Progress in Energy and Combustion Science 93 (2022) 101026

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Progress in Energy and Combustion Science

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

CO2 hydrate properties and applications: A state of the art

Saeid Sinehbaghizadeh a, Agus Saptoro a, *, Amir H. Mohammadi b, *
a
Department of Chemical and Energy Engineering, Curtin University, CDT 250, Miri, Sarawak 98009, Malaysia
b
Discipline of Chemical Engineering, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa

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

Keywords: Global warming is one of the most pressing environmental concerns which correlates strongly with anthropo­
CO2 hydrate genic CO2 emissions so that the CO2 decreasing strategies have been meaningful worldwide attention. As an
Gas hydrate applications option, natural gas hydrate reservoirs have steadily emerged as a potent source of energy which would simul­
CO2 sequestration
taneously be the proper places for CO2 sequestration if the method of CO2/CH4 replacement could be developed.
Hydrate-based carbon capture
Cold storage
On the flip side, CO2 hydrates as safe and non-flammable solid compounds without an irreversible chemical
CO2 separation reaction would contribute to different industrial processes if their approaches could be improved. Toward
desalination developing substantial applications of CO2 hydrates, laboratory experiments, process modelling, and molecular
Hydrate promoters dynamics (MD) simulations can aid to understand their characteristics and mechanisms involved. Therefore, the
CO2 hydrate properties current review has been organized in form of four distinct sections. The first part reviews the studies on
Molecular dynamics (MD) simulations sequestering CO2 into the natural gas hydrate reservoirs. The next section gives an overview of process flow
diagrams of CO2 hydrate-based techniques in favour of CO2 Capture and Sequestration & Utilization (CCS&U).
The third section summarizes the merits, flaws, and different effects of hydrate promoters as well as porous
media on CO2 hydrate systems at macroscopic and mesoscopic levels, and also how these components can
improve CO2 hydrate properties, progressing toward the more feasibility of CO2 hydrate industrial applications.
The final sector recapitulates the MD frameworks of CO2 clathrate and semiclathrate hydrates in terms of new
insights and research findings to elucidate the fundamental properties of CO2 hydrates at the molecular level.

absorbed into the soils, terrestrial plants and dissolved into the ocean
1. Introduction which leads to altering the ocean chemistry like ocean acidification. This
phenomenon is being followed by detrimental effects on the environ­
Among the major contributors to global warming, CO2 accounts for ment like damage to aquatic habitats and marine ecosystems.
about 76% of total greenhouse gas emissions whereas the other partic­ There are different industrial gas emission sources such as the
ipants are CH4, 16%; Nitrous oxide, 6%; and F-gases, 2%, respectively. steelmaking industry, coal power plant, cement industry, refinery,
The mitigation of CO2 emissions in the wake of the Kyoto protocol to petrochemical industries, and so on, a sum of which accounts for
control CO2 in the atmosphere has become a critical objective. The approximately 75% of anthropogenic CO2 emissions. Estimations indi­
concentration of CO2 in the atmosphere since the industrial revolution cated that a range from 85% to 95% of this content can be eliminated
has been unprecedentedly increased from 280 ppm to a high of 410 ppm through carbon capture and sequestration & utilization (CCS&U) tech­
which has resulted in the 0.7◦ C global surface temperature rise. Addi­ nologies [3]. To date, several reviews have been presented to evaluate
tionally, the prediction of the intergovernmental panel on climate the details of CCS approaches [4–7]. Broadly speaking, capturing
change (IPCC) revealed that by 2100, the atmospheric CO2 concentra­ methods in the industry have been classified into post-combustion,
tion, global temperature, and sea level will have experienced further pre-combustion, and oxy-fuel combustion, whereas mainly industrial
increase up to 570 ppm, 2◦ C, and 38 cm, respectively, [1]. Thereby, separation methods have been distributed into four main technics:
evidence of CO2 catastrophic consequences indicates that CO2 capture, adsorption [8], absorption [9–11], membrane [12], and cryogenic [13].
sequester, or utilization methods are essential to be developed imme­ The process of flue gas treatment before being released into the atmo­
diately. Fig. 1 exhibits the carbon distributions released into the atmo­ sphere is known as a post-combustion in which feed gas consists of CO2
sphere, ocean, and land. As is shown, CO2 in the atmosphere is being ranging between 15% and 20% is being balanced with N2 and roughly

* Corresponding authors.
E-mail addresses: s.baghizadeh@postgrad.curtin.edu.my (S. Sinehbaghizadeh), agus.saptoro@curtin.edu.my (A. Saptoro), amir_h_mohammadi@yahoo.com
(A.H. Mohammadi).

https://doi.org/10.1016/j.pecs.2022.101026
Received 3 July 2021; Received in revised form 12 June 2022; Accepted 4 July 2022
Available online 17 August 2022
0360-1285/© 2022 Elsevier Ltd. All rights reserved.
S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Nomenclature CTAB cetyl-trimethyl-ammonium bromide

ENP ethoxylated nonyl-phenol
Acronyms DAH dodecyl-amine hydrochloride
GWP global warming potential DN2Cl N-dodecylpropane-1,3-diamine hydrochloride
IGCC integrated gasifier combined cycle HTABr hexadecyl-trimethyl-ammonium bromide
CCS carbon capture and storage/ sequestration NPE nonyl phenol ethoxylates
IPCC international panel on climate change LAE lauryl alcohol ethoxylates
GIIP gas initially in place SDS sodium dodecyl sulfate
HBGS hydrate-based gas separation SL sulfonated lignin
HBCC hydrate-based carbon capture SHS sodium hexadecyl sulfate
NGH natural gas hydrate STS sodium tetradecyl sulfate
InSAR interferometric synthetic aperture radar SDBS sodium dodecyl benzene sulfonate
MRI magnetic resonance imaging DMSO di-methyl sulf-oxide
13
CNMR carbon-13 nuclear magnetic resonance TMS tetra-methylene sulfone
COC cyclic organic compounds SWNT single-walled carbon nano-tube
CN coordination number MWCNT multi-walled carbon nano-tube
GHSZ gas hydrate stability zone Na-MMT sodium mont-morillonite
CSMHYD colorado school of mines hydrate SW-CNTs single-walled carbon nano-tubes
T/KHI thermodynamic/kinetic hydrate inhibitor SAMs self-assembled monolayers
T/KHP thermodynamic/kinetic hydrate promoter TMS tetra-methylene sulfone
LMGS large molecule guest substance EO ethylene oxide
G.C. gas consumption LHA leonardite humic acid
S.Fr. split fraction TMO tri-methylene-oxide
S.F. separation factor FA formaldehyde
COP coefficient of performance CB cyclobutane
LHTS latent heat thermal storage MWCNT multi-walled carbon nano-tube
CTES cold thermal energy storage THT tetrahydrothiophene
PCM phase change materials THF tetrahydrofuran
ZLD zero liquid discharge ACF auto-correlation of the fluctuations
HBPR hydrate-based pollutant removal AOP angular order parameter
GGS gas hydrate power generation system APDF angular probability distribution function
AIMD ab initio molecular dynamics CGMC grand canonical Monte Carlo
TiAAB tetra-iso-amyl ammonium bromide DFT density functional theory
HBPFD hydrate-based process flow diagram DWC dodecahedral water cluster
TBAPS tri-butyl-ammonium-propyl-sulfonate FSICA face-saturated incomplete cage analysis
TBAF tetra-n-butyl-ammonium fluoride HCACF flux autocorrelation function
TAAC tetra-amyl-ammonium chloride MCG-OP mutually coordinated guest order parameter
DTAC dodecyl trimethyl ammonium chloride MCG mutually coordinated guest
TBMAC tri-n-butyl-methyl-ammonium chloride MSD mean square displacement
TBANO3 tetra-n-butyl ammonium nitrate NEMD non-equilibrium molecular dynamics
TBAB tetra-n-butyl-ammonium bromide PMF potential of mean force
TBAC tetra-n-butyl-ammonium chloride OACF orientation auto-correlation function
TBPB tetra-n-butyl-phosphonium bromide QLD quasi-harmonic lattice dynamics
TBPC tetra-n-butyl-phosphonium chloride TCF time correlation function
MEG mono-ethylene glycol VACF velocity auto-correlation function
GdmCl guanidinium chloride RDF radial displacement function
NH4Cl ammonium chloride RACF rotational auto-correlation function
LAE2 lauryl alcohol ethoxylate-2 RPMD ring polymer molecular dynamics
[EMIM]BF4 1-Ethyl-3-methylimidazolium tetrafluoroborate RMSF root mean square fluctuation
[C8min] BF4 1-methyl-3-octylimidazolium tetrafluoroborate RPMD ring polymer molecular dynamics
PDMAEMA poly(di-methyl-amino-ethyl-meth-acrylate) MFPT mean first-passage time
Gly-zw zwitterionic glycine
DTACl dodecyl-trimethyl-ammonium chloride Subscripts & Superscripts
ENP ethoxylated nonyl phenol H hydrate
LABS linear alkyl-benzene sulfonate F feed
SDBS sodium dodecyl-benzene-sulfonate G gas
DBSA dodecyl-benzene-sulfonic acid W water
DTAC dodecyl-trimethyl-ammonium chloride n molar number
DTAB dodecyl-trimethyl-ammonium bromide

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

5% O2. The pre-combustion process refers to the capturing CO2 from use CO2 as feedstock. In urea yield boosting, to convert ammonia to urea
combusted fuel gas including CO2 and H2 with a proportion of about and produce additional fertilizers, CO2 can also be utilized [32]. Besides
40% and 60%, respectively. In this type of CO2 capture, the more the the aforementioned indirect CO2 utilization technologies, several direct
content of CO2 in the fuel gas, the higher the efficiency can be achieved. methods in various industries have also been suggested. Super critical
However, pre-combustion is more effective than post-combustion. Fig. 2 CO2 as solvent is one of them in which CO2 can be applied as a solvent to
displays diverse CO2 removal methods. isolate targeted entities and the production of active pharmaceutical
Once CO2 is captured, transportation, sequestration/ utilization steps ingredients (API) in the pharma industry [33,34] or extract bioactive
must be implemented. In this regard, different viable approaches for compounds from plant matrices in food, and cosmetics industry [35]. In
CCS&U have been suggested. The captured CO2 can be indirectly uti­ enhanced geothermal systems of the renewable energy industry, su­
lized in various industries. In carbon mineralization technology, CO2 percritical CO2 transfers geothermal heat to generate power through
reacts with industrial waste products or minerals to synthesize products turbines [36]. Enhanced coal bed CH4 [37,38] or oil recovery [39,40] in
with enhanced properties [16,17]. In the concrete curing process, CO2 as coal & energy and oil & gas industries are the other direct methods. For
a nonreactive limestone is stored within the concrete to cure precast the former, CO2 is injected into partially depleted coal seams to displace
concrete [18]. As a soil amendment and reclamation of aluminum and release the adsorbed CH4 to the surface; For the latter, CO2 is
mines, CO2 can be used to decrease the alkalinity of slurry from the injected into a depleted oil well to increase the pressure and reduce the
aluminum industry which is known as bauxite residue carbonation [19, oil viscosity. In the light of these methods, CO2 injection into the
20]. Also, to produce biofuels through algae cultivation, microalgae can geological formations such as depleted gas fields, and carbonate storage
absorb CO2 and then get converted into biomass fertilizers and proteins to activate oil and gas wells and production enhancement would also be
[21,22]. In the liquid fuels-methanol approach which is useful for the an interesting alternative. On this wise, the CO2 sequestration and en­
transportation industry, at moderate pressure and temperature, CO2 and ergy production can simultaneously be accomplished. Fig. 3 (I) sche­
H2 can catalytically be converted to methanol as fuel by themselves, or matically demonstrates the CO2 sequestration from the power plant into
be blended with gasoline [23,24]. In electrochemical activation of CO2 depleted gas reservoirs and synchronously enhanced gas recovery. This
using metal-free electrodes and metallic modified cathodes, diverse process is strongly dependent on the physical properties of CH4 and CO2.
reduction products via different reaction pathways can be formed, the As shown in the CO2 phase diagram of Fig. 3 (II), CO2 at supercritical
most substantial of which is formic acid [25,26]. In the Polymer­ conditions can prevail in gas reservoirs. However, limitations of
s/Chemical feedstock technology, by employing zinc-based catalyst CO2/CH4 mixing in the reservoir in terms of transport properties (i.e.
polymer, CO2 can be transformed into polycarbonates [27]. In the steel viscosity, density, diffusion coefficient, etc.) are substantial. As exhibi­
and paper & pulp industries, using basic oxygen furnace and pulp ted in Fig. 3 (III-a), the physical properties of CO2+CH4 mixture strongly
washing operation technologies, CO2 can be, respectively, applied as a correlate with CH4 mole fraction. The density and viscosity of the mixed
bottom stirring agent in basic oxygen furnace [28] and be used to reduce gases can reduce with the increasing amount of CH4 mixed with CO2.
pH during pulp washing [29]. CO2 can also be utilized for water Apparently, temperature has notable effect on the physical properties of
demineralization after reverse osmosis in the water purification industry CO2, but little impact on those of CH4 as is evident in Fig. 3 (III-b).
[30,31]. In chemical system processes to produce ester, sugar, alcohols, Albeit, the changes in dynamic viscosity and density at higher temper­
acetic acid, etc., a wide range of chemicals with O and C as elements can atures are smaller. It is worth mentioning, CO2 undergoes a large change

Fig. 1. Anthropogenic activities of the carbon cycle in the atmosphere, ocean, and land. (Adopted from [2] with permission of the U.S. DOE biological and envi­
ronmental research information system and NASA Earth Observatory).

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Fig. 2. Options for the CO2 capture and separation (data taken from) [14,15].

in density near its critical pressure. Large viscosity and density of CO2 To gain a deeper insight into the role and importance of CO2 hy­
relative to CH4 is the limitation of mixing both in the reservoir. These drates, this review is arranged into four separate sections: (1) in­
differences are relevant to the pressure. Indeed, the higher the pressure, vestigations of CO2 sequestration into NGH reservoirs (2) proposed CO2
the more the differences, especially beyond the CO2 critical pressure. hydrate-based process flow diagrams, suggested for different industrial
The mixture of supercritical CO2 and CH4 at constant volume may also applications; (3) benefits, drawbacks and different impacts of additive
cause the pressurization of the reservoir which could offset the benefits promoters and porous media on CO2 hydrate specifications at macro­
of the CO2 utilization. Some examples of coupling CO2 sequestration and scopic and mesoscopic levels to improve the properties of gas hydrates,
gas production are the injection of CO2 to the aquifer of the Sleipner field progressing toward the more feasibility of their applications; finally (4)
located in the north sea [41], natural gas exploitation at Nankai, Japan to highlight the potency of MD simulations in manifesting different as­
[42], and Mallik-Mackenzie Delta, Northern Canda [43]. With injecting pects of CO2 hydrates, molecular dynamic (MD) investigations limited to
CO2 after the field abandonment, approximately 10% of gas initially in the CO2 clathrate/ semiclathrate hydrates and revealed findings at the
place (GIIP) could be produced while in case of CO2 injection during the molecular level will be overviewed.
lifetime of the field, the amount of recovery in comparison with con­
ventional production may be reduced. 2. Natural gas hydrates (NGH)
To mobilize the microchannels, super-critical CO2 due to its great
adsorption capacity in unconventional reservoirs like shale has received Since several overviews on prospects and challenges of gas produc­
much attention. However, under reservoir conditions, the low viscosity tion from natural gas hydrates (NGH) as an energy resource have been
of supercritical CO2 as a fracturing fluid (0.03− 0.1 cP) may cause poor presented [49,50], the following Sections consider the experimental
proppant carrying capacity and suspended sand effect which influences investigations of gas hydrate deposits and replacement phenomena.
the production channels. It was demonstrated that a response of core
wettability alteration is the thickener of supercritical CO2 fracturing
fluid which would impede the oil flow during the fracturing process [45, 2.1. Clathrate and semiclathrate hydrates
46]. Hence, thickening agents and cosolvents e.g. surfactants, polymeric
viscosifiers, and salts are required to increase the viscosity and thicken Clathrate hydrates are ice-like materials that can be formed where
the CO2 [47]. Currently, no compound as a thickener can be precisely water molecules as host in contact with guest gas species at prevailing
utilized and it is still in the process of exploring environmental and pressure-temperature conditions generate a crystalline lattice. Clathrate
efficient materials e.g. ultrashort and nanofibres [45]. hydrates are categorized into three types. Structure I, which can be
Worth highlighting for the case of CO2 sequestration through gas usually formed by small guest molecules (with a molecular diameter of
replacement in the natural gas hydrate (NGH) fields, the characteristics, 0.4-0.55 nm); structure II, which requires larger guest molecules (0.6-
and mechanisms of this process should comprehensively be compre­ 0.7 nm); and structure H, which needs small guest molecules (as a help
hended. Also, to cut down the risks, energy penalties, and costs associ­ gas) like those which form sI and large molecule normally liquid hy­
ated with CCS&U techniques, or even find new approaches, a broad drocarbons (0.75-0.9 nm) simultaneously. There are, however, some
range of processes have been suggested. In this regard, hydrate-based exceptions such as very small guest molecules like H2 and N2 which form
CO2 utilization for different technologies has recently received world­ structure II clathrate hydrates, and also intermediate guests that
wide scientific attention, and subsequently different hydrate-based generate different structures (sI or sII) depending on pressure and tem­
CCS&U processes for industrial applications have been developed/ perature conditions [51]. Besides the clathrate hydrate family, some gas
proposed. Recently, to utilize natural gas hydrates as an energy resource, species (e.g. H2S, H2, N2, CO2, CH4) in the presence of
CH4 hydrate R&D in Japan in the context of Japan’s evolving energy tetra-alkylammonium salts/halides (e.g. tetra-nbutylammonium bro­
policies was examined [48]. mide (TBAB), tetra-n-butyl phosphonium chloride (TBPC), and bromide
(TBPB), tetra-n-butylammonium chloride (TBAC)) can form

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 3. Schematic of a coupled CO2 sequestration and enhanced gas reservoir for the power plant (I); phase diagram of CO2 in the natural gas reservoirs (II); density
and dynamic viscosity of CO2+CH4 mixtures at 303.15 K (III-a). Effect of temperature (III-b). (Reprinted from [44] with permission of ACS).

semiclathrate hydrates [52,53]. In comparison with the clathrate hy­ magnitude greater than worldwide conventional natural gas reserves
drate family, the key feature of these crystals is their thermal stability at which were determined about 196 × 1012 m3. Therefore, NGH reservoirs
atmospheric pressure or ambient temperature conditions. Two main could be a future source of energy and, in parallel, suitable sites for CO2
structures of semiclathrate hydrates (reported for TBAB-H2O) are types sequestration if the technology of CO2/CH4 gas hydrate exchange could
A and B [54–56]. The number of gas capture cavities per host molecule be developed. As an example, the capacity of the Alberta field for CO2
for sII, sH, and semiclathrate hydrates is found to be 0.18, 0.09, and sequestration in form of the gas hydrate was determined at about 46 Gt
0.06/0.08 (type A/B), respectively. Fig. 4 displays the configuration of [64] whereas enhanced CH4 recovery can at least offset the cost impacts
cages, and unit cells of clathrate and semiclathrate hydrates [54]. A unit of injected CO2 to those locations [65]. However, recent evidence warns
cell of sI, sII, sH clathrate hydrates includes structure I, 2 (512).6 (51262): of widespread destabilization of climate-sensitive. NGH might liberate
46 H2O; structure II, 16 (512).8 (51264):136 H2O; and structure H, 3 large quantities of CH4 which is nearly 20 times more potent than CO2 as
(512).2 (435663).1 (51268): 34 H2O, respectively. a greenhouse gas [66]. Fig. 5 displays the gas hydrates that exist in five
geographic sectors and their response to climate change. From right to
left, respectively, these sectors of the gas hydrates realm are: in an area
2.2. Ocean and permafrost hydrate deposits of gas seeps, a deep-water marine, across a generic upper continental
slope, shallow offshore subsea, and onshore permafrost. Except in
Evidence demonstrates a tremendous amount of natural gas in form permeable sand layers (depicted with coarser-grained texture),
of hydrate exists in marine and permafrost-associated sediments. A good ice-bonded permafrost and gas hydrate stability zone (GHSZ) sediments
example of this is the natural gas hydrate in the Alaska North Slope typically have low CH4 hydrate saturations [67]. The volume of seafloor
which was confirmed by different well-log analysis [59]. In this regard, gas hydrates is not major within the global reservoir, even so, they
researchers have revealed that gas reserves in the continental regions elucidate how migrate across the water-sediment interface. Worth
and marine sediments are approximately 1 × 1017 m3 [60]. In other highlighting that, seafloor gas hydrates, authigenic carbonates and CH4
investigations, however, this value was reported 3 × 1015 m3 [61] which seeps can be momentous habitats for chemosynthetic organisms reliant
was then verified based on drilling assessments [62,63]. Although there on CH4 for their metabolic processes.
is no consensus on the NGH estimations, this at least is an order of

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Fig. 4. Configurations of clathrate and semiclathrate hydrates. (Reprinted from [54,57,58] with permission of RSC, Wiley and Elsevier).

