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1-Impact of CO2 Hydrates On Injectivity During CO2 Storage in Depleted Gas

This literature review examines the impact of CO2 hydrates on injectivity during CO2 storage in depleted gas fields, highlighting the risks associated with hydrate formation due to low temperatures from CO2 injection. It emphasizes the need for further research to address the challenges of CO2 hydrate formation and its effects on the permeability of porous media. Current industry solutions to manage this risk are noted to be costly and energy-intensive, indicating a need for more efficient strategies.

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0% found this document useful (0 votes)
10 views23 pages

1-Impact of CO2 Hydrates On Injectivity During CO2 Storage in Depleted Gas

This literature review examines the impact of CO2 hydrates on injectivity during CO2 storage in depleted gas fields, highlighting the risks associated with hydrate formation due to low temperatures from CO2 injection. It emphasizes the need for further research to address the challenges of CO2 hydrate formation and its effects on the permeability of porous media. Current industry solutions to manage this risk are noted to be costly and energy-intensive, indicating a need for more efficient strategies.

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duyenluu2003
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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123 (2024) 205250

Contents lists available at ScienceDirect

Gas Science and Engineering


journal homepage: www.journals.elsevier.com/gas-science-and-engineering

Impact of CO2 hydrates on injectivity during CO2 storage in depleted gas


fields: A literature review
Mahnaz Aghajanloo a, *, Lifei Yan a, Steffen Berg b, Denis Voskov a, c, Rouhi Farajzadeh a, b
a
Delft University of Technology, Department of Geoscience and Engineering, Stevinweg 1, 2628 CN, Delft, the Netherlands
b
Shell Global Solutions International B.V., Grasweg 31, 1031 HW, Amsterdam, the Netherlands
c
Energy, Science and Engineering, Stanford University, USA

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

Keywords: Carbon dioxide capture and storage in subsurface geological formations is a potential solution to limit anthro­
CO2 storage pogenic CO2 emissions and combat global warming. Depleted gas fields offer significant CO2 storage volumes;
Depleted gas fields however, injection of CO2 into these reservoirs poses some potential challenges for the injectivity, containment
CO2 hydrate
and well/facility integrity due to low temperatures caused by isenthalpic expansion of CO2. A key injectivity risk
Porous media
Injectivity
is due to possible formation of hydrates at the low expected temperatures. This study aims to address main causes
of CO2 hydrate formation and its impact on permeability of porous media. This review highlights the current
state of knowledge in the literature while emphasizing the need to bridge existing gaps in derisking CO2 injection
into (depleted) low-pressure gas reservoirs. In summary, according to the existing literature, the potential for
hydrate formation is assessed to be credible. Current industry solutions exist to manage this risk; however, they
are costly and energy intensive. Future research will be needed to provide capabilities to manage this risk more
efficiently.

1. Introduction stream before injection; however, this comes at a high cost given the
short duration of the risk exposure and is CO2 intensive resulting in
According to the newest report from the Intergovernmental Panel on reduced net CO2 storage capacity.,
Climate Change (IPCC), carbon dioxide (CO2), the predominant green­ The success of these projects largely depends on the injectivity of the
house gas released from anthropogenic activities, contributed to 80% of well, which is critical to reach injection targets to limit greenhouse-gas
the total greenhouse gas emissions (Levin et al., 2022; Parmesan et al., related temperature increase, the achievement of which is in practice
2022). Recent research indicates that Carbon Capture and Storage (CCS) imposed by contractual or regulatory commitments. Injectivity is
technologies offer an effective approach to mitigating the adverse effects defined as the mass or volume of injected CO2 for a certain pressure
resulting from excessive CO2 emissions (Davoodi et al., 2023). Among gradient (Hoteit et al., 2019; Yusof et al., 2022). Permeability can be
various geological formations, CO2 storage in depleted gas fields has impaired during the CO2 injection for a number of reasons both in hy­
significant benefits compared to other subsurface storage options such drocarbon recovery (Farajzadeh et al., 2019; Ikeda et al.; Ochi and
as aquifers and depleted oil fields (Pan et al., 2021; Peter et al., 2022; Vernoux, 1998; Valadbeygian et al., 2023) and CO2 sequestration
Tamáskovics et al., 2023). The risks and uncertainties associated with (Sokama-Neuyam et al., 2023; Xie et al., 2017), operations. There are a
the deplete gas fields are comparatively lower because of their extended number of possible countermeasures, which typically have either tech­
production history, proven sealing capacity, and (partial) availability of nical or economic limitations. For instance, to maintain the flowrate the
infrastructure and equipment required to store CO2. However, injection well pressure should increase. However, beyond a certain (fracture)
of CO2 into these reservoirs poses some potential challenges for CO2 pressure, the reservoir rock will break, which poses a serious contain­
injectivity, containment and well/facility integrity due to low temper­ ment risk and is typically not permissible. Therefore, either the CO2
atures caused by various thermodynamic phenomena including isen­ injection rate should be reduced, which would compromise sequestra­
thalpic expansion of CO2 (Chesnokov et al., 2023). The conventional tion targets, or the injectivity should be restored by remedial action.
solution to this issue is to heat CO2 at the surface and insulate injection Several factors or mechanisms can lead to impairment of injectivity

* Corresponding author.
E-mail address: [email protected] (M. Aghajanloo).

https://doi.org/10.1016/j.jgsce.2024.205250
Received 23 December 2023; Received in revised form 3 February 2024; Accepted 19 February 2024
Available online 24 February 2024
2949-9089/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

of CO2 wells. Injectivity impairment might be caused, for example, by no review has been done on CO2 hydrate formation/elimination in the
the evaporation of water into dry or undersaturated CO2 which can lead context of CCS projects, especially on the topic of CO2 injectivity in
to the precipitation of salt (mainly halite) and thus plugging of the depleted gas fields. There are only a few precedence cases from the
reservoir pores (Ott et al., 2021). literature for CO2 hydrate formation at field scale or field-related pro­
For CCS in low-pressure or depleted reservoirs, thermodynamic cesses or projects. Most field examples (Gauteplass et al., 2020b; Jad­
properties of CO2 play a major role. CO2 is usually transported to site hawar et al., 2006) are scattered and not at conditions relevant for CO2
location in liquid or supercritical state and injection is conducted in the injection in depleted gas fields. Nevertheless, these examples demon­
state of high mass density to achieve sequestration targets (Shotton strate that in principle CO2 hydrates or ice can form (Li et al., 2023;
et al., 2022). The injection of high-pressure CO2 into low pressure res­ Semenov et al., 2023) and, if hydrates or ice formed (by different pro­
ervoirs leads to isenthalpic expansion of CO2 which then causes a cesses) (Sloan and Fleyfel, 1991; Zhang and Guo, 2017), they can
decrease in temperature (Chesnokov et al., 2023; Loeve et al., 2014). significantly impair injectivity. However, there is no demonstrated case
The magnitude of the temperature reduction depends on CO2 flowrate, where CO2 hydrates form due to the isenthalpic expansion cooling effect
reservoir permeability, thickness and thermal properties of the rock and during CO2 injection. In a field containing mainly CO2, solids were
the in-situ brine, and well radius and completion (Mathias et al., 2010). formed which were identified as hydrates and/or ice (Xu et al., 2007);
For typical CO2 injection rates (~1Mtpa), the temperature is expected to this demonstrates that hydrates or ice can indeed form in the field.
be very low (Almenningen et al., 2021). If the temperature is below the Notice that in these cases, the solids were observed during production
hydrate phase boundary inside stability zone (see Fig. 1) and enough downstream of the separator and not during injection into the porous
water is available in the porous medium, solid hydrates can form, which medium. Provision had been made for methanol injection to suppress
can reduce the porosity and eventually the permeability. hydrates, but this proved ineffective. In a water-alternating gas (WAG)
While hydrate formation has always played an important role in pilot, hydrocarbon gas was injected, and due to expansion of the hy­
production, transportation and processing of hydrocarbons e.g. in drocarbon gases the temperature dropped, and hydrates formed.
pipelines (Sayani et al., 2020), and also methane hydrates at continental Consequently, gas injection rates dropped to zero in a matter of hours
slopes are considered as a potential source of hydrocarbons (Demirbas, (Jensen et al., 2000). However, in this example, gas was injected in a
2010; Englezos and Lee, 2005), there is a concrete case of relevance of well that had injected water for an extended period (44 million barrels).
CO2 hydrates when CO2 sequestration (CCS) in depleted gas fields is Consequently, the temperature in the near wellbore had dropped to
considered (Bui et al., 2018). Hydrate formation is considered as one of 285K from the initial 403K (12 ◦ C, 130 ◦ C) at a reservoir depth of
the major potential risks for the implementation of CO2 storage in approximately 3000 m. This occurred in an area where the surrounding
ultra-depleted reservoirs (<50 bar) (Sloan and Fleyfel, 1991). Formation seawater temperatures are low, and the pressure is about 300 bar
of hydrates in porous media, apart from pressure and temperature, is (Adeniyi and Ezeagu, 2020). These conditions fall within the hydrate
influenced by several parameters related to properties of the rock window for hydrocarbon gas. Note that these are different conditions
(permeability, porosity, mineralogy), water (saturation, composition, than the injection of CO2 in depleted gas fields. The low temperature was
salinity, type of salt) and gas (type, composition, or purity). To quantify most likely not due to isenthalpic expansion but to prolonged cold sea
and/or to design strategies to prevent or mitigate the impact of CO2 water injection.
hydrate on the injectivity, it is necessary to understand the impact of Besides the above-mentioned cases, an injectivity impairment was
different factors on hydrate formation in porous media. demonstrated in an integrated experiment where the cooling effects
Over the past decades, much research has been conducted on CO2 from injection led to a complete blockage (Maloney and Briceno, 2009).
hydrate inside the bulk under various conditions and materials (Yang All these examples show that the formation of hydrates in an injection
et al., 2013; Zheng et al., 2020). However, to the best of our knowledge, scenario is not just hypothetical. There are concrete precedent cases of
hydrate formation in the near-well region due to gas injection, although
the conditions and chemical composition of reservoir fluids varied and
none of them were close to the conditions expected for CO2 injection in
ultra-depleted gas fields.
The aim of this review is to provide an overview of the conditions
and factors that facilitate or hinder the potential of large-scale CCS in
depleted gas fields to support the assessment of the overall risk of hy­
drate formation for CCS in depleted gas reservoirs. Besides a set of ac­
tions that can be affordable and implemented to reduce the risk of CO2
hydrate formation during injection will be assessed. It will be demon­
strated that the kinetics of hydrate formation and propagation in porous
media exhibit distinct behavior compared to a bulk environment. The
properties of porous media, e.g., heterogeneous permeability, wetta­
bility, residual water saturation, gas impurity, and brine salinity, have
varying degrees of impact on the hydrate formation and dissociation,
which will be reviewed. The intrinsic factors of gas hydrate, e.g.,
memory effect (Rossi et al., 2021; Wen et al., 2021) and self-preservation
effect (Vlasov, 2019) have a significant influence on the kinetic behavior
of hydrate. Since, those factors compose a complicated system for
tackling hydrate issues in the depleted gas field, their impact on CO2
hydrate formation/dissociation process and its feasibility will be dis­
cussed. Furthermore, the likely simultaneous phenomenon of salt
dry-out and gas hydrate is theoretically argued for the CO2 injection.
The interactions between the injection well and reservoir will be
Fig. 1. Three-phase diagram of the CO2-water mixture. The symbols Iw, Lc, Lw,
H, and G represent ice water, liquid CO2, liquid water, hydrate, and gas, described for the corresponding thermodynamic conditions during hy­
respectively. HQP and LQP refer to high (LwHLCG) and low (IwHLWG) quadruple drate formation and dissociation. Following that, feasible prevention
points. The smooth line represent the three-phase equilibrium line, the dotted approaches will be reviewed. Finally, we will discuss the scientific and
line indicate the CO2 condensed line, and the dashed line is ice line. engineering problems facing hydrate formation in porous reservoirs,

