pubs.acs.

org/journal/ascecg Perspective

A Perspective on the Effect of Physicochemical Parameters,

Macroscopic Environment, Additives, and Economics to Harness the
Large-Scale Hydrate-Based CO2 Sequestration Potential in Oceans
Yogendra Kumar and Jitendra S. Sangwai*

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ABSTRACT: Subsea sequestration retains a huge potential in terms of the long-

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term viability of stable CO2 storage and, therefore, can contribute to global carbon
neutrality by addressing global warming challenges. However, macroscopic
parameters such as salinity, porosity, sedimentary types, and additives play a
vital role in tapping the fullest potential of subsea CO2 sequestration. This aspect
offers a wide range of opportunities for discussion and will open new avenues for
future development. Therefore, there is a wide scope for discussions in this area,
which will lead to new technological innovations in the future. CO2 sequestration
in subsea sediments in solid hydrate form is discussed in terms of interaction
chemistry and macroscopic environmental effects on pore-scale hydrate formation
and growth. This Perspective presents insights related to CO2 hydrate formation
and its long-term stability with relevance to porous media, CO2-sedimentary
interactions, the effect of additives, and possible cost estimates for large-scale CO2
storage in oceans. Insights into hydrate formation behavior and the effect of
physicochemical parameters (interfacial tension, water saturation, organic matter, salinity, and the chemical nature of the sediments)
have been additionally outlined. Light is shed on the economics of transportation and injection using cost estimates from the
literature along with the challenges and outlook associated with the current technologies. The chemical interactions between CO2
and hydrate-bearing sediments, additives, and marine environments would aid in understanding hydrate formation in subsea
sediments.
KEYWORDS: Additives, CO2 Sequestration, Gas hydrates, Porous media, Subsea sediments

■ INTRODUCTION
Emissions of greenhouse gases (GHGs), primarily CO2, are
and subsea beds, can permanently sequester CO2. However,
oceanic sequestration strategies such as deep-sea liquid CO2
causing global warming, a serious environmental problem storage and subsea basin storage are the best among the
hindering sustainable development.1,2 A total of 55.6% of aforementioned strategies owing to their huge storage
GHG emissions are attributed to industrial sectors (power, potential. However, environmental concerns related to
manufacturing/construction, and industrial processes) in eutrophication and ocean acidification also plague deep
India,3 while 8.64% are attributed to the transportation sector.
ocean storage in the form of liquid CO2. Thus, subsea
Global CO2 emissions are approximately 20% when only
energy-intensive industries (cement, steel, and chemicals) are sedimentary basins are the best among these and have enough
considered.4 To address this issue, CO2 emissions may need to space that can facilitate the storage potential for gigatonnes
be reduced, or anthropogenic CO2 may need to be captured (Gts) of CO2. Our oceans have enough potential to
and sequestrated at some place.5 The world is currently permanently store anthropogenic CO2 beneath the sea floor
producing a humongous amount of CO2 from its industrial for thousands of years.
activities.6 As the conventional absorption-based CO2 capture
technologies are in advanced stages, a new challenge of safe
storage of a large amount of CO2 will arise, given the fact that Received: April 21, 2023
not all of the CO2 that will be captured can be converted to Revised: June 30, 2023
value-added products. Indeed, one cannot store such large
quantities of CO2 in industrial or terrestrial warehouses. Thus,
large-scale geological formations, i.e., unmineable coal beds,
depleted oil and gas reservoirs, saline aquifers, and deep-sea

© XXXX American Chemical Society https://doi.org/10.1021/acssuschemeng.3c02336

A ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
Figure 1. Summarized depiction of the intended topic with a table of contents of the current manuscript.
In subsea sediments, water molecules form cavities through a
hydrogen-bonded linkage that can accommodate any gaseous
guest molecule (CH4, CO2) under gas hydrate forming
conditions. In polar regions and equatorial areas, natural
hydrates are already present in the tundra, permafrost, and
subsea sediments at hundreds of meters subsea depth and over
1000 m below the seabed at depths of 100−250 m and 400−
650 m, respectively. In certain areas around the globe, such as
Taiwan, the water depth can reach upto 1000 m just 30 km
from the coast. In these locations, the combination of thick
layers of organic sediment, oceanic thermocline and hydro-
static pressure creates an ideal environment for the formation
of gas hydrates.7 It is estimated that the total maximum
amount of methane hydrates in terrestrial permafrost and
marine sediments is up to 7.6 × 1018 m3, which has a future
prospect for energy extraction and utilization.8 Based on a
tentative estimate of 1 × 103 Gt C in gas hydrates, the CH4
volume would come out to be 3.1 × 1015 m3 (density of
methane taken to be 0.717 kg/m3). Assuming the release of
only 0.1% (1.8 Gt C) of this CH4 to the atmosphere, this
would result in a rise of CH4 concentration from 1774 in 2005
to 2900 ppb.9 Alternative to methane hydrates, the subsea
sedimentary region can also host CO2 hydrates inside subsea
sedimentary pores as a storage media.10 Therefore, gas
hydrate-based CO2 storage inside subsea sediments is
thermodynamically feasible and stores a huge amount of
anthropogenic CO 2 . However, the subsea storage of
anthropogenic CO2 in subsea sediments is challenging,
owing to transportation costs and kinetics-related concerns.
The salinity of seawater has an inhibitory effect on the hydrate
formation process in porous media and confronting a challenge
for large-scale utilization of this strategy.11 Thus, the study of
the role of other parameters, such as porous media,
sedimentary interactions, and organic sediments, is vital for
the in-depth study of hydrate formation in subsea basins. A
summarized depiction of the CO2 anthropogenic sources and
storage parameters affecting the overall gas storage capacity
and a summarized representation of the content covered in this
Perspective is given in Figure 1.
B https://doi.org/10.1021/acssuschemeng.3c02336
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The oceans are full of volcanogenic, lithogenic, and biogenic
sediment, especially in seabeds near the terrestrial land, owing
to the continuous deposition of soil and sand by rivers.
Organic content rich silt and mud were derived from river
erosion and deposited over the ocean bed for thousands of
years. Thus, the interaction chemistry of CO2 and the hydrate
formation process differ from other sedimentation kinds.
Therefore, the study of sedimentary interaction chemistry with
CO2 and the effect of porosity, water saturation, and organic
sediment will offer greater insights into the subsea-based CO2
sequestration process. This Perspective will facilitate an in-
depth analysis of the CO2 hydrate formation hypothesis, the
effect of salinity and geographical stability, its relevance with
porous media, CO2−sedimentary interactions, and interaction
with organic matter. Further, key insights into the role of
additives in thermodynamics and kinetics in oceanic conditions
are also discussed, which is still not well reviewed in the open
literature. Moreover, the current Perspective will envisage key
insights into CO2 storage in porous media, chemical
interaction with the storage medium and marine environment,
and the kinetics of heterogeneous nucleation, including the
above-mentioned topics. The effects of additives, salinity,
organic matter, and other storage conditions on gas storage in
oceanic/subsea conditions have been presented in this
Perspective. This review also gives insights into cost estimates
for CO2 transportation, injection, and storage with modern
drilling strategies.
■ HYPOTHESIS OF CO2 HYDRATE FORMATION AND
KINETICS IN SUBSEA SEDIMENTS
The CO2 hydrate formation process commences from the
dissolution of gas molecules, followed by nucleation and
crystallization steps.12,13 Hydrate formation is an exothermic
process, so high temperatures can inhibit the hydrate
nucleation and gas dissolution rates. Sundry kinetic promoters
are habituated to promote hydrate formation kinetics and to
reduce gas hydrates due to extravagant thermal progression
during the hydrate formation process. The kinetic promoters
foster the rates of nucleation and crystallization during CO2
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Figure 2. (a) Cluster size vs time for hydrate formation for the nucleation and growth phase (Modified with permission under Creative Commons
Attribution NonCommercial 3.0 (CC by 3.0) from ref 33. Copyright 2020 Royal Society of Chemistry). (b) Different stages of nucleation in the
labile cluster hypothesis (Modified with permission under Creative Commons Attribution NonCommercial 3.0 (CC by 3.0) from ref 33. Copyright
2020 Royal Society of Chemistry). (c) Pictorial representation of the sequential steps of the hydrate formation process. (d) Experimental profile of
pressure−temperature during the CO2 hydrate formation experiment (Reproduced with permission from ref 34. Copyright 2022 American
Chemical Society).

