not undergo structural alteration
win-win solution for both CO2 sequestration and disposal of depleted during the formation process (Zhu et al., 2019). In addition, the heat of
hydrate reservoirs. Specifically, the CH4 hydrate reservoirs are first decomposition of hydrate was measured by using a high-pressure calo­
extracted by the depressurization method and the depleted CH4 hydrate rimeter, and it showed that the heat of decomposition of hydrate is
reservoirs formed after exploitation. Then CO2 is injected into the higher when the proportion of CO2 in the hydrate is higher. Sun et al.
depleted CH4 hydrate reservoirs to achieve CO2 sequestration. However, (2014) simulated the depleted gas reservoir in northern Alberta using
considering a large amount of unconsolidated sand will be produced silica sand with diameters of 0.150–0.630 mm and then injected the
with the decomposition of CH4 hydrate, the injected CO2 cannot form CO2+N2 mixture with 10% N2 content into the laboratory sample con­
hydrates normally in this kind of hollow formation. CO2 sequestration taining residual CH4. The results showed that N2 reduced the hydrate
has certain environmental requirements, and safety, sustainable devel­ sequestration density. Zhou et al. (2018a,b) conducted experiments on
opment, environmental friendliness, and economy should be compre­ the sequestration of the CO2+N2 mixture in depleted CH4 hydrate res­
hensively considered. Therefore, the sequestration site should have a ervoirs and concluded that N2 accelerates CO2 hydrate formation in the
sufficiently stable geological environment. And the risk of submarine early stages of sequestration. However, pure CO2 is more suitable for
landslide and stratum collapse has always been a difficulty for CH4 CO2 sequestration in the long term for the sake of stability.
hydrates extraction. If CO2 can replace the previous CH4 and re-cement
with the sand particles by reinjecting the produced sand and water into 5. Conclusions and recommendations
the depleted deposit, thus the problems of maintaining the stability of
the stratum and disposal of the large amount of sand from hydrate This study outlines hydrate-based CO2 sequestration technology
extraction can be solved. And the residual hydrate cage structure in the research and development, focusing on CO2 replacement of CH4 hydrate
reservoirs and the memory effect of decomposed water can contribute to and technological techniques for directly creating CO2 hydrates in ma­
the formation of CO2 hydrates. However, the above scheme is a new idea rine and depleted reservoirs. This provides direction for future work on
and approach, and there is still a long way to go for practical field
application, and it can only be used as an alternative scheme for
hydrate-based CO2 sequestration. Table 8
Effects of various factors on the formation of CO2 hydrate (adapted from Song
Sequestration of CO2 in depleted CH4 hydrate reservoirs has the
et al., 2018; Zhu et al., 2019).
following advantages. First, the temperature and pressure conditions of
CO2 hydrate phase equilibrium are lower than those of CH4 hydrate, parameters SCH (%) nCO2inj (mol) nCO2 (mol) r

thus the temperature and pressure conditions of CH4 hydrate reservoir p (MPa) 3.0 25.6 0.11 0.027 0.25
can ensure the long-term stable existence of CO2 hydrate. Secondly, CH4 3.2 26.0 0.15 0.028 0.19
3.5 26.5 0.17 0.03 0.17
reservoirs are well sealed and often have a capping layer above, thus the
SWS (%) 24.5 25.8 0.18 0.037 0.2
sequestered CO2 is not easy to leak. Thirdly, depleted CH4 hydrate res­ 54.5 30.2 0.18 0.036 0.2
ervoirs generally have mining shafts, which facilitate the injection of 69.5 26.5 0.17 0.03 0.17
CO2. Fourthly, decomposed water from hydrate decomposition will V (m L/min) 1 26.9 0.08 0.031 0.37
remain in reservoir pores, and its memory effect could add to CO2 hy­ 2 26.0 0.15 0.028 0.19
4 26.5 0.17 0.03 0.17
drate formation. Finally, the strength of the formation structure may be

18
X. Cao et al. Journal of Petroleum Science and Engineering 219 (2022) 111121

hydrate-based CO2 sequestration technologies. The following conclu­ Declaration of competing interest
sions were drawn based on the summary of this study:
The authors declare that they have no known competing financial
(1) CO2 replacement of CH4 hydrate is feasible from the perspective interests or personal relationships that could have appeared to influence
of thermodynamics and kinetics; however, its low replacement the work reported in this paper.
efficiency is an important reason that hinders the commercial
exploitation of this technology. According to current research, Data availability
changing the temperature and pressure conditions, adding
chemical additives, changing the injected CO2 phase state, and Data will be made available on request.
adding N2/H2 and other gas components can improve the
replacement efficiency to a certain extent. Acknowledgments
(2) The ocean is enormous and the environment of the seabed sedi­
ment layer is ideal for CO2 hydrate formation. A particularly This work was supported by the National Natural Science Foundation
promising sequestration technology is the direct injection of CO2 of China (Grant No. 52074341 and No. 52104071).
into porous media in the seabed at the bottom. The formation
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