2
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

based on our current limited understanding. molar basis when all the cages are occupied (Martinez et al., 2022).
Structure I, which is the most common gas hydrate structure, includes
2. Gas hydrate types and structure two small pentagonal dodecahedra (512) and six tetrakaidecahedra
(51262) per unit cell. Hydrate sI is the simplest structure with an average
Gas hydrates or clathrate hydrates are ice-like crystalline compounds lattice structure of 12.1 Å, which holds small gas molecules (0.4–0.55
composed of a low molecular weight gas (usually light hydrocarbons nm) in a unit cell of 46 water molecules. Clathrate hydrate structure sII is
and water-soluble gases) and water molecules, combined under certain a 17.2 Å cube composed of 136 water molecules of 16 pentagonal do­
thermodynamic conditions (relatively high pressure and low tempera­ decahedrons (512) followed by 8 hexakaidecahedrons (51264) and trap­
ture). In a clathrate hydrate network, water as a host forms a cage-like ping larger gas molecules (0.6–0.7 nm). Structure H is the only structure
lattice structure through H-bonding surrounding the guest gas mole­ consisting of three cavities with the combination of three pentagonal
cules (Sloan, 2003). Depending on the size and purity of the guest gas dodecahedrons (512), two irregular dodecahedrons (435663), and one
molecules, the number of water molecules participating in lattice clus­ icosahedron (51268), with an average lattice structure between 12.2 Å to
ters varies and determines the type of hydrate structure (Cai et al., 10.1 Å. The sH hydrate structure requires concomitantly small gas
2022). In general, guest gas molecules have an important function in the molecules (as auxiliary gas) such as those forming sI and larger molecule
stability of the hydrate structures in which the water molecules form a typically liquid hydrocarbons (0.75–0.9 nm).
cage around the guest molecules. Because the structure of the clathrate In general, CO2 forms the most common hydrate structure sI in the
hydrates is not based on covalent bonds but rather a hydrogen bonded presence of free water under certain thermodynamic conditions depic­
framework, the process of their formation and dissociation is a ted in Fig. 1 (Wroblewski, 1882). In Structure I, the hydrate nuclei are
first-order phase transition rather than chemical reactions (Sloan and formed by connecting the large cages with pentagonal or hexagonal
Koh, 2008). The exothermic process of hydrate formation could be faces to the small cages. By joining these hydrate nuclei to each other,
characterized by two steps: (1) the nucleation step, which is the con­ hydrate clusters are formed and adsorb the CO2 molecule from the water
version from an unstable condition to stable growth (until critical par­ phase to their surface. The upper part of the interconnected surfaces of
ticle size is reached), and (2) the growth step. Hydrate nucleation can the two cages is the favorable adsorption site for CO2 molecules and can
occur in several ways. Because the transport of the gas and water mol­ prepare two common pentagonal faces for further CO2 hydrate forma­
ecules across the hydrate layers is limited, the growth step can be slow. tion. Next, the water molecules gradually and continually form cages
In general, the hydrate formation starts with dissolution of the gas around the CO2 molecules and encage the CO2 molecules into the
molecules in the aqueous phase followed by producing labile unstable clathrate structure. Theoretical and experimental evidence also supports
clusters (Sloan and Fleyfel, 1991). Hydrate nucleation is determined as the existence of metastable structures sII (Cabrera-Ramírez and Pros­
an activated microscopic phenomenon in which many molecules miti, 2022; Fleyfel and Devlin, 1991; Lee et al., 2023; Staykova et al.,
agglomerate and create individual clusters that subsequently transform 2003) and sH (Alavi and Woo, 2007; Cabrera-Ramírez and Prosmiti,
into hydrate nuclei. When these small nuclei reach a critical size, 2022) of CO2 hydrates under thermodynamic conditions approaching
consecutive growth begins (Lederhos et al., 1996). the ice melting point. Moreover, there is confirmation regarding the
The known hydrate structures are classified into three main types: formation of CO2 hydrate semi-clathrates with other guest components
the cubic structures I (sI) and II (sII) and the hexagonal structure H (sH), (Kumar et al., 2009; Torré et al., 2012; Zheng et al., 2017).
as schematically shown in Fig. 2. All structures consist of five different The following equation can be written for CO2 hydrate formation/
host water cages and are approximately 85% water and 15% gas on a dissociation process (Nagashima et al., 2020):

Fig. 2. Three common hydrate unit crystal structures, Adopted from (Gaidukova et al., 2022; Koh et al., 2011; Sloan, 2003).

3
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

CO2 +nh H2 O ↔ CO2 .nh H2 O + ΔH (1) Structural Control of Nanoparticles," 2018). Therefore, as the pore size
decreases, the risk of hydrate formation becomes lower (the hydrate
where nh is the hydration number or the number of water molecules per phase boundary shown in Fig. 1 displaces to the left). This is attributed
guest gas molecule. ΔH represents the enthalpy of formation/dissocia­ to the reduction of water activity in the porous medium owing to the
tion of hydrate (exothermic heat released or endothermic heat absor­ dominant impact of capillary forces (Wu et al., 2021). Furthermore, the
bed) during phase transition, which causes the difference in the slope temperature of hydrate dissociation in porous media is lower than the
between Iw-H-G and Lw-H-G lines (see Fig. 1). Formation of gas hydrate decomposition temperatures in bulk due to existence of the capillary
is closely linked to the hydration number. In the case of CO2 hydrate, force (Geng et al., 2021; Nair et al., 2016). This indicates that hydrate
which is mainly in the form of structure sI, the theoretical hydration formation is usually not a thermodynamically equilibrium step (it may
number is approximately 5.75. However, achieving this value requires not be repeatable) and depend on several factors, including agi­
full occupancy of both small and large cavities. tation/turbulency, cooling rate, presence of additives, fluid composi­
tion, water memory, and degree of subcooling (Gambelli et al., 2022).
3. Hydrate formation in porous media Inside individual pores of porous media, hydrates can assume several
different morphologies, which are sketched in Fig. 3. Pore filling hy­
In this section, we will review various aspects of affecting hydrate drates nucleate within pore spaces or along grain surfaces without
formation in porous media due to injection of CO2. Formation and bridging grain particles. Contact cementing hydrates nucleate at the
dissociation of CO2 hydrate under bulk conditions (i.e., two-phase contact points between grains, serving as a cement, and grow around
conditions in the absence of solid substrates) have been studied by these points. Patchy hydrates nucleate and grow within pore spaces.
many researchers (Dholabhai et al., 1993). The CO2 concentration (CO2 Grain-coating hydrates nucleate on grain surfaces and coats their sur­
flow introduced into the bulk) in the bulk condition has a considerable face. Load-bearing hydrates nucleate in pores or grain surfaces, growing
impact on the properties of CO2 hydrate formation and dissociation towards adjacent sands, while supporting matrix hydrates grow between
(Han et al., 2010). In the absence of flow, when the amount of CO2 is grains, integrating into the sediment framework.
inadequate to completely saturate the aqueous phase, pressure de­ Furthermore, the presence of the porous medium significantly affects
creases considerably outside the hydrate stability zone and prevents the the bulk properties in addition to influencing the hydrate morphology at
crystallization or breaking of the fragile hydrate crystals in their primary the pore level. This is because, apart from nucleation at the pore level,
stages. In contrast, for high CO2 concentrations, the aqueous phase is the growth requires capillary-driven transport, which limits the mass
entirely saturated by CO2 molecules and as a result, nucleation and transfer (Handa and Ohsumi, 1995). One of the practical consequences
crystallization of CO2 hydrate take place (Hosseini Zadeh et al., 2021; is that CO2 hydrates may preferentially form outside of the porous me­
Khurana et al., 2017). In addition, as the volumetric ratio of CO2 in­ dium than inside (Ballard et al., 2001); however, this statement cannot
creases, the time of decomposition and equilibration becomes longer be generalized because clay minerals have also been observed to act as
and leads to creation of dense and relatively stable hydrate. Generally, nucleation seeds for hydrate formation.
hydrate formation in a bulk condition is influenced by the gas concen­
tration, the gas–water interfacial area, mass transfer rate, and gas sol­ 3.1.1. Kinetics of CO2 hydrate in porous media
ubility in the aqueous phase, in addition to temperature and pressure The kinetics of CO2 hydrate formation and dissociation plays an
conditions. important role is assessing the injectivity of CO2 injection wells. The
regions with faster growth rates can lead to more severe hydrate plug­
3.1. Impact of porous media on hydrate formation ging of the pores, potentially affecting the injectivity of CO2 into the
reservoir. Similarly, the rate of hydrate dissociation determines how fast
There is a significant difference between formation of hydrate in the or slow the injectivity of the wells are retrieved.
bulk fluids and within porous media (Wang et al., 2022). The nucleation The nucleation of hydrates is a stochastic process that involves a
mechanisms involve interfaces, either gas-liquid (hydrates form at the substantial delay period lasting from hours to days, particularly in the
interface between connate water and gas) or liquid-solid (hydrates in absence of promoting agents. (Bai et al., 2015; Ke et al., 2019). To
super-saturated brine form at the solid surface, mainly at clay minerals), accurately determine the nucleation process and growth pattern in­
which are significantly different in porous media than in bulk fluid ex­ duction times, numerous individual experiments are required to gather
periments (Kvamme et al., 2020; Zhang et al., 2021). relevant statistical data. (Talaghat and Khodaverdilo, 2019). This is
Due to the exothermic nature of the hydrate formation, the nucle­ important when conducting laboratory experiments which need to be
ation and subsequent growth typically lead to an increase in the bulk designed to last for several hours to reach a nucleation probability of 1 to
temperature and a change in the bulk density of the phases (Yin et al., provide reliable evidence for or against the occurrence of hydrates.
2021). On the contrary, due to faster heat transfer in the porous medium, Experiments that last only few minutes may miss the nucleation of hy­
hydrate nucleation and growth do not have a noticeable effect on the drates. Also, in experiments, the conditions need to be kept stable for
pressure and temperature change inside porous medium (Zhang et al., many hours. The induction time before hydrates form can vary from
2021). Characteristics of porous media such as permeability (Xu et al., experiment to experiment even if conducted at nominally identical
2022), porosity, wettability (Li et al., 2022), mineral composition, pore conditions (Natarajan et al., 1994).
size distribution (PSD)(Chong et al., 2016; Zhang et al., 2021), rough­ The nucleating sites of the gas hydrates in pores directly determine
ness, and water saturation (Benmesbah et al., 2020; Jasamai et al., 2016) the spatial occurrence and distribution of gas hydrates. Depending on
have a decisive role on hydrate nucleation and growth (crystallization). the phase contact in the porous media, the nucleation may occur at the
A porous medium has a vast specific surface area that can lead to in­ solid-water, and water-gas interfaces in the porous medium (Hawtin
crease of the gas− water interface. Furthermore, the solid surface pro­ et al., 2008). Therefore, the interfacial tensions of these interfaces can
vides large area for water molecules to organize and promote nucleation determine gas hydrate stability and formation region, which are classi­
sites (Yang et al., 2010; Zatsepina and Buffett, 2002). Nevertheless, fied as homogenous nucleation of the spherical and heterogeneous
when the pore sizes are too large, the thermodynamic conditions of nucleation of cap-shaped (solid-water), lens-shaped (gas-water), and
hydrate formation are similar to the bulk conditions. This is because the film-shaped according to Fig. 4. Since the gas concentration at the
gas molecules are present in the micro pores, where water molecules gas–water interface is much higher than that in the bulk solution and
have minimum activity (Liu et al., 2022; Wang et al., 2022; Zhang et al., due to rock presence as the third phase (foreign substance), gas hydrates
2018). However, the inhibition impact of meso- and macro pores is mainly tend to be formed in pores, not on substrate surfaces, which
relatively weaker (2 nm < meso<50 nm < macro) ("Chapter 2 - indicates the heterogeneous nucleation of gas hydrates as lens-shaped

4
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Fig. 3. Morphology of the gas hydrates in porous media. Adapted from (Begum and Satyavani, 2022; Ma et al., 2019):

Fig. 4. Potential nucleation sites of the gas hydrates in porous media. Adapted from (Mirzaeifard et al., 2019):

clusters (Zhao et al., 2015b). where a configuration like a hydrate phase is obtained which stabi­
The interactions between the main components of the hydrate, i.e., lizes after reaching a certain size and crystals begin to grow.
water and gas, are the basis of the three main proposed theories 3. Surface-driven is the third theory introduced by Rodger, which states
regarding (kinetics of) hydrate formation and dissociation (Lehmkühler gas molecules are adsorbed on the water surface and are encapsu­
et al., 2009). lated in the middle of relatively constructed water cages (Rodger,
1990).
1. The cluster nucleation theory proposed by Sloan postulated that
unstable clusters preferentially agglomerate near the water surface The physical and chemical characteristics of porous media such as
after the dissolution of the gas molecules in the aqueous phase (Sloan particle size, roughness, wettability, and functional groups have a syn­
and Koh, 2008). When the cluster reaches a critical size, macroscopic ergistic effect on the kinetics of CO2 hydrate (Wang et al., 2022). For
nucleation begins. instance, surface roughness improves the nucleation sites (Wu et al.,
2. Radhakrishnan and Trout proposed the local structuring theory 2022). The wettability of surfaces is another property of the porous
based on the molecular dynamics (MD) simulation of the dense gas- medium, which has different manifestations depending on the solubility
water interface (Radhakrishnan and Trout, 2002). In this hypothesis, of guest molecules (CO2). It also impacts the mechanism and kinetics of
the water and gas molecules are placed stochastically to the point the gas hydrate nucleation by altering the structure of water molecules