The concept of coupling both sequestering CO2 and CH4 production schematic diagram of the idea of the CO2/CH4 replacement mechanism.
can be achieved owing to the fact that the hydrate formation conditions Although depressurization between suggested approaches has been
of CO2 are more thermodynamically stable than that in CH4 hydrate. determined as the most economic technique, a combination of the
Furthermore, the formation enthalpy of CO2 hydrate is about 20% aforesaid methods would be a promising alternative. As an example,
greater than the dissociation enthalpy of CH4 hydrate. During produc­ thermal stimulation in conjunction with depressurization has been
tion and CO2 refilling pore space, it is expected to see that the hydrate successfully carried out in the Mallik field [75]. Also, a combination of
mechanical stability is kept constant. To date, a wide array of methods CO2 injection and inhibitors (methanol/ NaCl/ MgCl2) revealed that
has been created aiming at producing natural gas hydrate reservoirs methanol can accelerate the hydrate decomposition rate more quickly
which have been categorized into several mechanisms. The temperature rather than an electrolyte solution [76] which can markedly reduce the
rising toward the above hydrate stability zone (HSZ) is called “thermal stability condition of CH4 hydrate containing ice in the low permeability
stimulation”. In this case, different approaches such as electromagnetic of sediments [77]. In this case, CH4 hydrate cages after having contact
heating, fire flooding, and steam injection to the hydrate deposits may with CO2 will become unstable which probably results in decomposing
be used [68]. The pressure decreasing below the HSZ is also known as CH4 hydrate [78]. In contrast, CO2 molecules penetrate the decompo­
the “depressurization technique”. Injecting chemicals to make a change sition site, leading to the replacement of the CH4 molecules in the hy­
in pressure and temperature is so-called “chemical injection” [69]. The drate phase [79,80]. Theoretically, at a given pressure, CO2 hydrate
“gas swapping” method refers to flue gas or CO2 injection into formation can occur at a higher temperature, as much as 35◦ C, than
hydrate-bearing sediments. By injecting CO2/N2 (14.6/85.4 mole%) at what is required for CH4 dissociation [80] as depicted in Fig. 7.
typical gas hydrate reservoir conditions, over 80 mole% CH4 may be As shown in Fig. 7, the left side is the region in which CO2 and CH4
exploited [70]. The “Gas exchange” method is also referred to as the case tend to remain in a gas phase whilst both guest molecules on the right
when CH4 in the hydrate phase is replaced with CO2 in the gas/ liquid side of the curves tend to remain in the hydrate phase. The region among
phase [71]. The replacement can also be implemented by a mixture of both curves is where the thermal balancing method can be practical. The
CO2+H2. Recently, novel NGH exploitations approached by either higher steeper of the bottom line in comparison with the top line rep­
CO2+H2 continuous or semi-continuous injection-production modes resents that the kinetic rate of CO2 hydrate is more than that of CH4
accompanied by H2 generation were proposed [72,73]. Fig. 6 shows the hydrate [80].

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Fig. 5. Schematic of CH4 hydrate dynamics and distributions in ocean and permafrost gas hydrate deposits. (Reprinted from [67] with permission of Wiley). White
material beneath mussel-coated carbonate rock shows the presence of NGH on the seafloor.

Fig. 6. CO2/CH4 exchange in the hydrate reservoir by either CO2 (left) [74] or CO2+H2 (right) [72]. (Reprinted with permission of Elsevier).

2.3. CO2 sequestration in reservoirs [86]. Since water migration in hydrate sediments is a determinative
factor that affects NGH exploitation, recently, a combination mode of
To sequester CO2 in reservoirs, geologic formation assessments such depressurization with continuous water flow in natural gas hydrates
as capacity, injectivity, trapping mechanisms, and confinement aspects sediment called “water flow erosion” has been proposed. This can
would be the initial steps of CCS projects. Given that, four trapping induce hydrate decomposition and take the advantage of using vast
mechanisms (structural, residual, dissolution, mineral) may cease the volumes of produced water [87,88]. Additionally, under the prevailing
migration of CO2 plume which acts on different timescales. Hence, thermodynamic conditions in the unlikely event of CO2 leakage through
leakages relevant to the mechanisms from the storage sites are the main the top seal overlying the CO2 injection goal, the CO2 can generate hy­
risk associated with every CCS project [81–83]. It was suggested that drate by reacting pore water. This implies that same as CO2 sequestra­
CH4 recovery and storing CO2 in hydrate reservoirs without disturbing tion in shallow marine aquifers, the CO2 hydrate self-sealing can be used
geological formation can be achieved by the usage of low dosage, for CO2 storage projects in permafrost settings. Technically speaking, the
bio-friendly, anti-agglomerate, and hydrate inhibition compounds [84]. key contributors of CO2 replacement efficiency for NGH would be the
Inhibitors like NaCl can also aid to increase the CO2 replacement process rate and volume of injected CO2 besides the P-T conditions [83]. The
by increasing the region existing between CO2 and CH4 curves, resulting water phase migration process on the exploitation of NGH hydrates can
in the more possibility of moving thermodynamic conditions farther increase the water permeability and local hydrate dissociation. The
from CH4 hydrate stability zone and ensuring the possibility of CO2 backpressure and seawater flow rate were also found to contribute to the
hydrate formation [85]. Morphological data on the dissociation kinetics final efficiency [89]. To analyse the phase transition and hydrate dis­
of the mixed CH4/CO2 hydrate in a porous medium showed that the tribution process in marine sediments, the nuclear magnetic resonance
multistep cyclic depressurization (MCD) method was found to improve (NMR) demonstrated that under the favourable pressure and tempera­
CH4 production and CO2 storage in bulk and unconsolidated coarse sand ture, high initial water saturation can be conducive to higher CO2

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 7. Phase equilibrium conditions of CH4 and CO2 [51].

storage efficiency. The pore water characteristics are barely influenced 2.4. CO2/CH4 replacement in NGH reservoirs
by the presence of chemical additives but the water conversion can be
improved by nearly 50% (0.15 wt% SiO2) and 25% (0.05 wt% SDS) over Since experimental studies on gas replacement can offset the short­
the pure seawater case [90]. An in-situ magnetic resonance imaging comings involved in the required knowledge for improving the mecha­
(MRI) displayed that the rate of hydrate dissociation in bearing sedi­ nism of gas hydrate exchange, conducting such laboratory exploration
ments for the sample with 23% saturation can be four times more than could be profitable. Experimental evidence confirmed the selective
38% saturation. Based on the saturation-permeability analysis, the replacement of CH4 by CO2 in which the CH4 average distribution co-
lower and higher hydrate-saturation samples were found to well-match efficient between gas and hydrate states was determined at approxi­
with the grain-coating and pore-filling approaches, respectively, [91]. mately 2.5 [98]. The CO2/CH4 replacement in sandstone core plugs was
During multicycle synthesis processes, the hydrate rate of the secondary also endorsed by MRI imaging [99]. Interferometric synthetic aperture
synthesis can be about 9 times higher than that of the primary stage radar (InSAR) verified that supercritical CO2 can be successfully
which proves the existence of the memory effect. CO2 molecules under sequestered with the aim of enhanced oil recovery [100] but by using
the primary synthesis mainly enter into small pores with a filling model, water injections during CO2 sequestration, the rate of hydrate formation
however, they occupy both small and large pores with a coating model can be upgraded [101]. Besides, at hydrate equilibrium conditions
as the secondary synthesis starts. For the pore filling model in the pri­ similar to the Alberta sedimentation, Canada, 40% to 60% of the original
mary synthesis, the earlier formed CO2 hydrate in large pores can pre­ water after injecting CO2 into a typical saline model reservoir sample
vent the water in small pores and participate in the formation of CO2 formed hydrate [102]. In the case of CO2 injection to the gas hydrate
hydrate whereas this blocking effect cannot be found in the coating reservoirs, CO2 breakthrough would be delayed by dissolving CO2 in the
model [92]. CO2 hydrate formation in the company of frozen quartz formation water resulting in 8% to 11% incremental recovery [103].
sands depicted that the decrease of particle sizes can increase the gas Also, under the same heating power, microwave heating showed a
storage capacities. For example, with particle sizes of 500, 380, and 250 quicker decomposition of gas hydrate compared to hot water heating
μm, the gas-storage hydrate capacity of 128, 144, and 153 L/L and the [104]. Worth noting that constructing an artificial impermeable CO2
conversion rate of 70%, 82%, and 91% can be attained [93]. Moreover, hydrate cap seals a large amount of CO2 and protects the geological
the hydrate saturation can affect the morphology of hydrate within stability of depleted CH4 hydrate zones [105]. The rate of replacement is
pores within which its increase would mechanically improve the stiff­ also related to different factors but a lower rate of injected CO2 provides
ness and strength of the sediments, leading to a decrease in the potential better sequestration in the reservoir. The 13C NMR spectroscopy after
risk of geological collapse. The morphology of CO2 hydrate during for­ the replacement process confirmed the presence of CH4 molecules in
mation is directly dependent on the sub-cooling. For example, by most of the small cages of structure II whereas just a limited amount of
increasing ΔTsub. from 0.9 to 5.4K, the crystal shape would be poly­ them was detected in that of structure I hydrate [106]. Captured CO2 in
hedral with facets, skeletal crystals, and dendrites [94]. Analysing the the hydrate phase is dependent on hydrate saturation and the
effects of acid dissolvable organic matters including lignin and protei­ temperature-pressure of the reservoir. Gas composition analysis of
n/amino sugars on CO2 hydrate formation showed that the existence of reformed hydrate after dissociation indicated a large proportion of CO2
such components on the seafloor would kinetically induce water trans­ which can slightly be varied by the temperature [107]. However, the
formation [95]. The self-preservation phenomenon of CO2 hydrate can replacement driving force is strongly affected by the differential fugacity
also help to reduce the risk of the geological setting for CO2 sequestra­ of components in the hydrate and fluid phases. The pressure of the
tion [96]. In comparison with pure water, the initial dissociation rate of injected CO2 is also another contributor that has a significant impact on
CO2 hydrate in the presence of silica gel powder, SDS, and a combination the replacement mechanism. For instance, in the case of structure II
of both can be reduced by 0.12, 0.12, and 0.16 mmole/min, respectively, CH4+C3H8 hydrate the more the injection pressure of CO2, the higher
[97]. the replacement rate and CH4 recovery [106]. Based on the other

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experimental results, the initial pressure has a slight impact on the rate analysis displayed that the rate of CH4 recovery can be increased by
of gas exchange but this rate tends to be reduced by decreasing the attacking N2 molecules on the CH4 hydrate. Subsequently, over 40% of
temperature. In the early phase of the CH4/CO2 exchange, the rate of CO2 from the flue gas by reaching the final pressure can be captured in
replacement is almost equal to the CO2 hydrate formation rate but the hydrate phase [114]. Compared to CO2+N2 injection, however,
gradually decreases in the later phase. There is no significant relation concentrated CO2 facilitates the formation of hydrate [115]. Injecting
between equilibrium conditions and the rate of gas exchange but the CO2 plus different fractions of N2 into the depleted reservoir demon­
fugacity difference between the formation of CO2 hydrate and decom­ strated that although pure CO2 was detected as a peak efficient from a
position of CH4 hydrate is a crucial factor. Also, increasing the hydrate long-term perspective, the addition of N2 enhances the hydrate forma­
saturation in the sediments grows the rate of replacement, and hydrate tion more quickly [116]. The inclusion of N2 can increase the CH4 re­
layers can remain stable once it occurs. Liquid CO2 can penetrate the covery from 64% to approximately 85% but the injection approach with
hydrate phase and simultaneously on the opposite side, CH4 can release. the aim of ocean storage needs pure CO2 (without N2) [71]. For the
Indeed, for CH4 hydrate with considerable free water in the reservoir, fracture-filled hydrate, the important factors of gas replacement are gas
CO2 injection in form of a liquid state is more favoured than the gas composition, hydrate morphology, and pressure [117]. Experiments
phase. Evidence elucidated that under excess water conditions, injecting suggest the maximum ratio of CO2 versus N2+CO2 in the hydrate phase
CO2 into hydrate sediments results in converting CO2 to either CO2 can be considered as optimum reservoir conditions [118]. In this
hydrate or mixed gas hydrate. This phenomenon may be associated with respect, CO2 composition ranging between 30% to 40% in the mixed
some negative implications. For example, the CH4 recovery can induce CO2+N2 gas injection may give the maximum recovery factor [119].
shrinkage and CO2 injection may result in swelling as well as perme­ In-situ Raman spectroscopy proved that structure and CO2 selectivity in
ability loss. Moreover, although researchers have confirmed the the case of CO2+N2 hydrate strongly depend on composition. For
CO2/CH4 exchange in the pore space and mechanical stability of the example, 1% to 2% CO2 in a feed forms structure II while ranging from
reservoir during a relatively short time [108], the rate of gas exchange 2% to 70% generates structure I with higher selectivity. Besides, the
over 24 h may not be considerable [109]. Attributed to wetting of the selectivity of 20% CO2 is about 2 times higher than this content [120].
unconsolidated-sediment during replacement, the combination of Based on the 13C NMR measurements during the replacement process,
hydrate-sediment ratio and thermal stimulation on the rate of CH4 re­ N2 and CO2 occupy the small and large cavities of sI hydrate, respec­
covery can be enhanced from 28% for a pure hydrate core to 82% for a tively, [121]. The spontaneous structural transition during the
hydrate-sediment core [110]. Since too much-injected CO2 gas in a short replacement process was also detected [71]. Researchers have shown
time may cover the original CH4 hydrate and block channels of the that, unlike pure CO2, the CH4 recovery rate for the case of mixed
porous medium, recognizing an optimized control range is required. CO2+N2 was found to become dependent on the pressure and balance
Although the influence of CO2 injection pressure affects the critical between CO2/N2 [122–124]. The increment of pressure to the above 8.5
boundaries for hydrate stability, increasing the CO2 injection tempera­ MPa for the case of CO2 results in changing contact angle from
ture exceeding the phase equilibrium of the CO2 hydrate induces higher water-wet to gas-wet whereas in the case of flue gas, with increasing
CH4 hydrate dissociation. Consistent with the core-shrinking hydrate pressure above 10 MPa, it can be changed to intermediate-wet [125]. In
exchange approach, it was established that under constant temperature, addition, a mixture of CO2 and N2 in contact with free water in the
the exchange rate may drop after a 5 µm layer. Therefore, the exchange reservoir is more favoured than pure CO2 injection [126]. The CO2+H2
progress can be blocked by the reformation of compact CO2 hydrate injection into the hydrate layer during the replacement and gas sweep
film. It was claimed that creating porous CO2 hydrate would overcome stages may also appropriately alter the stability condition of CH4 hy­
this annoyance [111]. CO2 and CH4 formation hydrates is also depen­ drate to higher accumulative production. However, with a higher mole
dent on P-T conditions along which the CO2 injection is performed fraction of H2, a higher accumulative gas production ratio but lower CO2
among the varying hydrate stability zones as shown in Fig. 8. Based on sequestration can be obtained. Therefore, the CO2 mole fraction ranging
the reported measurements, up to 52% and 71% CH4 recovery can be between 55% and 72% in the feed would be the optimal case that allows
achieved within the HSZ-I (permafrost) and HSZ-II, respectively, how­ the system to achieve the equality of captured CO2 and produced CH4
ever, high water saturation would diminish the recovery by 9.3% [112]. [127]. At the high flow rate of injection, the efficiency of displacement is
The presence of N2 can also boost the efficiency of the exchange slightly affected by the composition of the injected gas [72] while
mechanism [113]. For example, the ideal replacement efficiency of semi-continuous gas injection dramatically enhances the CH4 recovery
(CO2+N2) and CH4 was reported as nearly 85% [71]. A spectroscopic in the case of low CO2 concentration [73].

2.5. Summary of the section

Since in doing CO2/CH4 exchange in reservoirs, CO2 hydrate prop­

erties would be the central contributor, their analysis has been the
critical objective of many types of research. In the light of this, the
following Sections present some CO2 hydrate characteristics.