hydrate formation and in some cases can alter hydrate phase
equilibrium boundary conditions while simultaneously increas-
ing the hydrate formation kinetically. As a result of hydrogen
bonding between water molecules, tens to thousands of
molecules develop clusters and grow into small nuclei. As soon
as these nuclei reach critical size, perpetual growth kinetics
begins,14 as shown in Figure 2(a).
Researchers give three different hypotheses to expound on
the CO2 hydrate nucleation mechanism. The Rodger15 and
Kvamme16 interface nucleation hypothesis suggests that CO2
gas molecules are diffused to the interface where gas molecules
are adsorbed at the aqueous interface. Then, the adsorbed gas
species are diffused to the suitable locations where gas
molecules enclathrate in the vacancy engendered by water
molecules. Sloan and Fleyfel’s “labile cluster nucleation
hypothesis” suggests that pure water forms labile ring
structures that consist of pentamers and hexamers as shown
in Figure 2(b).17 These labile water rings form a labile cluster
around guest gas (e.g., CO2) molecules once the gas is
dissolved in the aqueous solution. The coordination number of
water molecules in labile structures will depend on the size of
the guest molecules.18 These clusters of dissolved gas
molecules form unit cells over time. The cluster transformation
of the unit cell to encaged dissolved gas species requires
C https://doi.org/10.1021/acssuschemeng.3c02336
activation energy. Walsh and co-workers19 demonstrated that
the pentagonal face of water molecules encages dissolved guest
gas molecules and creates a small cavity (coordination number
20) that tries to attach other dissolved gas molecules. The
initial cavities composed during this process are face-shared
partial diminutive cages. Steric constraints now obviate further
expansion of these partial cavities into face-sharing pentagonal
dodecahedrons circumventing the core pentagonal dodecahe-
dron. As a result, the coordination number of water molecules
must be adjusted to construct a structure I unit cell with well-
defined cavities.20 The labile clusters are rearranged in the
form of blob structures (large analogues of labile clusters) once
they reach a critical radius.21 An amorphous clathrate hydrate
nucleus is composed when the nucleus attracts fresh gas and
dihydrogen monoxide molecules from the solution. The water
molecules are locally ordered within the amorphous nucleus,
but the CO2 gas molecules lack the required order for a
crystalline hydrate structure. The amorphous clathrate nuclei
rearrange in a final level to yield a crystalline hydrate
containing components from structure I and structure II.22
The third hypothesis is proposed by Radhakrishnan and
Trout.23 They suggested the formation of the local structuring
nucleation mechanism, which assumes that CO2 molecules
arrange in the same configuration as the hydrate phase at the
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Figure 3. Pictorial representation of different classes of methane gas hydrate reservoirs: (a) Class I; (b) Class II; (c) Class III; (d) Class IV.
liquid water and CO2 interface. Owing to this fact, the
configuration of the local ordering of surrounding water
molecules is different from the bulk water phase. If the size of
this local ordering of CO2 molecules and water exceeds the
critical radius of nucleation, then the only stable formation of
hydrate nucleus starts; otherwise, local ordering is metasta-
ble.23
The total Gibbs free energy change (ΔG) in the
heterogeneous nucleation process equals the sum of Gibbs
free energy changes in phase transition and push work. Push
work is the energy required to push aside the old phase and is
represented as a product of the interfacial surface free energy
and surface area of the hydrate framework (assuming a
spherical structure with radius r).24
GT = G phase change + G push work
i4y
GT = jjj zzz r 3 H
G phase change + 4 r 2 surface
k3{
The molar densities of the hydrate phase and water are
reasonably close. ρH and σsurface are the molar density of the
hydrate phase and the surface free energy of the growing
hydrate phase and surrounding water. Simultaneously,
association and dissociation of hydrate nuclei happen if
2 surface
hydrate crystal size is smaller than r* = H phase change (which
G
is known as the critical radius of nucleation).25 The hydrate
nuclei are stable once the overall Gibbs free energy decreases
and the crystal size crosses the critical size.26
The hydrate growth stage follows the nucleation stage of the
hydrate once the size of the nucleus reaches the critical radius.
The conveyance of CO2 gas and water molecules (diffusive
mass transfer), hydrate growth kinetics, and degree of heat
accumulation during hydrate formation are key aspects that
control the overall CO2 hydrate growth phase.27 The heat
accumulation during growth kinetics inhibits the overall
growth process. The CO2 hydrate growth kinetics is a three-
step process:25,28,29 (1) dissolution of a gas molecule in the
aqueous phase, (2) diffusion of a gas molecule through a
stagnant diffusion layer between hydrate clusters, and (3)
incorporation of guest (gas) molecules in hydrate framework
structures. Initially, the step 1 growth process starts with
inward radial growth and simultaneous nucleation, followed by
simultaneous inward and outward radial growth and surface
growth. In the last growth step, inward radial growth
terminates, but outward radial growth continues until complete
coverage is attained, as depicted in Figure 2(c). Figure 2(d)
shows temperature, pressure, and time diagrams during
hydrate formation kinetics. The hydrate formation is a slow
process, and injected gas is initially dissolved inside the water
until it reaches supersaturation. The time from the injection to
pubs.acs.org/journal/ascecg Perspective
the first nuclei of the hydrate being formed is known as the
induction time. The sudden spike in temperature and decrease
in pressure are a signature of hydrate formation. The pressure
decreases continue even during the growth phase, but the
temperature remained nearly constant (Figure 2(d)). The
concentration gradient through the stagnant diffusion layer is
zero in steady-state conditions, which signifies that the
diffusion rate of dissolution of CO2 gas molecules in the
aqueous phase and the incorporation rate of gas molecules in
the water framework are equipollent in steady-state. Hence,
gases with high solubility facilely supersede gas molecules from
hydrate structures that have lower solubility. Owing to this fact,
gases like H2S and CO2 receive preferential treatment over
CH4 during hydrate formation.30,31 Other factors that may
affect the hydrate formation process are supersaturation, the
(1) molecular weight of the guest molecules, the polarity of the
guest molecules, the cage occupancy, and electronic interaction
between the species.32 The hydrate formation is very complex
(2) in subsea basins, and different components may affect the
growth rate and formation mechanism of hydrates, especially
the properties of pore water and porous media. Hydrate
formation is also influenced by the properties of porous media
in addition to thermodynamic conditions. Furthermore,
hydrate formation characteristics are determined by conditions
such as gas and water transport paths, migration characteristics,
salinity, and pore sizes discussed in upcoming sections.
■ CO2 SEQUESTRATION IN HYDRATE
Subsea Reservoir Type and Conditions of CO 2
Sequestration. It is important to understand how the
hydrate reservoir will form during or after CO2 sequestration
in the hydrate form in oceans. It is worth noting that natural
gas hydrates with respect to methane production from hydrates
are classified depending on overburden and underburden levels
of geological settings. The methane gas hydrate reservoirs are
classified in four distinct classes, namely,35,36 (1) Class I, (2)
Class II, (3) Class III, and (4) Class IV, as depicted in Figure
3. Class I reservoirs consist of a CH4 gas-hydrate-bearing layer
at the top of the free gas zone. The arctic gas hydrate reservoirs
are an example of Class I reservoirs. In Class II reservoirs, CH4
hydrate-bearing layers are over water, while in Class III
reservoirs, the CH4 hydrate-bearing zone is without any fluid
layer beneath it but surrounded by overburdened and
underburdened subsea sediments. Most of the offshore subsea
methane hydrate reservoirs are examples of Class II and Class
III reservoirs. Moreover, Class IV reservoirs consist of only
hydrate-bearing layers and are mostly found in marine subsea
deposits and permafrost. The dilution of chemicals/additives
in free water molecules affects the deliverability of chemicals to
targeted sites. Moreover, chemical addition is also prohibited
in Class II and Class IV reservoirs due to environmental
D https://doi.org/10.1021/acssuschemeng.3c02336
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ACS Sustainable Chemistry & Engineering
Figure 4. Pictorial depiction of different oceanic CO2 hydrate reservoirs, as proposed by us, after CO2 sequestration strategies in subsea ocean: (a)
Class I; (b) Class II; (c) Class III. The reservoir type may vary depending on the seawater depth (see Figures 5 and 6).
concerns. The free gas zone underneath the hydrate layer
makes Class I reservoirs most promising as temperature and
pressure conditions are proximate to the hydrate equilibrium
condition and the free gas zone beneath the hydrate layer.37
A similar classification of CH4 hydrate reservoirs cannot be
directly correlated to CO2 hydrate formation conditions under
the subsea and oceanic conditions, as the former is available in
nature (in the sea and permafrost), while we plan to form a
CO2 hydrate on or under the seabed. The type of CO2 hydrate
reservoirs depends on the way we inject the CO2 gas/liquid,
corresponding depths, and subsea geological conditions. More
promising possibilities of CO2 hydrate reservoir types that
could form over a period under subsea conditions are depicted
schematically in Figure 4, as proposed by us. Similar to CH4
hydrate reservoir types as discussed earlier, the CO2 hydrate in
the subsea sedimentary basin may form, closely resembling
Class I of CH4 hydrate reservoir conditions. Class I reservoir
CO2 sequestration depicts the subsea sedimentary sequestra-
tion condition in which CO2 is sequestrated below the hydrate
forming zone (HFZ). Reservoirs of Class II are hydrate
reservoirs at the sea surface where hydrate is deposited over
the sea surface in the form of mounds. Moreover, in Class III
CO2 reservoirs, the CO2 is stored in very deep ocean pools in
liquid form. Due to prevailing pressure and temperature
conditions and surrounding seawater, a hydrate layer forms
around the liquid CO2 pool, making it more confined in a
space. However, oceanic sequestration at the sea floor has only
limited geothermal and hydrostatic pressure. Any depth below
3500 m is suitable for CO2 sequestration (in the form of a
liquid CO2 pool). However, CO2 storage as a liquid pool
beyond 5000 m on the sea surface is less susceptible to
geothermal perturbations like earthquakes and volcanic
eruptions.38 Although all of these proposed classes will depend
on thermocline and geothermal gradients and pressure
conditions, as shown in Figure 5, as we go deeper into the
oceans, the density of CO2 increases more prominently than
the density of seawater. However, at approximately 750 m
depth, the oceanic T and P conditions are sufficient for the
CO2 gas to liquid transition (Figure 5). However, the density
of liquid CO2 is less than the density of seawater at this depth.
At a depth of approximately 2800 m, the density of CO2
supersedes the density of seawater that offers an extra
gravitational barrier.39
A suitable justification for the formation of a possible CO2
reservoir type has been provided henceforth. The temperature
profile of thermocline in the Gulf of Mexico (GoM) and
geothermal profile considering the average temperature rise
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Figure 5. Temperature and density variation in oceans and subsea
sediments as a function of depth (data taken from ref 39; thermocline
(Gulf of Mexico) data taken from ref 41; density data taken from ref
42).
and density profile in oceanic and subsea conditions is
depicted in Figure 5. Figure 6 provides a general understanding
of the various possible CO2 sequestration conditions in oceans
and subsea basins at different oceanic depths. In oceanic
conditions, temperature decreases as the depth from the sea
surface increases.39 However, temperature increases as the
depth increases in subsea sediments, owing to a geothermal
gradient. Further, the density of CO2 increases as we go deeper
inside oceans more prominently than the density of seawater.10
The CO2 hydrate formation condition prevails at approx-
imately ∼490 m, where the CO2 is in gaseous condition. The
region where hydrate forming conditions are established is
called the hydrate forming zone (HFZ) or hydrate stability
region (HSR) (Figure 6( a,b)). The CO2 turns into a liquid
phase from gas at the temperature and pressure conditions
prevailing at ∼750 m depth (Figure 6 (a,c)). However, the
density of seawater remains higher than the density of liquid
CO2. The CO2 plumes have a tendency to plume up in this
condition, owing to a lower density than that of the seawater
(as ρCO2 < ρsw). The upward movement of the CO2 plume is
due to lower CO2 creating no gravitational barrier. Thus, the
re-emission of the CO2 plume might be possible if not
converted into hydrate. It is interesting to note that the density
of the CO2 hydrate is always higher than the density of
seawater and the CO2 plumes at every depth. The density of
CO2 overshoots the density of seawater at a depth of ∼2800 m,
and CO2 plumes gain a tendency to sink in at this depth, owing
to gravitational barriers (ρseawater < ρCO2).10,40 The zone beyond
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ACS Sustainable Chemistry & Engineering
Figure 6. Different sequestration conditions in oceans and subsea basins at different depths: (a) Schematic profile of temperature and behavior of
CO2 at different concerning depths and geological conditions. (b) CO2 sequestration conditions at shallow sea depths (>490 m). (c) CO2
sequestration conditions at deep sea depths (>2800 m). (d) CO2 sequestration conditions at deep sea depths (>2800 m) in subsea basins. (e) CO2
sequestration conditions at very deep sea depths (>5000 m).
2800 m is termed the negative buoyancy zone, where the CO2
plume has a tendency to sink down. The region where the
density of CO2 is higher than the density of seawater is known
as the negative buoyancy zone (NBZ) (Figure 6(c,d)). The
chances of hydrate formation in the NBZ are relatively low or
rather kinetically slow due to the lower intermixing of phases
due to low oceanic currents and the reasonably high density
difference of H2O and CO2, but hydrate formation is possible
thermodynamically (Figure 6(e)). Assuming the geothermal
gradient 0.03 K/m in subsea sediments, the density of CO2
further increases due to temperature increase (Figure 5). The
NBZ region in subsea sediments prevails up to the point when
the density of seawater again supersedes the density of CO2.
However, the hydrate forming conditions (T, P) still prevail at
this depth. In subsea sediments at a certain depth, the hydrate
formation is kinetically enhanced due to the low density
difference between H2O and CO2 due to an increase in the
geothermal temperature. This storage of CO2 in subsea
sediments prevails over conditions of Class I reservoir type
of CO2 hydrate formation, whereas the oceanic sequestration
of CO2 in the form of hydrate grows like a Class II reservoir
type of CO2 hydrate at the sea floor. Very deep oceanic storage
(>5000 m) is totally different than normal shallow and deep
oceanic storage. The density difference between liquid CO2
and seawater is high enough to create diffusion barriers. The
lower possibility of sea currents and intermixing of phases is
the prevailing condition for Class III reservoir of CO2 hydrate
(Figure 6(e)). The storage in deep sea has a low ecological
signature, as only a very few marine animals are capable of
surviving at this depth. A second advantage of deep ocean
storage is that it has very high storage potential without any
porosity confinement. The storage potential in subsea
sediments will be affected by the porosity of the sediments.
However, the long-term ecological impacts of this technology
still need to be assessed and addressed.
Some of the recent studies related to advances in CO2
sequestration in subsea porous sedimentary basins (mainly at
lab-scale) are listed in Table 1. CO2 sequestration in the subsea
bed basin in sedimentary deposits requires rigorous feasibility
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pubs.acs.org/journal/ascecg Perspective
studies such as types of sediments, sedimentary properties, the
geothermal gradient, and the process economics which play a
vital role. The sequestration of CO2 at less than 2800 m depth
is considered less sustainable and safe under geological
perturbations and volcanic eruptions. Important factors must
be evaluated before choosing a sequestration site: (i) The
sedimentary depth must be thicker than the HFZ; (ii) the
permeability of sediments should be high, as the high
permeability sediments help to accommodate higher CO2
amount at higher sequestration rates; (iii) sequestration site
should not consist of steep slopes, as this may result in
landslides; (iv) CO2 transportation to the sequester site and
the sequestration process should be cost-effective.10,40,42
House et al.42 reported that a CO2 sequestration site with
300 m thickness under a seabed with 50% porosity and 50%
residual water has the capacity to sequestrate 6 Gt CO2 in an
80 km2 area. Moreover, ∼22% of USA’s economic zones have
permanent CO2 sequestration potential with an estimated
storage capacity >104 Gt liquid CO2 below deep sea depths
(>3000 m).42 Calcareous sediments might be a lucrative
option among other sedimentary types owing to their reactivity
with carbonic acid and higher permeability. Besides this,
bicarbonates are the most prominent storage state for CO2
(aq), as it may not directly degas from solution and remains
there longer.
Effect of Salinity and Porous Media on CO2 Hydrate
Formation. Upon injection of CO2 into the subsea bed,
salinity and porous media can affect the formation of CO2
hydrates. The stability of CO2 hydrates in a reservoir is
influenced by many factors, including salinity, fluid inter-
actions, hydrate crystal interactions, mineral interactions, and
pore water saturation. Moreover, hydrate formation in porous
media is influenced by porosity, permeability, water saturation,
surface area, surface roughness, capillary pressure, throat radii,
and pore radii.55 Linga et al.56 observed that packed bed
reactors formed more hydrates in pure water with silica sand as
compared to stirred vessel reactors. There is a higher uptake of
gas in silica-packed columns than in stirred vessels with bulk
water. The researchers found that reducing the particle size of
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 Table 1. Recent Advances in Gas Hydrate-Based CO2 Sequestration Technology
Author System Process parameters Remarks/Outcomes
Lee et al.43 Na-Montmorillonite (Na-MMT) and marine sediment suspensions are CO2-saline water, suspension pH = 6.5 1. In the presence of NaCl (3.5%), the nucleation kinetics of Na-MMT
contained in a stainless steel (STS) multicompartment pressurized vessel. , P = 2.2, 2.5, and 3 MPa, T = 0.3, 1, suspensions (1.7 times) were enhanced by heterogeneous nucleation sites on Na-
and 1.5 °C. MMT surfaces.
2. Oxygen-rich Na-MMT encourages prehydrate structure during nucleation.
3. Induction time increase with a decrease in pressure and an increase in
temperature.
Sun In situ, water-saturated clay-packed reactor (montmorillonite or Illite) connected with NMR. CO2−water, P = 1.39−3.5 MPa, 1. Illite clay that contains low levels of strongly bounded water observed an
et al.44 T = 275.2 K, water saturation = increase in hydrate formation at low water saturation (5−20%).
0−30% 2. In the case of montmorillonite, a decrease in CO2 storage capacity is reported at
low water saturation (0−15%), while an increase is reported at higher saturation
(15−30%).
Kuang In situ pressure oscillation porous media reactor connected with low field nuclear magnetic CO2-water, P = 2.5 and 3 MPa, 1. Hydrate nucleation from the top in a sand-packed reactor and propagates from
et al.45 resonance. T = 274.2 K top to bottom.
2. As a result of pressure oscillation, mass transfer barriers are effectively reduced,
and hydrate formation is increased.
Zhang Quartz sand-packed reactor particle size = 700 μm CO2−water, P = 3.9−5.1 MPa, 1. Larger gas storage capacity and higher formation rate were obtained under
ACS Sustainable Chemistry & Engineering

et al.46 T = 274.5 K liquefaction conditions.