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

and gas distribution near the connection surface (Bai et al., 2015; Ke water can not only be uptaken into the inner part to bind water but also
et al., 2019). The activity of water confined in the pores could be can create a hydrate structure (Jacobs et al., 2015). The water absorp­
depressed by the bonding of water molecules with the hydrophilic sur­ tion indirectly increases the free water salinity, resulting in the hydrates
faces of pores, which inhibited hydrate formation (He et al., 2021; Wang formation under more stringent thermodynamic conditions (lower
et al., 2022). Moreover, a higher degree of wettability results in a shorter temperatures and higher pressures). A similar result is obtained by Ma
induction time for hydrate formation and a faster nucleation rate. et al. (2016) regarding the impact of the amount of the residual water on
Furthermore, the smallest rock particles increase the available specific the hydrate dissociation conditions in the clays, indicating that actual
surface area, provide more area for water distribution, and increase the salinity increases, especially when the water content is low owing to
interfacial contact between multiple points (water-gas-rock). Such a binding with clay (Ma et al., 2016).
configuration promotes the proliferation of hydrate nucleation sites,
giving rise to multiple simultaneous hydrate growth locations (Kvamme 3.2. Impact of water saturation on hydrate formation
et al., 2009).
In the bulk phase, when thermodynamic conditions are conducive to
3.1.2. Impact of pore size on nucleation CO2 hydrate formation, the limiting factor lies in the availability of
The microscopic and macroscopic properties of porous media are sufficient amounts of water or CO2. In the CCS projects, CO2 is contin­
strongly affected by the pore size distribution. For example, apart from uously supplied to the reservoir, and therefore, the final volume of the
connectivity of the pores, permeability of a porous medium has a direct hydrate is determined by the water content of the porous formation or
relationship with its mean pore size. Therefore, pore size and distribu­ water saturation (Benmesbah et al.). Consequently, the water degree
tion of pore size along the porous rock are expected to affect hydrate affects the spatial availability of sites where hydrates can nucleate,
properties. Research has shown that the porous medium with small- growth and accumulate inside the pore. Moreover, water saturation
diameter pores affects the phase conditions and shifts the hydrate retards the cold front, and slightly increases the minimum temperature
equilibrium curve (Smith et al., 2002). As an example, porous medium (Chesnokov et al., 2023).
with a 4 nm pore diameter displaces the hydrate phase equilibrium to Fig. 5 shows the correlation between hydrate volume and water
lower temperatures by − 12 ◦ C compared to − 0.5 ◦ C for the porous saturation. The calculations were performed using HydraFLASH soft­
medium of 100 nm (Uchida et al., 2002). These effects are mainly due to ware version 3.8 with Soave-Redlich-Kwong (SRK) Equation of State
the additional resistance caused by capillary forces and surface tension (EoS) for different water saturations at P = 30 bar. Hydrate saturation
between phases, which results in a decrease in the water activity, (SH) was the calculated hydrate volume normalized to the pore volume
consequently affecting the hydrate phase boundary. Kang et al. (2008) of the porous medium according to the following equation:
investigated the hydrate phase equilibrium for CO2/water systems in ( )
various porous media with three pore diameters of 6, 30, and 100 nm mH = conv × nH2 O MwH2 O +
MwCO2
(2)
and concluded that the pores with 6 nm diameter improved the CO2 nH
hydrate thermodynamic stability, while the pore with diameter of 30 nm
and 100 nm performed inhibition effect in the dissociation equilibria. Hydrate volume (m3 ) mH
SH (%) = = (3)
A decrease in the grain size potentially increases the rate of hydrate PV (m3 ) PV × ρˎH
formation. Mekala et al. (2014) conducted CO2 hydrate formation ki­ Where mH is the mass of hydrate, conv is the water fraction that has
netic experiments in the presence of pure water and seawater (3.3 wt% converted to hydrate (%), nH2 O , MwH2 O and MwCO2 are the total moles of
salinity) using silica beds with three pore sizes. They observed that the water, the water and CO2 molecular weight, respectively. Hydration
CO2 consumption in hydrate and the induction time of hydrate forma­ number (nH ) is the average number of water molecules per guest
tion at the end of seawater experiment were both lower than those of the molecule in the hydrate. In equation (3), the term ρˎH is density of hy­
pure-water experiment. A smaller silica size exhibited an enhanced drate and PV is the pore volume of the porous medium.
average rate of hydrate formation in the pure-water experiment. There is a linear relationship between hydrate volume (or hydrate
saturation or hydrate volume fraction in the porous medium) and water
3.1.3. Impact of minerals on hydrate formation saturation. Hydrate saturation refers to the volume fraction of pore
Reservoir rocks, generally sandstone and carbonates, consist of space (containing water and hydrate) occupied by hydrate (You et al.,
various minerals, such as quartz, kaolinite, bentonite, feldspar, calcite, 2019). High water saturation enables a more interconnected network of
dolomite, etc., which also play important role in formation and disso­
ciation of hydrates in porous media (Rehman et al., 2021). Compared
with sandy sediments, clay sediments are distinguished by an extensive
specific surface area through small particle diameters, high capillary
pressure, and massive content of bound water, influencing different
features of hydrate-formation process (Nair et al., 2016). Mu and Cui
investigated the hydrate equilibrium conditions under bulk and clay
sediment with various salt content and showed that there is no coupling
impact between the clay and salt (Mu and Cui, 2019). They also
observed that the temperature changes in the clay and bulk phase were
almost identical in the presence of salts. Consequently, due to the
stronger interaction forces between the clay and water particles, as well
as the water absorption characteristics of the clay that reduce the
effective porosity of the sediment through swelling, the coupling impact
mostly occurs in the clay-containing systems (Geng et al., 2021).
Therefore, the porosity reduction inhibits gas transmission and thus
negatively impacts hydrate formation and dissociation (Kumar et al.,
2015). Besides, there exist many exchangeable cations among the Fig. 5. The relationship between the water saturation and hydrate saturation at
layered structure of the clays, particularly for bentonite as a lamellar different temperatures and P=30 bar. At T=-10 ◦ C, no ice formation was
aluminosilicate mineral (Bergaya et al., 2011). Therefore, this specific assumed. The density of the hydrate was calculated as 804.2 ± 0.1 g/L
structure is characterized by its large water absorption capacity, where (HydraFLASH version 3.8, SRK EoS).

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

water molecules, facilitating the construction and accumulation of CO2


hydrate lattice. However, the impact of Sw on hydrate volume can vary
depending on the prevailing thermodynamic conditions of the system,
especially at low temperatures when hydrate coexists with the ice. The
simulation outcome suggests that when the reservoir conditions fall
within the hydrate stability region, the impact of temperature on the
volume of hydrate during CO2 injection is relatively low. This limited
influence of temperature could stem from the fact that, when CO2 con­
centrations are higher (due to CO2 inflow), the water is rapidly saturated
with CO2. Consequently, any additional temperature variations do not
substantially alter the solubility of CO2 in water— an essential factor for
the formation of hydrates. This insight underscores the complex inter­
play between temperature, CO2 concentrations, and water saturation in
determining hydrate volume within the porous system.
Furthermore, the temperature profile during cold CO2 injection is
influenced by water saturation, which in turn affects the hydrate sta­
bility and phase transitions. The increase in water saturation results in
retardation of the cold front, and slight increase of the temperature in
the reservoir due to heat content of the water (Mathias et al., 2010).
Moreover, considering that the water in the reservoirs usually contains
high amounts of salt, hydrate formation has the potential to form con­
Fig. 6. Representation of memory effect in CO2 hydrate formation process. All
centration gradients and initiate the precipitation of salts or minerals
three stages of hydrate formation process (dissolution, induction, and growth)
within the pore space of the rock formation, leading to a further are affected by water memory effect.
reduction in porosity (Zhang and Liu, 2016). The volume of the salt is
determined by the volume of the available water in the pores.
previous hydrate formations in the porous medium. This process can
lead to a self-sustaining cycle, where dissociation of the existing hy­
3.2.1. Memory effect on formation of hydrates
drates triggers formation of new hydrates, especially if there is a
The water memory effect in the nucleation of gas hydrates refers to
continuous supply of gas molecules. This phenomenon can have impli­
the phenomenon that gas hydrates nucleate easier or faster in water that
cations for the stability of the gas hydrates within the reservoir and their
has a history of gas hydrate formation compared to fresh water (water
potential to reform after dissociation. However, other parameters such
without hydrate history) (Gao et al., 2023; Wei and Maeda, 2023). While
as the nature and purity of the guest compound, the mechanism and the
research on the water memory effect in bulk systems is relatively
temperature of the dissociation, and the specific characteristics of the
abundant (Fandiño and Ruffine, 2014; Uchida et al., 2002; Zhao et al.,
porous medium all contribute to shaping these changes (Rossi and
2023), its influence on the behavior of CO2 hydrate in porous media has
Gambelli, 2021).
received less attention due to the complexity of the problem. Based on
Another hypothesis for water memory effect is the reduced salinity of
the molecular hypothesis, the water memory effect can lead to changes
water with every hydrate formation/dissociation cycle, which affects
in the molecular structure and configuration of the water molecules after
both CO2 dissolution and the phase diagram. This is schematically
dissociation of the CO2 hydrate. The occurrence of the residual structure
shown in Fig. 7. As only water molecules enter the hydrate structure
is recognized by the difference in water viscosity before hydrate for­
(Shen et al., 2023), the salinity of the remaining brine increases to the
mation and after hydrate dissociation. This altered water structure acts
saturation point, such that eventually salt drop out or precipitation oc­
as a kinetic promoter and influences the kinetics of CO2 hydrate
curs in the pores. During dissociation of the hydrate, water molecules
nucleation and growth in the subsequent hydrate formation cycle. For
exit the lattice; however, due to the limiting mixing and relatively slow
example, the remaining arrangements of the water molecules reinforce
rate of salt re-dissolution, for the following hydrate formation cycle the
the ability of the CO2 molecules to incorporate into the hydrate lattice or
brine salinity is effectively lower. Part of the salt could precipitate in
impact the nucleation of the hydrate crystals, when initiated by the
small corners and crevices making the dissolution process even slower.
pre-existing clusters/structures in water. According to another hypoth­
The decrease in salinity increases the CO2 solubility in brine and pro­
esis, a significant number of nanobubbles, due to hydrate dissociation in
motes hydrate formation in the subsequent cycle.
porous media, remain dispersed in the dissociated water for a long time
(more than one day). The CO2–water interfaces of these nanobubbles
3.2.2. Self-preservation effect on dissociation
may act as nucleation sites for heterogeneous nucleation of the hydrate
Hydrate self-preservation is interrelated to the ice capping theory
in porous media and subsequently impact the history of distribution/­
(Falenty and Kuhs, 2009), which explains the process of development of
accumulation and growth of the CO2 hydrate (Hassanpouryouzband
a thin liquid water layer on the hydrate surface and subsequently
et al., 2020; Khurana et al., 2017). Furthermore, the induction time (the
freezing to create an ice cap. This phenomenon could pose another po­
duration between the introduction of CO2 into the system and the first
tential challenge concerning the dissociation of CO2 hydrates, when
instance of CO2 hydrate nucleation) is also influenced by the water
favorable conditions for hydrate dissociation, such as pressure reduc­
memory effect (Gauteplass et al., 2020a). This implies that the temporal
tion, arise. Although regasification can be achieved by increasing the
interval for the onset of the hydrate nucleation can be altered due to the
temperature above the ice melting point, more extended stability of
historical interactions of water with its surroundings (Fig. 6).
hydrate within the self-preservation region has been experimentally
On the other hand, gas hydrate dissociation is an endothermic pro­
observed (Li et al., 2021). Due to limited available research, the exact
cess and requires an input of heat energy (depending on the occupancy
mechanism of self-preservation is obscure, and these knowledge gaps
of the hydrate cage) to break the hydrate structure and release the gas
must be comprehended especially for feasible CCS technologies. Under
molecules. This energy can be sourced from the surrounding environ­
normal conditions, the CO2 molecules rupture from the hydrate struc­
ment, leading to cooling of the system. During subsurface CO2 storage,
ture, reducing the stability of the hydrate and allowing CO2 to escape
the cooling effect resulting from gas hydrate dissociation could establish
into the gas phase (Kainai et al., 2023; Myshakin et al., 2009; Sum et al.,
conditions conducive to the reformation of the new gas hydrates. This is
1997). With self-preservation, the dissociated gas molecules are
especially relevant if there are residual hydrate structures or memory of

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Fig. 7. Impact of water memory on brine salinity and CO2 hydrate formation/dissociation at the pore scale. The departure of water molecules into the hydrate cage
leaves salt behind, which is unlikely to be fully dissolved during dissociation of hydrate. The reduced salinity of the brine enhances hydrate formation in the
subsequent cycles.