2.5.1. Transport properties of CO2 hydrates

Rheology analysis of CO2 hydrate slurry to ensure an economical and
environmentally safe flow through HBCS&U facilities is of great
importance. To characterize the evolution of hydrate slurry during
emulsion, agglomeration, growth, deposition and after then, variables
such as relative viscosity as a function of shear rate/water conversion,
yield stress with different water-cut, change of fractal dimension with
time and shear rate/strain as a function of shear stress have been
measured [128–134]. In this regard, a high-pressure autoclave is an
alternative way to reveal the effects of hydrate behaviours on the slurry
viscosity e.g. agglomerate breakage, fractal dimension, and morphology
Fig. 8. CO2+CH4 hydrate phase diagram in three hydrate stability zones. [135]. By performing such tests, it was displayed that hydrate formation
(Reprinted from [112] with permission of ACS). steps are associated with a jump in viscosity [136]. During hydrate

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formation in the high-pressure flow loop, the slurry viscosity, and fric­ 2.5.3. CO2 solubility and dissociation enthalpy
tion coefficient experience an abrupt increase from 50 mPa.s and 0.05 to The estimation of CO2 moles in the hydrate phase needs information
over 160 mPa.s and 0.45, respectively, as the water cut increases from on the CO2 solubility. Due to the greater solubility and diffusion rate of
60% to 100% [137]. Also, the nature of the guest gas molecules (e.g. CO2 in liquid water, CO2 forms hydrate more quickly than CH4. Except
CO2, CH4) has little effect on the viscosity of hydrate slurry whereas the for the high-pressure range, the increase of pressure or temperature
addition of SDS with a concentration below CMC possesses a pseudo­ enhances the CO2 solubility in an aqueous solution [155], however, it
plastic behaviour. However, the impacts of production mode e.g. stirred can be reduced by the salting-out effect of semiclathrate components.
tank reactor associated with the flow loop on slurry viscosity was found For example, CO2 solubility for the case of 1 and 3mole% TBAB solution
to have several times higher than the presence of the additive [138]. The at 290K and 6MPa was estimated at nearly 0.6 and 0.7 mole% which
rheological studies performed on CO2 hydrate slurries in a dynamic flow shows the salting-out effect on the CO2 solubility at near hydrate for­
loop are presented in Table S1 of the Supplementary Materials (SM). The mation conditions would be less sensitive [147]. Also, the gas con­
temperature difference between the CO2 hydrate mixture and the sur­ sumption at induction time can be mainly caused by the CO2/CH4
rounding area can also significantly affect the continuous hydrate for­ dissolution ratio in the liquid phase [156]. Measurements of CO2 solu­
mation properties. The experiments demonstrated that pressure drop bility in liquid water, THF, and THF+SDS solutions at 2.8MPa and room
and heat transfer coefficient at various P-T conditions can be in a range temperature (1.3, 1.5, and 1.6 mole%, respectively) highlighted that
of 0.1 to 1 MPa and 54 to 2883 W/m2.K, respectively, [139]. Addi­ although the presence of THF may reduce the CH4 solubility in the water
tionally, increasing the volume fraction of CO2 hydrate slurry flow up to phase, it can improve the CO2 selectivity [157].
14% can enhance the Nusselt number and heat transfer coefficient by
nearly 2.5 times greater than that of liquid water [140]. 2.5.4. CO2 hydrate dissociation enthalpy
Dissociation enthalpy of CO2 hydrate systems as a working medium
2.5.2. Interfacial/surface tension and wettability would also be useful for hydrate applications. Using a modified Clausius-
To prevent CO2 leakage in geological storage, the interfacial tension Clapeyron equation, the dissociation enthalpy during phase trans­
(IFT) between supercritical CO2 and brine is critical. In addition, the formation from the hydrate to vapor and the aqueous solution of the
molecular interfacial properties and environmental conditions would be hydrate formers can be appropriately determined [158]. In this regard,
the main contributors [141]. Due to the lower entropy difference be­ the dissociation enthalpies of different CO2 hydrate systems are reca­
tween CO2 and CH4 hydrates, the imposed driving force for CO2 is lower pitulated in Table S3 of SM. As is evident, the decomposition enthalpy of
than that for CH4. Moreover, since the lower tension can reduce the sII and semiclathrate CO2 hydrates are considerably higher than sI or sH
barrier height, at the same subcooling, the CO2 barrier is lower than the CO2 hydrates.
one for CH4. It was estimated that the hydrate–water interfacial tension
for CO2 and CH4 are around 26 and 32 mJ/m− 2, respectively, [142]. 2.5.5. Effects of particle size
Conducted MRI study on the interfacial phase transitions of CO2 hydrate Identifying the factors affecting the stability of hydrate-bearing
also revealed that in terms of appearance, the formation morphologies at sediments, strength, and stiffness of deep-ocean sediments e.g. specific
the different interfaces with water (above and inside a water phase) are surface and shape of particles will increase the feasibility of performing
quite dissimilar. Hence, the morphological evolution of CO2 hydrate reservoir reformation by CO2/CH4 exchange [159–161]. The dis­
during formation and dissociation can correspond to a wide range of tribution/variation of hydrate particle sizes is also significant for the
relevant geometries encompassing a gas-water interface [143,144]. dissociation rate of HBCS&U processes. Generally, hydrate particles by
Additionally, a large number of nucleation sites and strong thermal forming a circular distribution law tend to locate near the pipe wall
conductivity of nanofluids can accelerate the gas dissolution by reducing region. Hydrate particle agglomeration can enlarge the particle size,
the surface tension and accelerating heat transfer during the hydrate further depositing to the pipe wall which is known as the segregation
formation [145]. The presence of surfactant molecules can also improve phenomenon [131,162]. It was indicated that the higher the initial
the water activity and water-to-gas contact, reduce the surface tension pressure of CO2, the higher the final conversion rate [163]. The effect of
and thus enhance the gas diffusion rate [146]. However, in an earlier sediment particle size on the mechanical properties of the hydrate res­
stage of hydrate formation, this property may block CO2 permeability ervoirs can also seriously affect the hydrate stability [164]. Uneven
into bulk water so that a low gas uptake can be achieved [147]. By distribution of pressure at the exploitation wellbore of hydrate-bearing
adding 100 and 500 ppm SDS to the aqueous solution, the interfacial sediments may produce the widespread gradation of sediment
tension at the gas-liquid interface can be decreased by 12% and 42%, matrices and lead to the failure strength of hydrate-bearing sediments.
respectively, [148] while by reaching the CMC, surface tension cannot On this issue, a bigger proportion of large particles in the sediment
significantly be altered [149]. Such additives may also increase the gas matrix, higher strain rates, and lower temperatures may be the main
solubility as well as diffusion coefficient in the liquid phase [150] and contributors to such engineering hazards [165]. The CH4 and CO2
drop the resistance of gas molecules for the entrance of the gas-liquid hydrate-bearing silty sediments possess similar compression and
interface [151]. However, in the salty environment, compounding swelling indexes. However, weaker contraction behaviours for CO2 hy­
non-ionic and zwitterionic surfactants cannot diminish the surface ten­ drate were recorded [166]. The accumulation mechanism of gas hydrate
sion [152]. An axisymmetric drop shape analysis also determined that is also relevant to the particle agglomeration which is a key parameter in
during CO2 hydrate formation, the increase of pressure significantly rheological models for optimizing fluid flow operations. The heteroge­
reduces the interfacial tension between CO2 and aqueous solution neity of the porous media induces water to be converted into hydrate in
whereas the temperature impact seems to be not substantial. The sum­ the larger pore spaces, however, the smaller particle sizes provide the
mary of surface tension between the CO2 hydrate systems and the so­ higher gas consumption as well as the formation rate [167]. In addition,
lution is presented in Table S2 of SM. It is worth noting that, at the initial the particle agglomeration by escalating the pressure drop can increase
stage of hydrate formation, the hydrate particles with the combination the risk of hydrate plugging. Particle video microscope probe and
of NaCl and MEG can be joined less tightly with each other. It may focused beam reflectance measurement probe unveiled that the hydrate
reduce the hydrate viscosity and boost the wettability of the solution on dissociation appears in 3 dissociation stages: agglomeration, breakage,
the wall surface through the adhesion of hydrates on the reactor wall and thorough dissociation [168,169].
[153]. The wettability of hydrate surfaces can also affect the hydrate
film growth and agglomeration in which increasing the annealing time 2.5.6. CO2 hydrate cage occupancy
reduces the hydrate surface wettability [154]. The fraction of CO2 adsorption into the cavities is of great impor­
tance for upgrading HBCS&U. Evidence suggests the occupancy of cage

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types is not the same. Gas chromatography and NMR analysis for gas mixture also plays a crucial role in gas separation through gas hy­
CH2+CH4 hydrate displayed that although the CO2 adsorption in the drates. The equilibrium phase diagram of diverse pure gas hydrates is
large cages (0.67) is more than that of CH4 (0.31), the CO2 cage occu­ presented in Fig. 9 which exhibits the lower stability pressure conditions
pancy in the small cages (0.1) is much lower than that of CH4 (0.66) for H2S, Xe, R134a, R-141b, and R22 hydrates compared to the CO2
[170,171]. Also, experimental pieces of evidence clarified that one hydrate are required. The equilibrium pressure and temperature ranges
S-cage type of semiclathrate with the maximum fractional occupancy of of H2 hydrate were reported 220-234 K at 180-220 MPa [189]. Hence, at
40% would be more effective for CO2 capture than the other S-cage type a certain temperature, the corresponding pressure formation conditions
[172,173]. Several parameters may contribute to the final occupation of of N2, H2, and CH4 hydrates are higher than that in CO2 hydrate. This
cavities. In the macroscopic measurement of CO2+TBAB semiclathrate, circumstance can be the basis for the HBCC/HBGS processes. Thereby,
the final volume ratio of CO2 to hydrate (v/v) and cage occupancy was CO2 enrichment by hydrate formation from the gas mixture can be
found to increase from 74.5 (v/v) and 57% to nearly 122 (v/v) and 94% attained. In this context, the higher difference between the hydrate
once the pressure was increased from 1 to 2 MPa. Meanwhile, the formation pressure of CO2 and other gas species in the mixture could
temperature increase was found to possess a negative impact [174]. The give greater separation efficiency. For example, at 276 K, the minimum
occupancy of CO2+CH4 hydrate by adding surfactants can also be pressure to generate pure CO2 CH4, N2, and H2 hydrates are about 1.8,
changed from 22% to nearly 28% [175]. 3.6, 22, and 366 MPa, respectively, [190]. Accordingly, it is expected to
see better performance for the mixture of CO2 and H2.
3. CO2 hydrate-based process flow diagrams
3.2. Hydrate-based CO2 capture (HBCC) approaches
As an environmentally friendly option, gas hydrates without an
irreversible chemical reaction have the potential to solve energy The processes of HBCC can be designed in form of single or multi-
resource-related issues. Since different CO2 hydrate-based process flow stages or combined with other approaches. The advantages of such
diagrams (HB-PFDs) or relevant applications for the aim of CCS&U in coupled techniques would be the lower costs or higher efficiencies
the industry have been designed, in this section, intriguing suggested compared to using standalone. As Fig. 10 displays, in the single-stage
HB-PFDs in the literature will be briefly overviewed. HBCC, the gas mixture at the first step is fed to the hydrate formation
reactor, followed by the routing to the separator to split the associated
3.1. Storage capacity and thermodynamic feasibility of HBGS residual gas from the hydrate slurry. At this stage, CO2 lean gas is
separated whereas rich CO2 hydrate is entered into the dissociation
Hydrate-based separation techniques mostly operate at medium reactor. Finally, by changing the operation condition where proper for
pressure ranges which can regenerate to separate gas mixtures via a hydrate dissociation, the trapped gas mostly CO2 is released to produce
unique mechanism [51,176]. Estimations suggest a fully loaded sI CH4 the rich CO2 [192]. Experiments have elucidated that the concentration
hydrate can store 170 volumes of gas (STP) per volume of hydrate [177]. of CO2 in the released gas is at least 4 times higher than that in the feed.
Also, the storage potential of sH CH4 hydrate was determined nearly 201 The X-ray diffraction pattern and GC analysis of the mixed sI CO2+H2
m3 which would be acceptable in comparison with the storage capacity hydrate formed from 80 mole% of H2 being in balance with CO2 showed
of LNG (600 m3 v/v at -160◦ C) [178,179]. However, according to the that the entrapped amount of H2 and CO2 in the hydrate phase are
recent evaluations of the gas to hydrate (GTH) method alongside five appeared to be 7.5 and 92.5 mole%, respectively, however, some single
other technically viable gas transformation technologies, this method or double H2 molecules were enclathrated in small cages [194]. To
may not be the best option for CH4 transformation [180]. Besides, due to capture CO2 (and H2S) from syngas which are derived from natural gas
the concerns about energy availability and increasing energy costs, one or integrated gasifier combined cycle (IGCC) power plants, the SIM­
of the major areas of renewable energy has always been H2 storage and TECHE conceived the low-temperature HBCC continuous process as
the hydrate approach could be a candidate [181]. On this subject, to illustrated in Fig. 11. Based on this diagram, CO2 and H2S in the syngas
verify the stability of the THF+H2 hydrate, the Raman spectra in the interact with water to generate hydrate. This is followed by the physical
THF+H2 hydrate (with 0.003 THF) at 255 and 70 MPa after 7 days separation of the associated H2 gas which cannot mostly be trapped by
showed no decreasing trend in the cage occupancy of H2 which implies hydrate cavities. Then, at elevated temperature, the hydrate slurry is
the proper stability and capacity of clathrate hydrates for the aim of gas melted to give acid gases and the water is recycled to the first step for the
transportation and storage [182]. next cycles. Ammonia refrigeration is also employed to cool the system
Application of hydrates in strong greenhouse fluorinated gases and control the formation/ dissociation conditions of the hydrate.
capturing has also been suggested. It is conceivable that the lack of in­ Regarding this technique, a novel set-up to reduce the energy con­
dustrial management of F-gases e.g. perfluorocarbons (PFCs), hydro­ sumption of CO2 hydrate using TBAB demonstrated that the CO2 sepa­
fluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), NF3 (17,200 ration factor and split fraction can reach 8.15 and 0.80, respectively,
times higher global warming potential (GWP) than CO2), and SF6 [195].
(23,900 times more GWP than CO2) without extreme caution results in The process of HBCC is sensitive to water saturation when the silica
unfortunate consequences as well as environmental risks [183]. To sand bed is utilized. It was experimentally demonstrated that the rate of
reduce the emissions of these gas species, different technologies such as water conversion to hydrate for the system inclusion of 100% water
liquefaction, adsorption [184], and membrane separation [185] have saturation in silica sand bed is approximately 3 times less than in the
been proposed, however, since most F-gases can form clathrate hydrates case when 50% water saturation is used [197]. Based on the experi­
at very low stability conditions, applying a hydrate method would be a mental investigations at the equilibrium condition of 274 K and 3 MPa,
safe alternative [186]. For a certain feed, the hydrate-based method the bubble method can change the rate of the CO2 separation from IGCC
recovers a higher concentration of HFC-134a than the liquefaction in which the ideal condition for gas flow rate and bubble size is 6.75
method and would be preferable for SF6 recovery [187]. Experimental mL/min/L and 50 micro-meter, respectively, [198]. The number of
evidence also showed that the hydrate phase can effectively separate stages is also a key parameter that must be optimized based on the
various F-gases from their mixture with N2 gas. In addition, experi­ components, operation conditions, and process specifications. For
mental evidence proved that CHF3 in the binary of CHF3 and N2 can be example, a decrease in the number of stages is not efficient for CO2 and
concentrated from 40% to above 88% by just one stage of hydrate-based H2S removal from natural gas while higher stages result in the loss of
capturing. Also, the separation of CHF3 from exhaust gas would be more valuable gas components like CH4, C2H6, and C3H8. In general,
effective when a hybrid method is employed [188]. three-stage for the case of capturing CO2 and H2S from natural gas [199]
The stability condition of different gas species that contribute to the or four-stage for CO2 enrichment from 17% in the feed to more than 90%

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Fig. 9. The equilibrium phase diagrams of different gas hydrates [186,189,191].

Fig. 10. Flow diagram of the HBCC processing unit (data taken from [193]).

Fig. 11. Block flow diagram of the SIMTECHE CO2 capture process (data taken from [196]).

would be the optimum numbers [200]. Also, for the continuous CO2 produced from the Sabatier process showed that depending on the
separation from CO2(40%)+H2(60%) at 277K via the HBCC method, the methanation efficiency, through different conditions, both of them tend
same stages are needed to be designed [201]. In addition, the partial to form hydrates [202].
pressure of gas species is the critical variable. The mixture of CH4/CO2 To improve the CO2 recovery and eliminate the remaining CO2 in the

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lean gas outlet from the HBCC plant, hybrid techniques have been the current hybrid process and three stages of HBCC (almost 99.4 and 95
suggested in which HBCC is coupled with the other conventional tech­ mole%, respectively) shows the proper performance of hydrate-based
niques (as shown in Fig. 2 e.g. membrane, cryogenic, absorption, or coupled approaches [207].
adsorption approaches). Fig. 12 depicts a hybrid hydrate-membrane To separate CO2 from flue gas, there are some porous materials e.g.
process where after three stages of CO2 enrichment, the membrane activated carbons with an acceptable selective adsorption ability [208,
separates the remaining CO2 content from N2. The CO2-rich gas for 209]. Within the range where hydrates form, through dispersing water
further process is also recycled into the first or second stages [203]. in these materials, CO2 can be captured by a cooperative effect of
Synergy analysis for post-combustion CO2 capture indicated that a adsorption and hydration [210]. Employing a hybrid adsorption− hy­
combination of hydrate-membrane separation technique decreases the dration method by dispersing 1.0 mole% aqueous THF solution into
energy consumption compared to their standalone processes. Also, by activated carbons (at 2.3 MPa and 274 K) showed a recovery value of
applying TBAB+DTAC promoters, the cost and energy consumption of 90.3%. For the adsorption part of this process, 4 activated carbons as
hybrid hydrate-membrane can be reduced [204]. dispersion media with diverse particle sizes need to be utilized to reach
As a well-established method, the cryogenic technique was patented the aforesaid recovery. Although the water content changes from 20.8 to
to purify the natural gas by condensing CO2. The combination of cryo­ 60.4 wt% cannot affect the adsorption process, excess water reduces the
genic and capturing CO2 in form of hydrate has been satisfactorily separation efficiency of the hybrid process. Also, recycling wet-activated
operated in the pilot phase [205] as schematically exhibited in Fig. 13. carbons did not display any sign of deteriorated working capacity for
In this regard, CO2 is condensed at 5.3 MPa and -55◦ C to remove 75 mole CO2 separation [211].
% of CO2. The residual CO2 with the addition of promoter forms the
synthetic hydrate at 5 MPa and 1◦ C which leads to reduce at least 7 mole
% of CO2. The benefits of the integrated cryogenic and hydrate method 3.3. Hydrate-based CO2 sequestration and vital component production
are the higher CO2 recovery, lower energy demand, as well as costs
whereas more than 90% H2 can be produced, and simultaneously So far, several hydrate-based processes for CO2 sequestration have
95-97% concentrated CO2 from the feed can be eliminated [205]. been conceived and some of them are in rapid development. Alterna­
Energy and exergy analysis between MEA-based CO2 separation and tively, the CH4 hydrate (from seafloors) could be fed to produce an array
HBCC processes exhibited that, the first law efficiency for the former and of vital industrial compounds. It was suggested that CH4 in form of
the latter is 88.19% and 74.15% while the second law efficiency is hydrate in the geological sites can be exploited on a floating platform
38.32% and 38.85%, respectively, [206]. In these methods, solvent and then reformed to produce H2. Since this process is endothermic,
regeneration and refrigeration processes are the major proportion of partial CH4 to supply energy demand needs to be burned. In the
energy consumption of these techniques. To reduce the costs imposed, reforming plant, CH4 combined with steam first passes to the primary
the continuous separation of CO2 from IGCC syngas using the HBCC in reformer which in the presence of a nickel catalyst (at approximately
conjunction with the chemical absorption method can be also used. In 800◦ C) can produce H2 and CO. The stream then routs to the CO shift
this case, the plant operates at least 30% lower cost than the cryogenic converter which operates at 370◦ C and uses an iron oxide catalyst. The
technique [196]. Fig. 14 represents the process flow diagram of the next is the separation stage using mono-ethylene amine (MEA) and
hybrid two stages hydrate/ MEA-based to recover CO2 from IGCC syn­ cuprous ammonia acetate (CAA) systems by which the CO2 and CO are
thesis gas. The positive aspect of this combination is to offset the low absorbed, respectively, and the outlet stream including H2 is passed out
efficiency of the third stage of HBCC which was replaced by the chemical to H2 storage [212]. The produced CO/CO2 from the platform is
absorption. The major benefits of this method are an increase in gas sequestered in the sea sediments where CH4 deposits. Fig. 15 exhibits the
consumption as well as CO2 selectivity. The content of H2 released from block flow diagram of simultaneous CO2 sequestration and H2 produc­
tion from the CH4 deposited site. By applying the current process, H2 as a

Fig. 12. A hybrid hydrate-membrane process for CO2 recovery from flue gas (data taken from [203]).

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 13. Process flow diagram for integrated cryogenic and hydrate CO2 capture (data taken from [205]).