2. The hydrate formation rate is significantly promoted under partial liquefaction
conditions, whereas complete liquefaction is unfavorable to CO2 hydrate
formation.
Zhao Glass bead packed reactor (porosity of 34.8%) connected with high field MRI spectrometer. CO2-water, T = 3.0 MPa, P = 277.15 1. Overpressure close to 7 MPa is required to form a hydrate cap that forms a
et al.47 K, Water saturation = 21.6%-67.8% permeability barrier to block CO2 leakage.
2.CO2 leakage was reduced in different cases with an increase in water saturation in
the packed bed reactor.

G
Lu et al.48 Molecular dynamics simulations of hydrate formation using N2/CO2 mixture. CO2−N2−water, P = 50−150 MPa, 1. The selectivity of CO2 for 51262 is decreased as pressure rises, and lower
T = 260 K subcooling makes it easier for CO2 to enter 51262 cages, whereas the reverse is
observed for N2.
2. Subcooling has a weaker influence on N2 selectivity between 512 and 51262 cages
than on N2 molecules.
Qureshi Silica sand packed reactor made of SS-316. CO2−L-tryptophan−water, 1. Pore size, permeability, and sediment type determine the stability of CO2
et al.49 P = 0−10 MPa, T = 274−277 MPa hydrates in porous beds.
2. Theoretical analysis shows that CO2 storage beyond 3 km from the sea surface
has permanent sequestration potential.
Liu el al.50 Clay-packed reactor packed with different clays (porous layered montmorillonite, SA sediments, CO2−water, CO2−saline water, 1. Montmorillonite shows the highest depression in hydrate dissociation
kaolin, and smooth and flat surface silt). Specific surface area of different clays: montmorillonite > Salinity = 1.5; 3.5%, P = 7−16 MPa temperature, followed by SA sediments and kaolin, while silts have the lowest.
SA sediments > kaolin > silt and clay. 2. Thermodynamic equilibrium condition 15−35% saturated silt is the same as
pubs.acs.org/journal/ascecg

bulk.
3. The order of hydrate phase equilibria inhibition by different sands:
montmorillonite > SA sediments > kaolin > silt.
Zhang Quartz sand-packed reactor made of SS-316. Sand size = 700 μm, Ice particles size = 500 and 700 CO2−water, P = 2.45−3.0 MPa, 1. The gas storage capacity of the quartz sand pack increased when ice particles of
et al.51 μm. T = 270.15 K the same size (700 μm) were mixed with sand.
2. Hydrate formation is better when the temperature approaches the freezing point
but not below freezing.
Qureshi Silica sand-packed reactor. Particle size = 0.5−1.4 mm CO2-saline water, P = 3.5−10 MPa, 1. Hydrate form above the porous bed is relatively unstable and more likely to
et al.52 T = 277 K dissociate.
Fuji Numerical simulation of microscopic CO2 hydrate formation in the sand-packed reactor CO2−water, P = 6 MPa, T = 1. The phase field model of hydrate formation inferred that the difference in the
et al.53 274−280 K solubility of CO2 and CH4 gases at the gas−liquid interface is the major
contributor to hydrate growth kinetics.
2. As water saturation and the angle of contact between water and sand at the
interface determine the flow path, CO2 hydrate shape distribution has a notable
Perspective

influence.

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porous media improved gas storage capacity and hydrate

1. Gas diffusion kinetics and overall hydrate growth rate are significantly improved

2.CO2 hydrate will grow in the periphery inwardly in patchy morphology and
formation rates by improving interconnections between
pores.11,57,58 Further, in the presence of salinity, hydrate
formation rates are also significantly reduced, as salinity
negatively affects hydrate kinetics, reducing the conversion rate
by six times and reducing the rate of hydrate formation
significantly.11,59 Added minerals with differing interfacial
properties to the solution shortened hydrate induction time
and enhanced their formation rates, according to a study by
Remarks/Outcomes

Dai et al.60 Crystal morphologies and growth kinetics of

hydrates in porous media were affected by the wettability and
by adding sodium dodecyl sulfate (SDS).

capillary forces. Various porous media were tested in the

laboratory to study the formation and dissociation kinetics of
hydrates, including kaolinite, quartz, silica sand, calcite,
CaCO3, and carbon. The swelling and nonswelling nature of
clays influences hydrate formation in clay minerals. Hydrogen
bonds bind octahedral and tetrahedral sheets together in the
coexist with water.

clay particles. Clay sheets are held together by these bonds,

and so it is difficult for them to expand. The interlayers hold
the water molecules in place, regulating the swelling ability of
the clay. In swelling clay minerals, such as smectite and
bentonite, this increases the interlayer spaces. Swelling clays
dissolve gas into bulk water molecules within pores in their
swelled interlayer spaces and outside their boundaries.
CO2−water−SDS, P = 1.52−6.01

The gas dissolution in nonswelling clay takes place on the

Process parameters

outside of the interlayer spaces.55 Hydrate forms within the

interlayer spaces and on the surface of the clay minerals after
MPa, T = 274.2 K

the gas diffuses into the clay. There are two locations where
clay minerals form hydrates: (1) within their swollen
interlayers (in the case of swelling clay) and (2) on their
surfaces (in both swelling and nonswelling clays). Clay
contains cations on the surface of its interlayers that control
the swelling behavior. When water molecules bind to clay
surfaces with large surface areas and ionic layers, water activity
is reduced, and thus, hydrate formation is reduced. As a result,
the hydrate phase boundary is shifted to higher pressures than
in pure water due to capillary pressure within the clay pores.
Illite and kaolinite are classified as nonswelling clays whereas
Na-MMT is observed to have swelling behavior in water
saturation conditions. The chemistry behind this distinct
behavior can be explained in terms of the chemical structure.
Illite is a phyllosilicate (2:1) mineral, typically found in silt and
the sand fraction of subsea soil.61 In Illite clay, K+ is situated at
hexagonal holes sandwiched between tetrahedral sheets.
Octahedral sheets in Illite clay are also located between two
tetrahedral sheets, and these two conditions makes Illite clays
System

nearly unexpendable. Kaolinite is another phyllosilicate (1:1)

clay that consists of one silicon tetrahedral sheet and one
aluminum octahedral sheet.61 In water-saturated kaolinite,
hydrogen bonds hold the adjacent tetrahedral and octahedral
sheets together, preventing the expansion between them. It is
Quartz glass bead-packed reactor

likely that CO2 hydrate formation may have occurred on

kaolinite or Illite’s outer surface due to the fact that water
molecules cannot enter inside the layers. In Na-MMT,
octahedral layers are sandwiched between tetrahedral layers,
making it a popular smectite group clay.61 Water molecules can
Table 1. continued

be intercalated inside its interlayer, which can swell as they are

accepted and held.62 A significant factor in controlling Na-
MMT clay’s swelling behavior is the presence of interlayer
cations on the surface of the interlayers. The increase of basal
spacing from 10.88 to 12.97 Å, along with the other simulation
Author

et al.54
Zhang

studies suggests that the CO2 hydrate formed predominantly

between the Na-MMT intercalated layers.61,63,64 Capillary
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pressure and interactions between MMT clay, cations, and
water may affect hydrate formation within clay inter-
layers.61,65−67 It is possible for water molecules to be
associated with the surfaces of soil minerals, reducing their
water activity, especially on clays, such as MMT, which have
extensive surfaces and very distinct ionic double layers.65
Electrostatic attraction is stronger than hydrogen bonds or van
der Waals forces, which is believed to result in cations
interacting with water molecules’ dipoles, resulting in a severe
decrease in water activity. Na-MMT interlayer cations
significantly inhibited CO2 hydrate formation, which resulted
in significant changes in the phase equilibrium of the CO2
hydrate in Na-MMT suspensions. The effect of Illite, kaolinite,
and Na-MMT clay suspensions on the gas hydrate phase
diagram is shown in Figure 7.
Figure 7. Effect of different clay structures and organic matter on the
CO2 hydrate phase diagram (data taken from ref 61).
In similar accounts, hydrate formation occurs at the water−
gas interface and interstitial space between sand particles
owing to capillary action and water presence between silica
sand. Moreover, silica gel particles have smooth surfaces. Thus,
nucleation occurs at pore walls, owing to negligible diffusion
into interparticle pores. The comprehensive analysis of all sand
structures and physicochemical properties suggests that the
order of CO2 storage potential in different sediments is
bentonite ≪ kaoline ≪ silica gel ≪ silica sand, as shown in
Table 2.
Sediments that are not completely saturated with water tend
to have grain coatings. The sediment-bound water facilitates
hydrate formation over the grain surface, and the hydrate
formation tends to surround grains and clogged pores, known
as cementing. The clogging of distributed pores by the formed
hydrates eventually separates the pore space from the
interconnected pores.69 The hydrate adhering to the sediment
grains works as cement itself and increases hydrate strength,
resulting in increased seismic velocity.58 The pore filling occurs
when the guest gas (methane or CO2) is fully saturated inside
the water, and hydrate formation occurs in the middle of the
pore without any contact with the surrounding sediments. The
hydrate phase may or not fill the pore space between sediments
but forms hydrate clusters by joining surrounding grains.58,69
The hydrate clusters between sediments increase the hydrate-
bearing sediment’s mechanical strength and decrease porosity
and pore space interconnectivity, known as load-bearing
growth. Load-bearing growth propagates hydrate growth and
facilitates hydrate stability by decreasing the interconnectivity
of the pore space with hydrate saturation.58 Smaller size
particles inside porous media increase the interconnectivity of
pores and the surface area for gas−liquid contact, thus
facilitating improved hydrate formation kinetics.11,70 Research-
ers observed that porous media that contain particles of
different sizes facilitate hydrate formation in the middle of
pores rather than the grain surface owing to preferential
wetting of sediments by water rather than gas. The gas
molecules migrate through interconnected pores, and hydrate
formation occurs in the center of pores by gas−liquid contact.
The aforesaid hydrate formation in the center is true for large
grain sizes (>0.0313 mm), whereas hydrate formation occurs at
the grain surface for smaller grain sizes (<0.070 mm) (around
the grain).71 Another critical factor during hydrate formation
in porous media is the water saturation. Nearly 100% water-
saturated pores are rigid to replace water with incoming gas;
thus, the hydrate formation occurs only owing to gas
dissolution in water. Contrarily, partially saturated pores
develop interconnections by creating dedicated gas channels
with higher interfacial areas for gas−liquid contact. Addition-
ally, Chong et al.72 studied hydrate formation in porous media
with different grain sizes. Larger pebbles show greater surface
hydrate formation near the top of porous media compared to
smaller silica sands. It is evident that coarse-grained hydrate-
bearing reservoirs in nature do not consist of coarse-grained
hydrates, as observed from the visual observation and
temperature response of porous media surfaces made of coarse
sand and granular pebbles. Graphite surfaces with hydrophobic
surface charge could adsorb CO2 molecules so strongly that
they are nearly covered with CO2, thereby lowering the

Table 2. Effect of Different Sediments on the Hydrate Formation Process and Their Storage Capacity
Types of sediment And
their storage capacity#
Silica sand68
(0.2562 mol)ΔnH)a
Silica gel68
(0.1037 mol)ΔnH
Clay55
Bentonite (0.0232 mol)ΔnH
Kaoline (0.0288 mol)ΔnH
Hydrate formation location
1. Within sand bed at gas−water interface
2. Interstitial space
Nucleation occurs at pore walls owing to a smooth surface
and negligible diffusion.
1. Clay minerals swelled within their interlayers (swelling
clay).
2. Gas dissolves into bulk water molecules in clay both inside
and outside of swelled interlayer spaces.
Remarks/proposed mechanism
1. The surface area of the sand strongly influences gas dissolution.
2. The permeability of the gas depends on the size of the silica sand
particles in the interstitial spaces of the sand bed.
1. In the interparticle pores, silica gel affects the dissolution of gases
owing to smooth surface.
2. Low/poor gas dissolution
1. Unlike swelling clays, nonswelling clays dissolve gas outside the
interlayers.
2. On the surfaces of their sheets (both swelling and nonswelling clay)

a
ΔnH is the average CO2 mol consumed.