prevented from leaving the hydrate lattice due to capillary forces that can shift with these variations in pressure and temperature. Moreover,
arise from the small pore size of the CO2 hydrate structure, or a pro­ the magnitude of temperature reduction and the position of the cooling
tective layer of the ice around the hydrate particles (Chen et al., 2021; front caused by isenthalpic expansion effect is a function of gas
Mestdagh and De Batist, 2015). In the context of subsurface CO2 storage, composition (Ziabakhsh-Ganji and Kooi, 2014). The macroscopic
this layer can be formed due to heat absorption during hydrate disso­ transport properties of the rock such as relative permeability and
ciation (endothermic reaction) (Pandey et al., 2021; Singh et al., 2020; capillary pressure function can also be altered by presence of impurities
Yang et al., 2021) or exposure to cold regions. Indeed, during the in the gas phase (Anderson et al., 2009).
dissociation of CO2 hydrate in the porous media, heat is absorbed by the Fig. 9 compares the thermodynamic conditions of CO2 hydrate in the
rock and the in-situ fluids, leading to the formation of a cold or frozen presence of impurities with different concentrations inside the reservoir
layer in the surrounding layer. This layer acts as a thermal barrier, using HydraFLASH software and Cubic Plus Association (CPA) EoS. In
insulating the remaining CO2 hydrate from further dissociation (Burla the case of H2S, its higher solubility results in a greater concentration of
and Pinnelli, 2023; Majid and Koh, 2021). In addition, this cold zone can dissolved H2S available for hydrate formation. The increased concen­
induce the nucleation of hydrate around the ice layer. This phenomenon tration of H2S can enhance the likelihood of hydrate formation. In
is schematically shown in Fig. 8. This condition is more pronounced for addition, H2S can influence the thermodynamic conditions of the sys­
higher dissociation rates due to limited time for heat exchange. On the tem, impacting the stability conditions for CO2 hydrate formation,
other hand, pore size, geometry, and arrangement are interrelated fac­ which favors the formation of hydrates at higher temperatures and
tors that influence heat transfer in porous media. lower pressures (Mohammadi and Richon, 2015). The presence of N2 has
minimal impact on CO2 hydrate formation conditions compared to other
3.3. Impact of impurities and mixing on hydrate formation impurities like CH4 or H2S. Since nitrogen does not strongly interact
with water molecules or compete for hydrate cage occupancy, its pres­
During CO2 storage in a depleted gas field, the injected CO2 will mix ence has little effect on the stability or formation of CO2 hydrate. The
with the native gas (usually light hydrocarbons such as CH4). Moreover, impact of gaseous impurities on CO2 hydrate formation conditions tends
the injected CO2 stream might contain small traces of other gases. The to be more pronounced at higher pressures. At lower pressures, typically
composition of gas affects both isenthalpic expansion cooling and hy­ below 40 bar, the solubility of these impurities decreases in the solution,
drate properties (Chapoy et al., 2011; Kvamme, 2022). Depending on resulting in reduced interaction between the gas and water phases.
the specific conditions and the nature of the impurities, the presence of Consequently, CO2 hydrate formation is less affected by these gases, and
residual impurities can influence CO2 phase behavior affecting its sol­ the stability zone is closer to the pure CO2 phase (the stability zone
ubility and miscibility. Consequently, the stability conditions of hydrate becomes wider).

Fig. 8. Self-preservation mechanism impacting the stability of CO2 hydrate within a porous medium as a result of heat absorption during dissociation of CO2 hydrate.

8
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

in contact with the cold CO2 converts to hydrates. As a result, with more
water coming to near wellbore, the saturation of hydrate might increase
resulting in more severe injectivity decline. This is similar to the halite
precipitation or the dry-out process, which occurs due to the evapora­
tion of water into the gas phase (Talman et al., 2020). Moreover,
capillary crossflow can occur between the layers of different perme­
ability, drawing more water from the low permeability layer to the high
permeability layer (Roels et al., 2016). For the salt dry-out process, this
phenomenon accumulates the brine (and eventually salt) inside the high
permeability layer with the highest salt concentration at the interface of
the two layers. The capillary pressure gradient is determined by the
difference between the layers, the magnitude of the (horizontal and
vertical) permeability, while the relative permeability and injection rate
determine the magnitude of capillary-driven water backflow and
crossflow. These effects are schematically shown in Fig. 10.
It should be noted that because of the key differences between the
dynamics of the dry-out and hydrate formation processes, the impact of
the capillary-pressure heterogeneity on the two processes could be
different and needs further investigation.

3.5. Simultaneous salt dry-out and hydrate formation during CO2


injection
Fig. 9. Thermodynamic conditions of CO2 hydrate in the presence of residual
gaseous impurities with 1 wt% NaCl inside the reservoir (HydraFLASH, Under favorable thermodynamic conditions, two processes of salt
CPA EoS). dry-out and hydrate formation can simultaneously occur in the reservoir
during CO2 injection. However, the interaction between the two
3.4. Impact of capillary heterogeneity competitive phenomena is not well-understood. Research is needed to
investigate how the presence of simultaneous salt precipitation and CO2
For CO2 storage applications, it is noteworthy to gain a better un­ hydrate affects mass and heat transport in porous media.
derstanding of the impact of the geological heterogeneity on the During injection of cold CO2, the saturations of water, salt, and hy­
multiphase flow properties of porous media, particularly in the CO2/ drate vary continuously, at least near the wellbore area. When the
brine distribution during the long-term activity (Saadatpoor et al., temperature of CO2 is above the hydrate equilibrium temperature, the
2010). The inherent heterogeneity of the sedimentary rocks gives rise to near wellbore region has temperatures that are outside of the hydrate
the issues in the variation of capillary pressure corresponding to local stability zone (the right region of diagram in Fig. 1). In this case, due to
changes in porosity and permeability, for both perspectives of micro­ evaporation of water into the gas phase, a dry zone appears. The extent
scopic and macroscopic scenarios. The effect of heterogeneities can be of this dry-out zone depends on reservoir properties, injection rate and
commonly explained by the Leverett J-function and reflected on the Pc – salinity of brine. However, when the wellbore temperatures are below
S and kr – S relationship of a porous medium (Pini et al., 2012). This can the hydrate stability zone, the appearance of the dry-out zone depends
be calculated by using the data of the measured capillary pressure. on the rates of water evaporation (salt precipitation) and hydrate for­
Leverett (1941) gave the scaling relationship of Leverett J-Function for mation. If evaporation rate is faster, a dry-out zone with high salt con­
characterizing rock sample capillary heterogeneity: centration might appear. However, the rate of water evaporation is very
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ low at low temperatures, especially when the temperature drops below
/ ̅
kref φref zero (see Fig. 11). If hydrate formation rate is larger, then hydrates will
Pc (Sw , k, φ) = σ cos θ J(Sw )
k/φ form first and the available water will be consumed in the hydrate
structure. With departure of the water molecules, the brine salinity in­
where J is the dimensionless J-Function characteristic of a given rock creases leading to salt precipitation occurring simultaneously in the
type determined by the measured capillary pressure data, σ and θ are the potential hydrate zone (Liu and Flemings, 2007; Shen et al., 2023). The
interfacial tension and contact angle of the fluid systems, φref and kref are competition between water evaporation rate and hydrate formation rate
the reference porosity and permeability, and φ and k are the porosity needs to be discussed and requires more scientific investigation.
and permeability of the rock. Many studies of numerical modeling have Hydrate formation rate is affected by multiple factors, e.g., temper­
revealed that heterogeneity plays a crucial role in CO2 migration (or CO2 ature and pressure, surface active agents, salinity and ion types, pore
trapping) and that the permeability dominates the plume migration size, water saturation, etc. (Zhao et al., 2016). This complexity makes it
distance and the sweep area (Han et al., 2010; Nghiem et al., 2009). difficult to quantify the formation rate and to compare it with the loss
Residual CO2 trapping has an inverse function to the permeability, while rate of water. Wells et al. (2021) measured the CO2 hydrate propagation
a higher variance in lnk results in an decreased residual trapping. in a microchannel at a rate over 1000 mm/s, under − 2 ◦ C and 400–500
However, the impact of capillary heterogeneity on hydrate formation psi. Additionally, the propagation rate increased with the increase in the
is still not well understood. When CO2 flow encounters a rock, CO2 subcooling temperature and pressure. In porous media, hydrate induc­
displaces the in-situ brine, if the saturation is above the residual or tion time in salt water is shorter than in pure water but the formation
connate water saturation. The non-uniform saturation of water leads to a rate is the opposite (Yang et al., 2016). Gauteplass et al. (2018) per­
capillary pressure gradient, that in turn results in back flow of water formed a series of core flooding experiment on the Bentheimer sand­
from the displacement front toward the injectors (Cui et al., 2018). The stone for three cases of brine salinity, 3.5 wt%, 5 wt% and 7 wt%, under
magnitude of the backflow depends on the shape of the the experimental pressure of 70 bar and temperatures of 4 ◦ C, 6 ◦ C and 7
capillary-pressure function, which is determined by the pore size dis­

C. They observed that after around 0.3 PV of CO2 injection, the core
tribution (heterogeneity), and permeability of the rock. The samples were completely plugged due to hydrate formation. They also
capillary-driven backflow accumulates water close to the injector, which noticed that water saturation played an important role on the hydrate
formation and pore blockage. In Zhang et al. (2019) experiments were

9
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Fig. 10. Schematic of the capillary-driven backflow from high-permeable region to low-permeable region during CO2 injection. The red arrows present the capillary
backflow due to capillary pressure gradient and the yellow arrows present the capillary pressure difference between layers.

pressure. Consequently, a prompt decrease of the pore space through the


ongoing hydrate growth leads to a space blockage and a high-pressure
gradient (White, 2011). To mitigate this issue, it is crucial to gain a
thorough understanding of the relationship between the permeability
and the geometrical features of the porous medium (porosity and
permeability), and CO2 hydrate saturation. Such understanding can
provide insights into the mechanisms behind this challenge and aid in
developing strategies to prevent or alleviate the adverse effects of CO2
hydrate formation near the wellbore (Deng et al., 2021; Jianzhong Zhao
et al., 2015).
Kneafsey et al. (2011) showed that the permeability of porous sedi­
ments appertains to porosity, pore geometry, hydrate morphology, as
well as fluid characteristics. Priegnitz et al. (2015) proposed an empir­
ical model, based on which the permeability of the porous medium is
mainly influenced by porosity, pore size, and gas hydrate morphology.
Hydrate formation in the pore space leads to a decrease in effective
permeability, influenced by the hydrate morphology, its distribution
and saturation (Sahoo and Best, 2021). In addition, the effective water
permeability decreases with the decrease in the pore size, which is
further affected by the rock heterogeneity. However, gas-hydrate mor­
Fig. 11. Water solubility into CO2 as a function of pressure for various tem­ phologies that inhibit inner-pore connectivity (switch off pore network
peratures (data generated using HydraFLASH). pathways) are more than the hydrate morphologies that only confine
permeability within pores (reduce flow uniformly through the entire
carried out in frozen sand and hydrates were forming from ice pores network) (see Fig. 3 for illustrations).
(Sice~13%). The formation rates were actually quite low (9.4 × 10− 4 Verma and Pruess (1988) proposed a porosity-permeability rela­
mol/h~17 mg/h, and the tests ran for ~140 h to reach a 66% conversion tionship of the tube-in-series model, which is commonly used in nu­
of ice to hydrates). merical simulations. This model treats capillary as a 1-D tube consisting
Furthermore, with evaporation of water, salinity of the reservoir of wide and narrow segments. The value of the permeability is deter­
brine starts to increase. The hydrate equilibrium temperature is shifted mined by the local radii of the narrowest part of the tube. Therefore, it
to lower temperatures. As a result, hydrate formation might be hindered can be used for correlating the changes in the permeability and the
when water evaporation is relatively high. porosity induced by the clogging in the processes of mineral dissolution
and precipitation, shown as
3.5.1. Impact of hydrate formation on rock permeability k 1 − Γ + Γ/ω2
A significant challenge in successful geological storage of CO2 is the = θ2 ( )2 (4)
k0
permeability impairment, and ultimately, injectivity loss due to CO2 1 − Γ + Γ θ+ωθ − 1
hydrate formation in the near-wellbore area. At the early stages of the
injection, CO2 density undergoes a substantial decline due to the dense- φ − φc
θ= (5)
to-gas state transition, which subsequently impacts the wellhead φ0 − φc

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

( )
φc = πΓ ̃r2 − r2 (6)

where, k0 and φ0 are the initial permeability and porosity, θ is the


normalized porosity, φc is a finite porosity, Γ is the fraction of the total
length of a capillary tube has a ̃r while the remainder 1 − Γ has a smaller
radius r, and ω is the ratio of cross sectional areas of the tube segments
(̃r/r)2 .
When Γ = 0.8 and φr = 0.9, is the porosity for the pore radius with r,
Equation (2) can be fit by a power law as below (Pruess and Müller,
2009), meaning that the permeability reduces to 0 while 10% of pore
space is clogged. The relationship
(φ )2
k − φr
(7)
φ0
=
k0 1 − φr

was proposed as a model in a numerical simulation (Liu et al., 2013).