Fig. 14. Flow-chart for two-stages hydrate/ MEA hybrid CO2 separation process (data taken from [207]).

valuable product without CO2 emission to the atmosphere can be employing cold thermal energy storage (CTES) and secondary re­
generated and then transported to the market [213]. frigerants supported by a closed refrigeration circuit. CTES refers to an
energy storage approach such as phase change materials (PCMs) and
chilled water which have become extensively applied technologies in
3.4. CO2 hydrate-based cooling systems space cooling with both solar sorption and electric-driven chillers. CTES
conserves cooling capacity by extracting heat from a storage medium
As the world becomes warmer, demand for cooling is expected to [214]. Because of the large storage capacity available in a phase tran­
soar in major developing economies. This may cause a surge in sition, among energy storage strategies, latent heat CTES is believed to
employing chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), and be superior [215]. In this regard, the melting enthalpy of pure CO2 hy­
hydrochlorofluorocarbons (HCFCs), which may hamper managing drate and ice is 507 kJ/kg and 333 kJ/kg, respectively, [216]. Stem from
global warming. To reduce the concerns, the refrigeration industry has the extra latent heat of CO2 hydrates and more thermal capacity in
been led to minimize the use of greenhouse F-gases and seek novel comparison with conventional coolants and commonly-used PCMs
systems of refrigeration that have a less destructive impact on the showed that they can appear to have obvious advantages and better
environment. One of the solutions researchers have suggested is

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Fig. 15. Schematic diagram of the combination of H2 production and CO2 sequestration (data taken from [213]).

energy efficiency over many other types of PCM [217]. Also, having TBAF) used under atmospheric pressure render them easier for cold
proper phase change temperature between 5 to 12◦ C, CO2 hydrates suit storage applications [219,220]. Operating temperatures above the
the characteristics of practical CTES air conditioning systems [218]. freezing point of water [221] and proper cold storage capacity lead
Using a process design with a combination of simultaneous cold and heat hydrate-based methods to be an environmentally sustainable candidate
storage, the latent heat of phase change resulting from the formation and for air-conditioning and refrigeration systems [222]. To develop a
dissociation of refrigerant hydrates can be converted into cold and heat hydrate-based secondary refrigerant, several studies have been con­
energies for air conditioning. In this design, the formation characteris­ ducted on the rheological and thermo-physical properties of hydrate
tics of CO2 hydrate and semi-hydrate plus promoters (e.g. THF, TBAB, slurry of CO2 in a flow loop [223,224]. More Recently reviews on

Fig. 16. Conceptual diagram of CO2 hydrate refrigeration system (data taken from [216]).

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

hydrates for cold thermal energy storage and transport aims have been 3.5. Hydrate-based effluent/ heavy metal separation, and desalination
presented elsewhere [225,226]. Fig. 16 shows the schematic of
hydrate-based secondary refrigeration. The system is charged by There is an interest in effluent concentration arising from zero liquid
gaseous CO2 from a tank gas followed by gas compression through a discharge (ZLD) operation as the ultimate technique for the prevention
compressor to pressurize a hydrate formation reactor. Once, the CO2 of pollution. In the pulp and paper industry, recovering clean water or
hydrate slurry is generated, it will be conveyed to the user via a slurry removing dissolved materials from the effluent is an essential part of a
pump. After absorbing thermal energy from the surrounding, hydrate is ZLD plant. Processes for water recovery can be carried out by membrane
dissociated into liquid and gas phases which can be separated via a separation, crystallization, and evaporation methods. In this context,
separator [216]. generating hydrate crystals followed by their physical separation and
Investigation of the effects of heat transfer fluid (HTF) temperature then melting formed hydrate has been suggested as a freeze concen­
on the charging and discharging processes showed that HTF temperature tration method [237]. Owing to the fact that CO2 clathrate [238,239] or
can enhance the discharge rate of CO2 semi-hydrates. Also, by varying semiclathrate [240,241] hydrate formers can generate hydrates near
the pressure of CO2 hydrate CTES, it offers an adjustable discharging ambient temperature (e.g. CP (295 K) [242] and TBAF (302 K) [243]) or
rate which is not available in other conventional PCMs [214]. Sub­ atmospheric pressure (at temperatures below 7.7◦ C) [244], the required
stantial subcooling increase and the external loop flow rate also play a energy is notably lower than that in crystallization method which
significant role in improving the hydrate storage capacity and the con­ operates at water freezing point. Also, these temperatures are not high
vection heat transfer between CO2 and water, respectively, which enough to cause loss of volatile components or corrosion scaling as is the
contribute to the effective charge of the CTES. The required chilled case with evaporation. In hydrate-based desalination (HBD) or
water temperature and the charged capacity of using “constant pres­ hydrate-based pollutant removal (HBPR) processes, water molecules
sure” are greater than that of using “constant mass” so that they are more encage the hydrate former molecules and generate the clathrate hydrate;
practical for cold storage systems [227]. The system composed of a so that salts and other impurities become excluded. Crystalline hydrate
hydrate slurry storage vessel and shell-and-tube fluidized bed heat can then be decomposed into potable water and the hydrate former is
exchanger to remove heat by circulating the hydrate slurry revealed that then recovered and recycled. The technologies of HBD are dependent on
the coefficient of performance (COP) and latent heat thermal storage the type of hydrate former. It has been suggested that C3H8 [245], CO2
(LHTS) can be 23% to 43% more than that of a conventional system [246,247], SF6 [248], cyclopentane [249], and refrigerant gases (HFC,
[228]. In addition, the increase of the initial pressure from 4.5 MPa to R141b, R134a, R410a, R507, R22) [250–252] have a potential for
6.0 MPa induces the hydrate growth, leading to 330% gas consumption effluent concentration and desalination. Results of dissociation behav­
growth. However, it nearly triples the induction time [229]. Although iour of brine on HFC-125a hydrate displayed that the existence of brine
up to 2.4 MPa, for higher pressure and temperature, CO2 hydrate for­ substantially affects the gas consumption, formation rate, and stability
mation occurs sooner with the shorter induction time, the increase of of HFC-125a hydrate. However, outcomes of the hydrate specimens
initial pressure from 2.4 MPa to 3.2 MPa decreases the charging time by using powder X-ray diffraction evidently showed no structural change
a factor of 3. With an initial pressure of 3.2 MPa, the maximum energy [250]. Because of the lower global warming potential of HFC-152a and
stored by CO2 hydrate slurries is up to 300% more than water which HFE-254 [253] than other F-gases like HFC-125a, HFC-134a, and also
allows users to decrease the size of the storage tank for the same amount relatively less hydrate equilibrium pressures, they can be an alternative
of energy [230]. Worth noting that the higher flow rate leads to the hydrate former for HBD. The experimental measurements revealed that,
formation of larger-size hydrate particles which increases the pressure despite 31% less initial driving force of HFC-152a compared to
drop by blocking the mass transfer between phases [229]. Despite a HFC-134a, it possesses higher hydrate conversion and formation kinetics
pressure drop (ΔP) in the recirculation of hydrate slurry due to its vis­ [254,255]. Also, the increase in subcooling may improve
cosity, it is possible to achieve ΔP lower than water. For example, by salt-enrichment efficiency. The energy analysis of the developed process
reducing the slurry flowrate and fraction to 25 kg/h and 8 wt.%, a flow sheet for producing freshwater for HBD highlighted that the salt
pressure drop can be two times less than water at 100 kg/h with higher content, water recovery rate, and hydrate former recycling would be the
heat exchange [231]. Also, there is a close relationship between the main contributors. Although the increase in water recovery rate from
system efficiency and types of working fluids. For example, the second 30% to 50% raises the total energy consumed by 40%, it reduces the
law efficiency of combined cooling and power system based on hydrate specific energy consumption (SEC) (total energy consumed/volume of
using pure R22 or R32 and mixed R22+R32 as working fluids were water recovered) by 18%. However, the rise of NaCl concentration from
determined 0.48 and 0.57, respectively, [232]. A recently proposed 10% to 30% can increase the SEC by 5% [256]. Since CO2 possesses a
process using CO2+TBPB hydrate demonstrated that adding vapor dual character, a coupled CO2 capture and HBD may become the right
compression for the management of vapour release (after the heat choice for both global warming and desalination [257]. A hybrid process
exchanger when the slurry and released gas enter a cyclone to separate for CO2 capture and seawater desalination is displayed in Fig. 17. In this
slurry from CO2 gas) can save up to 75% of the total storage volume regard, energy consumption, efficiency as well as process safety are
[233]. Besides, for the district cooling system of 51,600 refrigeration found to be the critical factors. Experimental investigations proved that
tons, applying the CO2+1.5 mole% THF hydrate slurry at 1.5 Mpa can the inclusion of CP in CO2 hydrate-based desalination can positively
reduce CO2 emissions by 20,684 tons per year. Accordingly, the COP of provoke the process [258]. As a candidate for desalination, commer­
11.55 for the cycle of hydrate cooling system can be obtained [234]. The cialization perspectives of CP have been discussed elsewhere [242].
COP for the current hydrate system under the formation pressure of 0.4 Using 3 mole% CP, nearly 60% of the NaCl from the feed solution after
MPa was also found to be over 7 [235]. Based on the service life of 20 hydrate formation and vacuum filtering can be removed [259]. To
years, the transportation distance of 10 km, and the cooling capacity of improve purification efficiency, if the vacuum-filtered hydrate crystals
5000 RT, the total life-cycle cost (LCC) consists of energy cost (EC), are subjected to centrifuging, washing, or sweating, the salt removal
maintenance cost (MC), and initial cost (IC) for the conventional district efficiency of 96%, 93%, and 95% can be accomplished, respectively,
cooling system (DCS) is 2 times more than the CO2 hydrate cooling [260]. Recently, hybrid approaches based on reverse osmosis (RO)+CP
system which indicates an economical superiority of the latter over the hydrate [261] and capacitive deionization (CDI)+CO2 hydrate [262] to
former [223]. For this case and by utilizing CO2+THF hydrate slurry, the improve desalination performances were proposed in which the former
COP can be up to 14.3 [236]. coupled process lowers the energy consumption whereas the latter im­
proves the ions removal efficiency.
Although a novel apparatus at the pilot phase for hydrate-based
desalination in the ocean were successfully tested, this technology has

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 17. Block flow diagram of the hybrid process for CO2 capture and seawater desalination process (data taken from [263]).

yet to be commercialized. To become industrialized, the main barrier is formation or the hydrogen bonds between water molecules. Therefore,
the challenge of separating hydrate-former from dissociated water the ionization of salts in the aqueous phase acts as a hydrate inhibitor
[264]. [278].
As a consequence of overconsumption or anthropogenic processes, Due to being potent greenhouse gases and the high flammability of
the quality of the groundwater or other water resources is receding at an HCFC, HFC, and CFC hydrate formers, they are not environmentally
alarming pace, the effect of which, trace amounts of heavy metals in acceptable. Gaseous hydrate formers like CH4 and CO2 also require
such resources are being increased. Besides, a large number of industries higher operating pressure and limited water conversion to hydrate
before adequate treatment, discharge their metal-containing effluents which is vital for maximizing freshwater recovery [279]. As a result of
into different environmental compartments. As a kind of salt, many the low hydrate formation pressure of CP and its immiscibility in water,
heavy metal ion solutions (e.g. selenium, zinc, cobalt, chromium, mer­ it could be very promising [242]. Recently, a hybrid process of
cury, nickel, cadmium, arsenic, lead) are toxic even at very low con­ hydrate-based desalination using CP and LNG cold energy to strengthen
centrations which harm human beings and environments [265]. To the energy-water nexus was successfully designed [280]. However, CP
remove heavy metal ions, the methods such as membrane [266], ion suffers from slow kinetics of hydrate growth in comparison with F-gas
exchange [267], adsorption [268], electrochemical [269], freezing/ hydrate formers. This restriction can be handled by the use of gaseous
thawing [270], and chemical precipitation [271] are some of the hydrate former (e.g. CO2) and kinetic promoters in conjunction with CP.
existing techniques. However, they carry different drawbacks. The as a result, gaseous guest plus bio-kinetic promoters induce the kinetics
negative aspects of using reverse osmosis (RO) and membrane in of hydrate growth and CP enhances the hydrate nucleation and lowers
nanofiltration, ultrafiltration, or microfiltration are a large accumula­ the formation pressure to milder equilibrium conditions [274].
tion of waste throughout the cleaning method, the requirements for
intermittent washing, and significant membrane pre-treatment support,
replacement, maintenance, scaling, and fouling of the membranes. 3.6. Concentration or preservation of food through gas hydrates
These may incur massive capital investments. In the same vein,
multi-flash distillation can be an energy-intensive process. Also, the The products and by-products of the citrus industry play a significant
aforesaid technologies for small scale e.g. rural applications may be very role in the global economy. It was determined that in 2018, over 30
exorbitant [272,273]. As a green process, a hydrate-based method for billion litters of fruit juice were related to concentrated juices [281].
removing salt ions from wastewater without producing a sludge has However, the use of a wide array of conventional concentration methods
been suggested [274,275]. Experimental investigations showed that to remove water from fruit juices involves a high level of energy con­
HCFCs, HFCs, and CFCs hydrate formers such as R141b, R22, and sumption as well as equipment. In this regard, the evaporation method is
CHClF2 because of their proper thermodynamic stability (they can the one that has been applied to concentrate juices in many cases. To
operate under or close to ambient conditions), non-toxicity, and remove extra water from juices at a degree of concentration up to 85%,
immiscibility with water have a good potential to remove heavy metal energy between 180 and 2160 kJ/kg of water should be provided [282].
and salt in wastewater. In this respect, Raman spectroscopy analysis For volatile compounds (e.g. aroma) or substances like polyphenols, and
confirmed the removal efficiencies ranging between 88% and 91% for heat-sensitive vitamins, evaporation may impair product quality. The
Zn2+, Ni2+, Cu2+, and Cr3+ ions in water using R141b hydrate. Also, a membrane concentration method (MCM) is the other alternative but this
higher R141b–effluent volume ratio contributes to a higher yield of process technique is associated with the obstruction of the membrane
dissociated water and enrichment factor but lower removal efficiency stops which can lead to a high cost for maintenance and a shortening of
[276,277]. Based on analysing the controlling factors of R141b hydrate the membrane’s life. Alternatively, gas hydrate technology such as CO2
to exclude the heavy metal ions from water, the increase of initial hydrate in recent years has gained interest in the food industry [283,
concentration of Cu2+ from approximately 17 to 907 mg/L can improve 284]. Because of the low temperature and moderate pressure condition
the removal efficiency from 72% to closely 90% whereas changes the of CO2 hydrate and low energy consumption to concentrate juices by the
water yield from about 80% to 72.5% [277]. An explanation for this use of energy (approximately 252–360 kJ/kg of water), this approach
phenomenon is that electrolytes in an aqueous solution reduce water may be more innovative [285]. Regarding this, the presence of food
activity and prevent the linking of water molecules with hydrogen ingredients, juices, or sugars (e.g. glucose, fructose [286], sucrose
bonds. The ion-dipole interactions between water molecules and ionized [287]) have inhibitory effects on CO2 hydrate formation kinetics and
mineral salts become stronger than the van der Waals forces for hydrate equilibrium conditions. The preservation of CO2 clathrate hydrate in the
presence and absence of glucose or fructose (sugars) are different [288].

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

It came to light that under atmospheric pressure at 238-258 K, the emulsion to a pressure greater than 0.5 MPa should be flashed [301]. To
preservation of CO2 hydrate in the absence of those two monosaccharide store the produced CO2 hydrate desserts, vendor freezers and standard
sugars is higher than CO2 hydrate with the sugars. The significant factors home can be employed but to stabilize their packing pressure, a few
in the preservation of CO2 hydrate were found to be the occurrence of tenths of MPa more than a soda storage pressure must be used [302].
super-cooled water in the sample hydrate particles and the viscosity of The list of experimental investigations on hydrate-based utilization for
super-cooled sugar aqueous solution [289]. However, temperature and the preservation of different food types is presented in Table S4 of SM.
pressure are the key factors in the concentration process. The case of
tomato juice concentration using CO2 hydrate showed that tomato juice 3.7. Fire extinguishment using CO2 hydrate
can accelerate the CO2 hydrate formation rate. Besides, with increasing
juice volume, the dehydration ratio first reached up to 65% and then It was suggested that hydrates utilizing non-flammable gases such as
dropped to below 45% which indicated the insufficient mix of tomato CO2 can be employed as fire extinguishing agents. As previously stated,
juice and CO2 gas [290]. CO2 hydrate in the presence of orange and the dissociation heat of hydrates is comparable to or even larger than
apple juices manifested that the concentration factors in one concen­ that in a fusion of ice [222]. Simultaneously, because of the release of
tration step were determined between 1.2 and 2.2. Besides, high pres­ the non-flammable gases during hydrate dissociation in the combustion
sures e.g. over 4MPa can reduce concentration efficiency. Hydrate field, this phenomenon can control the flames by reducing the fuel
technology during the concentration of fruit juices can concentrate concentration and preventing the supply of oxygen. Additionally, the
betanin, vitamin C, carotenoids, and polyphenols. Due to the fact that amount of CO2 hydrate would be much less than that of a conventional
these components are too large to be part of the hydrate structure, the fire extinguishing method such as water spraying. Experimental evi­
remaining small amount of these substances in the hydrate phase is an dence indicates a flame from container liquid methanol with a diameter
influence processing, particularly concerning the separation technique of 90 mm can gradually vanish from its centre to the periphery when
[291]. Comparing hydrates of pure water and orange juice in the 10, 13 1.25g of CO2 hydrate reaches the flame. Also, for a methanol container
and 16 brix (the amount of solute sugar per 100 g of solution) showed of 50 mm diameter, the critical mass of both the dry ice and the CO2
that impurities in juice disrupt the gas entry into the water cages. This hydrate is 0.3g whereas the volume of gas released from 1 m3 CO2 hy­
lowers the pressure drop in the reactor, resulting in the final pressure drate and dry ice at STP are 122 m3 and 800 m3, respectively.
increase. Indeed, a higher Brix extends the induction time. For example, With increasing the size of pole flame to 100 mm, the required
nucleation time for brix=16 at 277K and 2MPa was determined critical mass of dry ice can be less than CO2 hydrate whereas the volume
approximately 3 min while it was less than that in brix=10 to 13. This of CO2 released from the critical mass of dry ice would be higher. This
behaviour is valid for the relaxation time but the initial hydrate for­ evidently indicated that a flame with less value of CO2 can be extin­
mation rate decreases with the increase of the brix. The interesting point guished if CO2 in form of hydrate instead of dry ice is operated.
is that, in the atmospheric pressure, the relaxation times for various brix Therefore, by taking the advantages of CO2 hydrate, it could be a good
and the pure water are almost identical [292]. Concerning the increase fire extinguishing agent [303]. According to the national fire protection
of feed pressure from 2 to 4.1MPa, the formation rate can be enhanced association (NFPA) standard, fire extinguishers have been classified into
by over 2.8 times [293]. At formation pressures and induction times 5 fire classes; Class A: Fires in ordinary combustible materials (e.g. cloth,
more than those required by the distilled water, xenon (Xe) in the coffee wood, plastics); Class B: Fires in flammable/combustible liquids or
solution can form hydrate but higher temperatures result in a larger size gases; Class C: Fires that involve energized electrical equipment; Class D:
of Xe hydrate [294]. With the increase of Xe gas dissolving in the so­ Fires in combustible metals (such as zirconium, titanium, magnesium);
lution and temperature, the concentration efficiency may become less and Class K: Fires in cooking appliances that involve combustible
[295]. Also, to prevent the deterioration of frozen agricultural products cooking media (animal oils, fats or vegetable). CO2 is ineffective at
(e.g. barley coleoptile cells), the freezing process can be replaced by Xe extinguishing Class A fires because it may not be able to displace enough
hydrate which can form inside the intercellular spacing of cells [296]. By oxygen to successfully put the fire out (Class A materials may also
employing ethylene hydrate for the concentration process, although smoulder and reignite). Therefore, CO2 hydrate has a class B fire rating.
orange juice slightly shifts the formation pressure of ethylene hydrate In challenging circumstances such as large fires in buildings or forests,
higher than pure water, the maximum dehydration ratio of 92.8% at CO2 hydrate in comparison with the fluid or conventional fire extin­
4.4MPa feed pressure can be achieved [297]. To suppress biological guishing agents (halon gases [304]) could be a suitable candidate.
activities such as respiration after harvest, preserving the freshness of However, the probable alternatives to supply CO2 hydrate fire extin­
vegetables and fruits is an important consideration. A method to extend guishers e.g. in-situ cooling need to be investigated.
the shelf life of these products is, reducing water mobility within the
living cell. Although, freezing process to inhibit the water mobility in the 3.8. Nuclear power plants using CO2 hydrate
tissues for food preservation is an effective method, controlling water
crystallization to prevent forming large ice crystals which bring about Evidence suggests a large amount of waste heat from nuclear and
damage to the tissues yet to be solved. In this context, the use of argon thermal power plants is being disposed into oceans, rivers, lakes, and air.
(Ar) and Xe hydrates as a means of maintaining the quality of fruits and On the basis of the heat generated by nuclear reactors, power plants
vegetables has been suggested [298]. For processing carbonated frozen typically have a generation end efficiency of between 33% and 35%
food using CO2 hydrate, the water to CO2 hydrate transformation ratio while over 60% of generated heat is being wasted. However, in a few
depending on the type of fresh produce are different. However, X-ray cases, such waste heat is used for seawater desalination, farm cultiva­
diffraction revealed the same crystallographic structure with pure tion, fish farming, etc. Since the location of large-scale nuclear power
crystalline [299]. Also, to carbonate the dessert or ice cream, some or all plants (NPPs) are not close to energy-consuming areas, the effective
of the ice can be replaced by carbonated frozen dessert (CO2 hydrate utilization and recovery of their waste heat is a critical objective.
dessert) which has greater CO2 concentration than carbonated bever­ Because small-scale organic Rankine cycle (ORC) power systems [305]
ages, as a result, it is useful for the strong perception of CO2 [300]. To and small temperature difference power generation using the Carina
form CO2 hydrate frozen dessert, a flash-freezing process was developed cycle [306] to convert the waste heat of NPPs into electricity are
which involves the combining liquid dessert with liquid CO2 at economically difficult to install, other technologies to obtain higher
high-pressure and then spraying the mixed fluids into a chamber at a conversion efficiency should be developed. Given that the efficiency of
lower pressure for being freeze. At this stage, the CO2 can evaporate the gas hydrate power generation system (GGS) is over 20%, it is capable
once absorb the heat of vaporization from the dessert mixture. To avoid of small temperature difference power generation with energy storage
ice formation, the mixture in fine droplets must be dispersed and the [307]. Recently, the performance of heat cycling with CO2 hydrate