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Figure 8. (a) Illustration of hydrate growth mechanisms with hydrophobic graphite and hydrophilic silica porous media (Reproduced with
permission from ref 73. Copyright 2021 Elsevier.). (b) Mechanism of H2O−C and CO2−C interaction and hydrate formation in carbon porous
media (Reproduced with permission under Creative Commons Attribution 4.0 (CC by 4.0) from ref 74. Copyright 2019 Science and Technology
Review Publishing (AAAS).). (c) Hydrate formation process in porous media using the labile cluster hypothesis.

aqueous CO2 concentration. The hydrophilic silica surface,
however, adsorbed a partially cylindrical CO2 nanobubble,
resulting in high aqueous CO2 concentrations. Hydrate
nucleation begins at the bulk and grows toward surfaces in
graphite and silica nanopores, as shown in Figure 8(a). He et
al.73 observed that ordered interfacial water plays a critical role
in encouraging hydrate formation on hydrophobic graphite
surfaces, which is still covered by strongly adsorbed CO2
molecules. Upon contact with interfacial water, silanols on
silica surfaces form strong hydrogen bonds to form semi-cages
that are capable of entrapping CO2 molecules. Interaction
between the CO2 hydrate solids and silica surfaces is primarily
through the interfacial semi-cages (Figure 8(a)), with only a
few cages making direct contact. When it comes to the
hydrophobic graphite surface, CO2 molecules are strongly
adsorbing and covering the surface, which prevents the
formation of ordered interfacial water, which is a crucial
component of the nucleation of CO2 hydrate and the
interaction of hydrate cages with the surface.73 When CO2
was added to porous carbon that was already completely
saturated with water, a significant amount of CO2 was
absorbed as a result of several intriguing processes, such as
(I) the replacement of the water that had been adsorbed on
the carbon surface by CO2 (driven by entropy) and (II−IV)
the further replacement of the water that had been present in
the pore by CO2, which was accompanied by the growth of gas
hydrate crystals from the pore, as shown in Figure 8(b).74 The
first process is owing to the higher entropy of CO2 despite
having a higher binding energy of C−CO2 than C−H2O
(driven by entropy). Moreover, calculated binding energy of
C−CO2 is slightly weaker than that of C−H2O. The water
inside pores can by replaced by increasing the CO2 chemical
potential (Process II). At the end, the CO2 hydrate forms
outside the confined space, and the remaining CO2 is
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condensed within the pores. Initially, in nanoconfined spaces,
microhydrate crystals form and then move out to grow into
larger crystals to decrease the surface free energy when
pressure reaches the level necessary for CO2 hydrate formation
(Process IV). In the meantime, CO2 absorbs and condenses
within the pores (Process III).74 This conclusion led to the
observation that gas hydrates cannot form in the nanoconfined
spaces. When water is driven outside the pores to form gas
hydrates, the excess gas in artificial gas hydrates results from
gas adsorption and condensation.74 According to the labile
cluster hypothesis, hydrate nucleation first develops in the bulk
area before moving toward the surfaces. The hydrate
nucleation is highly stochastic, and nucleation is highly
randomized, as shown in Figure 8(c).
Water activity generally declines when salts or organic
inhibitors are added to bulk water. Porous sediments, on the
other hand, have various surface forces acting on the pore
water, unlike bulk water. Physicochemical interactions between
water and mineral surfaces cause surface tension at gas−liquid
interfaces and adsorption forces at mineral surfaces. Because of
these forces, pore water exhibits different water activities in
comparison to bulk water, even under identical thermody-
namic conditions. Three different mechanisms can explain the
inhibition of hydrate thermodynamic conditions in sedimen-
tary conditions: (1) the capillary effect, (2) surface
interactions, and (3) soluble salts. Due to interfacial tension
at the gas−water interface, the capillary effect significantly
inhibits the hydrate phase equilibrium. Hydrate formation in
subsea sediments is also affected by surface adsorption. The
sedimentary properties, physiological characteristics of the
sediment, and surface interactions play an important role in
hydrate formation. In clay sediments, surface adsorption can be
categorized into two categories: surface hydration and
interlayer cation hydration.75 Since clay particles usually have
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Table 3. Summarized Depiction of Different Parameters and Their Effects on Hydrate Formation
Parameter Remarks Microscopic nature Effect on CO2 hydrate phase equilibrium/hydrate formation
Sediments Illite Chemical (nonswelling) Hydrate formation occurs at the surface of clay owing to nonswelling nature of clay. The Illite clay
phyllosilicate (2:1) clay does not inhibit phase equilibrium of CO2 hydrate.61
Kaolinite Chemical (nonswelling) Hydrate formation occurs at the surface of clay owing to nonswelling nature of clay. The kaolinite
phyllosilicate (1:1) clay clay does not inhibit phase equilibrium of CO2 hydrate.61
Na-MMT Chemical (swelling clay) Presence of interlayer cation reduces water activity, thus inhibiting hydrate formation, and shifts
smectite clay hydrate phase diagram (HPD) toward low temperature and high pressure.61
Organic matter Illite Chemical (nonswelling) Organic matter inclusion in Illite clay suspension inhibits hydrate formation and shifts hydrate phase
phyllosilicate (2:1) clay diagram (HPD) toward low temperature and high pressure.61
Kaolinite Chemical (nonswelling) Organic matter inclusion in kaolinite clay suspension inhibits hydrate formation and shifts hydrate
phyllosilicate (1:1) clay phase diagram (HPD) toward low temperature and high pressure.61
Na-MMT Chemical (swelling clay) Organic matter inclusion in Na-MMT clay suspension promotes hydrate formation and shifts HPD
smectite clay toward high temperature and lower pressure.61
Interfacial Physical Reduction in IFT promotes hydrate formation.
tension IFT of CO2-water decreases with increase in pressure and temperature.85
(IFT)
CO2 saturation Chemical IFT decrease with CO2 dissolution in the water.86
If water is completely saturated with CO2, then hydrate forms between the sediments and connected
grains reduce overall porosity of overall hydrate bearing sediments.58
Water Chemical 100% water saturated pore hinders gas flow, and hydrate formation occurs by dissolution at the
saturation contact surface.
Partially water saturated form hydrate at the grain surface.
Salinity Chemical Increase in salinity inhibits hydrate formation and shifts hydrate phase diagram (HPD) toward low
temperature and high pressure.81
Particle size Physical Smaller size particles have higher interconnectivity of pores and surface area for gas−liquid contact;
induces hydrate formation.71
Hydrate form at the center of pore for large grain size whereas hydrate formation occurs at the
surface of grain for small grain sizes.71