Here, the pore space is considered as cylindrical capillaries with a radii r
and was either water-filled or completely dry. The capillary pressure had Fig. 12. Rock permeability as a function of hydrate saturation – a compilation
a relative change with pore volume due to mineral precip­ of analytical models provided in Table 1.
itation/dissolution. The permeability change can be described as follows
(Le Gallo et al., 1998). lowest impact is observed in a layered system with layers parallel to flow
k √̅̅̅[ ( ( √̅̅̅)m ) ]2 direction where most of the hydrate is formed in the layers with smaller
= τ (δ − 1) 1 − 1 − m S +1 (8) pores (which have the larger water contents due to higher capillary
k0
pressure).
where τ is the tortuosity factor, and τ = 1 − Sp + δ2 Sp , Sp is the effective Core flooding experiments imaged by MRI (Ji et al., 2019) suggest
brine saturation at the time when mineral reaction starts, δ is the that it is possible that eventually the whole pore space of a large-scale
multiplied proportionality factor for calculating new pore-size distri­ rock sample is filled with hydrates, which is the worst case for perme­
bution after reactions, and S is the effective water saturation during ability reduction.
reactions. It is important to mention that the larger scale spatial distribution of
Other correlations have been developed considering different pore hydrates is not only a consequence of the rock heterogeneity but also a
shapes than the simple capillary model (e.g., capillary tube model and matter of the injection regime (Shagapov et al., 2015), in a similar way
Kozeny grain model) and the location of hydrates in the pore space (e.g., as the dissolution patterns in rock during reactive transport (frontal
surface coating and pore-filling), are presented in Table 1. dissolution, homogeneous dissolution, wormholing etc. (Snippe et al.,
The permeability calculated by different models are shown in Fig. 12. 2020). For gas hydrate formation, the dominant regimes are based on a
The pore-filling models appear to allow for full blockage of the pores conceptual mathematical model (Shagapov et al., 2015) considering
with formation of hydrates after a certain hydrate saturation. volumetric zone, and frontal zone.
Additionally, the porosity change with the hydrate formation and However, the initial distribution of the gas is not necessarily uniform.
accumulation can be described as: A similar observation was also made by CT scanning (Ji et al., 2019).
Note that in the CT scanner, hydrates are identified via their lower
φt = φi (1 − SH ) (9)
density.
where φt and φi are the total porosity of the porous domain with and
without hydrate, respectively (Rempel and Buffett, 1997). 3.5.3. Dynamics of well-reservoir interaction
The temperature at the bottomhole depends on the back pressure
3.5.2. Impact of heterogeneity on permeability reduction induced by the porous medium connected to the well (Liu et al., 2016),
The hydrate nucleation pattern above pore scale level in combina­ which is largely determined by the permeability of the rock. The tem­
tion with rock heterogeneity has a major impact on the permeability perature at the sand face decreases with higher permeability. Therefore,
reduction as illustrated in Fig. 13. The largest permeability reduction is for a heterogeneous reservoir with different permeability layers, the
observed for a cross-sectional hydrate pattern (Pan et al., 2021). The high permeability layers will be at higher risk for formation of hydrates
due to combined effects of high CO2 flowrates in these layers and low
temperature at the boundary. If the bottomhole temperature is already
Table 1 lower than equilibrium hydrate temperature (see Fig. 15A2), then CO2
Analytical models for water permeability in porous media in the presence of
hydrate will form immediately starting from the sand face. Formation of
hydrates.
hydrate reduces the rock permeability, resulting in increased pressure in
Capillary Grain- krw = (1 − SH )2 the well (P1 in Fig. 14), which in turn results in increase of temperature
tube coating
(T1 in Fig. 14). The speed of pressure increase depends on the rate of
Pore-filling krw = 1 − SH 2 + 2(1 − SH )2 / hydrate formation and the magnitude of permeability reduction induced
ln (SH ) by the hydrate. The rock permeability can also be affected by other
Kozeny Grain- krw = (1 − SH )n+1 if 0<SH < 0.8 then mechanisms such as salt precipitation, fines migration, dissolution of
grain coating na = 1.5 secondary mineral due to reduced pH, clay swelling, etc. If the tem­
it SH > 0.8 then perature rises above the equilibrium hydrate temperature, hydrate will
na>1
start to dissociate. With the dissociation of hydrate, the reservoir
Pore-filling krw = na = 0.7 SH+0.3
(1 − SH )n+2 /(1 + SH 0.5 )2
permeability increases, and thus the pressure starts to decline (P2 in
Kozeny- krw = (1 − SH 3 )/(1 + 2SH )2 Fig. 14). Hydrate dissociation releases significant volume of CO2, which
Carman can increase the pressure locally. The slope of P1–P2 line in Fig. 14 de­
a
n: saturation exponent. pends on the dissociation rate of the CO2 hydrate. The rate of

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Fig. 13. Impact of the hydrate nucleation pattern and the rock heterogeneity on the permeability reduction. Adopted from (Pan et al., 2021).

dissociation is influenced by injection of hydrate inhibitors (HIs) and in relative permeability, which also depend on an often-changing water
thermal stimulation. The extent of heat exchange between the sur­ saturation (Ott et al., 2011, 2021).
rounding formations and the hydrate-bearing formation can also affect In addition, in certain types of pore geometries and heterogeneous
the rate of dissociation. With the reduction of pressure, the well tem­ settings, hydrates may form with hardly an impact on permeability (Ott
perature also comes down. Because of the self-preservation effect, all the et al., 2015; Pan et al., 2021). Therefore, pressure drop measurements
encaged CO2 might not be released, which could result in higher pres­ alone are not considered a reliable method to detect hydrate formation.
sure and temperature than those of the previous step. Moreover, with They provide indications and complementary information is required.
injection of more CO2 the average reservoir pressure increases. Once To provide a clear and reliable indication of hydrate formation, in-situ
again, if the temperature drops below the equilibrium hydrate temper­ monitoring methods are required. Several reliable in-situ imaging
ature, hydrate starts to form. Because of the water memory effect, hy­ methods have been used in the literature including NMR (bulk) (Ji et al.,
drate might form faster in the following cycles with potentially larger 2019; Vaessen et al., 2000; Zuniga, 2020), MRI (imaging) (Haneda et al.,
volumes or more compact structure. 2002; Ji et al., 2019; Mooijer, 2004), CT – (Meyer et al., 2018), micro-CT
This dynamic behavior in the boundary between the well and the (Chaouachi et al., 2015), optical microscopy (2D only) (Lv et al., 2021),
reservoir continues until the average reservoir pressure increases above electrical resistance (Chen et al., 2020), and Raman spectroscopy (Ikeda
the HQP in Fig. 1. The value of the HQP is influenced by many param­ et al., 1998, 2018; Nakano et al., 1998; Sum et al., 1997). NMR and MRI
eters including brine salinity, composition, gas composition, concen­ are considered very sensitive to the formation of hydrates because the
tration of chemical, etc. At this point, the well temperature stays above water bound in hydrates is NMR silent (relaxation time is very short),
the hydrate equilibrium temperature and the situation becomes similar which make hydrates easily and unambiguously detectable (Haneda
to Fig. 15. For this scenario, formation of hydrate inside the porous et al., 2002).
medium depends on the magnitude of the pressure drop (which even­ 2D-micromodels are usually applied to monitor the hydrate forma­
tually leads to low temperatures due to isenthalpic expansion cooling tion and kinetics under controllable observation domain and pore
effect), largely influenced by rock permeability, thickness of the reser­ structure (Christiansen and Sloan Jr, 1994; Muraoka et al., 2020; Pandey
voir, injection rate, among other parameters (Mathias et al., 2010). The et al., 2022). The formation of gas hydrates in the 2-D micromodels can
higher temperature of CO2 near wellbore can result in faster evaporation be well explained (Wang et al., 2021). Some inside on interactions be­
of water into the CO2 stream leading to zone with low water saturation tween wettability, supercooling and hydrate formations and dissociation
and high salt concentrations. can be discovered using pedant drop (Daniel-David et al., 2015) and
capillary tubes experiments (Touil et al., 2019).
3.5.4. Multi-scale visualization of hydrate formation in porous media
To detect the formation of hydrates in laboratory experiments, 4. CO2 hydrate prevention/remediation approaches
several experimental methods are available. They in general group into
Pressure-drop measurements (indirect), and imaging of the hydrates Gas hydrate controlling techniques (e.g. dehydration, thermal stim­
(direct). Pressure-drop measurements utilize the effect of permeability ulation, and chemical additives, etc) rely on comprehending the mech­
reduction when hydrates form. Even though one of the key questions is anisms by which hydrates form and dissociate (Koh et al., 2002; Mooijer,
the extent of the permeability reduction, the more basic question is 2004; Peters et al., 2012). In the context of CCS, the utilization of hy­
whether hydrates are formed in the first place, and how much. Pressure drate inhibitors (HIs) represents the most effective and practical chem­
drop is not only impacted by permeability reduction but also by changes ical approach to control hydrate formation. This involves altering

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Fig. 14. The continuous change of wellbore temperature and pressure during hydrate formation and dissociation.

hydrate phase boundaries, thereby situating the existing operating cage formation (Holzammer et al., 2016; Zhang et al., 2018; Zuo and
conditions outside the Hydrate Stability Zone (HSZ), which is useful in Stenby, 1997). The hydration of salt ions with water molecules in a
preventing injectivity decline due to the hydrate formation. HIs are saline solution enhances the ion charge, which leads to a decrease in the
segregated into three main groups based on the different inhibition solubility of nonelectrolyte molecules (CO2) so-called salting-out effect
mechanisms, thermodynamic hydrate inhibitors (THIs), kinetic hydrate (Englezos and Bishnoi, 1988; Holzammer et al., 2016; Li et al., 2020).
inhibitors (KHIs), and anti-agglomerates (Ke et al., 2019). The effectiveness of the salting-out effect depends on the ionic radius of
the salt ions, and as the ionic radius increases, the ability of the ions to
4.1. Impact of thermodynamic hydrate inhibitors (THIs) induce the salting-out effect decreases. This is because larger ions have a
weaker influence on water molecules, resulting in weaker solvation and
Under low water content, THIs is the best chemical to protect the a smaller impact on the solubility of nonelectrolyte molecules. Never­
system from hydrate formation by shifting the equilibrium boundary theless, cations and anions can have distinct interactions with water
towards lower temperatures or higher pressure (Kelland, 2019; Koh molecules or may form complexes with CO2 molecules. According to
et al., 2012). However, the amount of chemicals required to eliminate research studies, the inhibition impact of cations on CO2 hydrate for­
the hydrate formation condition may exceed half of the water content. mation can be presented in the following order: Mg2+>Ca2+>Na+>K+
Therefore, their utilization in the CCS project should be considered from (Falahieh et al., 2022; Pahlavanzadeh et al., 2023). However, the rela­
two perspectives: (1) functional mechanism and antisolvent effect, (2) tive solubility and ionization properties of monovalent (NaCl and KCl)
economic costs. The THIs can be predominantly classified into three and divalent (CaCl2 and MgCl2) salts in water can indeed have different
distinct categories: glycols, alcohols, and salts. influences on kinetics, stability, and thermodynamic properties of CO2
hydrate in distinct ways (Dholabhai et al., 1993; Zha et al., 2012).
4.1.1. Salts (mono and di-valent salts) Fig. 16 shows the formation conditions of CO2 hydrate in the pres­
Salts or electrolytes are types of THIs that dissociate into cations and ence of single and binary salt solutions using HydraFLASH software. It is
anions when dissolved in water and interact with water molecules seen that increasing salinity of the solution enhances the inhibitory ef­
through strong coulombic attractions which disrupt the hydrogen- fect on CO2 hydrate formation, which was observed at both high and low
bonding network of water and reduce its availability to participate in pressures in different saline solutions. However, at high pressures,
the hydrate network (Dholabhai et al., 1993; Javanmardi and Moshfe­ increasing the solution salinity leads to a more pronounced inhibitory
ghian, 2000; Liu et al., 2021). Smaller ions with higher charge density property, resulting in a larger decrease in the hydrate dissociation
have a stronger ability to interact and bond with water molecules, temperature. Regarding the information provided, at moderate pres­
showing tendency to disrupt water structure, therefore, hinder hydrate sures and concentrations below 5 wt%, MgCl2 and CaCl2 show a