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

[308] and controlling the power output of an expander using the Platteeuw [314]. Afterward, statistical thermodynamic models based on
expansion properties of hydrate dissociation [309] have been presented. this theory coupled with Kihara spherical-core potential function [315,
Fig. 18 displays the configuration of a gas hydrate heat cycle (GHC) 316], Lennard-Jones-Devonshire cell model [317–319], the effect of
where the waste heat is obtained from the condenser by an lattice stretching [320], the classical thermodynamic equations [321]
absorption-refrigerator (an absorption chiller). Indeed, the waste heat of and incorporating the spherical asymmetry [322] were established.
a pressurized-water reactor (PWR) is used as a heat source for the Fundamental details and extensions of aforesaid work were recently
dissociation mode of the GGS and the absorption chiller. Seawater is overviewed elsewhere [323]. The basis for various modelling of reaction
used for cooling the buffer tank of the GGS, reactors, and the condenser regimes of the CH4/CO2 hydrate conversion mechanism is the difference
of the absorption refrigerator. The cold heat of the absorption chiller in thermodynamic characteristics. In addition, to determine the prop­
provides a low-temperature heat source for the hydrate reactor. In the erties of CO2 hydrate such as enthalpy, diffusion coefficient, viscosity,
GHC system, CO2 gas fills a reaction vessel at an initial pressure of 3 and density of hydrate suspension in a solution, different models or
MPa. Cooling the reactor to -5◦ C for the formation mode reduces the correlations have been generated [324,325]. Since the latent heat of CH4
pressure of the reactor and buffer tank to 2.1 MPa while heating up to and CO2 hydrate dissociations are 427 and 414 kJ/kg, respectively, the
15◦ C for the dissociation mode increases the reactor pressure to 3.5 MPa. temperature of the injected CO2 to initiate the substitution reaction must
Released CO2 gas from dissociated hydrate after passing through a be such as to cause CH4 hydrate dissociation. The key parameters
generator changes the pressure of reactor and buffer tank from 3.5 MPa affecting this process were found to be the initial P-T condition, porosity,
and 2.1 MPa, respectively, to an initial pressure which provides the and hydrate saturation. Although thermodynamics imposes several re­
conditions for the next cycles. The proposed design showed that GGS can strictions on permissible parameters of replacement reaction, hydrody­
improve the power generation efficiency by 8.7% and the generation namics plays a major role in the process and injection regime. Similarity
end efficiency of the GHC can be over 40% [310]. solution analysis showed that the dissociation of the CH4 hydrate may be
suppressed by the high injection pressure. This may be caused by the
dependency of the thermal energy of the physical system and the initial
3.9. Hydrate acidic gases
temperature [326]. Broadly speaking, to explain the kinetics of hydrate
nucleation and growth, three key controllers have been introduced:
Same as CO2, there are several gas species like hydrogen sulfide
mass transfer resistance [327], heat transfer resistance [328], and the
(H2S), nitrogen oxides (NOx), sulfur oxides (SO2 and SO3), hydrogen
intrinsic kinetics of water-guest molecules to form crystals [329]. The
fluoride (HF), and hydrogen chloride (HCI), which can be dissolved into
proportion of mentioned resistances would be dependent on the oper­
water and provide an acidic solution. Most of the above components can
ation conditions and configuration of the hydrate formation reactor. For
often be found in natural gas. The presence of traces of such substances
example, using stirred reactors, the heat transfer resistance can be
despite purifying CO2 is unavoidable which changes the process of hy­
ignored [330]. Given that the combination of mentioned resistances
drate formation from both thermodynamic and kinetic aspects. For
may govern the growth rate, analytical/ numerical/ semi-empirical
example, unlike NO2, the presence of SO2 increases the conversion rate
models. By considering these controller mechanisms and the effects of
of CO2 hydrate formation [311]. Between different acid gas components,
fluid flow, several models have been developed [331]. To model the gas
SO2 and H2S are stronger hydrate formers than CO2 [312]. Also, due to
exchange in clathrates, a mathematical description for the
the high solubility of H2S in water, its presence can enhance the kinetics
non-equilibrium binary permeation of guest molecules based on the
of CO2 hydrate growth [313].
microscopic diffusive mechanisms was introduced. This model involves
two-stage processes in which swapping can be initiated by instantaneous
3.10. Modelling approaches of CO2 hydrates mixed hydrate formation, followed by a very smaller
permeation-controlled process [332]. Generally, hydrate distributions
To represent the many different properties of clathrate hydrates in within porous media can be categorized into three types: pore spaces
terms of thermodynamics, kinetics, thermo-physical/mechanical, and filled with hydrate lumps, grain coating, and grain bridging between
heat/mass transfer characteristics, prominent frameworks have been sand grains by hydrate. A proposed model to investigate the perme­
conducted. Historically, the development of phase equilibrium model­ ability decrease as CO2 hydrate forms in porous media confirmed that in
ling of the clathrate hydrates was started when the basic solid solution a case of CO2 leakage in the geological formation up to a depth where
theory named “clathrate solutions” was disclosed by van der Waals and

Fig. 18. Power plant with exhaust-heat recovery by CO2 hydrate heat cycle. (Reprinted from [307] with permission of Elsevier).

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

hydrate is formed, the hydrate suppresses or even block the outflow exergy analysis of CO2+THF/TBAB revealed that by increasing the ad­
[333]. An approach to explain the mechanical influence of generated ditive concentration from 1 to 3mole%, 10% of total electrical power
bubbles from the dissociation of hydrate-bearing particles moved consumption can be saved [343]. Moreover, a model in Aspen Plus
through the water on the drag force and boundary layer disturbance software was established to analyse the ability of two stages
showed that the released gas increases the interaction forces between a hydrate-based approach in purifying the biogas in the presence of 5wt%
particle and the water [334]. To improve quantifying the CH4-(N2+CO2) TBAB. By evaluating the variables such as the process reaction time,
exchange ratio and CH4 recovery, governing equations composed of handing capacity, energy consumption, and recovery factor, the energy
mass and energy conservation equations for the numerical simulation cost was found to be 0.36-0.39 kWh/kg biogas while more purity
were developed which determined that the CO2 concentration in the product gas for the lower gas-liquid volume ratio can be obtained [344].
range of 30-40 mole% can maximize the CH4 gas recovery factor [119].
Experiments indicate that a start-up of CO2 injection into depleted gas 3.12. CFD frameworks of CO2 hydrates
fields results in a highly transient flow phenomenon. Therefore, for
minimization of the risks associated with this case, a homogeneous A computational fluid dynamics (CFD) method has been established
relaxation model by considering the heat transfer between expanding to estimate the flux of hydrate formation/ dissociation in different en­
fluid, well layers, and gravitational field effects was proposed [335]. vironments e.g. porous media, subsea, and pipelines at a large/meso­
scale. These models have been developed based on the molar Gibbs free
3.11. Simulations of CO2 hydrates energy difference/ free chemical energy difference (Δμ) as the driving
force at different P-T conditions, flowrates, and concentrations [345,
In academia and industry, there are several reservoir simulators to 346]. On the basis of the finite volume method with unstructured mesh
predict gas hydrate properties. STOMP-HYD-KE simulator was devel­ and periodic boundary conditions, simultaneous analysis of momentum,
oped to study the kinetics and equilibrium of CH4/CO2 mixed hydrate. mass, and heat transfer for CO2 hydrate phenomena in liquid/gas phases
Using the CMG Starts simulator, the feasibility of storing CO2 inside the or homogeneous porous media have been carried out [347]. Analysing
hydrate stability zone below the seafloor can be examined. By applying the flow pattern of CO2 hydrate slurry determined that except near the
this simulator, nearly 61 Mt of CO2 by decreasing the reservoir pressure pipe wall, the mean viscosity of slurry flow, and pressure drop so that
to under the fracture pressure in deep-water aquifers can be stored. energy loss can be reduced with particle dissociation [348]. CFD simu­
However, the main limitation would be the breakthrough of CO2 which lation of the radial cross-section of the pipeline considering both hydrate
can be delayed by CO2 hydrate formation [336]. The third version of the agglomeration and hydrate breakage showed that hydrate particles near
STOMP family (STOMP-HYDT-KE) can be used to simulate the kinetics wall and center regions possess larger and smaller diameters, respec­
of mixed CH4/CO2/N2 ternary hydrates. For the hydrate-phase transi­ tively, [349]. To understand heat transfer and flow of CO2 hydrate slurry
tions, TOUGH + HYDRATE has the ability to use for both equilibrium in pipes, a coupled non-isothermal heat transfer and turbulent multi­
and kinetic models. The Computer Modelling Group (CMG) has also phase model by analysing phase transition, particle distribution, and
developed a geomechanical and compositional reservoir simulator mixture flow in COMSOL Multiphysics software was developed. A
named STARS. To simulate the conventional gas production from NGH two-dimensional CFD approach by coupling the energy, momentum,
reservoirs through the injection of CO2 and N2 into the hydrate, Mix3­ and mass equations for CO2 hydrate mixture in a tube specified that
HydrateResSim can also be applied. The MH21-HYDRES simulator has during flow even under high operational velocity, pressure drop can be
been employed to reproduce the behaviour of NGH hydrate e.g. hydrate linearly increased whereas CO2 hydrate particles were found to settle
dissociation/ formation in reservoirs. However, to characterize the down [350]. Due to simultaneous effects of variables such as hydrate
behaviour of hydrate in reservoirs, the coupled dynamic phase transi­ deposition onto the surface, forces (lift, gravity, drag, and adhesion),
tions and local hydrate dissociation processes need to be comprehended molecular diffusion, particle-boundary hydrodynamic, and colloidal
in more detail. By applying Retraso-Code-Bright (RCB) simulator pack­ interactions, slurry flow in pipes would be an extremely complicated
age, the rates of CO2 hydrate formation and dissociation process. In addition, the adhesive distance cannot be calculated from
under/over-saturation by implementing a non-equilibrium thermody­ theoretical considerations. In this regard, CFD models to simulate the
namic module were also simulated which verified that the hydrate forms behaviours of hydrate particle motion and dissipation in flowlines were
at stable conditions, so that gradually plugs the fractures [337]. The proposed [351,352]. Also, to study the hydrate aggregation, the
relationship between particle size, porosity, and permeability in hydrate CFD-DEM coupling method based on CFD and discrete element method
sediments by employing TOUGH2/EOSHYDR2 simulator showed that (DEM) using Fluent and EDEM software was performed [353]. In the
under a specific water saturation, higher porosity induces a larger water interest of better insight into the process of hydrate slurry as a Bingham
relative permeability and the percolation characteristics in hydrate can fluid, numerical simulation of slurry dynamics can be suitably incor­
be affected by reservoir composition [338]. The rapid increase and porated into the dynamic multiphase flow simulator named OLGA.
decrease in the rate of permeability decline can also be caused by the Although it is unable to precisely reproduce the dependency of hydrate
clogging and clumpy types of hydrate distribution [339]. Simulations viscosity in slurry flow and spatial distribution or mobility of particles,
focusing on combined CO2/N2 injection and depressurization from by coupling the semi-empirical population balance model (PBM) and
permafrost hydrate deposits determined that N2/CO2 injection with the CFD, such rheological patterns can be simulated [354]. CFD-modelling
concentration of 50mole% at 5MPa can result in the most CH4 produc­ investigations of CO2 hydrate slurry for optimizing HBCU aims e.g.
tion efficiency [340]. cooling systems as well as food industries would also be worthwhile. To
To simulate the process flow diagrams of HBCC&U technologies a analyse the degree of concentration of orange and apple juices inside a
number of process simulators (e.g. HYSYS, Aspen Plus, Pro/II, ProMax) bubble column with the utilization of CO2 gas hydrate technology, CFD
can also be applied. Since the wasted cold energy at the LNG regasifi­ calculations using Ansys software indicated that the juice concentration
cation terminals around the world has been estimated to be 830 kJ/kg process by more mixing the gas and liquid phases can be markedly
[341], this energy wastage could be prevented by utilizing it in devel­ accelerated once a bubble column is used [285].
oped cold recovery technologies. By applying HYSYS software and
mathematical programming it was highlighted that for an optimized 3.13. Summary of the section
hydrate-based seawater desalination process using LNG cold energy
(ColdEn-HyDesal process), the specific energy consumption with and The CO2 hydrate growth rate is the critical objective of developing
without considering hydrate former recycling can be 0.60 and 0.84 the HBCC&U technologies. In this context, controlling kinetic mecha­
kWh/m3, respectively, [256,342]. Energy consumption, sensitivity, and nisms, reactor types, and formation methods are found to be the main

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

contributors whereas evaluating the quantification of growth rate as stochastic processes can be described by the probability function to the
well as model development can help to establish their approaches. theoretical probability distribution function which is fitted with the
Moreover, to identify the improvements and limitations of HBCC&U induction time data for hydrates [359,360]. In the case of gas storage as
technologies, evaluating the efficiency, energy, and costs of these well as gas separation, lower induction time would be desirable but the
methods would be particularly favourable. The critical performances of issues associated with the kinetics of hydrate formation hinder the
HBCC&U technologies are also specified in Table S5 of SM. Since developing potential of hydrate-based approaches [361]. History of
emerging renewable and sustainable technologies have created a water, supercooling, and the interfacial area are also affecting variables
competitive circumstance, before being industrialized, hydrate-based of the hydrate growth. Evidence suggests the impacts of additives are
capturing (C), sequestration (S), or utilization (U) approaches (HBCC/ dependent on gas species [362]. Worth noting that reaching constant
S/U) must primarily answer to different challenges. Table S6 of SM pressure for gas mixture systems cannot be independently considered as
presents the sum of the main issues associated with HBCC/S/U a sign of thermodynamic equilibrium, and at the final pressure, further
technologies. changes in the composition of various phases occur [114].