negative charges, hydrogen bonding between surface hydroxyl
ions and water molecules is a major factor in clay hydration.
Additionally, clay interlayers usually contain exchangeable
cations to cancel out the negative charge. Cation hydration
may be induced in clay minerals by the negatively charged end
of the water dipole. A fully developed cation hydration layer
can reach tens of nanometers and facilitate phase interaction.
This binding of water molecules to mineral surfaces reduces
the water activity and suppresses the hydrate phase
equilibrium. High water saturation is required for hydrate
formation in sediments with strong water affinity.76,77 Hydro-
phobic clays promote gas hydrate at the interface by increasing
the density of former gas at the solid−liquid interface. On the
contrary, hydrophilic clay inhibits hydrate formation by
distorting the water structure and reducing water activity and
owing to the low density of former gas at the liquid−solid
interface.78 Additionally, salinity inhibits the formation of
hydrates in sedimentary waters. Aqueous solutions containing
salt also exhibit strong electrostatic interactions between
dissolved cations and anions.79 When hydrates form, salt
ions compete for water molecules, and fewer water molecules
will be available to form water cages through hydrogen
bonding. During the formation of hydrate molecules, the
salinity also increases in the surrounding area of the hydrate.
CO2 hydrates are formed when water molecules take part in
the formation of salt molecules during hydrate formation.
Increasing salinity levels result in a dramatic decrease in
hydrate formation and fill fractions.80,81 Moreover, the sea salts
dissolved in the entire volume of pore water and affect hydrate
formation inside the entire volume, whereas the surface charge
on the clay and the cations on the interlayer affect hydrate
formation to a few nanometers distance in the pore water. The
reasoning behind this obvious behavior is that salinity affects
the water activity of the entire volume of pore water. On the
contrary, the surface interaction, surface charge, and cations
affect the water activity in the near interacted surface.
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As the hydrate formation in porous sand progresses, salinity
levels rise (as salt is excluded), which increases the induction
time and decreases the hydrate fill fraction.81 As a result, salts
suppress equilibrium conditions toward higher pressures or
lower temperatures. Salinity and porous media can be
circumvented by adding a surfactant or other additives.
Through the addition of surfactant, it is possible to alter the
physicochemical properties of hydrates to facilitate the
reduction of mass transfer resistance and the increase in gas
solubility.
Effect of Organic Matter on CO2 Hydrate Formation.
Carbon dioxide hydrate formation is enhanced in sediments
when organic material (sediment organic matter, SOM) and
inorganic material (sediment minerals) are present. Alkaline
extracts contained SOM of amide and amine group structures
and lignin, while sediment extracts contained SOM of aromatic
ring structures. Despite this, subsea basin pore fluids contain
organic matter and are chemically different from seawater. As a
result of diffusive transport and diagenetic reactions, subsea
sedimentary deposits contain ancient seawater that has slightly
changed over time. Moreover, pore fluids contain a higher
concentration of calcium and sulfide than seawater and a lower
concentration of magnesium and sulfate.82 Except for hydro-
carbons, altered pore fluids have little difference in chemistry
from seawater.
A significant impact of SOM on the CO2 hydrate induction
time in the Ulleung Basin (UB) sediment suspensions
negatively impacts the stability of the UB as a gas hydrate
reservoir and its suitability for storing CO2. By interacting with
water molecules and cations in the interlayer surface, the
organic matter intercalated into the Na-MMT interlayer and
could alter the formation and dissociation processes of the
CO2 hydrates. Ionic species can be trapped and attracted by
organic matter via electrostatic interactions and ionic bonds.61
As a result, interactions between cations and organic matter
might counteract the inhibition effects of cations, leading to
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improved equilibrium conditions for the CO2 hydrates. The
basal spacing values of Na-MMT were increased from 12.97 Å
to 15.63, 15.04, and 14.06 Å, respectively, with the addition of
0.5 mol % glucose, glycine, and urea solutions.61 This suggests
that the organic substances were inserted into the interlayer of
Na-MMT, potentially impacting the processes of CO2 hydrate
formation and dissociation through their interaction with water
molecules and cations on the interlayer surface. However,
kaolinite and Illite sediments show inhibitory phase behavior in
the presence of organic matter as compared to pure clay
suspension in water (Figure 7).61 Natural sea sediments
containing low water content result in a higher fluid−CO2
interaction, forming CO2 hydrates at a faster rate.83 Surface
minerals and organic chemicals in sediment can affect the CO2
hydrate nucleation kinetics. The majority of UB sediment is
composed of phyllosilicates, including 15.1% muscovite, 4.5%
chlorite, 7.1% Illite, and 17.3% kaolin, followed by quartz
(17.3%) and albite (13.2%) along with other mineral
components. The UB sediments also contains 10% organic
contant out of which 3.4% organic carbon. As a result, the mix
of soil minerals does not significantly affect the accelerated
nucleation kinetics of CO2 hydrates in UB sediment
suspensions.83 Iron compounds and lipid-like structures were
found to enhance hydrate growth at lower sedimentary depths.
Proteinaceous sedimentary materials inhibit hydrate growth,
while lipid-like sedimentary materials have a positive effect.84 A
summary of the effect of different parameters on hydrate
formation is been listed in Table 3.
Chemistry of Long-Term CO2 Interaction with Sedi-
ments and Rocks. The CO2 mineralization over a longer
period through the CO2 and sedimentary solid interaction at in
situ temperature and pressure inside a subsea sedimentary
basin is an important aspect to cover. The mineralization over
a longer period will further secure CO2 storage in subsea basins
for the long-term since it locks the gas into a form that cannot
be re-emitted. CO2 is generally considered a stable molecule to
react directly with rocks. However, it is absorbed over the rock
surface by physical bonds and dissolves in water to form
carbonic acid over a period. The carbonic acid then reacts with
sediments or rocks to form the CO2-mineralized rock solids.
Interestingly, water molecules attack the CO3 structure and
break the Si-O structure to form carbonate ions that further
react with the dissolved metal cations for stable mineralization.
The interfacial tension between water and CO2 decreases with
an increase in pressure. The surface tension variability depends
on dissolved organic and inorganic species in water.87 It is
interesting to note that the interfacial tension between CO2
and the solid/water surface decreases with pressure; however,
the interfacial tension (IFT) between water and the solid
surface remains nearly the same with an increase in pressure.
The decrease in interfacial tension increases the CO2 solubility
in pore water; contrarily, the interfacial tension increases with
an increase in temperature initially and then starts decreasing
at higher temperatures.85 A decrease in interfacial tension
improves the CO2 rock interactions and may promote
mineralization. Furthermore, an IFT reduction also has a
positive effect on gas hydrate formation in subsea sediments.
Jia et al.88 observed that both carbonation (physical adsorption
over rock) and hydrolysis (reacting with water) are
thermodynamically favorable. Physical parameters such as
permeability and porosity are macroscopic parameters that are
affected by rock and CO2 interaction in the presence of pore
water. Changes in the microscopic morphological structure of
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pubs.acs.org/journal/ascecg Perspective
pores, which affect the overall pore radius distribution of cores,
eventually determine how rock permeability changes. The
process of CO2 interaction with sedimentary rocks in the
presence of pore water can proceed in two stages: (1) primary
carbonate rock dissolution to bicarbonates and (2) secondary
mineral precipitation. Carbonic acid formed due to CO2 pore
water interaction dissolves carbonate rocks into bicarbonates
and feldspar. The chemical reactions involved during
dissolution and mineral precipitation are given below.
CO2 (aq) + H 2O H 2CO3 (3)
H 2CO3 H+ + HCO3 (4)
Ca 2 + + CO32 CaCO3 (5)
Mg 2 + + CO32 MgCO3 (6)
Ca 2 + + Mg 2 + + 2CO32 CaMg(CO3)2 (7)
CaCO3 + H 2O + CO2 (aq) Ca(HCO3)2 (8)
Thus, the interaction of CO2 with carbonate and feldspar
rocks in subsea sediments improves permeability. Both above-
mentioned rocks are severely eroded at some areas, and
dissolution intensifies with an increase in pressure that
generates secondary pores to improve rock permeability.89
However, uncontrolled carbonate precipitation promotes
uneven pore distribution and rock permeability in rock
structures.90 On the contrary, iron- and magnesium-rich
aluminosilicate and carbonate minerals precipitate from basalt
rocks during secondary mineral precipitation in a carbonic acid
environment. Ankerites were formed when Fe was in the
ferrous oxidation state (Fe2+) during the initial stages of the
reaction. Further, the reaction proceeds by oxidizing ferrous to
ferric (Fe2+−Fe3+), thereby reducing the available Fe2+ and
changing Mg to Fe ratios in ankerites, resulting in formation of
Mg-rich rims in rock structures.91,92 The aqueous carbonic acid
also precipitated aluminosilicate-rich minerals (clay or zeolites)
containing other ions in the fluid. The porosity and
permeability of rocks can be increased by rock dissolution;
however, their porosity and permeability can be decreased by
secondary mineral precipitation. CO2−water−rock reactions
can result in a more or less connected pore network depending
on which process dominates.93 However, the CO2−rock
interaction mechanism will depend on rock composition,
pressure, and temperature. The brine−rock interaction caused
by CO2 dissolution may be bifurcated into two stages. In the
first step, the susceptible minerals (e.g., ankerite, chlorite,
feldspar, and calcite minerals) dissolve rapidly under an acidic
environment. Dissolving ankerite or chlorite facilitates siderite
precipitation, whereas anorthite and albite dissolve to form
smectite-Ca and Dawsonite, respectively. Dawsonite, which is
dissolved in albite, becomes smectite-Na, followed by Illite and
smectite-Ca as intermediate products that react with CO2 and
brine in the subsequent stages.94 In the second step of the
reaction, these clay minerals become kaolinite and paragenetic
quartz. Geochemical reactions between CO2, brine, and rock
can be divided roughly into two stages. Minerals such as
calcite, ankerite, chlorite, and feldspar are the main reactants in
the first stage (probably the first 10,000 to 100,000 years).94
Siderite, Dawsonite, smectite-Na, and smectite-Ca are
carbonate minerals and clay minerals formed during the first
stage of reactions, and they become reactants for the second
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Figure 9. Different sedimentary soils and the CO2 interaction reaction in the context of long-term stability in the form of minerals.
stage when the initial reactants have completely dissolved (i.e.,
chlorite and feldspar). Carbonate minerals precipitate and
could immobilize CO2 (i.e., mineral trapping). Simulations by
Zhu et al.94 suggest that carbonate minerals may dissolve as the
reaction continues. On the geologic time scale associated with
the CO2 geologic storage project, which ranges from 5,000 to
10,000 years, carbonate minerals (i.e., Dawsonite and siderite)
can precipitate significantly.94−96 There are many sedimen-
tary−CO2 interaction reactions that can occur depending on
the phase present in sediments and the reaction condition.
Some of these reactions are listed in Figure 9.
Long-term CO2 and sedimentary interactions for thousands
of years can lead to the physisorption of CO2 onto the
sediment surface or surface mineralization. The surface
chemistry of the sedimentary interaction with pore fluids and
CO2 plays an essential role in it. The CO2 is dissolved in pore
fluids, forming carbonic acid that eventually reacts with mineral
silicates. Mineral silicates decompose chemically to produce
carbonates because of carbonation. A divalent cation (Me2+) is
released through the dissolution of silicate, such as Ca2+, Mg2+,
and Fe2+.97
First step:
MexSiO2 + x + 2xCO2 + x H 2O
xMe2 + + 2x HCO3 + SiO2 (9)
It is thermodynamically possible for carbonate minerals to
precipitate when saturation is reached with respect to them. A
pictorial depiction of the carbonation reaction from mineral
silicates is given in Figure 10(a). The stabilization of carbonate
occurs in the second step. However, the first step is rate
limiting.97
Second step:
x Me2 + + 2x HCO3 x MeCO3 + xCO2 + x H 2O
(10)
Overall reaction:
MexSiO2 + x + 2xCO2 + x H 2O
x MeCO3 + x CO2 + x H 2O + SiO2 (11)
Several factors will affect the interaction of CO2 with sediment
in subsea basins, such as the presence of organic matter in pore
fluid, salinity, the acidity of water, CO2 dissolution in the pore
fluid, and release of a divalent cation.
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pubs.acs.org/journal/ascecg Perspective
Direct CO2−SiO2 polymerization for the mineralization of
CO2 is another approach but occurs at very high pressures and
moderate temperatures. The reaction was initiated with CO2
molecular bending at very high pressure followed by chemical
bonding with Si present in SiO4 tetrahedra, as given in Figure
10(b). The interaction of CO2 over the zeolite surface causes a
five-coordinate Si center. The coordination linkage is
developed with the incoming CO2 with O and Si atoms.98
The O atom of newly added CO2 may interact with other CO2
molecules and initiate polymerization between zeolites, as
shown in Figure 10(b). However, the aforementioned
mechanism of mineralization occurs only at very high
pressures. The long-term interaction of CO2 with quartzite at
moderate pressures and high temperatures may lead to a
similar type of CO2 mineralization under subsea conditions
during long-term storage.
Promoters for CO2 Hydrate Formation for Sequestra-
tion. The presence of dissolved salts in seawater shifts the
hydrate forming conditions toward higher pressures and lower
temperature and inhibits hydrate formation’s kinetics. To
reduce the inhibitory effect of salts on hydrate formation, a
hydrate promoter was used. Hydrate promoters are additives
that were used to improve the gas consumption kinetically
(kinetic promoters) or shift the hydrate phase boundary
toward lower pressure and higher temperature (thermody-
namic promoters). Many thermodynamics promoters are being
explored for CO2 hydrates to foster hydrate nucleation’s
feasibility. Water activity and hydrogen bond interactions are
all that are changed by these thermodynamic hydrate formers
(THFs). Several thermodynamics promoters have been tested
for CO2 hydrate at the lab scale such as cyclopentane,
tetrahydrofuran (THF), tetra-n-butylammonium bromide
(TBAB), and propane.99,100 The kinetic promoter decreases
the surface tension of the liquid phase, increases gas diffusion
from the bulk to the interface, increases the interfacial surface
area for enhanced mass transfer, and increases the gas
consumption during hydrate formation, thus improving the
overall kinetics of the nucleation process. Sodium dodecyl
benzenesulfonate (SDBS), tetrahydrofuran (THF), tetra-butyl
ammonium bromide (TBAB), and sodium dodecyl sulfate
(SDS) are widely investigated as kinetic accelerators for CO2
hydrate formation. Chemical surfactants such as TBAB, SPAN-
80, and TWEEN-80 (with lower concentration) are reported
to be environment benign and biodegradable in the open
literature and can be effectively used to foster hydrate
formation in subsea sediments.101−103 The hydrate cage is
formed owing to the temporal unsymmetrical redistribution of
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Figure 10. Mechanism of long-term CO2 interaction with sediments: (a) CO2 interaction with mineral silicates in water;97 (b) interaction of
quartzite with CO2 at very high pressure and moderate temperatures.98

electrons and the generation of temporary dipoles. Moreover,
the kinetics of hydrate formation increases significantly when
THF is used in lower concentrations. However, a significant
reduction in hydrate formation is observed when the THF is
used in higher concentrations.104,105 The primary aim of
integrating these kinetic additives with nanoparticles is to
truncate induction time, increase gas consumption, and
facilitate dissolution of guest molecules by lowering surface
N https://doi.org/10.1021/acssuschemeng.3c02336
tension,106,107 as discussed in forthcoming sections. The roles
of different additives in hydrate formation and inhibition are
listed in Table 4.
Thermodynamic Promoters for CO2 Sequestration As
Hydrates under Subsea Conditions. It is necessary to
understand the effect of thermodynamic hydrate promoters
(THPs) on the gas hydrate phase equilibrium. Gas hydrate
equilibrium curves determine the conditions under which gas
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
 Table 4. Role of Different Additives in the Hydrate-Based CO2 Sequestration Process
Class of additives Promoters/Additives Process conditions
Thermodynamic Tetrahydrofuran (THF) CO2/N2/THF
promoter N2 = 83.1 mol %; CO2 = 16.9 mol %,
CO2/N2/THF
N2 = 83.1 mol %; CO2 = 16.9 mol %,
CO2/H2/THF
N2 = 60.8 mol %; CO2 = 39.2 mol %
Tetra-n-butyl ammonium CO2/TBAB
bromide (TBAB) 15.6 mol %; CO2 = 46.8; H2 = 53.2,
84.8 mol %, CP = 30, 50 vol %
40 mol % CO2 + 60 mol % CH4
TBAB concentrations (0.29, 0.62,
1.38, and 2.57 mol %)
CO2/H2/CH4/TBAB
CO2 = 14.81, 39.52, 75.01 mol %,
H2 = 85.19, 60.48, 24.99 mol %
O
TBAB and tetra-n-butyl CO2/TBAB + TBPB (molar ratio
phosphonium bromide 1:1)
(TBPB)
Cyclopentane (CP) CO2/H2/cyclopentane
Kinetic promoter Sodium Dodecyl Sulfate CO2/SDS/H2O
(SDS)
SDS Graphene oxide (GO)/sodium
dodecyl sulfate (SDS)/CO2/H2O
TBAB/SDS or nano graphite/CO2/
H2O
L-Tryptophan L-Tryptophan/Liq. CO2/H2O
1,3-Dioxolane 1,3-Dioxolane/CO2/H2O
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
https://doi.org/10.1021/acssuschemeng.3c02336
Remarks/Conclusion Author
1. Pressure reduces from 7.7 to 2.5 MPa with the inclusion of 1 mol % THF. Linga et al.108
2. Induction time reduces with an increase in THF concentration.
3.CO2 consumption increases
√ 17 to 36.9 mol % (single-stage reactor)
√ 17 to 94 mol % (three-stage reactor)
1. Pressure reduces from 7.7 to 0.345 MPa with CO2/N2 + 1 mol % THF. Linga et al.109
2. Hydrate formation grew faster with the CO2/H2 mixture than the CO2/N2 mixture.
3. Induction time reduced to <1 min from 16.3 min by the inclusion of 1 mol % THF.
1. TBAB improved the flow behavior of hydrate slurry owing to antiagglomerate behavior. Li et al.110
2. Equilibrium formation pressure decrease with an increase in TBAB concentration.
1. High CO2 selectivity and moderate hydrate forming conditions. Wang et al.111
ACS Sustainable Chemistry & Engineering
2. Best CO2 selectivity is obtained at 2.57 mol % conc.
3. Low CO2 separation efficiency is a major challenge.
1. Equilibrium hydrate formation conditions modified toward high-temperature and low-pressure stability regions. TBAB may Mohammadi
have greater promotion effects on CO2+H2 systems than on CO2+CH4 systems. et al.112
2.278.4 K,10.5 MPa ≫ 288.6 K,12.17 MPa at 5% TBAB
278.4 K, 10.5 MPa ≫ 288.6 K, 4.07 MPa
1. Induction time was reduced from 190 to 95 min at 6 K degrees of subcooling (with TBAB/TBPB = 1:1). Wang et al.113
2.CO2 consumption increased (with TBAB/TBPB = 1) by 33.7% and 20.7% as compared to TBAB and TBPB solutions.
1. Pressure reduction from 5.3 to 1.3 MPa with the inclusion of 1.5 mol % CP. Zhang et al.114
2.CO2 conc. reached 98% from 40% with the inclusion of 1.5 mol % CP.
1.SDS additives (0−5000 ppm) had no effect on the mechanism and kinetics of gas hydrate formation under a large driving Molokitina
force (Δx ≥ 5.0 × 10−3). et al.115
2. Capillary-driven growth had analyzed for medium SDS concentration 1000 ppm and small driving force (Δx ≤ 1.0 × 10−3).
pubs.acs.org/journal/ascecg
1. Hydrate was formed 69.7% faster in the combined system than with pure water, while 12.2% faster when using a 0.005% GO Li et al.116
system.
2.CO2 gas consumption increased by 11.24% and 3.2%.
1. Induction (nucleation) time is reduced when TBAB is combined with SDS or nano graphite. Wang et al.117
2. When SDS concentration was increased, the nucleation time increased at first and then decreased.
1. Increase water-to-hydrate conversion by 82−98%. Qureshi et
2. Decrease induction time by a factor of 2−3. al.118
1. Clear phase separation between water-rich and DIOX-rich phases at high pressure (3.09−3.76 MPa) owing to CO2 solubility Yao et al.119
difference in both phases. Phase separation of DIOX/H2O above 3.1 MPa weakens the promotion effect of DIOX.
2. The significant solubility difference in water/DIOX phases shifts the equilibrium toward less favorable regions.
3. Hydrate grows from slurry > musky > snow-like form with an increase in DIOX concentration.
Perspective
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