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Fig. 15. Impact of wellbore CO2 temperature on the temperature, water saturation, and hydrate saturation profiles in porous media during injection of cold CO2.

comparable inhibitory effect on CO2 hydrate formation. However, at low 4.1.2. Glycols and alcohols
pressures and concentrations above 10 wt%, MgCl2 demonstrates a Research has revealed that reducing the molecular weight (MW) of
greater capacity to decrease the equilibrium temperature of CO2 hydrate alcohol or glycol compounds can lead to enhanced performance in
compared to CaCl2. In the binary combination of NaCl + MgCl2, MgCl2 suppressing hydrate formation. This effect is attributed to the ability of
has a stronger inhibitory impact compared to NaCl due to its smaller size compounds to form more stable complexes with water or CO2 molecules.
and stronger interaction of Mg2+ ions with water molecules. On the It’s noteworthy that, lower-MW inhibitors are generally more efficient
other hand, in the NaCl + KCl mixture, Na+ and K+ ions, being even as they yield higher molar/molal concentrations than higher-MW in­
larger in size, exhibit a relatively lower inhibitory effect due to their hibitors at the same mass concentration. In this scenario, monoethylene
weaker interaction with water molecules, however, NaCl exhibits a glycol (MEG) exhibits more effective inhibition performance compared
dominant inhibitory effect. to diethylene glycol and triethylene glycol (TEG) due to its lower density
The presented data is a general trend observed in the laboratory and and viscosity (Aminnaji et al., 2017; Gauteplass et al., 2020a; Munck
modeling studies, but the precise impacts can vary under reservoir et al., 1988; Nielsen and Bucklin, 1983). Moreover, methanol exhibits
conditions based on thermodynamic conditions and medium properties. greater efficacy compared to ethanol. However, one significant draw­
In the scenario where the reservoir experiences a significant drop in back of these oxygenated inhibitors, like methanol, is their dis­
temperature, there is a possibility of salt precipitation occurrence. The tribution/evaporation behavior (more volatile/lower boiling
cooling effect caused by the endothermic dissociation of CO2 hydrates is temperature), leading to a decrease in their concentration below the
another problem that leads to further precipitation of salts, exacerbating desired level compared to non-oxygenated inhibitors like MEG (Brustad
the issue. This can lead to the salts losing their effectiveness, especially et al., 2005). Fig. 17 compares the corresponding weight fraction of
when operating below their eutectic temperature. In this regard, the different glycols and alcohols as inhibitors for a 10 ◦ C depression tem­
maximum concentration of NaCl before precipitation is approximately perature of CO2 hydrate using HydraFLASH. According to the diagram,
23.3 wt% at − 21.1 ◦ C, while for a 30 wt% CaCl2 solution, precipitation methanol is preferred due to its strong hydrate inhibition properties, and
begins at a lower temperature of − 51.5 ◦ C. This parameter can also be is often used as selective inhibitors in various applications. However, it
impacted by the introduction of other chemicals like MeOH into the should also be worth evaluating other factors such as antisolvent effect,
reservoir, which can be the subject of future research. solubility, potential side effects, safety, and economic feasibility when

14
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Fig. 16. Impact of different salt types and their concentrations on the CO2 hydrate equilibrium temperature at elevated pressures. Light column: 30 bar; dark column:
20 bar (HydraFLASH, version 3.8).

Fig. 17. Inhibitor requirements in the aqueous phase for depression tempera­
ture of 10 ◦ C (HydraFLASH version 3.8).

selecting an appropriate inhibitor for CO2 hydrate inhibition (Cao et al.,


2020). The presence of MeOH at low temperature might result in pre­
cipitation of salt, that can adversely affect the rock permeability.
In addition, the thermodynamic conditions of CO2 hydrate in the
presence of effective alcohols and glycols have been obtained in a wide
range of pressure and concentrations by utilizing HydraFLASH (Fig. 18). Fig. 18. Impact of Methanol and MEG on hydrate phase of CO2-water system
Accordingly, the effectiveness of MEG and Methanol can vary depending in the absence of additional salt (HydraFLASH v. 3.8).
on their concentration in the system. At low concentrations, the differ­
ences in their ability to shift the phase diagram of CO2 hydrate may be considered as part of the depression temperature to ensure that opera­
relatively small, and their inhibitory effects may be comparable, while tion remains outside HSZ. (3) In terms of THIs selection, MEG is
as the concentration increases, the differences in their effectiveness commonly used in gas-dominated systems due to its lower volatility or
become more pronounced. lower gas solubility compared to MeOH. (4) Due to the viscosity contrast
Nevertheless, when considering the efficiency of MEG and MeOH as between MEG and water, the mixture might be non-uniform, leading to
the most efficient and common THI in the context of CCS, the following less contact with the hydrate phase in porous media, which can affect its
points should be considered: (1) Due to dissociation of hydrate, the effectiveness. (5) The rate at which MeOH is injected needs to be aligned
water content of the porous medium increases leading to dilution of with the reservoir’s salinity level, as MeOH is not compatible with high-
MEG or MeOH solutions, which in turn reduces their effectiveness, (2) salinity brines, particularly at lower temperatures. With precipitation of
The temperature drop during CO2 hydrate dissociation should be the salts, the inhibitory effect of electrolytes becomes less pronounced.

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Moreover, the precipitation of salts can also impact the injectivity of CO2 for hydrate formation at field scale or field-related processes or projects.
by reducing the reservoir’s porosity/permeability. (6) The compatibility Most of these examples from the field are scattered and not represen­
of these chemicals with the reservoir minerals should also be evaluated. tative of the conditions of CO2 injection in depleted gas fields. Never­
theless, these examples demonstrate that in principle CO2 hydrates or ice
4.2. Impact of kinetic hydrate inhibitors (KHIs) can form and, if formed, can significantly impair injectivity. But there is
no demonstrated experimental case where CO2 hydrates form due to J-T
One of the primary mechanisms of KHIs is the prolongation of the cooling during CO2 injection.
nucleation induction time by adsorption and forming a protective layer Under non-equilibrium conditions, the hydration number is usually
or altering the interfacial properties between water and gas phases slightly higher than 5.5, indicating that there is 5.5 times more water
(Aghajanloo et al., 2022; Bavoh et al., 2016; Li et al., 2019; Sun and than CO2 on a mole fraction basis. This value is influenced by the sol­
Englezos, 2016). When it comes to large-scale subsurface CO2 storage, ubility of CO2 in liquid water and various thermodynamic conditions.
the most superiority of KHIs is that they can be applied in relatively For instance, CO2 solubility tends to increase significantly with a slight
small concentrations, typically 0.1 wt% to 1 wt%. This can reduce the rise in temperature, but it slightly decreases with increasing pressure in
cost of materials and investment as well as minimize any potential/side the hydrate-water region. As such, the permeability impairment is
effects of inhibitors on the overall injectivity performance (Kelland, water-saturation dependent. In the context of continuous CO2 injection
2019). A major limitation of KHIs in the CCS context is the relatively low into depleted gas fields, water saturation serves as the limiting factor
degree of subcooling; if subcooling is larger than a specific value and prevents hydrate saturation from exceeding a certain threshold. For
(depending on the type of the KHI), the inhibitory property of these the water saturations representative of depleted gas fields, the formation
chemicals will be greatly diminished, and it may act as a promoter. At of hydrate is expected to partially damage the injectivity. Nevertheless,
low subcooling temperatures pure KHIs are sufficiently effective, while it is important to note that the formation of CO2 hydrates is not guar­
under high subcooling, synergistic HIs may be appropriate (Clarke and anteed and depends on a variety of factors.
Bishnoi, 2005). There is a wealth of fundamental studies on many different aspects of
The potential KHIs to be applied for CO2 storage include: (1) Poly­ hydrate formation where typically one or two parameters are varied at a
meric KHIs such as polyvinylcaprolactam (PVCap), poly­ time. These aspects range from the impact of pressure, temperature,
vinylpyrrolidone (PVP), which are water-soluble polymers or oligomers rate, fluid composition, gas composition, impact of mineralogy in
that possess both hydrophobic and hydrophilic characteristics (Kelland particular presence of clays, and the impact of heterogeneity on
et al., 2021). The hydrophobic portion of the KHI molecule inhibits permeability impairment. Moreover, it is very unlikely that all field
hydrate formation by binding to the hydrate cages or occupying specific conditions can be reproduced in the laboratory to full extent. It is
sites within the water structure (Yagasaki et al., 2015). KHIs reduce the important to realize that pressure, temperature, and compositional
availability of water molecules for hydrate nucleation and inhibit the gradients in the field are much larger than what can be realized in the
growth of hydrate crystals. At the same time, the hydrophilic portion of laboratory within a single or a combination of experiments. That means
the molecule interacts with water molecules, also reducing the contact that laboratory experiments need to focus on the window in terms of
surface area between water molecules and CO2, thus limiting the op­ pressure, temperature and other parameters that bear the highest risk for
portunity for hydrate formation (Liu et al., 2020). However, from a hydrate formation.
chemical perspective, there are concerns regarding the KHI compounds, Numerical simulations are required to estimate the magnitude of
potentially adsorbing onto the surface of reservoir rocks. This adsorption temperature reduction, pressure, and compositional gradients in the
could limit their effectiveness and result in increased costs for field, on which basis the window with the highest risk can be identified
compensating for the adsorption phenomenon. (2) Biodegradable In­ (for example by comparison to known bulk behavior for gas hydrates)
hibitors or environmentally friendly KHIs such as polylactic acid (PLA) and reproduced in experiments by active control. Currently, these sim­
and polyhydroxyalkanoates (PHA) that can degrade over time, reducing ulations still have the drawback that they have difficulty with dealing
the long-term impact on the reservoir and surrounding environment. (3) with the continuous phase transitions (gas to liquid, gas to solid, etc).
Synergistic combinations of KHIs with THIs such as methanol or MEG to These simulations are still only an estimate of the gradients because
enhance the efficiency and cost-effectiveness of KHIs that have the ad­ these simulations require an input such as permeability reduction as a
vantages of both types of inhibitors. The biodegradability and efficacy of function of hydrate fraction, which is an outcome of an experimental
the synergistic method can vary depending on the specific combination program (for which these simulations are an input). That means that
and the volume fraction of each inhibitor used. Furthermore, unlike there is a feedback loop between field scale simulations to estimate the
THIs, the KHIs performance is time-dependent thus they are mainly relevant parameter ranges, and the experimental program providing
applicable to dynamic flow systems, where the hydrate formation and estimates of permeability reduction.
dissociation rates are significant (Yang et al., 2018). The selection of the Identification of hydrates in in-situ experiments can pose a signifi­
most suitable KHI for CO2 storage requires a comprehensive evaluation cant challenge. Identification on pressure drop alone may not be suffi­
of factors such as inhibitor performance, compatibility with the CO2 cient, since pressure drop is also influenced by saturation changes and
stream and reservoir properties, cost-effectiveness, and large-scale other phenomena such as salt precipitation, thus masking the pressure
availability, and operational considerations. response. Instead, utilizing imaging equipment such as MRI and CT
scanner is recommended.
5. Discussion on gaps and future research There is a significant likelihood of false positives and false negatives.
This means that the impact of hydrates is not seen in the lab but plays an
Formation of hydrates during injection of cold CO2 poses potential important role in the reservoir, or hydrate impact is established in the
challenges for low-carbon and cost-effective implementation of CO2 lab but plays no significant role in the reservoir. A field pilot is more
storage in depleted gas fields. This paper provides a brief review of CO2 likely to address the hydrates risk than laboratory experiments. How­
hydrate and its impact on the rock permeability and well injectivity. ever, such a pilot needs to have appropriate parameters in terms of
There have been numerous experimental studies in the literature, which temperature and pressure and for calibration of observations may need
have focused mainly on CH4 hydrate and more recently on CO2 hydrate. experimental information that is currently not available in literature.
However, the reported experimental data are not exactly representative In combination with the role that heterogeneity plays on the impact
of CCS in depleted gas fields. Most of the experiments are designed of hydrates on permeability reduction, it is not clear which factor in the
within the hydrate stability zone, i.e., hydrate formation is forced to end dominates with respect to formation and impact on injectivity. That
form in the porous medium. There are only few reported precedent cases makes the question of the hydrate formation risk very specific to the