4. The impacts of promoters on CO2 hydrates 4.2. The role of promoters on CO2 hydrates

Despite the benefits of HBCC technology namely the ease of recycling The major impediment to hydrate-based methods is the sluggish rate
aqueous phase and low energy consumption for hydrate dissociation of hydrate formation, which originates from the nature of hydrate in­
[355], there are several associated limitations such as high induction duction time. Also, the pressure of the system plays a crucial role in the
time and relatively high pressure operating conditions. Therefore, to separation efficiency and the formation rate [363]. Problems plaguing
address the restrictions, the solutions should be both cost-effective and the development of these processes are influenced by operating condi­
technically efficient. In this regard, focusing on energy efficiency and tions, formation pathways, guest molecule size, and formed hydrate
techno-economic analyses, process simulation, and optimization has structure. Constant interaction between gas and water is also extremely
been encouraged. To empower the current technology for commercial vital for incessant hydrate formation. In this context, the solution would
applications, rapid nucleation coupled with proper crystallization ki­ be the mechanical and chemical base. Mixing mechanisms e.g. gas
netics at convenient thermodynamic conditions are mainly demanded. bubbling [364], spraying liquid by a nozzle [365], electrostatic spraying
To this end, understanding the mechanism of hydrate growth with the [366], ultrasonic waves [367], stirring and agitating mechanisms [368])
utilization of thermodynamic and kinetic promoters at macroscopic, can help to break mass transfer resistance by increasing guest-host
mesoscopic, and microscopic levels would be the fundamental objective contacts, dispersing the gas into water, and continuous regeneration of
[356]. In this context, although, the impacts of some promoters on the water and gas at the interface, so as to guest molecules get rapidly
HBCC performance parameters of CO2 hydrate systems were previously absorbed into the water cavities. In the bubble method, due to the
analysed [357,358], more and different effects of single and synergic buoyancy force, produced bubbles rise up and burst in the liquid phase
thermodynamic and kinetic promoters on pure and mixed CO2 hydrates which brings about higher supersaturation. Indeed, bubbles provide
are still needed to be overviewed. This section considers the effects of all higher gas solubility in liquid through the more specific surface area as
aforesaid CO2 hydrate systems uncovered from experiential exploration. well as internal pressure [369]. Besides, the effects of configurations of
different impellers on kinetic analysis of CO2 hydrate formation showed
that Rushton turbine compared with other types possesses higher per­
4.1. HBCC performance parameters formance for interaction between liquid and gas in radial flow [370].
Employing water spraying in the gas phase and water and liquid hy­
The efficiency of hydrate-based CO2 separation is often described by drocarbon jets impinging to enhance the contact area have also been
five specific parameters: hydrate equilibrium pressure, hydrate induc­ favourably utilized [371]. Implementing these methods can reduce the
tion time, gas consumption (G.C.) or Gas uptake, split fraction (S.Fr.), or mass transfer resistance once the rate of dissolution by facilitating the
CO2 recovery and separation factor (S.F.) as formulated in equations contact area is increased.
below: The chemical alternative to upgrading the HBCC performance pa­
nHG rameters as well as hydrate-based utilization techniques is the addition
G.C. = (1) of promotion components which have been subdivided into kinetic hy­
nW
drate promoters (KHPs) and thermodynamic hydrate promoters (THPs).
nHCO2 The former type mostly boosts gas consumption, rate of formation, and
S.Fr. = (2) induction time whereas the latter induces the equilibrium condition.
nFCO2
However, the utilization of both types can affect the split fraction as well
nHCO2 × nGG2 as the separation factor. To date, plenty of additives have been identi­
S.F. = (3) fied, with the addition of which, CO2 forms different hydrate structures
nGCO2 × nHG2
at various kinetics and phase equilibrium conditions [51]. The structural
The G.C. is the number of moles of gas in the hydrate phase (nHG ) over transition or coexistence between sI, sII, sH clathrate, and semiclathrate
the number of moles of water in the solution (nW); nFCO2 denotes the hydrates may also occur which is related to both equilibrium conditions
number of moles of CO2 in the feed; nHG2 , nHCO2 and nGG2 , nGCO2 represent the and hydrate formers. The utilization of thermodynamic models can aid
molar numbers of other gas and CO2 in the hydrate and gas phases, to determine the hydrate phase equilibrium and structure of different
respectively. guest molecules [372–375]. Fig. 19 displays the list of additive pro­
The hydrate formation starts with dissolving gas in liquid followed moters which play a critical role in changing the properties of gas hy­
by a supersaturation stage before the formation of critical hydrate nuclei drates in the interest of hydrate-based capture, sequestration, and
in the course of the induction time. The next stage is the formation of utilization aims. Bearing in mind that the efficiency for each application
hydrate nuclei greater than the critical radii. The mass and energy of gas hydrates relies on the quantity of water transformed to hydrate
barriers at the interface of gas-liquid to form hydrate nuclei manage the and the kinetics of the hydrate formation.
nucleation process. Indeed, the induction time is called the period be­
tween the times when the system pressure is increased or temperature is 4.2.1. CO2 hydrates in the presence of a single promoter
lowered to the equilibrium T–P condition at the time of hydrate nucle­ To achieve more efficient separation with less energy consumption,
ation [57]. Based on classical nucleation theory (CNT), the behaviour of as is exhibited in Fig. 19, the behaviour of a wide variety of additives

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 19. the role of additives in the HBCC/S/U processes. (THI: thermodynamic hydrate inhibitor; KHI: kinetic hydrate inhibitor; THP: thermodynamic hydrate
promoter; KHP: kinetic hydrate promoter).

ranging from large molecular guest substances (LMGSs), semiclathrate, maximum capacity) if CH4 molecules occupy all the small and large
kinetics, nanoparticles, and nanotubes on pure and mixed hydrates cages one by one [376]. Researchers have certified that kinetic pro­
including CO2 has been experimentally examined. Empirical evidence moters such as activated carbon [377], synthetic surfactants [378],
showed that using dry water (silica-stabilized free-flowing powder) and carbon nanotubes [379], glass beads and porous silica [380], nano­
without any mixing, gas uptake with the capacity of 175 v/v in 160 min particles [381], and sand grains [382] through enhancing surface ac­
can be reached. This is quite close to the 180 v/v at STP (sI hydrate tivity can improve the gas molecules to resolve or disperse in the

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

solution. For instance, lowering the surface tensions of the solution af­ presence of weakly polar or non-polar promoters is dependent on the
fects the wetting, spreadability, and detergency in the system. Among dissolution characteristics between the different components in the
the three major types of surfactants (anionic, cationic, and non-ionic), system [398]. For a non-polar promoter or weak polar, the gas uptake
anionic surfactants are the most effective in enhancing the rate of hy­ depends on the dissolution characteristics among the different sub­
drate formation and/or reducing the induction time [383]. Between the stances in the system. Lower mutual solubility among the components
surfactants, the influence of non-ionic was found to be lesser, whereas, results in higher independence in which with small interactions, each
the cationic at low and high concentrations may show behaviour exactly phase has an equal chance to fill the hydrate cavities, leading to a
opposite to that of the anionic [384]. Experiments revealed that relatively high gas uptake. Regarding the exothermic and
non-ionic surfactant promoters are found to be better than the cationic thermal-inhibition properties of gas hydrate formation, researchers have
ones [385]. A higher degree of rate improvement in stirred and unstirred suggested the use of nanofluids (such as nano Al2O3, Ag, Cu, and so on)
configurations was observed by anionic surfactants. Under similar for­ with high thermal conductivity to promote gas hydrate formation. These
mation conditions, amongst the analysed surfactants, those having tiny particles by improving heat and mass transfers, providing numerous
longer carbon chain lengths were found to be required in substantially hydrate nucleation sites, decreasing the wetting angle and interfacial
lower concentrations to show a similar promotion effect of SDS [386]. tension of the hydrates can dramatically decline the induction time
The enhancing liquid-gas contact is the dominant mechanism of SDS as along with upgrade the gas consumption [400]. Although the larger
the surfactant promotes gas crystallization. The emergence of micelles in particle sizes of activated carbon (AC) can promote the CO2 hydrate
the liquid phase for SDS concentration over the critical micelle con­ formation with shorter induction time, the synergistic of AC and SDS
centration through dissolving guest molecules in the microdomains of compared to AC can increase the gas uptake more effectively [401].
SDS micelles (known as the domain mechanism) increases the solubility Thermodynamic promoters depending on the gas species, by changing
and removes gas diffusion hindrance into the liquid phase [387]. Con­ the equilibrium pressure of hydrate formation to lower stability condi­
centrations higher than 4–5 ppm SDS can change hydrate film at the tions also play a crucial role. An experimental equilibrium study of pure/
liquid-gas interface to hydrate layers on the reactor sidewall along binary of CO2 and SF6 proved the promotion potential of SF6 as dis­
which the hydrate layers then grow and the capillary force sucks the played in Fig. 20 [402]. This binary can be advantageous for the CO2
reaction solution to the hydrate surface to maintain liquid-gas contact sequestration aim.
continuously. The critical micellar concentration (CMC) for SDS was Some booster additives such as TBAB [192] and THF [403] act as
determined to be about 2350 ppm so that the higher concentrations can bifunctional promoters which intensely improve both thermodynamic
be chosen to investigate the effect of micellization on the formation of and kinetics of gas hydrates. Also, additives as a function of different
CO2 hydrate [155]. CMC with increasing the molecular size of surfactant concentrations mainly show dissimilar behaviours. The impacts of a
is decreased. For example, the CMC of SC10S, SC14S, and SC18S is 8600, single promoter on CO2 hydrates are recapitulated in Table S7 of SM.
665, and 86 ppm, respectively, [388]. The SDS can also alter the hydrate
morphology through adsorbing onto the bubble surfaces leading to the 4.2.2. CO2 hydrates in the presence of synergic promoters
hydrate formation in the form of heterogeneous structures [389]. The Despite some positive impacts of single promoters, more improve­
ion environment, carbon-chain, and headgroup of the surfactant struc­ ments in all aspects of performance parameters should be fulfilled. Be­
ture as well as hydrate surface property play a crucial role in the sur­ sides, the HBCC separation factor could not be evaluated through
factant adsorption [390]. This produces a proper wettability on the experiments in the previous section. Hence, to find a proper energy-
reactor sidewall which may cause upward hydrate growth toward hy­ saving and time-efficient path, investigations on the synergic influence
drate propagation [391]. Although most conventional surfactants from of additives like those in the preceding part which have proved them­
environmental aspects are not acceptable, the use of bio-surfactants (e.g. selves as effective promoters would be beneficial. In this regard, the
amino acids) possesses favourable characteristics such as better stability, coupled promoters can be classified into three kinds: KHP+THP,
lower cost, less toxicity, and biologically degradable. Generally THP+THP, and KHP+KHP. The combined promoters namely SDS (0.01
speaking, amino acids comprise amine groups, carboxylic acid, and a mole%) + THF (5.6 mole%) or SDS (0.01 mole%) + TBAB (0.1 mole%)
side chain, ranging from a polar alkyl chain (hydrophobic) to a negative which could be options for the HBGS field, were found to show proper
or positive charge moiety (hydrophilic) with their physical and chemical results with around 10 mole% extra water conversion compared to the
properties vigorously depending on the particular side chain. The existence of single THF, doubled the initial rate of hydrate formation for
dual-functional behaviour of amino acids and their role in CO2 capture single SDS and significantly increases the CO2 uptake [404]. Previously,
and sequestration have already been reviewed [392]. The first research the synergic CP+THF impact occurring in promoted CO2 hydrate was
which denoted the capability of natural amino acids (leucines) in pro­ analysed. THF and CP are five-sided cyclic ether and five-sided cyclo-­
moting CH4 hydrate at low concentrations (up to 1 wt%) amino acids alkane which show full and little miscibility in water, respectively. In
was reported in 2015 [393]. Compared to hydrophilic amino acids, addition, THF and CP are the most efficient pressure reduction additives
hydrophobic ones show stronger flue gas hydrate promotion capability but from a kinetics point of view, nucleation in THF often occurs rapidly.
[394]. In this regard, hydrophobic amino acids e.g. L-valine, L methio­ Researchers revealed that although CP+CO2 equilibrium hydrate data
nine, L-histidine, and L-arginine (3000 ppm concentrations) have near has less formation pressure conditions than THF+CO2 hydrate, the
similar promotion capabilities as SDS on flue gas [395]. These compo­ simultaneous utilization of CP (0.05 mole%)+THF (0.05 mole%) pro­
nents depending on their physical and chemical properties have also vides 20% enhanced thermodynamic promotion in comparison with CP
shown a large CO2 gas storage potential in the form of hydrates, even at similar temperatures [405]. Although CH4 hydrate is the same mo­
under a non-stirred configuration [396]. Recent experiments exhibited lecular structure (sI) as CO2 hydrate, the capillary phenomenon does not
that 78% water conversion, an average CO2 uptake of 114 v/v, and a occur during the CO2 hydrate formation with the use of SDS as it does for
significant decline of induction time with the utilization of only 300 ppm CH4 hydrate [388,406]. For such cases, researchers have suggested the
l-tryptophan can be attained [397]. It was also clarified that a higher inclusion of alongside materials, such as THF, porous silica, activated
increase of L-tryptophan concentration cannot result in significant carbon, and metal nanoparticles, to promote CO2 hydrate formation
additional improvement. Since strong polar ionic promoters quickly which would be highly effective [407]. The combinations of nano­
form dense hydrate layers, this phenomenon at the liquid-gas interface particles and surfactants have greater impacts on accelerating the hy­
hinders the gas diffusion from the gas phase to the bulk solution [398]; drate formation process than in the case of employing them separately
hence, polarity plays a critical role. It seems that most polar amino acids [408]. Under such circumstances, the obstacle to applying nanoparticles
such as serine, threonine, phenylalanine, and glutamine are generally in the industry is the difficulty of their separation for reusing them.
kinetic hydrate inhibitors (KHIs) [399]. Also, the gas uptake in the However, the magnetic field for the retrieval of magnetic nanoparticles

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 20. Phase equilibrium data of pure/binary CO2 and SF6 hydrates [402].

such as Fe3O4 would be a solution. The combination of nano CuO and exploring the effect of normal liquid (NL) and pre-cooling liquid (PL) on
SDS was reported to complete hydrate formation within 40 min with a H2+CO2+CP hydrate demonstrated that CO2 recovery of hydrate for­
storage capacity of over 170 v/v [409]. The induction time of hydrate mation in NL and PL systems can be 81.8% and 89.4%, respectively.
formation can also be reduced once synthesized copper nanofluids plus Although less H2 molecules can be enclathrated in the PL hydrate system
CTAB is included in the solution [410]. Non-metal nanoparticles and and higher CO2 concentration in the residual gas phase. The gas-liquid
nanofluids e.g. silica, activated carbon, carbon nanotube, and graphene ratios (GLR) would also be determinative in either S.F. or S.Fr. param­
oxide have also recently been introduced as impressive hydrate forma­ eters. Different CP concentrations in the H2+CO2+CP hydrate system
tion promoters which provide a large liquid-solid interface where the indicated that by the addition of 23.4 vol% and GLR=5/6, the 98.8%
hydrate can readily nucleate; They can also serve high heat transfer CO2 recovery value from IGCC syngas by just a single stage hydrate
efficiency [411]. Therefore, the coupling of the above-mentioned addi­ formation can be obtained. Meanwhile, X-ray diffraction and Raman
tives to elevate the efficiency of performance parameters would be the spectroscopy detected the presence of some H2 molecules trapped in the
desirable alternative. However, the combination of promoters may not hydrate phase. In the other case, the use of 3.0 vol% and the same GLR
always be effective. A good example of this is the R-134a+CO2+SDS brought about the 90.9% CO2 recovery with no captured H2 molecules.
hydrate in which although the presence of 2-8 mole% R-134a and SDS, Thereby, the last case plus the PL method would be the optimum sce­
respectively, decline the CO2 hydrate equilibrium pressure and the in­ nario for the current system through just a single HBCC stage [415].
duction time by several times, the addition of SDS to CO2+R-134a hy­ Cage analysis of CO2+H2+CP and CH4+THF hydrates highlighted that
drate unexpectedly does not affect the induction time [412]. To show in the presence of CP (C5H10) with a molecular diameter of 6.7 Å [416],
the more effectiveness of coupled promoters, Table S8 of SM summarizes CO2 molecules occupy both the large and small cages whereas the same
the impacts of synergic promoters on CO2 hydrates. result was not obtained for the THF (C4H8O) with the molecular diam­
eter of 6.3 Å [417] which only offers small cavities for the CH4 molecules
4.2.3. Mixed gas hydrates including CO2 in the presence of a single [398]. Therefore, the real mechanism and behaviour of promoters
promoter affecting the gas uptake as well as selectivity are not as straightforward
Single promoters can manifest their separation performances when as it seems. Since the behaviour of promoters in the existence of mixed
they are employed to come in contact with the mixture of gas hydrates. gas hydrates compared to pure CO2 is not the same, conducting such
Investigations of these systems can help to determine the key control­ experimental analysis can elucidate their potential. To understand the
lers. Explorations indicate that in the existence of 0.29 mole% TBAB, the influence of these hydrate systems, Table S9 of SM tabulates the impacts
CO2+H2 hydrate formation from the gas mixture can be instantaneously of a single promoter on the mixed gas hydrates including CO2.
accelerated by shortening the induction time to less than a second [413].
The comparison of gas uptake in the CO2+CH4+THF system at ΔP =2.5 4.2.4. Mixed gas hydrates including CO2 in the presence of synergic
and 4.0 MPa displayed that hydrate growth was improved as the driving promoters
force was increased whereas CO2 recovery was halved. This implies the To overcome the HBCC barriers which are associated with the sys­
hydrate phase traps more CH4 molecules with growing the driving force tems of previous sections, the effectiveness of coupled additives on
[157]. The induction time of CO2+N2+DMB sI or sH hydrate with mixed CO2 hydrates needs to be analysed. Such combinations have
various CO2:N2 compositions showed that as the CO2 concentration shown a higher capability relative to using standalone. For example, gas
grows, the induction time declines. Also, the total gas uptake of sH hy­ uptake for H2+CO2 hydrate in the presence of CP, TBAB, and CP+TBAB
drate is slightly better performance than that of corresponding sI hy­ at 275 K and 4 MPa were determined 0.03, 0.13, and 0.22 mole,
drate. Although the differences in sI and sH induction times are not respectively, [413]. Also, compared to the utilization of CP or TBAB,
substantial, the sH exhibits shorter induction times than sI once the CO2 their mixture can reduce the induction time of either fresh or memory
concentration in the feed is reduced [414]. Generally, a longer induction solution by at least 10 times. In the other case, the synergy of TMS and
time causes higher gas uptake. However, large variations in the amount TBAB declines the formation pressure of biogas (CO2+CH4+H2S) hy­
of that mostly originate from the stochastic nature which appears to drate by closely 80% and changed the induction time to less than a
markedly influence the induction time. For both sI and sH hydrates, the minute. Plus, the gas storage capability and gas consumed rate of 2 times
S.F. parameter reduces sharply as the N2 concentration increases; also, higher than TBAB can be obtained [418]. An experimental analysis
in terms of CO2 capture at CO2 compositions of more than 50%, the S.F. recently revealed that the combination of cyclooctane (as sH hydrate
in the sH shows gives higher performance than sI [414]. Recently, former) and L-tryptophan amino acid can enhance the water conversion