hydrates are stable. There is a direct correlation between the

Zhou et al.121
Firoozabadi
Author hydrate equilibrium curve and the composition of the former

et al.120
Rajabi hydrate gas and any additives (thermodynamic inhibitors/
promoters). The selection of thermodynamic promoters
usually depends on the environmental impact and cost factors
1. Hydrate formation increases with an increase in NPs conc. up to 0.15 wt %, then starts decreasing owing to aggregation.

for the sequestration process. Thus, all thermodynamics

promoters cannot be used during CO2 sequestration in
The positive effect of NPs is more pronounced than CTAB (400 ppm) solution but lesser than SDS (400 ppm).

offshore conditions to avoid environmental concerns. The

comparative analysis of different thermodynamic promoters on
the phase equilibria of the CO2 hydrate is given in Figure 11(a,
b). It is evident from Figure 11(a, b) that increasing wt %
positively affects the thermodynamic equilibrium toward lower
pressure and higher temperature. Furthermore, the synergism
of THF + TBAB thermodynamic promoters more positively
affects the thermodynamic equilibrium than THF and TBAB
alone. Apart from surfactants, the effect of nanoparticles on the
hydrate equilibrium phase diagram is slightly inhibitory.
Furthermore, the hydrophobicity and hydrophilicity of nano-
particles do not affect hydrate formation thermodynamics
Remarks/Conclusion

1. Hydrate conversion increases by 50.75% at 0.08% GN concentration.

significantly and their role is only restricted to kinetically.122

Nanoparticles such as Cu, ZnO, and graphite have an
(Fe3O4 + SDS) solution decreases 70.6% of the induction time.

3. Graphite NPs had a minor effect on hydrate phase equilibrium.

2. 16.6% decrease in induction time at 0.08% GN concentration.

inhibitory effect on the hydrate phase equilibrium as they

interact with water and thus decrease its activity to form a
hydrate cage. In spite of the fact that carbon nanotubes have
similar properties to graphite, they show different properties
and have a positive effect on the hydrate formation kinetics.123
Moreover, few thermodynamic studies have been done using
nanoparticles and promoters.123,124 To bring gas hydrate
160% increase in gas consumption.

technology to industrial applications in the future, using

120.5% increase in apparent rate.

nanoparticles and additives as promoters in low dosages is a

potential and effective approach for marine applications;
however, studies on their biodegradability and the long-term
sustainability of the approach are essentially required.
Kinetic Promoters for CO2 Sequestration as Hydrates
under Subsea Conditions. Kinetic promoters help to lower
the surface tension, increase the diffusion of gas from the bulk
to the interface, increase the interfacial surface area for mass
transfer, which eventually increases gas consumption rates, and
2.
3.
4.
5.

improve the hydrate nucleation and growth rate. The salinity

NPs concentration: 0.05, 0.09, 0.15,

NPs concentration: 0.04, 0.06, 0.08,

CO2, H2O, SDS (400 ppm), CTAB

of water also affects the hydrate stability and increases the

induction time during CO2 hydrate formation in porous media.
Process conditions

Seawater contains salt ions that interact with water molecules,

(400 ppm), Fe3O4 NPs

disrupting their structure and inhibiting hydrate nucleation.

CO2, H2O, TBAB, GN
0.20, and 0.25 wt %

Some research studies demonstrated that the presence of silica

inhibits the salinity effect on the water activity. As a result of
and 0.1 wt %

hydrophilic interactions with the silanol groups in sediments,

changes in OH− stretching vibrations were correlated with
NaCl concentrations in ice water, thus reducing the effect of
salinity on hydrogen bond formation.127 Moreover, the
presence of weekly bound water associated with Illite clay
cetyltrimethylammonium

increases hydrate formation more than strongly bound water

Promoters/Additives

nanoparticles (GN)

associated with montmorillonite clay. The extremely low

bromide (CTAB)

TBAB and graphite

mobility of strongly associated water inhibits hydrate

formation.44 It is well understood that the seawater salinity
decreases the overall hydrate formation kinetics and shifts
SDS and

hydrate forming conditions toward high pressure and low

Table 4. continued

temperature, as shown in Figure 12, which is relevant for

offshore conditions.
Class of additives

The role of kinetic promoters is very important in enhancing

the CO2 hydrate formation kinetics under subsea conditions.
Kinetic promoters (chemicals, surfactants, natural products,
and nanoparticles) are used to increase gas consumption and
nucleation rates. Researchers used three different types of
P https://doi.org/10.1021/acssuschemeng.3c02336
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Figure 11. (a) Effect of TBAB and TBAB−THF mixtures on the CO2 hydrate phase equilibrium. (b) Effect of THF and THF−TBAB mixtures on
the CO2 hydrate phase equilibrium (numbers in the legend indicate composition in wt %). (Data taken from refs 125 and 126.)

Figure 12. (a) Effect of salinity on hydrate forming temperature and pressure conditions. (Data were taken from refs 81 and 128.). (b) Effect of
salinity on a CO2 phase diagram. (Data is taken from ref 129.)

surfactants (cationic, anionic, and nonionic) to promote
hydrate formation and truncate induction time.106,130,131
Ramaswamy et al.132 studied the formation of hydrates using
different anionic and cationic surfactants. They found that
aggregates can take the form of spherical micelles, worm-like
micelles, spherical vesicles, lamellar sheets, etc. Micelles are
generally shaped and sized according to their molecular
geometry. There are also many factors that affect it, including
the composition of the solution (concentration of surfactants,
temperature, pH, and ionic strength). Aggregation of the
molecules minimizes the solution’s free energy. The Gibbs free
energy solution of micellar solutions is minimized by
aggregating surfactant molecules. They found that hydrate
forms much faster at the critical micelle concentration, and the
presence of micelle structures or foreign materials increases the
overall nucleation site. During these experiments, they found
that non-spherical micelles were found to serve as nucleation
sites for gas accumulation and encapsulation by water. The
increase in nucleation sites eventually increases hydrate
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formation rates, while foaming increases the gas−liquid
interfacial area, eventually decreasing the induction time.
Karaaslan et al.133 observed that anionic surfactants are more
effective in enhancing hydrate formation as compared to
nonionic surfactants. Moreover, cationic surfactants are most
effective at lower concentrations and show two opposite
behaviors at lower and higher concentrations. In another study,
keshavarz Moraveji et al.134 observed that a cationic surfactant
(HTABr) had the maximum effect on the induction time in
comparison with an anionic (SDS) and a nonionic (TritonX-
405) surfactant.134 It has been observed that the surfactant
SDS does not affect the formation kinetics of CO2 hydrates,
since CO2 is much more soluble in water than hydrocarbons,
so its effect on CO2 hydrate formation is much less than its
effect on methane hydrate formation.135
Environment-Friendly Kinetic Promoters for Hydrate-
Based CO2 Sequestration. Additives such as alcohols, amino
acids, ionic liquids, and salts have significantly influenced the
hydrate formation kinetics positively or negatively. The
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Figure 13. (a) Pictorial illustration of the spacer effect influencing hydrate formation chemistry. (b) Pictorial depiction of amine hydrate chemistry.
(c) CO2 uptake with time in decylamine, amylamine, and methylamine systems. (d) Induction time of different amine systems in comparison with
pure water. Adapted with permission from ref 34. Copyright 2022 American Chemical Society.

Figure 14. Effect of different amines on CO2 gas consumption individually and in combination. (Data were taken from ref 140.) Normal GH
represents pure CO2 hydrate.