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

actual field situation. However, it’s crucial to acknowledge that the modern hydrate
Capillary back flow and cross flow can be driven by the capillary simulation models assume that hydrate formation and dissociation are
pressure gradient in the process of hydrate formation or salt dry-out and driven by pressure differences relative to the hydrate equilibrium curve.
by the capillary pressure difference between heterogeneous reservoir This assumption is valid within specific regions of the thermodynamic
layers, respectively. Water saturation and distribution in the reservoir space where three phases (vapor, liquid water, and hydrate) can coexist.
would have dynamic change that potentially causes the accumulation of In cases with limited brine or gas saturations, hydrate formation can still
hydrate formation near wellbore, which enhances the reduction of CO2 occur at pressures exceeding those predicted by the equilibrium curve.
injectivity. On the other hand, within the processes of hydrate formation Furthermore, when modeling hydrate phase equilibria under equilib­
or dissociation, reservoir heterogeneity improves the change of local rium assumptions in TOUGH-HYDRATE, the simulator relies on tabu­
capillary force where alters the thermodynamic conditions and affects lated equilibrium constants (Moridis, 2003). This approach simplifies
hydrate stability. Unstable hydrate gives the uncertain water saturation the calculation of equilibria but may not capture the dynamic nuances of
and distribution and causes change of relative permeability of water. hydrate behavior under all conditions. Molecular dynamics simulations
However, few studies have considered the role of heterogeneity in hy­ have also long been proven as a valuable tool, which not only provides
drate formation, or elucidated its influence on the wellbore impairment. insights into molecular phenomena, but is also useful for predicting the
It is critical to figure out the extent of heterogeneity effect and to tackle macroscopic mechanisms of hydrate formation, dissolution, and stabil­
the potential problems in the wellbore integrity and injectivity ity in porous media (Cheng et al., 2024; Ji et al., 2023).
reduction. Rock heterogeneity in combination with non-uniform fluid distri­
When CO2 temperatures are above the hydrate equilibrium temper­ bution affects hydrate behavior even at core scale. To deal with hydrate
ature, dry-out may be more pronounced due to increased water evapo­ complexity, an effective inversion of core experiments should be per­
ration. In some cases, especially when wellbore temperatures are below formed first and then the modeling results should be regressed to the
the hydrate stability threshold, the competition between the water experimental observations. These observations include pressure mea­
evaporation rate and hydrate formation rate may lead to the precipita­ surements at different core locations and dynamic imaging, e.g., CT
tion of salts in the reservoir. This can further complicate the dry-out scans or MRI and allow to inverse the kinetic parameters of hydrate
challenges. It is therefore imperative to conduct further research to formation at different conditions and parameters. In addition, such
comprehensively explore the impacts of dry-out and hydrate formation model will allow an effective interpolation/extrapolation of experi­
on mass (effective permeability) and heat transport within porous mental results in the parameter space of practical interest for hydrate
media. Clarifying these interactions will not only advance our funda­ formation and mitigation.
mental understanding of reservoir behavior during CO2 injection but The developed model needs to be translated then to the reservoir
also contribute to the development of more effective mitigating strate­ scale. That is not an easy problem since upscaling of the compositional
gies for subsurface carbon storage. and thermal models are sensitive to the scale of representation. Prob­
The dynamic behavior of hydrate formation and dissociation induces lems of practical interest often require an effective representation at a
pressure and temperature changes. Hydrate formation near wellbore can coarse scale of almost every component in the governing equations.
cause permeability reduction and therefore pressure and temperature Several approaches have been proposed for a coarse-scale representa­
increase in the wellbore. Once the temperature is over the equilibrium tion, but most of them are limited to the flow phenomena. In addition,
hydrate level, hydrate starts to dissociate and release pressure and the kinetic description of hydrate formation and dissociation requires to
temperature. resolve the timescale of the problem when integrating conservation
Mitigation strategies (e.g., dehydration, thermal stimulation, and equations. All these time and space sensitivities poses serious challenges
chemical additives, etc.) to eliminate the impact of CO2 hydrate for­ to gas hydrate upscaling process.
mation and dissociation are crucial in the context of CCS. Future
research efforts should focus on various aspects of this challenge. For CRediT authorship contribution statement
instance, the development of novel chemicals that can effectively pre­
vent/inhibit CO2 hydrate formation to maintain conditions outside of Mahnaz Aghajanloo: Writing – original draft, Conceptualization.
the hydrate stability zone, and to avoid injectivity decline caused by Lifei Yan: Writing – original draft, Conceptualization. Steffen Berg:
hydrate formation. These inhibitors should meet criteria such as effec­ Writing – review & editing. Denis Voskov: Writing – review & editing,
tiveness, safety, affordability, and biodegradability. Their correct se­ Supervision, Conceptualization. Rouhi Farajzadeh: Writing – review &
lection is vital for maintaining the integrity of CCS systems during CO2 editing, Writing – original draft, Supervision, Project administration,
injection and storage. Investigating the compatibility of these inhibitors Methodology, Conceptualization.
with formation water and reservoir minerals is another key point. Un­
derstanding how these chemicals interact with different types of reser­
voir fluids is also critical for their effective use. Determining the optimal Declaration of competing interest
dosage of inhibitors required to effectively prevent CO2 hydrate for­
mation is essential, especially since recycling these inhibitors from for­ The authors declare that they have no known competing financial
mation water may not be feasible. interests or personal relationships that could have appeared to influence
Numerical simulation of gas hydrates in porous media has histori­ the work reported in this paper.
cally faced limitations due to general complexity of the hydrate forma­
tion and dissociation processes. This problem requires consistent Data availability
thermodynamics and chemistry incorporated into thermal-
compositional modeling formulation and by construction represents Data will be made available on request.
interaction of several physical phenomena performed at different scales.
The complexity of the existing models varies from a kinetic description Acknowledgement
with simplified thermodynamic interactions as in CMG STARS (CMG,
2007) and finishing with the most advanced simulation framework for Authors thank Shell Global Solutions International for granting
modeling hydrate dynamics in porous media as in TOUGH-HYDRATE permission to publish this work. Zaynetdinov, Timur is acknowledged
(Yin et al., 2018). for detailed review of the draft manuscript.

17
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Nomenclature

AAs Anti Agglomerates


CCS Carbon Capture and Sequestration
Convw Water Conversion
CPA Cubic Plus Association
CT Computed Tomography
DEG diethylene glycol
EoS Equation of State
G Gas
GHSZ Gas Hydrate Stability Zone
H Hydrate
HB Hydrogen Bond
HSZ Hydrate Stability Zone
HQP High Quadruple Point
IL Ionic Liquid
I Ice
J dimensionless J-Function
k permeability
k0 initial permeability
krw relative permeability
kref reference permeability
KHIs Kinetic Hydrate Inhibitors
L Liquid water
LDHIs Low Dosage Hydrate Inhibitors
LQP Low Quadruple Point
m mass
MD Molecular Dynamics
MEG Mono-Ethylene Glycol
ME Memory Effect
MRI Magnetic Resonance Imaging
Mw Molecular Weight
NG Natural Gas
NMR Nuclear Magnetic Resonance
n mole
nH hydration number
P Pressure
PBH Borehole pressure
Pc Capillary pressure
PHA polyhydroxyalkanoates
PLA polylactic acid
PSD Pore Size Distribution
PV Pore Volume
r radius of capillary tube for the remainder 1-Γ
S effective water saturation
SRK Soave Redlich Kwong
SH hydrate saturation
Sp effective brine saturation
Sw water saturation
T Temperature
TBH Borehole temperature
Teq
hyd Equilibrium temperature for hydrate
Tc critical temperature
TEG Triethylene Glycole
THIs Thermodynamic Hydrate Inhibitors
V vapor
WAG Water Alternating Gas
wt mass fraction

Greek Character
ΔH enthalpy of hydrate formation/dissociation
φ porosity
φref reference porosity
φ0 initial porosity
φc finite porosity

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M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

φr porosity for the pore radius with r


φt total porosity of the porous domain with hydrate
φi total porosity of the porous domain without hydrate
θn normalized porosity
σ surface tension
Γ fraction of the total length of a capillary tube
̃r radius of capillary tube
ω ratio of cross sectional areas of the tube segments (̃r/r)2
τ tortuosity factor
δ a multiplied proportionality factor

Subscript & Superscript


BH Bottom Hole
c carbon dioxide
eq equilibrium
H hydrate
f final
m mole
r relative
t time
w water

References dependencies. J. Phys. Chem. C 126 (35), 14832–14842. https://doi.org/10.1021/


acs.jpcc.2c04140.
Cai, W., Huang, X., Lu, H., 2022. Instrumental methods for cage occupancy estimation of
Adeniyi, A.T., Ezeagu, V.I., 2020. Estimation of Bypassed Oil Volume after Waterflooding an
gas hydrate. Energies 15 (2), 485. https://www.mdpi.com/1996-1073/15/2/485.
Undersaturated Reservoir SPE Nigeria Annual International Conference and
Cao, C., Liu, H., Hou, Z., Mehmood, F., Liao, J., Feng, W., 2020. A review of CO2 storage
Exhibition. https://doi.org/10.2118/203656-MS.
in view of safety and cost-effectiveness. Energies 13 (3), 600. https://www.mdpi.
Aghajanloo, M., Reza Ehsani, M., Taheri, Z., Jafari Behbahani, T., Mohammadi, A.H.,
com/1996-1073/13/3/600.
Mohammad Taheri, M., 2022. Kinetics of methane + hydrogen sulfide clathrate
Chaouachi, M., Falenty, A., Sell, K., Enzmann, F., Kersten, M., Haberthür, D., Kuhs, W.F.,
hydrate formation in the presence/absence of poly N-vinyl pyrrolidone (PVP) and L-
2015. Microstructural Evolution of Gas Hydrates in Sedimentary Matrices Observed
tyrosine: experimental study and modeling of the induction time. Chem. Eng. Sci.
with Synchrotron X-Ray Computed Tomographic Microscopy, vol. 16,
250, 117384 https://doi.org/10.1016/j.ces.2021.117384.
pp. 1711–1722. https://doi.org/10.1002/2015GC005811 (6).
Alavi, S., Woo, T.K., 2007. How much carbon dioxide can be stored in the structure H
Chapoy, A., Burgass, R., Tohidi, B., Austell, J.M., Eickhoff, C., 2011. Effect of common
clathrate hydrates?: a molecular dynamics study. J. Chem. Phys. 126 (4) https://doi.
impurities on the phase behavior of carbon-dioxide-rich systems: minimizing the risk
org/10.1063/1.2424936.
of hydrate formation and two-phase flow. SPE J. 16 (4), 921–930. https://doi.org/
Almenningen, S., Graue, A., Ersland, G., 2021. Experimental investigation of critical
10.2118/123778-pa.
parameters controlling CH4–CO2 exchange in sedimentary CH4 hydrates. Energy &
Chapter 2, 2018. Structural control of nanoparticles. In: Naito, M., Yokoyama, T.,
Fuels 35 (3), 2468–2477. https://doi.org/10.1021/acs.energyfuels.0c03841.
Hosokawa, K., Nogi, K. (Eds.), Nanoparticle Technology Handbook, third ed.
Aminnaji, M., Tohidi, B., Burgass, R., Atilhan, M., 2017. Gas hydrate blockage removal
Elsevier, pp. 49–107. https://doi.org/10.1016/B978-0-444-64110-6.00002-0.
using chemical injection in vertical pipes. J. Nat. Gas Sci. Eng. 40, 17–23. https://
Chen, X., Li, S., Zhang, P., Chen, W., Wu, Q., Zhan, J., Wang, Y., 2021. Promoted
doi.org/10.1016/j.jngse.2017.02.003.
disappearance of CO2 hydrate self-preservation effect by surfactant SDS. Energies 14
Anderson, R., Tohidi, B., Webber, J.B.W., 2009. Gas hydrate growth and dissociation in
(13), 3909. https://www.mdpi.com/1996-1073/14/13/3909.
narrow pore networks: capillary inhibition and hysteresis phenomena. Geological
Chen, Y., Li, K., Han, Y., 2020. Electrical resistance tomography with conditional
Society, London, Special Publications 319 (1), 145–159. https://doi.org/10.1144/
generative adversarial networks. Meas. Sci. Technol. 31 (5), 055401 https://doi.org/
SP319.12.
10.1088/1361-6501/ab62c4.
Bai, D., Chen, G., Zhang, X., Sum, A.K., Wang, W., 2015. How properties of solid surfaces
Cheng, L., Li, Y., Cui, J., Wu, Q., Liu, B., Ning, F., Chen, G., 2024. Molecular simulation
modulate the nucleation of gas hydrate. Sci. Rep. 5 (1), 12747 https://doi.org/
study on carbon dioxide replacement in methane hydrate near the freezing point.
10.1038/srep12747.
Gas Science and Engineering, 205220. https://doi.org/10.1016/j.
Ballard, A., Jager, M., Nasrifar, K., Mooijer, M., Peters, C., Sloan, E., 2001. Pseudo-
jgsce.2024.205220.
retrograde hydrate phenomena at low pressures. Fluid Phase Equil. 185, 77–87.
Chesnokov, C., Farajzadeh, R., Kahrobaei, S., Snippe, J., Bedrikovetski, P., 2023.
https://doi.org/10.1016/S0378-3812(01)00458-7.
Analytical model for joule-thomson cooling under heat exchange during CO2 storage
Bavoh, C.B., Lal, B., Keong, L.K., Jasamai, M.b., Idress, M.b., 2016. Synergic kinetic
in geological formations. Int. J. Greenh. Gas Control. https://doi.org/10.2139/
inhibition effect of EMIM-Cl + PVP on CO2 hydrate formation. Procedia Eng. 148,
ssrn.4441293.
1232–1238. https://doi.org/10.1016/j.proeng.2016.06.474.
Chong, Z.R., Yang, M., Khoo, B.C., Linga, P., 2016. Size effect of porous media on
Begum, S., Satyavani, N., 2022. Permeability estimation of gas hydrate-bearing
methane hydrate formation and dissociation in an excess gas environment. Ind. Eng.
sediments from well log data in the Krishna–Godavari basin. Acta Geophys. 70 (4),
Chem. Res. 55 (29), 7981–7991. https://doi.org/10.1021/acs.iecr.5b03908.
1473–1490. https://doi.org/10.1007/s11600-022-00824-5.
Christiansen, R.L., Sloan Jr., E.D., 1994. Mechanisms and kinetics of hydrate formation.
Benmesbah, F., Doria Ruffine, L., Clain, P., Osswald, V., Fandino, O., Fournaison, L.,
Ann. N. Y. Acad. Sci. 715 (1), 283–305.
Delahaye, A., 2020. Methane hydrate formation and dissociation in sand media:
Clarke, M.A., Bishnoi, P.R., 2005. Determination of the intrinsic kinetics of CO2 gas
effect of water saturation, gas flowrate and particle size. Energies 13. https://doi.
hydrate formation using in situ particle size analysis. Chem. Eng. Sci. 60 (3),
org/10.3390/en13195200.
695–709. https://doi.org/10.1016/j.ces.2004.08.040.
Bergaya, F., Jaber, M., Lambert, J.F., 2011. Clays and Clay Minerals. Rubber-Clay
Cui, G., Ren, S., Rui, Z., Ezekiel, J., Zhang, L., Wang, H., 2018. The influence of
Nanocomposites: Science, Technology, and Applications, pp. 1–44.
complicated fluid-rock interactions on the geothermal exploitation in the CO2 plume
Brustad, S., Lken, K., Waalmann, J.G., 2005. Hydrate Prevention Using MEG Instead of
geothermal system. Appl. Energy 227, 49–63.
MeOH: Impact of Experience from Major Norwegian Developments on Technology
Daniel-David, D., Guerton, F., Dicharry, C., Torré, J.-P., Broseta, D., 2015. Hydrate
Selection for Injection and Recovery of MEG. https://doi.org/10.4043/17355-MS.
growth at the interface between water and pure or mixed CO2/CH4 gases: influence
Bui, M., Adjiman, C.S., Bardow, A., Anthony, E.J., Boston, A., Brown, S., Fennell, P.S.,
of pressure, temperature, gas composition and water-soluble surfactants. Chem. Eng.
Fuss, S., Galindo, A., Hackett, L.A., Hallett, J.P., Herzog, H.J., Jackson, G.,
Sci. 132, 118–127.
Kemper, J., Krevor, S., Maitland, G.C., Matuszewski, M., Metcalfe, I.S., Petit, C.,
Davoodi, S., Al-Shargabi, M., Wood, D.A., Rukavishnikov, V.S., Minaev, K.M., 2023.
et al., 2018. Carbon capture and storage (CCS): the way forward. Energy Environ.
Review of technological progress in carbon dioxide capture, storage, and utilization.
Sci. 11 https://doi.org/10.1039/c7ee02342a.
Gas Science and Engineering 117, 205070. https://doi.org/10.1016/j.
Burla, S.K., Pinnelli, P.S.R., 2023. Experimental evidence on the prolonged stability of
jgsce.2023.205070.
CO2 hydrates in the self-preservation region. Case Studies in Chemical and
Demirbas, A., 2010. Methane hydrates as potential energy resource: Part 1 – importance,
Environmental Engineering 7, 100335. https://doi.org/10.1016/j.
resource and recovery facilities. Energy Convers. Manag. 51 (7), 1547–1561.
cscee.2023.100335.
https://doi.org/10.1016/j.enconman.2010.02.013.
Cabrera-Ramírez, A., Prosmiti, R., 2022. Modeling of structure H carbon dioxide
clathrate hydrates: guest–lattice energies, crystal structure, and pressure