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

and gas uptake of CO2+CH4 hydrate by roughly 210% and 172%, of silica gel can act as a promoter in destroying the interfacial tension of
respectively. Also, the induction time can be dropped down close to zero water [434]. Although, emerging CO2 capture technologies is dependent
which denotes the power of combining promoters [419]. Researchers on being able to consistently and reliably grow CO2 hydrate in packed
have reported that the addition of SDS to CH4+CO2+TBAB hydrate media, kinetic data for CO2 hydrates at this length scale are not plenty.
system can reduce the time required to reach 90% of the total gas con­ In this context, conversion and propagation rates of CO2 hydrate
sumption (t90) and induction time by 25%. However, the CO2 separa­ through the microchannel were determined to be over 47% within 1 h
tion factor corresponding to the presence and absence of SDS were and 1000 mm/s which is approximately 5 times quicker than CH4 hy­
determined around 15.3 and 36.4, respectively. This may be attributed drates. This may be due to less enthalpy of crystallization for CO2 hy­
to the fact that hydrate cages trapped more CH4 molecules with the drate compared to CH4 [435]. The combination of porous environment
addition of SDS which implies that the coupled promoters may not al­ and promoters can also be profitable. For example, CO2+N2 hydrate in
ways be effective. Applying mixed promoters would also change the the presence of coupled TBAB+THF+glass beads showed a large CO2
final structure of the formed hydrate. For instance, the PXRD patterns for separation factor caused by little N2 enclathrated in hydrate cages [436].
the CP+TBAB+H2+CO2 identified two coexistence structures of semi­ The more pore size for the hydrate-based CO2+H2 gas separation in the
clathrate and sII clathrate hydrate [420]. To clarify further impacts of existence of THF+SDS+soda glass gives rise to the higher CO2 diffusion
such hydrate systems, Table S10 of SM reports the experimental and gas consumption [437]. To elucidate the influences of porous media
outcomes. on CO2 hydrates, Table S11 of SM summarizes the experimental out­
comes of such systems.
4.2.5. . CO2 hydrates in the porous media
The porous media like (clay, zeolite, silica, quartz sand) exhibits 4.3. Summary of the section
various characteristics which significantly impress the hydrate forma­
tion mechanism. The main factors affecting the kinetics and thermo­ The proportions of pure and mixed gas hydrates including CO2 in the
dynamics of hydrate formation by using a porous medium are particle presence of single or synergic promoters studied in the literature are
size, bed height, water saturation, permeability, and Porosity [421]. The presented in Fig. 21. As is shown, the largest percentage of experiments
effects of pore and particle size on the process of CO2 hydrate formation has been focused on CO2+single promoters. The experimental analysis
have been discussed elsewhere [422]. Depending on the amount of of the mixed gas hydrates with the utilization of synergic promoters and
water content, liquid distribution within the bed exhibits diverse con­ porous media needs to be further investigated.
figurations which determine the gas flow and liquid-gas interaction. Table S12 of SM also exhibits the classifications of empirical explo­
Moreover, sufficient bed saturation results in efficient hydrate forma­ ration that have been carried out to realize the effects of different pro­
tion. Usually, a larger surface area of media leads to higher gas con­ moters on pure and mixed CO2 hydrates. As shown, more analysis for the
sumption and hydrate formation. However, the main difficulty of using synergic promoters + mixed gas hydrate systems should be imple­
porous medium is the separation of porous medium from hydrate. In this mented. More importantly, since cyclodextrins as nucleation promoters
regard, many experiments have precisely evaluated the CO2 hydrate for accelerating hydrate formation have recently been introduced [438],
systems surrounded by porous media or in the sediments. It was proved investigations on such eco-friendly or green promoters could be the
that liquid CO2 in the porous media can spontaneously be converted to priority in future research. Since comparing the effects of promoters on
hydrate but mass transfer limitation of CO2 sequestration at the field CO2 hydrate may be beneficial, Table S13 of SM summarizes the per­
scale plays a significant role. The Joule-Thomson effect of the water formance parameters of the aforesaid systems. Also, the influences of
zone in the near area of the well and the sealing mechanism near the gas promoters on CO2 hydrate in terms of induction time, thermodynamic
hydrate stability zone (GHSZ) are some of the flow hindrances of liquid improvement, and gas uptake is exhibited in Fig. 22. It is worth high­
CO2 sequestration in the reservoirs. Also, applying emulsion of CO2 in lighting that to store CO2 in the hydrate phase, a theoretical sI hydrate
the porous media is more favoured than liquid CO2 for CO2/CH4 capacity (CO2⋅5.75H2O) can be up to 425 mg/g (174 mmoleCO2/
replacement. Free water in the pores of sediments also affects the moleH2O) [439].
replacement rate in which after 120 h, about 80% of the formation water Kinetic performances of different promoters on mixed CO2+CH4/N2/
originally in the reservoir can form CO2 hydrate [423]. On this subject, H2 hydrates are tabulated in Table S14 of SM. Based on these experi­
pore-filling of CO2 hydrate at different saturations of water was ments it can be concluded that the variables such as optimum concen­
acknowledged. Besides that, replacement efficiency conspicuously de­ tration of promoters as well as P-T conditions, the driving force
pends on the temperature and the rate of CO2 injection whereas gas (subcooling), gas to liquid ratio (GLR), and fresh or memory condition of
mobility plays a major role in the process of CO2/CH4 hydrate conver­ the sample have the most important influences on the performance
sion. However, the concentration of brine water can delay the growth of parameters of HBCC. With reference to Tables S13 and S14 of SM, the
CO2 hydrate in sediments [424]. Apart from that, to upgrade the effi­ maximum enhancement of THP, KHP, and THP+KHP in comparison
ciency of HBGS processes, new approaches to improve the liquid-gas with the absence of these components is shown in Fig. 23.
contact such as the use of fixed bed reactors with porous medium, flu­
idized bed, and slurry bubble columns in recent years have been sug­ 5. Molecular dynamics simulations of gas hydrates
gested [425,426]. The most proportion of investigations on gas hydrates
in the porous environment e.g. aluminum foam [427], metallic packing As a computational framework in the fields of science and engi­
[428], silica gel [429], polyurethane foam [430], glass beads [431] has neering, molecular dynamics (MD) simulations have received attention
been focused on kinetics as well as the storage capacity of gas hydrates. due to their power in calculating the details of motions of individual
The higher gas uptake and enrichment of CO2 in the fixed bed reactor molecules or atoms and relating these to equilibrium and kinetic prop­
with silica gel compared to the stirred tank reactor are the other ad­ erties of bulk phases. MD simulations at the molecular scale aid to
vantages of employing porous media which corresponds to the particle achieve knowledge concerning the dynamical as well as structural
size distribution and pore size [432]. Evidence suggests the rate of hy­ properties of components in either simple or mixture of gases and liq­
drate formation would be directly proportional to the driving force uids. In classical MD, the laws of mechanics are applied to predict the
which can be affected by pore sizes in the porous medium environment equation of motions and energies of molecules under various thermo­
[433]. For example, the impact of the driving force on gas consumption dynamic conditions. In molecular systems, the velocities and positions
and hydrate formation rate was more significant in silica sand rather are dependent on the chemical structure, pressure, and temperature of
than in silica gel beds. Also, silica gel particles with 100 nm provide a the simulated system. The atomic interactions are usually described
higher water conversion rather than smaller particles [425]. The surface using empirical interatomic potentials, which include a short-range

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 21. Proportions of experimental investigations of pure and mixed gas hydrates including CO2 in the presence of single or synergic promoters.

Fig. 22. The most improvements of different THP, KHP, and THP+KHP types on pure CO2 hydrates.

repulsive/attractive force and a long-range Coulombic force. Ordinarily, specifications of clathrate hydrate phenomena can assist the applica­
molecular dynamics can be conducted in two approaches. In the non- tions of gas hydrates [440], more specifically those which were dis­
equilibrium mode, the system is stimulated away from the equilibrium cussed in previous sections. To provide unique insights into the
and the system response is followed whereas, the macroscopic property characteristics of hydrate phenomena at an exceedingly small time/­
of interest in the equilibrium model is calculated from the time average length scales, atomistic simulators have been successfully applied. Pre­
of that property during the simulation. The common applications of MD viously, exploration of hydrate properties/ phenomena e.g.
are either to predict the properties of materials or provide explanations thermodynamics, nucleation, dissociation, energy storage, memory ef­
by determining the mechanisms involved. Understanding different fect, electromagnetic and external electric fields using molecular

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 23. Maximum improvments of THP, KHP and THP+KHP on performance parameters of mixed CO2 hydrates. (The ideal scenario could be: growth rate: 100
(mmole/ mole.min), gas uptake: 174 (mmoleCO2/moleH2O), IT: 0 min, S.F.: 250 for e.g. CO2(40%)+CH4(60%), and S.Fr.: 1).

simulations were reviewed [441,442]. MD findings in the area of Various aspects of gas hydrates through different molecular-
geological CO2 storage and sedimentary sites with the aim of environ­ simulation approaches e.g. potential models, classical MD, Free-energy
mental as well as mechanical/ structural analysis such as swelling methods, MD simulation timescales, massively parallel MD, and ab ini­
properties, contact angle, interfacial tension, and sorption/diffusion of tio calculations can be evaluated. Most investigations of MD simulations
gases were also overviewed elsewhere [57,445–447]. Based on MD in the scope of clathrate hydrates have been performed based on clas­
simulations, it was shown that within brine aquifers, the intercalation of sical MD, DFT, ab initio calculations, and Monte Carlo simulations. It is
CO2 in minerals can cause considerable changes in the spacing between conceivable that the results of these studies can be worthwhile for either
the mineral layers and modify the wetting characteristics of the clay HBCC/ HBGS or other applications of gas hydrates [448]. To elucidate
surfaces [443]. Also, formed hydrate inside the water layers nearest to the CO2 hydrates phenomena/ properties in more detail, the following
the hematite surface is unlike the liquid water which would be ther­ Sections come up with a summary of MD approaches to analyse the CO2
modynamically favoured to adsorb on hematite as it possesses lower hydrates.
chemical potential [444].

Fig. 24. CH4/CO2+N2 replacement mechanism in naturally occurring hydrates.

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

5.1. CO2/CH4 gas exchange phenomena presence of Na2CO3, the AIMD and DFT calculations demonstrated that
the kinetics of the reaction at the surface is not a controller of the
MD simulations revealed that the process of replacement can occur carbonation reaction of the Na2CO3 and the apparent reaction rate of
by either a transient co-occupation of CO2 and CH4 in one cavity or via K2CO3 in comparison with Na2CO3 is significantly faster [466]. It was
direct swapping without a breakup of cages [449]. Fig. 24 presents the also elucidated that the kinetic rate of CO2+CH4 hydrate dissociation in
schematic of the CH4/CO2+N2 replacement mechanism in naturally the presence of calcite is remarkably lower than that in the hydrate
occurring hydrates. formation [467]. Based on the simulations of
With reference to the MD results, it was found that the assumption of CO2+CH4+namontmorillonite clay to study the transport properties of
vdWP theory which ignores the guest-guest interactions can contribute CH4 and CO2 hydrates in clay, increasing CH4 and CO2 molecules in
to some deviation in predicting the Helmholtz free energy and subse­ namontmorillonite interlayers may result in a decrease of self-diffusion
quently hydrate equilibrium conditions. Also, the mass transfer, memory coefficients [468].
effect, and chemical potential of guest molecules are the main control­ The role of N2 in the replacement process was discussed in Section 2.
lers of CO2/CH4 replacement phenomena which represent the dissolu­ Since N2 guests do not compete directly with CO2 during CH4 substitu­
tion of CO2 molecules in the water phase and partial melting of hydrate tion, it may be used as a carrier gas. It was reported that the substitution
surface without structural change [450]. This phenomenon occurs first of CH4 in the small cavities with N2 has positive free energy [469].
in small cages, followed by partial collapse of hydrate in large cages at Indeed, N2 helps CO2 diffuse into both small and large cages of the CH4
the water-hydrate interface and entering CO2 molecules into the cages hydrate on a broader scale. However, this diffusion is sensitive to the
[79]. It is worth highlighting that a significant feature during the ratio of CO2 to N2 [449]. In addition, an MD study based on Gibbs free
replacement at the macro level is the free water [451,452]. Interfacial energy calculations of CO2+ H2S/ SO2 showed that the presence of SO2
properties of brine water and CO2+CH4 mixture showed that the and H2S at lower concentrations can also give rise to better hydrate
interfacial tension (IFT) of CH4+brine aqueous system in the existence stability and the storage capacity of captured CO2 [470].
of CO2 decreases but consistent with experimental evidence, the degree
of decline is directly dependent on the CO2 concentration [453]. The 5.2. CO2 hydrate nucleation and growth
properties of spherical nanoclusters of CO2/CH4 hydrates and the effects
of surrounded water/gas/porous environment can also be analysed by The main proposed hydrate nucleation molecular mechanisms have
MD [454,455]. Recent MD research manifested that CO2+CH4 mole­ been divided into the local structure hypothesis (LSH) and labile cluster
cules in the existence of THF+DMSO can diffuse into the hydrate hypothesis (LCH). In the former, the guest molecules arrange themselves
structure more easily which brings about a greater amount of enclath­ in a structure and then water molecules rearrange around the locally
rated gas molecules than using a single THF [456]. Also, due to the very ordered guest molecules whereas the latter describes the formation of
strong distortion of SDS in the interaction with CO2, SDS+CH4 and isolated cages followed by agglomerate to form a critical nucleus of the
SDS+CO2 behaviours consistent with experiments are entirely different hydrate. The basis of both, however, are hypotheses and any provided
[457]. Probably, to face CO2 with both SDS apolar and polar ends, the mechanism cannot fully explain it [471]. In this context, MD suggested a
SDS molecule will lose its shape, and with respect to water molecules crystallization pathway of hydrates of hydrophobic guests as is dis­
will become unable to exert any substantial driving activity [458]. Given played in Fig. 25. Based on the findings of researchers, the crystalliza­
that to promote the kinetics and thermodynamics of gas hydrates for tion mechanism of clathrate hydrates is consisting of three steps. The
suggested hydrate-based applications discussed in Section 4, identifying formation of blobs is the first step in which dilute solution is in equi­
the key controllers is particularly critical. The replacement process librium with solvent-separated guest molecules (the blue polygons
elucidated that gas exchange phenomena take place at small and large represent the half-cages). In the next step, clathrate cages are organized
cage types with partially CH4 hydrate collapse, at the surface of which, by the water which leads to the formation of amorphous clathrate. In the
the hydrate is partially melted so that the interface becomes active [79]. last step, the crystalline phase is formed by amorphous maturation
It was also evidenced that considering the host-host/guest intermolec­ [472].
ular interactions, the process of CO2/CH4 replacement can be divided In addition, the hydrate nucleation and growth mechanisms of
into 3 steps: the breakup of the cage, scape of CH4, and cage occupation different guest molecules are dissimilar and the aggregation step is an
by CO2 molecules [459]. In addition, the formation of CO2 amorphous important controller of hydrate nucleation rate [473]. The CO2 clathrate
layer forms on the CH4 hydrate surfaces with utilizing MD was detected growth using TIP4P-Ew and EPM2 force fields to describe the in­
as a barrier against mass transfer which leads to a slower replacement teractions of water and CO2 molecules at 260 K revealed that with
rate [450]. Due to a larger size of CO2 relative to CH4, it has less stability increasing the pressure from 3 to 100 MPa, 37% decrease in the rate of
if it occupies the small cages [460]. During the gas exchange, CO2 CO2 hydrate growth can be observed. In contrast, the increase in pres­
molecules in the mixed bubble environed the CH4 molecules which sure enhances the CH4 hydrate growth rate and unlike CO2, the solu­
indicate a significant impact of bubble formation on gas exchange spe­ bility of CH4 in water entirely depends on pressure [474]. Nucleation
cifically at the initial stages [461]. In addition, crystal growth of and growth of CH4+CO2 hydrate manifested that the difference in hy­
CH4+CO2 hydrate showed that the concentration of CO2 plays a major drophobicity between CO2 and CH4 may influence the nucleation rate
role in its kinetics, however, maximizing CO2 concentration in the and stability of nanobubbles in the water phase. Metastable cages
aqueous phase cannot give quicker growth [462]. The host and guest (4151062, 4151063, and 4151064) during hydrate growth were also
rotational dynamics depicted that changing the proportion of each gust observed [475]. In addition, during the crystal growth, 51263 cages were
molecule in mixed CO2+CH4 hydrate results in altering the rotational formed but changed into 51262 cavities as time proceeded [476]. To
motion of both guests and water molecules. Also, the CO2 molecules identify the key factor which governs the nucleation of CO2 hydrate
have a more rapid relaxation time than CH4 which promotes the motion under the water freezing point (250 K and 50 MPa) it was acknowledged
of water molecules [463]. MD simulations suggest the most stable that using TraPPE and TIP4P-Ice models for CO2 and water, the
structure can be attained when the small and large cages are fully adsorption of CO2 molecules around the hydration shell (HS) is crucial to
occupied by CH4 and CO2, respectively. Moreover, because of distinct stabilize the hydrogen bonds formed therein and catalyse the trans­
solubility conditions of CH4 and CO2 in water, the size of bubbles for formation of HS into the cavity [477]. Additionally, free energy barriers
each guest molecule would be unique [464]. Also, CH4 hydrate in con­ are strongly dependent on guest size but equilibrium thermodynamics
tact with CO2 gas is more stable than with CO2 solution and nearly 20% govern the nucleation process. Also, 4151062 cavities during the nucle­
of the dissociated CH4 hydrates can be replaced by CO2 [465]. To ation stage are the most popular cavity-type [478]. Homogeneous
evaluate the reaction rate and diffusion control of CO2 hydrate in the nucleation mechanism of CO2 hydrate at 260 to 273 K through transition

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

Fig. 25. Multi-step blob mechanism of crystallization pathway of clathrate hydrates. (Reprinted from [472] with permission of ACS).

path sampling showed that amorphous structures at low temperature are calculations (MP2, M05-2X, and DFT-D) revealed that the maximum and
predominantly generated with 4151062 cavities but increasing temper­ an optimum number of CO2 molecules in all cavity types of three
ature changes them to 51262 so that form the sI crystalline [478]. With structures would be varied between one to even seven molecules [491].
reference to the relationship between hydrate nucleation and dynamical Based on the simulations of CO2 storage in sH hydrate (CO2+LMGS),
properties, the hydration shell of guest molecules can become more although a single CO2 molecule can occupy the small and medium cages,
ordered with increasing their concentration which leads to a decrease in occupancy of 3 to 5 molecules in large cages would be the most favoured
entropy and mobility [479]. In addition, the consistency of structural case [492]. In addition, the rate of CO2 occupation in the small cavities
biased dynamics and the rugged funnel-shaped potential-energy land­ of sI hydrate at below 1 MPa is insignificant whereas with increasing the
scapes associated with hydrate nucleation were also confirmed else­ pressure, the rate of CO2 fractional occupancy in large cages gradually
where [480,481]. increases [493]. Also, to determine the reference chemical potential and
reference energy of sI CO2 hydrate, intermolecular potentials obtained
5.3. CO2 hydrate stability and dissociation by ab initio quantum mechanical and the VAS model estimated that
fractional occupancy for small and large cavities can be approximately
To utilize CO2 hydrates in the industrial division, identifying the 32% to 51% and 98%, respectively, [494]. Structural and energetic
molecular elements of CO2 hydrate stability and dissociation mecha­ investigation of CO2 hydrate using DFT methodology illustrated that
nisms would be substantial [482]. MD simulation results suggested that although the cage distortions are largely isotropic, a loss in the ideal
to prevent the nucleation phenomenon, destabilizing the formation of symmetry of the empty structure is caused by CO2 molecules, and they
blobs could be a proper strategy [483,484]. Simulations of CO2/CH4 also prefer to occupy the larger cages [495]. According to the mobility
hydrates by applying SPC/E, EPM2, or TraPPE potential models for CO2 analysis of CO2 hydrate, the negligible change in a cage composition
and water demonstrated that two-step hydrate dissociation including leads to considerable effects on the mobility of CO2 molecules. For
the break-up of cavities and escape of guest molecules is valid [485]. example, altering 3% cage occupancy would give rise to 2 orders of
Also, hydrate stability is less sensitive to CO2 molecules in small cages magnitude change in the diffusion coefficient [496]. By comparing the
compared to CH4 [486]. Although CH4 hydrate can dissociate somewhat diffusion barriers of CO2, H2, and CH4 using ab initio calculations, it
above the bulk melting temperature, this is not the case for CO2 hydrate became clear that both the overall occupancy and residence of specific
which confirms that at the grain boundaries, the guest types and grain cavities play an important role in the dissociation of CO2 hydrate.
boundary structures (both) may affect the thermal stability of poly­ Indeed, CH4 and CO2 molecules can penetrate after the breakup of
crystalline hydrates [487]. Decomposition analysis of CO2 and CH4 cavities while H2 molecules because of little penetration barrier, may
hydrates at 180-280 K and 0.1-10 MPa determined that hydrate stability diffuse during the early stages [497].
using isochoric conditions is lower than that in isobaric conditions
[454]. A faster layer-by-layer decomposition rate in the gas-solid 5.5. Thermo-physical and mechanical properties of CO2 hydrate
interface than in the liquid-solid interface during the CO2 decomposi­
tion cab also be observed. In this phenomenon, due to gas aggregation Molecular simulations have aided to investigate the CO2 hydrate
and mass transfer barrier (e.g. the presence of water film and bubbles), specifications e.g. specific heat capacity, thermal conductivity, and co­
the dissociation difference can raise from 13% to 53%, however, drops efficient of thermal expansion. Previously, first-principles DFT was
to 27% as the interface barriers become negligible [488]. Moreover, employed to determine the thermal properties of gas hydrates which
equilibrium and non-equilibrium MD simulations (EMD, NEMD) carried bridged the gap that existed at very low temperatures/ high pressures,
out on the thermal-driven breakup of CO2 hydrate (at 300 to 320 K) that experiment is unable to get so close to [498]. It is worth mentioning
showed that fluctuations in the equilibrium state decay on average that at extremely low temperatures, replicating experiments by DFT will
based on macroscopic laws (known as Onsager’s hypothesis) would be outperform MD simulations. The evaluation of dynamical and structural
applicable for an initial period of CO2 hydrate dissociation [489]. properties for CH4, CO2, and Xe encaged molecules demonstrated that
the lattice expansion of CO2 hydrate by elevating the temperature is
5.4. CO2 cage occupancy higher than that in either Xe or CH4 hydrates. However, the thermal
conductivities of CO2 are less than that of those guests [499,500].
The proposed MDs can confirm or complete the findings of most of Identifying the key mechanical contributors to the geo-mechanical
the previous experimental observations and theoretical simulations. The stability of hydrate-bearing sediments would also be substantial to
relationship between CO2 occupancy and dissociation rate using TIP4P/ control the implications of geological hazards. In this regard, a series of
2005 and TraPPE potentials for water and CO2 molecules showed that compression tests revealed that in both brittle and ductile regions, gas
identical total occupancy cannot result in the same dissociation behav­ hydrate has a measurably different strength than ice. Fundamental
iour and the surrounding environment of crystals as well as whether elastic properties of CO2 hydrate including the shear modulus and
large or small cavities are filled or empty, are the main contributors Young’s modulus have also been recently studied [501,502]. In addi­
[490]. The cage analysis for different types of cavities using quantum tion, the space of the water-hosted cages at low temperatures may