hydrophobic characteristics of chemical additives and nano-
particles positively affect the CO2 hydrate formation process.
In contrast, substances such as ionic liquids and hydrophilic
nanoparticles inhibit the hydrate formation and clustering
process.136 The emphasis of the current research is on the
environmental sustainability of the hydrate-based CO 2
sequestration process. As natural compounds, amino acids
have improved biodegradability and can be used as kinetics
hydrate promoters and kinetic hydrate inhibitors. Amino acids
R https://doi.org/10.1021/acssuschemeng.3c02336
consist of carboxylic acid and amine groups that can form
hydrogen bonds with water molecules.137,138 Apart from this,
amino acids can also form zwitterions in a solution that
facilitate electrostatic interactions. The literature suggests that
longer alkyl chains enhance amino acids’ hydrophobicity,
eventually promoting their functionality as kinetic hydrate
promoters.137,139 Hydrogen bonds are strengthened when
amino acids have hydrophobic side chains, causing water
molecules to form clathrate-like structures. In contrast, amino
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ACS Sustainable Chemistry & Engineering
acids with hydrophilic chains disturb the hydrogen bond
network in water, making it incompatible with the structure of
clathrates. However, hydrogen bond perturbations between
water molecules are primarily responsible for the kinetic
hydrate inhibitor mechanism of amino acids.
Sahu et al.34 demonstrate that a long-chain amine has higher
CO2 uptake during formation and better dissociation stability
than short-chain amines. They observed that decylamine
performs better than amylamine and methyl amines. The order
of their performance to improve the CO2 hydrate stability and
gas uptake is as follows: decylamine > amylamine >
methylamine.34 The performance parameters of different
amines (methylamine, amylamine, and decylamine) in CO2
uptake, proposed mechanism, and induction time are given in
Figure 13. Decylamine proved to be more effective at higher
concentrations than methylamine and amylamine (at both low
and high concentrations) during the CO2 hydrate formation
experiments. During the hydrate dissociation experiments, pure
carbon dioxide hydrates showed a higher degree of
dissociation, while hydrates with additives showed a lower
rate of dissociation. This bodes well for the process and
enhances the thermodynamic and kinetic stabilities of the
sequestered CO2 hydrate under subsea sediments. Decylamine
aqueous solutions also converted water and gas into hydrate at
higher rates than pure water. Environmentally friendly amino
acids such as L-leucine, L-methionine, and L-trytophan are
other tested amino acids that enhance the kinetics of CO2
hydrates. The effect of amines on hydrate promotion/
inhibition will depend on a guest molecule. Srivastava et
al.140 demonstrated that not every amino acid gives equal
results in kinetics promotion rather than combinational use of
amino acids, especially leucine + methionine + lecithin, which
has a greater impact on the promotion of the hydrate
formation kinetics. CO2 consumption of 19.64% in a normal
gas hydrate (GH) condition is observed as compared to
21.53% in leucine + methionine, 16.71% in leucine + lecithin,
19.71% in methionine + lecithin, and 25.67% in leucine +
methionine + lecithin, which demonstrate higher gas
consumption during hydrate formation, as shown in Figure 14.
Studies have demonstrated that amino acids with higher
hydrophobicity are superior kinetic promoters.141 However,
hydrophobic amino acids (valine and leucine) promote CH4
hydrate formation kinetics significantly but do not significantly
alter the CO2 hydrate formation kinetics.140 However, based
on these findings (Figure 14), the order of gas consumption is
observed as methionine > leucine# > valine# > cysteine# (#
mark shows CO2 hydrate kinetic inhibition for specific amino
acids). However, in reality, the order of hydrophobicity is
valine > leucine > cysteine > methionine.140 So, does the
hydrophobicity of an amino acid play any role in kinetics
promotion or do other factors have important roles (such as
functional group, chain length, etc. of amino acids) are matters
of investigation.
Other than amine complexes, ionic liquids are also potential
agents to enhance the kinetic promotion of CO2 hydrate
formation. Liu et al.142 observed that the complex anion
([FeCl4]−) with larger size and lower charge promotes
hydrogen binding networks by weakening electrostatic charges
between Cl− and water as compared with iron ion (Fe3+) and
chloride ion (Cl−). In the electrolyte solutions, the complex
anion ([FeCl4]−) with a lower charge and larger size can
promote the formation of the hydrogen-bonding networks by
weakening the electrostatic charges between Cl− and water.142
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pubs.acs.org/journal/ascecg Perspective
Thus, the formation of coordinate bonds between water and
the vacant ferrous orbital fortifies the local network formed
around [FeCl4]− by hydrogen bonding. [FeCl4]− has a large
molecular volume, contributing to the mass transfer of H2O
and CO2. In the same way that surfactants enhance interfacial
interactions between gas and water, [BMIM][FeCl4], with its
hydrophilic anion and lipophilic cation, enhances interfacial
interactions between gas and water phases. This may also help
researchers to understand how surfactants promote gas
hydrates.142
Nanoparticles as a Kinetic Promoter for CO 2
Sequestration. Nanoparticles (NPs) play an essential role
in improving the kinetics of gas hydrates, and the evolution of
nanotechnology demonstrates its utility in biofuels,143,144 CO2
capture,145 pharmaceuticals,146 and enhancing the mass
transfer and chemical kinetics of processes.147,148 Said et
al.149 have reported that nanoparticles with higher interfacial
surface area and tuning surface parameters positively affect gas
uptake during CO2 hydrate formation. They observed that
SiO2 NPs have a more pronounced effect on gas consumption
than Al2O3 and Cu nanoparticles.149 The enhanced heat
transfer mechanism reduces heat accumulation and offers
better heat rejection during exothermic hydrate formation, and
stirring promotes a driving force for diffusion that positively
affects gas consumption.149−152 Cheng et al.153 have reported
that the SiO2/TBAB solution has the shortest induction time
and that gas consumption is highest in the Al2O3 NPs/TBAB
system. The addition of nanoparticles facilitates active sites and
hetero surfaces for nucleation. Nanoparticle’s hetero surfaces
could act as seeds for heterogeneous nucleation and facilitate
more nucleation sites; therefore, chances for hydrate formation
increase.123 Similarly, Al2O3 NPs demonstrated significant
improvement in thermal conductivity; therefore, they accel-
erated absorption rates and mass transfer rates by 26%.154
Furthermore, nanoparticles such as Ni considerably enhance
the interfacial activity of CO2−saline water and can raise CO2
dissolution rates in aquatic deep saline aquifers.155
He et al.156 found that surfactants such as SDS give superior
results compared to nonsurfactant promoters such as nano-
particles and porous materials. However, coalescing nano-
particles with a surfactant conspicuously found a synergistic
effect over promotional efficiency. Furthermore, when used to
promote CO2 hydrate formation, SDS and metal nanoparticles
(e.g., ZnO and Al2O3) demonstrated significantly better results
than the individual components, demonstrating the synergistic
effects of metal nanoparticles and surfactants in gas hydrate
formation. However, the hydrate formation process is
diffusion-controlled, not reaction-controlled initially.157
Some nanoparticles are observed to have an inhibitory effect
on hydrate formation. However, the roles of hydrophilicity,
water absorption capacity, the decrease in entropy, and water
activity are responsible for their inhibitory behavior.
Furthermore, because hydrophilic nanoparticles have a strong
affinity toward the water, they have been shown to absorb
more water on their surfaces than gas molecules, decreasing
entropy and inhibiting hydrate formation and gas consumption
rates.123 Liu et al.124 observed that nonmodified and
hydrophilic Al2O3 nanoparticles reduce induction time,
whereas hydrophobic nanoparticles extend induction time.124
Furthermore, the inhibitory effect on hydrate formation was
observed with hydrophilic silica nanoparticles, and the
inhibitory effect increased with an increase in particle size
under a constant concentration. The inhibition effect of
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Figure 15. (a) Different stages of nanoparticle-supported hydrate formation (heterogeneous nucleation) in surfactants: (i) micelle formation, (ii)
gas entrapment and gas transport to the interface, (iii) interaction of gas molecules with associated water at the reaction zone, (iv) nucleation at the
reaction zone. (b) Comparison of surfactant-supported and nanoparticle + surfactant-supported hydrate formation via the micelle theory.

Figure 16. (a) Gas species transport mechanism from bulk gas to the hydrate interface via nanoparticle assisted migration. (b) Capillary theory for
hydrate formation and effect of surfactant and nanoparticles on nucleation, induction time, and gas consumption.

hydrophilic silica nanoparticles first increased and then
decreased with increasing nanoparticle concentration under a
constant particle size.158 The formation of hydrates is favored
by hydrophobic nano-CaCO3 particles, while the formation of
hydrates may be inhibited by hydrophilic ones, depending on
the particle size and concentration.159 More studies are needed
to validate the synergistic effect of nanoparticles and additives
on the hydrate formation and gas consumption rates. Though
these aforesaid studies about NPs-supported hydrate kinetics
are related to CO2 capture, environmentally benign nano-
particles can also be used in subsea sequestration through
investigations on cytotoxicity, cost, and environmental
factors.160−163
Theories of Hydrate Growth in the Presence of
Surfactant. Even though different theories, such as micelle
theory, adsorption theory, and capillary theory, have been
proposed to expound on the kinetic mechanism of surfactant-
promoted hydrate formation, no consensus has been
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reached.156 However, despite some opposition, the micelle
and adsorption theory is commonly utilized in research.123,149
In micelle theory, when a micelle appears in a liquid solution
above the CMC, it attaches water molecules on the micelle
surface and dissolves the guest molecule in microdomains of
surfactant molecules. The nucleation of gas hydrates is initiated
by the reaction between gas molecules within micelles and the
water molecules associated with them,164−166 as shown in
Figure 15(a, b). The proposed mechanism of hydrate
formation using micelle theory in the presence of surfactant
alone and surfactant + nanomaterial combined is represented
in pictorial form in Figure 15(b).
Some researchers believe that some nanoparticles act as
carriers for fragmented gas bubbles from the bulk to the
interface as they act in the absorption process, as shown in
Figure 16(a). The adsorption theory suggests that surfactants
and nanoparticles promote the formation of gas hydrates by
adsorbing them on their surfaces. Alternatively, in the capillary
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ACS Sustainable Chemistry & Engineering
Figure 17. (a−d) Schematic representations of well injection profiles for subsea CO2 injection under subsea sediments: (a) vertical injection; (b)
horizontal injection; (c) multilateral injection; (d) fish bone injection. (e−g) Injection profiles for CO2 injection on the seabed: (e) vertical
injection; (f) horizontal injection; (g) distributed injection.
theory, the hydrate particles would then move along the
reactor sidewall and form centric hydrate layers retained by the
reactor sidewall, preventing the formation of hydrate films at
the gas−liquid interface and removing obstacles to gas
diffusion into the liquid phase. In the capillary mechanism,
when SDS concentrations reached above 4−5 ppm, this
resulted in porous hydrate layers on the reactor sidewall as
opposed to hydrate films at the gas−liquid interface (barrier
between gas−liquid contact) shown in Figure 16(b). Capillary
hydrate formation occurs as liquid solution is sucked upward
due to capillary action along the wall, resulting in upward
capillary hydrate growth.167,168 Zhang et al.169 proposed that a
reduction in interfacial tension reduces induction time,and that
SDS promotes hydrate formation by absorbing guest molecules
and reducing energy and mass transfer barriers. Hydrophilic
groups that combine with hydrate crystals under hydrogen
bonds and hydrophobic groups that protrude into the aqueous
phase could replace HCO3− that originally adhered to the
hydrates surface. When the SDS reaches an optimum level,
adsorption saturation is achieved and monolayer formation on
the hydrate interface occurs. In addition to reducing hydrate−
liquid interfacial tension, the monolayer also provided
hydrophobic microdomains on the surface of the hydrate. As
a result, hydrate nucleation could be accelerated, and hydrate
formation could increase. In addition, the negative charge
created by SDS on the hydrate surface could strengthen the
hydrogen bond between water molecules, thus promoting
hydrate formation. SDS above a certain concentration did not
regularly affect the hydrate induction period once the
adsorption reached saturation. This specifically explains why
SDS above a certain concentration did not regularly influence
the hydrate induction period.169−171 The micelle theory is
efficient while considering the surfactant concentration above
the CMC; contrarily, below the CMC the capillary theory
U https://doi.org/10.1021/acssuschemeng.3c02336
pubs.acs.org/journal/ascecg Perspective
efficiently defines hydrate formation, especially in porous
media.
Well Drilling Strategies and Cost Considerations
(Transport and Storage) for CO2 Sequestration in
Oceanic Conditions. Well drilling is an important aspect
that needs to be considered before CO2 injection in subsea
sedimentary basins. The water depth, salinity, long-term
corrosion, geological conditions, and subsea depths are
important parameters that need to be considered before
drilling. The advent of technological advances in drilling
allowed us to drill to a higher depth with more complexity in
land and subsea terrains. This will allow us to dispose off the
humongous amount of CO2 safely and economically in subsea
basins at higher depths. Researchers’ current focus is on
advancement in drilling fluids, mud motors, expandable
casings, wellbore stability, and hydraulics. Offshore drilling
rigs can fall into two basic categories: those that can move from
one site to another and those that are permanently or
temporarily positioned on a fixed platform. The advancement
in rigs with the advent of drilling technology allows us to
sequester CO2 at different depths. Platform rigs and jack-up
rigs are commonly used at shallow depths, whereas semi-
submersible rigs and drill ship methodologies are used for
moderate depths. The more advanced tension leg platform rig
is used for higher depths of petroleum exploration. However,
these rigs can also be used for CO2 sequestration into oceans
and subsea basins. Drilling strategies such as Casing while
Drilling (CWD), Dual Gradient Drilling (DGD), Managed
Pressure Drilling (MPD), and Managed Pressure Casing
Drilling (MPCD) can also be applied for subsea drilling.172
The drilled holes are caged holes or open holes with or without
sand control media. Apart from this, different CO2 drilling and
injection profiles can be used for CO2 injection into
sedimentary basins. Figures 17(a−d) show the schematic
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

Figure 18. (a) Cost components of CO2 shipping under case assumptions. (Data taken from ref 173.) (b) Cost comparison of CO2 transport costs
range for onshore and offshore pipelines per 250 km in 2005 and 2019 (minimum cost estimates given by dotted lines and maximum with solid
lines). (c) Cost comparison of costs for onshore pipelines, offshore pipelines, and ship-based transport, by distance, in US$/tonne CO2. Pipeline
costs are given for a CO2 mass flow of 6 MtCO2/year. Ship costs include intermediate storage facilities, port fees, fuel, and loading costs. These
costs also include additional liquefaction costs beyond compression. (Data taken from refs 174, 182, and 183.) (d) Total retained fraction of
injected CO2 in oceans with respect to depth of injection and years after injection. (Data taken from ref 175.)

schemes for CO2 injection under the seabed, while Figures
17(e−g) show the schemes for CO2 injection on the seabed.
Different injection profiles are used to improve gas distribution
into subsea sediments, as shown in Figure 17. Vertical,
horizontal, multilateral, and fish bone injection techniques can
be applied for CO2 injection into subsea basins.172 The vertical
injection profile is a commonly adapted technique for CO2
injection (Figure 17(a)). However, the horizontal injection
profile can distribute CO2 gas to a greater volume of subsea
sediments (Figure 17(b)). Furthermore, multilateral injection
helps in the gas distribution of CO2 gas at varying depths
(Figure 17(c,d)). The fish bone injection is also a feasible CO2
injection profile for the multilateral distribution of CO2 gas,
horizontally and vertically (Figure 17(d)). The pros of fish
bone injection are that it distributes sequestered CO2 gas to
different vanes of pores for hydrate formation.
Alternatively, CO2 injection can also be done on the seabed
by using three injection profiles, namely, (1) vertical injection,
(2) horizontal injection, and (3) distributed injection. The
vertical and horizontal injection schemes are less preferred, as
they create large mounds that may affect ocean currents. The
distributed injection profile is used to store CO2 in a
distributed manner without creating larger mounds, as shown
in Figure 17(e−g).
Global subsea drilling and transportation costs have risen
exponentially in the past few decades. However, the major
focus of current drilling and transportation techniques is to
reduce the overall cost of operation. The total cost of
transportation is majorly divided into three parts: (1) Capex;
V https://doi.org/10.1021/acssuschemeng.3c02336
(2) Opex; (3) Fuel cost. The majority portion of the total
expenditure during shipping is spent on covering operating
costs (Opex-43%), whereas only 30% and 27% of this cost is
spent on fuels and capital expenditure (Capex), respectively.173
The overall distribution of different cost segments in Opex,
Capex, and fuel cost is given in Figure 18(a). The cost
associated with CO2 capture, transportation, drilling, and
storage is a major concern for academia and industries. The
cost of transportation to offshore sites is higher than that to
onshore sites. Furthermore, the cost of per tonne CO2
transportation decreases drastically with an increase in mass
flow rate (MtCO2 yr−1), as shown in Figure 18(b).174 The
figure shows that a higher cost range is available for onshore
pipelines owing to a larger variety of material options than that
for offshore pipelines in 2005. The addition of newer emerging
materials of construction for pipelines in 2019 is further
widening the gap between the maximum cost and minimum
cost of pipelines, which effectively reduces the overall median
cost for CO2 transportation. The pipeline-supported trans-
portation is more cost-effective on land or for shorter
distances. Contrarily, ship-based transport is cost-effective for
oceans or for offshore transportation to the sequester site. The
onshore pipelines are more economical than offshore pipelines
due to corrosion and temperature and pressure stresses that
make materials and design selection tedious, as shown in
Figure 18(c).174 The transportation cost increased significantly
in last two decades owing to inflation in material procurement
and associated labor and construction costs. For offshore
pipelines, material requirements are stringent owing to
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

corrosive environment and transportation hurdles. For gaseous

(US$/tonne CO2net stored)175

CO2, pipeline-based transportation is the best alternative,

Ocean storage cost

whereas tank- or ship-based transportation is the most cost-
effective for liquid CO2. The fixed cost of pipeline-based