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S. Sinehbaghizadeh et al. Progress in Energy and Combustion Science 93 (2022) 101026

restrict the free-rotating motion of CO2 molecules. Whereas the stability initial stages, MDs can be an effective tool to analyse the kinetic
and mechanical stiffness of CO2 hydrate would be boosted by increasing behaviour of CO2 hydrate growth in the existence of salts and some al­
thermal vibration as temperature increases. Also, the behavioural cohols. In this context, the influence of electrolyte solutions (NaCl,
analysis of CO2 and CH4 hydrate manifested that their shear modulus is MgCl2) on CO2 hydrate growth in terms of ions mobility and cage con­
directly and inversely dependent on temperature [503]. By analysing tent was simulated which specified that the inhibition effect of MgCl2
the mechanical properties of CO2 and CH4 hydrates, it was shown that compared to NaCl is higher. To explore the hydrogen bonding in
under a uniaxial mechanical load, the stability of gas hydrates is criti­ CO2+ethanol hydrate at 100-250 K, MD demonstrated that ethanol
cally dependent on the guest molecules. Therefore, hydrate mechanical forms long-lived proton-donating and accepting hydrogen bonds with
properties may probably be related to the size, shape, and polarity of the water molecules while maintaining the general cavity integrity of the sI
guest molecules [504]. Based on the mechanical and vibrational features hydrate [517,518]. Kinetically speaking, the dissociation mechanisms of
of CO2+Neohexane sH hydrate by applying ab initio DFT-based IR CO2 hydrate in the presence of different inhibitors are quite dissimilar.
technique, the vibrational frequencies were found to be relatively For example, MD simulations of CO2 hydrate + glucose/ glycine illus­
dependent on interatomic distances of hydrate and the pressure [505]. trated that the ring-shaped structure of glucose accelerates the CO2
hydrate dissociation whereas owing to the aggregation of hydroxyl
5.6. Thermodynamic and kinetic enhancement of CO2 hydrate formation (eOH) and amidogen (eNH2) with water hydrogen bond, glycine accu­
mulates on the solid-liquid surface and then destroys the cluster [519].
To comprehend the microscopic impacts of promoters discussed in
Section 3, some of such systems have been studied via MD. It is worth
5.8. CO2 semi-clathrate hydrate
highlighting that, at low temperatures, single-crystal X-ray diffraction
may not detect the hydrogen bond formed between water and THF
Aqueous solutions of quaternary ammonium salts through forming
whereas a small percentage of hydrogen bond was confirmed through
semiclathrate hydrate at atmospheric pressure would be an option for
MD. The existence of hydrogen bonding guests also increases the
HBCC/HBGS or cold storage aims. The ionic guests such as TBAB can
migration of CO2 and improves the kinetics of hydrate formation [506].
form ionic semiclathrate hydrates which have two distinct types of D
Analysing CO2 storage capacity at 269-289 K and 2.5 MPa revealed that
cages (DA, DB) so that CO2 molecules can be entrapped with them [520].
although THF markedly improves the CO2 diffusion at the liquid-hydrate
Although these cages have nearly equal volume, the distorted DA and DB
interface, preferential THF-water hydrogen bonds reduce CO2 storage
cavities have individual cage occupancies with each cavity having
capacity [507]. Moreover, by making a comparison between C3H8 +
anisotropic angular distribution. In this context, the RDF results
CO2 and C3H8 + CH4 binary hydrates, it was elucidated that the specific
demonstrated that CO2 molecules prefer the elongated and distorted
heat capacity and isothermal expansion coefficient of C3H8 + CO2 hy­
aspherical DA cavity whereas CH4 molecules tend to occupy the regular
drate are somewhat higher than that in THF+CO2 hydrate. Besides,
quasi-spherical DB cavity. MD calculations can also predict the diverse
dissimilar to CH4 binary hydrate, small cages occupied by CO2 molecules
properties of semiclathrate hydrates such as equilibrium conditions,
can lead to an increase in compressibility and expansion coefficient but
enthalpies, and densities. However, compared to clathrate hydrate sys­
decrease the heat capacity [508]. Although guests in the small cavity do
tems, very few studies have been conducted on their systems. Previ­
not themselves form hydrogen bonds with water, the THF effects on
ously, MD simulations of the rotation angle in two cavities of CO2+TBAB
hydrogen bonding occur, so that the nearest neighbour guest-guest in­
semi-clathrate hydrate showed a new lattice structure of TBAB induced
teractions can affect the stability and structure of the cluster [509]. MD
by CO2 molecules which were characterized by NMR, X-ray, and MD
assessments demonstrated that with the utilization of CNT designed by
simulations. It was also displayed that the lattice vibrations of Br− and
hydrogen peroxide (− H2O2), carboxyl (− COOH), and
[TBA]+ groups about their equilibrium positions are small and they are
aquaporin-mimicking peptide (− CONH2), the transport properties of
kept in place by van der Waals and electrostatic interactions with the
CO2 hydrate such as permeability and diffusion coefficient during for­
neighbouring water molecules [172].
mation can be noticeably improved. This suggests the membrane as an
inexpensive, safe, and environmental-friendly approach has the poten­
tial for HBCC aims [510]. MD also confirmed the propensity of the CO2 5.9. Summary of the section
cluster to generate clathrate hydrate in the presence of SDS [458]. In
addition, molecular investigation of the promotion mechanisms of urea Using classical MD, large-scale simulations (i.e. thousands of parti­
in the CO2 hydrate growth showed that urea increases the mass transfer cles) for multiple phases over relatively long times (i.e. hundreds to
by catalysing the formation of cages at the solid-liquid interface [511]. thousands of nanoseconds) can be performed to investigate a wide va­
Probably, the preference of urea surfaces to replace water molecules and riety of physical and chemical processes associated with CO2 hydrates.
the subtle balance between urea-water interactions help to act as a These simulations can answer many different questions such as the
catalyst for the growth of CO2 hydrate layers [512]. MD exploration also mechanisms of surface absorption, crystal growth, phase separation, etc.
displayed how specific concentrations of the metal particles (e.g. Cu, Fe, The phenomena and properties associated with CO2 hydrates have been
Ag) can accelerate the formation of CO2 hydrate, however, at values extensively explored by MD (see, Fig. S1 of the supplementary mate­
higher than those, because of strong Brownian motion in the solution, rials). There are also different parameters that researchers have applied
they may act as an inhibitor for the CO2 hydrate growth [513,514]. to investigate the microscopic mechanisms/ phenomena, intermolecular
Moreover, the effects of graphite and hydroxylated-silica surfaces on behaviours, and properties of CO2 hydrate crystals. Some examples of
CO2 hydrate growth revealed that hydrophobic graphite surfaces these parameters are lattice parameter, potential energy, thermal con­
strongly adsorb CO2 molecules while the silica surfaces by interacting ductivity, diffusion coefficient, surface tension, dissociation enthalpy,
with CO2 hydrate solids (mainly via strong hydrogen bonds), may lead and heat capacity [521–523]; To exhibit the movement of guest/host
to a critical role in promoting hydrate formation [515]. molecules and display the characteristics of structure I/II/H under
different thermodynamic conditions, mean square displacement (MSD)
5.7. CO2 hydrate in the presence of inhibitors and radial displacement function (RDF) can be, respectively, analysed.
The list of analysis parameters as well as software employed for a variety
The risk of pipeline plugging during CO2 injection for sequestration of hydrates is exhibited in Fig. S2 of SM. Since the results of MD
requires developing cost-efficient and efficient hydrate inhibitors [516]. exploration of other gas hydrates could be beneficial for further analysis
Since some CO2 utilization approaches e.g. hydrate-based desalination of CO2 hydrates, Table S15 of SM classifies such carried out MD
requires understanding the microscopic processes involved during the simulations.

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6. Future directions of renewable energy techniques and hydrate cold storage to

discover a competent process design in future exploration could
To address the fundamental issue of CO2 emissions, there has been an be implemented.
increased call to develop novel technologies. To capture, sequester, or (viii) Using MD simulations, a variety of gas hydrate characteristics
utilization of CO2, different hydrate-based approaches have been sug­ have been revealed as overviewed in section five. However,
gested. In this regard, the experimental measurements, process designs, additional MD studies on synergistic impacts of different pro­
and MD simulations of previous research at macroscopic, mesoscopic, moters and inhibitors (such as KHP+THP and KHI+THI) on
and microscopic levels convey the message that, although an effectible clathrate or semiclathrate hydrates to clarify the relationship
progress has been achieved, coordinated studies on different limitations between hydrate formation and additives can be conducted.
of the gas hydrate applications to find feasible approaches are still These evaluations may aid to understand the specifications which
required. Therefore, in the light of these investigations, the following contribute to enhancing the performance parameters of HBCC/S/
suggestions can be taken into consideration: U or other hydrate-relevant applications. Besides, MD simulation
studies on heterogeneous nucleation with fast mass transfer in the
(i) Commercial exploitation of natural gas hydrates in sediments and hydrate growth, describing memory effects and the role of
reservoirs is still technologically challenging. Based on exhaus­ nanobubbles in hydrate nucleation could be the further intriguing
tive reviews focused on the interaction of climate change and CH4 aspects.
hydrates in the sediments of marine continental, permafrost areas (ix) To analyze the effects of hydrate-formation methods, surface
[67], and the arctic ocean [524], the risk of collapse of marine tension, and grain wettability on permeability in hydrate-bearing
sediments while releasing CH4 gases under harsh engineering sediments, more research should be carried out.
conditions can exacerbate greenhouse warming. As a result, to (x) CH4/CO2 replacement mechanism is presently hampered by a
avoid engineering failures that may lead to damaging the marine lack of in-depth understanding of the insufficient rate of
ecosystem during the CO2 sequestration and CH4 production from replacement. Hence new chemical/mechanical methods need to
NGH, accurate strategies are needed to be implemented. Because be provided.
of the influences of fluid flow characteristics which can affect the (xi) Considering the suggested application of CO2 hydrate as a fire
field stability, migration in reservoirs must be attentively extinguishing agent and the high dissociation enthalpy of CO2
analyzed. Also, comprehending hydrodynamics of CO2 injection semiclathrate (e.g. CO2+TBAB), new investigations should be
is highly crucial for CO2/CH4 replacement in NGH. To improve conducted. In addition, the performance of CO2 hydrate extin­
the safety of operation, a risk assessment scheme by evaluating guishers in terms of operational design could be evaluated.
mechanisms that may induce the generation of leakage paths in
CO2 geological sites must also be developed. 7. Final statement
(ii) The use of hydrates for controlling greenhouse gases and CO2
separation from the gas mixtures, as an alternative, can be an Modren industries place a premium on environmentally friendly
effective method. However, despite the tremendous efforts of technologies. As was exposed, this review highlighted the extensive ef­
researchers to improve the HBCC performance parameters, forts in the CO2 hydrates geological sequestration into natural gas hy­
making a breakthrough in providing a low-cost technology has drates, designed hydrate-based process flow diagrams for the industrial
yet to be achieved and the bottlenecks like slow rate of hydrate applications, the role of promoters/ porous media on CO2 hydrates, and
formation, designing continuous setups, and a type of reactor for MD simulations as effective frameworks for understanding fundamental
continuous operation are still needed to be developed. Toward characteristics of CO2 hydrates. For a couple of decades, although a large
realistic applications, developing an optimized process, finding body of work on flow assurance and pipeline blockage had dominated
environmentally-friendly promoters based on the important fac­ the early era of hydrate exploration, having innovative applications in a
tors of non-toxicity, stability, eco-friendliness, availability, and wide range of sustainable chemistry revealed from experiments backed
economic viability, and improving the cooling methods to make by theoretical calculations, gas hydrates have received widespread sci­
convenient operating conditions can be favorable. entific attention toward developing different capabilities of this phe­
(iii) Despite many efforts on seeking effective and reliable hydrate nomenon to support an economic, help to make a cleaner atmosphere,
promoters from the aspects of interfacial tension, the impact of and sustainable development. However, elucidating a modern master
the number of hydrogen-bond, ion-specific effect, size of the ad­ plan based on green industrial policies and making a cleaner atmosphere
ditive molecule, and solution activity, lack of valid screening needs to be created.
method is still a critical objective.
(iv) The formation rate of gas hydrate without active agitation to CRediT authorship contribution statement
boost gas-liquid mixing is not appreciable. Moreover, the per­
formance of promoters in the continuous operation in the static Saeid Sinehbaghizadeh: Conceptualization, Investigation, Meth­
reactors needs to be examined. Conclusively, to overcome these odology, Data curation, Formal analysis, Writing – review & editing.
shortcomings further investigations should be carried out. Agus Saptoro: Conceptualization, Investigation, Writing – review &
(v) Toward energy-saving, hydrate-based hybrid technologies over­ editing, Supervision. Amir H. Mohammadi: Conceptualization, Inves­
viewed in section three have shown a good potential to become tigation, Writing – review & editing, Supervision.
industrialized but the industrial feasibility of such designs should
be examined. Declaration of Competing Interest
(vi) In the case of long distances between CO2 capture plants and CO2
sequestration sites, the costs of CO2 transportation may be higher The authors declare that they have no known competing financial
than capturing process. To facilitate CO2 transportation, various interests or personal relationships that could have appeared to influence
aspects associated with the performance and safety of CO2 the work reported in this paper.
transportation were discussed elsewhere [525]. Thus, in­
vestigations on the mobility and transport efficiency of hydrate Acknowledgment
slurry in future explorations can be considered.
(vii) The coefficient of performance (COP) of the hydrate cold storage The authors would like to thank Curtin University Malaysia for
exhibits a strong capacity but more analysis on the combination providing Curtin Malaysia Postgraduate Scholarship (CMPRS) for the

31
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Saeed Sinehbaghizadeh is a Ph.D. student at Curtin University (Malaysia), department of
doi.org/10.1016/j.energy.2021.121260.
chemical engineering. He is currently investigating the formation and dissociation
[516] Saikia T, Al-Jaberi J, Sultan A. Synthesis and testing of monoethylene glycol
mechanisms of pure and mixed CO2 hydrates in the presence of promoters using molecular
carbon quantum dots for inhibition of hydrates in CO2 sequestration. ACS Omega
dynamics simulation. He obtained his master’s degree in chemical engineering from Shiraz
2021;6:15136–46. https://doi.org/10.1021/acsomega.1c01355.
University of Technology. As a senior process engineer, he has 8 years’ experience in oil &
[517] Alavi S, Ohmura R, Ripmeester JA. A molecular dynamics study of ethanol–water
gas refining and petrochemical industries. The work focused on the process simulation of
hydrogen bonding in binary structure I clathrate hydrate with CO2. J Chem Phys
oil and gas treatment, distillation, extraction, absorption, adsorption, purification, reactor,
2011;134:54702. https://doi.org/10.1063/1.3548868.
and polymerization. He is also experienced in phase equilibrium calculations for precip­
[518] Makiya T, Murakami T, Takeya S, Sum AK, Alavi S, Ohmura R. Synthesis and
itation of hydrates, asphaltenes, waxes, and CO2 separation/ conversion methods from
characterization of clathrate hydrates containing carbon dioxide and ethanol.
industrial gas flaring.
Phys Chem Chem Phys 2010;12:9927. https://doi.org/10.1039/c002187c.
[519] Liu N, Zhou J, Hong C. Molecular dynamics simulations on dissociation of CO2
hydrate in the presence of inhibitor. Chem Phys 2020;538:110894. https://doi. Agus Saptoro is currently a Professor at Curtin University (Malaysia). He received
org/10.1016/j.chemphys.2020.110894. Bachelor of Engineering (First Class Honours) in chemical engineering from Gadjah Mada
[520] Muromachi S, Udachin KA, Alavi S, Ohmura R, Ripmeester JA. Selective University Indonesia and obtained his PhD in chemical engineering (process system en­
occupancy of methane by cage symmetry in TBAB ionic clathrate hydrate. Chem gineering) from Curtin University Australia. He has been a Visiting Professor/Academic for
Commun 2016;52:5621–4. https://doi.org/10.1039/C6CC00264A. University of Hyogo, Japan, National Institute of Technology (ITENAS), Bandung,
[521] Naeiji P, Varaminian F, Rahmati M. Thermodynamic and structural properties of Indonesia, and University of Aberdeen, UK. His research expertise and interest include
methane/water systems at the threshold of hydrate formation predicted by energy efficient CO2 capture processes, intelligent data and image analysis, process
molecular dynamic simulations. J Nat Gas Sci Eng 2016. https://doi.org/ modelling, simulation and optimisation, and thermal engineering especially microwave
10.1016/j.jngse.2016.03.044. technology. He is a Chartered Professional Engineer with Engineers Australia.
[522] Reshadi P, Modarress H, Dabir B. Amjad-iranagh S. Molecular dynamics
simulation for studying the stability of structure H clathrate-hydrates of argon
Amir H. Mohammadi has academic qualifications from Université Paris XIII (Université
and large guest molecules. J Dispers Sci Technol 2018;0:1–10. https://doi.org/
Sorbonne, Paris Cité), École Nationale Supérieure des Mines de Paris, Heriot-Watt Uni­
10.1080/01932691.2018.1446145.
versity and the University of Tehran, known for pioneering research. He has been a
[523] Adibi N, Mohammadi M, Ehsani MR, Khanmohammadian E. Experimental
Visiting Professor/Professeur Invité at the University of Calgary and Université Laval, an
investigation of using combined CH4/CO2 replacement and thermal stimulation
Adjunct Lecturer at École des Mines de Nantes and École Nationale Supérieure de Tech­
methods for methane production from gas hydrate in the presence of SiO2 and
niques Avancées, a Visiting Scholar at Technical University of Denmark (DTU), University
ZnO nanoparticles. J Nat Gas Sci Eng 2020:103690. https://doi.org/10.1016/j.
of KwaZulu-Natal (UKZN), Instituto Politécnico Nacional (IPN), Planta Piloto de Ingeniería
jngse.2020.103690.
Química (PLAPIQUI) and Tomsk Polytechnic University and an Honorary Research Pro­
[524] James RH, Bousquet P, Bussmann I, Haeckel M, Kipfer R, Leifer I, et al. Effects of
fessor at Durban University of Technology (DUT). He is the recipient of a prize from the
climate change on methane emissions from seafloor sediments in the arctic ocean:
Institute of Materials, Minerals & Mining and Outstanding Research Awards from the
a review. Limnol Oceanogr 2016;61:S283–99. https://doi.org/10.1002/
University of KwaZulu-Natal (UKZN).
lno.10307.

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