15.7

31.1

13.2
transportation is higher; thus, liquid CO2 transportation using
ships or tanks is preferred. The research community is now
considering three strategies for CO2 transportation to the
sequester site: (1) moving ship dispersion; (2) injection
through a floating platform; (3) injection by stationary fixed
pipelines. Estimates show that the cost of CO2 injection into

Ocean storage cost (US$/tonne CO2

shipped) (3000 m deep and 500 km
the sea (3000 m) to a sequester site 500 km away from the
seashore is 13.2 US$/tCO2, 15.7 US$/tCO2, and 31.1 US
$/tCO2 in the case of injection through a floating platform,

offshore distance)175
dispersion through ship, and injection through stationary
pipelines, respectively.175 However, the localized distribution

15.2

12.8
n/a
of the CO2 concentration into the sea is lower in the case of
moving ship CO2 injection to avoid a higher localized pH
decrease than by injection by stationary fixed pipelines. The
different costs associated with transportation, injection, and
storage are listed in Table 5.

■ CHALLENGES AND OUTLOOK

CO2 injection through stationary

CO2 injection methodologies

platform (CO2 tanker ship of

CO2 injection through floating
CO2 injection through moving
Hydrate formation in porous sediments is a stochastic process
and is difficult to control and predict. The chemistry of CO2
interactions with crystallite and sediments, pore water, and

80,000 m3 capacity)
salinity are vital to analyzing the full potential of current
understandings. The humongous CO2 storage potential inside
pores of sedimentary subsea basins makes it a front-runner

pipeline
among other sequestration strategies. Mimicking actual subsea
ship
conditions on a laboratory scale to understand the kinetics of
hydrate formation and the CO2 storage potential is difficult.
Furthermore, the cost concern associated with onshore capture
($/tonne CO2stored)174
Offshore storage cost

and transportation is a major roadblock. Studies show that a

minimum ∼500 m depth is required for possible solid hydrate-

50−100
12−16
range

based CO2 sequestration in oceans, considering that CO2

3−14

6−20

6-31
2−9

hydrate has a higher density than seawater and will sink over
time.178,179 The potential risk of ocean acidification during
Table 5. Cost Analysis of CO2 Transportation, Injection, and Storage

injection is another concern, as complete conversion of hydrate

from injected CO2 is not possible. However, re-emission of
Depleted oil/gas

Depleted oil/gas
Offshore storage

injected CO2 from oceans is unlikely, as 63% and 97% of

methodologies

field−reusing

reusing wells

carbonation
Ocean (ship)
formations

injected CO2 can be retained for 100 years at a sea depth of

(pipeline)
field−no

1000 and 2000 m, respectively. Furthermore, some studies

Mineral
wells

Ocean
Saline

show that 65% and 85% of injected CO2 remains trapped in

oceanic conditions even after 500 years. The fractional
retention of injected CO2 in oceans after years of injection is
Total 6500 km pipeline in
∼100 M tonne CO2/year

given in Figure 18(d).174,175 One estimate shows that 2000 and

>70 M tonne CO2/year

9200 Gt direct injections of CO2 are capable of reducing the

176

overall pH of the sea by 0.1 and 0.5 units. Direct injection

Capacity

beyond 2000 m is considered relatively stable, and depth

operation

beyond 3000 m offers an extra gravitational barrier to avoid re-

emission.175 Direct injection into the sea is not considered a
n/a

n/a

safe strategy for CO2 disposal, as the dissolution of CO2

reduces the pH of nearby regions. It is not advisable to directly
∼0.053 (by rail)
cost ($/tonne/
Transportation

inject CO2 into the oceans even if only a few marine animals
km)176,177

live below 3000 m and have a tolerance of 5000 ppm of

∼0.11 (by
0.02−0.04

0.03−0.08

CO2.175 However, local acidification may have a drastic effect

truck)

on marine ecology. However, hydrate conversion efficiency at

n/a

this depth is still unknown and lower hydrate conversion

efficacy results in the remission of unconverted CO2 gas owing
Transportation

dense phase)
(vapors and

Ships (liquid

to plume-up behavior. Even if we consider 50% hydrate

methods
Pipelines

conversion efficiency in the open sea, then 50% of uncaged

Tankers
CO2)

CO2 will contribute to local acidification of seawater. However,

sequestration beyond 2800 m sea depth is considered safer for
W https://doi.org/10.1021/acssuschemeng.3c02336
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
Figure 19. (a) CO2 storage capacity of different injection states. (Data taken from ref 184.) (b) Major challenges and outlook with CCS
technologies.
geological and volcanic perturbation owing to the higher
density of CO2 compared to seawater, which facilitates the
gravitational barrier against CO2 leakage. An alternative to
hydrate-based storage in the open sea, storage of CO2 in
subsea sediments, is the best viable solution for large-scale
sequestration without affecting marine ecology. Thus, the
hydrate-based CO2 storage (HBCS) techniques in subsea
sediments are a more benign approach to sequestering
anthropogenic CO2. However, HBCS techniques are still in
the conceptualization stage; however, some researchers are
scaling up the processes to technology readiness level (TRL) 4
and TRL 5 levels.180 Apart from this, scalability, cost cognate,
and design challenges make operation cumbersome at higher
subsea depths. A small-scale study shows that the sedimentary
basin in western Canada has a sequestration potential of 46 Gt
as hydrates.181
Sun et al.184 studied the effect of the injection state on CO2
storage capacity in a laboratory sand bed reservoir using a
double spiral tube gas injection system at the bottom of the
bed. They observed that 18.7 kg/m3 of CO2 can be stored in
the form of hydrates and 18.8 kg/m3 of CO2 can be stored in
gaseous form. However, they reported that the highest CO2
storage capacity (the mass of CO2 stored per volume of
reservoir, kg/m3) in the laboratory reservoir can be achieved
via supercritical (171 kg/m3) and near critical injection states
(114.3 kg/m3), as shown in Figure 19(a). The injection states
are never a concern for the scientific community; however,
associated costs and logistics issues make large-scale
implementation challenging. Apart from these challenges,
societal adaptability, lack of funds, and clear international
policies make adaptability of large-scale subsea sequestration
difficult, as shown in the infographic in Figure 19(b).
Technological barriers such as injection pore blocking, gas
dispersion barriers, subsea drilling, and operational challenges
in subsea sediments still need to be solved. Other than this,
CO2 injection losses due to reduced permeability during
operation and injection point clogging are a major techno-
logical barrier.55 Lack of proper funding mechanisms, CCS
regulations, and carbon pricing are some of the societal,
governmental, and economic hurdles in adapting HBCS
X https://doi.org/10.1021/acssuschemeng.3c02336
pubs.acs.org/journal/ascecg Perspective
technologies.39,185 The storage in subsea sediments is also
associated with preinjection costs such as sedimentary testing
(porosity, composition), depth feasibility, and subsea drilling,
apart from previously mentioned capture, transportation, and
injection costs. The use of artificial-intelligence-based models
may solve cost-cognate and logistic issues in subsea
sedimentary environments. The fluid behavior, interaction
kinetics, and hydrate growth mechanism in subsea sediments at
3000 m depth can be evaluated by these models. The public−
private partnership initiatives, support funds, regional CCS
corridors, and CCS knowledge centers can play a vital role in
overcoming societal and economical hurdles.
Indeed, studies of the environmental concerns of and the
effect of geological perturbations and volcanic eruptions on
HBCS are still not numerous, and these remain new avenues
for future developments. Nevertheless, gas-hydrate-based
sequestration has a huge industrial and academic potential;
more research is still needed to surmount design cost-cognate
and logistic challenges. Moreover, more feasibility and
economic viability studies still need to be performed to attract
investments in hydrate-based CO2 subsea sequestration
strategies.
■ CONCLUSION
Climate change, which is caused by aggravated carbon dioxide
emissions, is the greatest challenge facing modern society.
Almost all kinds of industrial operations release CO2, but the
composition of their emissions varies depending upon process,
feedstock, and energy requirements. Capturing CO2 directly
from the source industry is a more cost-effective way to deal
with tonnes of CO2 than direct air capture. Making industrial
clusters carbon neutral is of utmost importance to achieve our
climate goals.
Hydrate-based carbon sequestration (HBCS) in subsea
basins is ecologically sustainable and technologically possible.
However, economic, kinetics, and diffusion barriers present
challenges for its large-scale field implementation. The
technology readiness level (TRL) of HBCS technology is
currently between 4 and 5, and researchers are now focused on
the study of macroscopic parameters to reduce kinetic barriers
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Perspective

during hydrate formation. This Perspective gives insights into Biographies

the effect of the macroscopic environment (pore water
saturation, salinity, and organic matter) on the sustainable
chemistry of sedimentary interactions. The effects of long-term
CO2−sedimentary interactions on the permeability and
porosity of sediments have been additionally outlined. It has
been analyzed that reduction in IFT, salinity, and grain size
positively affects hydrate formation. The nature of sediments,
water saturation, and organic matter are also of crucial
importance. The nonswelling clays (Illite, kaolinite) do not
affect the hydrate equilibrium, whereas swelling clay (Na-
MMT) inhibits hydrate phase equilibrium owing to water Yogendra Kumar is a Prime Minister’s research fellow at the
activity reduction by interlayer cations. Organic matter Department of Chemical Engineering in the Indian Institute of
Technology (IIT), Madras. His research focuses on large-scale CO2
promotes hydrate formation in Na-MMT clays and inhibits capture and sequestration using nanoparticles and additives. He has
hydrate formation in the presence of Illite and kaolinite clays. published papers in reputed international journals and received the
HPCL New Generation Ideation Award. He holds an M. Tech.
Environmentally friendly nanoparticles and additives can be degree in Process Engineering from IIT Mumbai. His research
used in smaller fractions to foster hydrate formation kinetics interests include CO2 capture and sequestration, gas hydrates, process
intensification, and nanotechnology.
and thermodynamics. Surfactants usually reduce the kinetic
barrier during hydrate formation, whereas different nano-
particles have a distinct mechanism to affect hydrate formation
positively or negatively. Hydrophobicity and hydrophilicity
along with other surface features are crucial to identifying their
formation/inhibition behavior. The cost-based analysis of
HBCS technologies has been provided to aid newer insights
into this domain. Carbon sequestration can become cost-
effective, and associated environmental risk can be minimized
by choosing the right site for sequestration. This Perspective
discusses that systematic scientific research should be pursued
Jitendra S. Sangwai is a Professor of Chemical Engineering at the
for commercializing and storing CO2 as hydrates in subsea
Indian Institute of Technology, Madras (Institute of Eminence). He
basins within the appropriate economic and environmental has published about 165 research articles in peer-reviewed interna-
jurisdictions. tional journals and has several patents to his credit. He has been
recognized as the Top 3% Highly Cited Authors from India by the

■ AUTHOR INFORMATION
Corresponding Author
Jitendra S. Sangwai − Department of Chemical Engineering,
Indian Institute of Technology Madras, Chennai 600 036,
India; orcid.org/0000-0001-8931-0483;
Email: jitendrasangwai@iitm.ac.in
Author
Yogendra Kumar − Department of Chemical Engineering,
Indian Institute of Technology Madras, Chennai 600 036,
India; orcid.org/0000-0003-2353-5115
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.3c02336
Notes
The authors declare no competing financial interest.
American Chemical Society. He received the National Award for
Technology Innovation and the National Geoscience Award from the
Government of India for excellence in research and development.
■ ACKNOWLEDGMENTS
This work was supported by a Prime Minister’s Fellowship
(SB22230926CHPMRF008450). The authors have received
research and facility support from the Indian Institute of
Technology, Madras.
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