19
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Deng, W., Liang, J., Kuang, Z., Zhang, W., He, Y., Meng, M., Zhong, T., 2021. Jadhawar, P., Mohammadi, A.H., Yang, J., Tohidi, B., 2006. Subsurface Carbon Dioxide
Permeability prediction for unconsolidated hydrate reservoirs with pore Storage through Clathrate Hydrate Formation. Advances in the Geological Storage of
compressibility and porosity inversion in the northern South China Sea. J. Nat. Gas Carbon Dioxide. Dordrecht.
Sci. Eng. 95, 104161. Jasamai, M., Idress, M., Saaid, I.M., Sabil, K.M., 2016. Effect of Water Saturation on
Dholabhai, P.D., Kalogerakis, N., Bishnoi, P.R., 1993. Equilibrium conditions for carbon Relative Permeability and Porosity in Hydrate Bearing Sand. International Petroleum
dioxide hydrate formation in aqueous electrolyte solutions. J. Chem. Eng. Data 38 Technology Conference.
(4), 650–654. https://doi.org/10.1021/je00012a045. Javanmardi, J., Moshfeghian, M., 2000. A new approach for prediction of gas hydrate
Englezos, P., Bishnoi, P.R., 1988. Prediction of gas hydrate formation conditions in formation conditions in aqueous electrolyte solutions. Fluid Phase Equil. 168 (2),
aqueous electrolyte solutions. AIChE J. 34, 1718–1721. 135–148. https://doi.org/10.1016/S0378-3812(99)00322-2.
Englezos, P., Lee, J.D., 2005. Gas hydrates: a cleaner source of energy and opportunity Jensen, T.B., Harpole, K.J., Østhus, A., 2000. EOR Screening for Ekofisk. SPE European
for innovative technologies. Kor. J. Chem. Eng. 22 (5), 671–681. https://doi.org/ Petroleum Conference.
10.1007/BF02705781. Ji, Y., Hou, J., Cui, G., Lu, N., Zhao, E., Liu, Y., Du, Q., 2019. Experimental study on
Falahieh, M.M., Bonyadi, M., Lashanizadegan, A., 2022. Effect of different salts on the methane hydrate formation in a partially saturated sandstone using low-field NMR
kinetic parameters of the carbon dioxide hydrate formation. J. Nat. Gas Sci. Eng. technique. Fuel 251, 82–90.
100, 104461 https://doi.org/10.1016/j.jngse.2022.104461. Ji, Z., He, C., Sun, Y., Yue, X., Fang, H., Lu, X., Liu, S., Lyu, W., 2023. Molecular dynamics
Falenty, A., Kuhs, W.F., 2009. Self-preservation of CO2 gas hydrates—surface simulation of CO2 storage in reservoir pores with a dead-end. Energies 16 (21), 7341.
microstructure and ice perfection. J. Phys. Chem. B 113 (49), 15975–15988. https:// https://www.mdpi.com/1996-1073/16/21/7341.
doi.org/10.1021/jp906859a. Kainai, D., Zhang, J., Bai, D., 2023. The melting kinetics of gas hydrate with different
Fandiño, O., Ruffine, L., 2014. Methane hydrate nucleation and growth from the bulk cage occupancy and empty cage distribution. J. Mol. Liq. 370, 121006 https://doi.
phase: further insights into their mechanisms. Fuel 117, 442–449. https://doi.org/ org/10.1016/j.molliq.2022.121006.
10.1016/j.fuel.2013.10.004. Kang, S.P., Lee, J.W., Ryu, H.J., 2008. Phase behavior of methane and carbon dioxide
Farajzadeh, R., Zaal, C., van den Hoek, P., Bruining, J., 2019. Life-cycle assessment of hydrates in meso- and macro-sized porous media. Fluid Phase Equil. 274 (1–2),
water injection into hydrocarbon reservoirs using exergy concept. J. Clean. Prod. 68–72. https://doi.org/10.1016/j.fluid.2008.09.003.
235, 812–821. https://doi.org/10.1016/j.jclepro.2019.07.034. Ke, W., Svartaas, T.M., Chen, D., 2019. A review of gas hydrate nucleation theories and
Fleyfel, F., Devlin, J.P., 1991. Carbon dioxide clathrate hydrate epitaxial growth: growth models. J. Nat. Gas Sci. Eng. 61, 169–196. https://doi.org/10.1016/j.
spectroscopic evidence for formation of the simple type-II carbon dioxide hydrate. jngse.2018.10.021.
J. Phys. Chem. 95 (9), 3811–3815. https://doi.org/10.1021/j100162a068. Kelland, M.A., 2019. Challenges with gas hydrate formation. IOP Conf. Ser. Mater. Sci.
Gaidukova, O., Misyura, S., Strizhak, P., 2022. Key areas of gas hydrates study: review. Eng. 700 (1), 012057 https://doi.org/10.1088/1757-899X/700/1/012057.
Energies 15 (5), 1799. https://www.mdpi.com/1996-1073/15/5/1799. Kelland, M.A., Zhang, Q., Dirdal, E.G., Mady, M.F., 2021. Reliability and performance of
Gambelli, A.M., Filipponi, M., Rossi, F., 2022. Sequential Formation of CO2 hydrates in a vinyl lactam-based kinetic hydrate inhibitor polymers after treatment under a range
confined environment: description of phase equilibrium boundary, gas consumption, of conditions. Energy & Fuels 35 (2), 1273–1280. https://doi.org/10.1021/acs.
formation rate and memory effect. Sustainability 14 (14), 8829. https://www.mdpi. energyfuels.0c03519.
com/2071-1050/14/14/8829. Khurana, M., Yin, Z., Linga, P., 2017. A review of clathrate hydrate nucleation. ACS
Gao, Q., Zhao, J., Guan, J., Zhang, C., 2023. Influence of the memory effect during CO2/ Sustain. Chem. Eng. 5 (12), 11176–11203. https://doi.org/10.1021/
CH4 mixed gas hydrate reformation process. Fuel 353, 129249. https://doi.org/ acssuschemeng.7b03238.
10.1016/j.fuel.2023.129249. Kneafsey, T.J., Seol, Y., Gupta, A., Tomutsa, L., 2011. Permeability of laboratory-formed
Gauteplass, J., Almenningen, S., Barth, T., Ersland, G., 2020a. Hydrate plugging and flow methane-hydrate-bearing sand: measurements and observations using X-ray
remediation during CO2 injection in sediments. Energies 13 (17), 4511. htt computed tomography. SPE J. 16 (1), 78–94.
ps://www.mdpi.com/1996-1073/13/17/4511. Koh, C.A., Sloan, E.D., Sum, A.K., Wu, D.T., 2011. Fundamentals and applications of gas
Gauteplass, J., Almenningen, S., Ersland, G., Barth, T., 2018. Hydrate seal formation hydrates. Annu. Rev. Chem. Biomol. Eng. 2, 237–257.
during laboratory CO2 injection in a cold aquifer. Int. J. Greenh. Gas Control 78, Koh, C.A., Sum, A.K., Sloan, E.D., 2012. State of the art: natural gas hydrates as a natural
21–26. https://doi.org/10.1016/j.ijggc.2018.07.017. resource. J. Nat. Gas Sci. Eng. 8, 132–138. https://doi.org/10.1016/j.
Gauteplass, J., Almenningen, S., Ersland, G., Barth, T., Yang, J., Chapoy, A., 2020b. jngse.2012.01.005.
Multiscale investigation of CO2 hydrate self-sealing potential for carbon geo- Koh, C.A., Westacott, R.E., Zhang, W., Hirachand, K., Creek, J.L., Soper, A.K., 2002.
sequestration. Chem. Eng. J. 381, 122646 https://doi.org/10.1016/j. Mechanisms of gas hydrate formation and inhibition. Fluid Phase Equil. 194–197,
cej.2019.122646. 143–151. https://doi.org/10.1016/S0378-3812(01)00660-4.
Geng, L., Cai, J., Lu, C., Qin, X., Qi, R., Meng, F., Xie, Y., Sha, Z., Wang, X., Sun, C., 2021. Kumar, A., Sakpal, T., Kumar, R., Roy, S., 2015. Methane hydrate formation in a test
Phase equilibria of natural gas hydrates in bulk brine and marine sediments from the sediment of sand and clay at various levels of water saturation. Can. J. Chem. 93 (8),
south China sea. J. Chem. Eng. Data 66 (11), 4064–4074. https://doi.org/10.1021/ 874–881. https://inis.iaea.org/search/search.aspx?orig_q=RN:50024653.
acs.jced.1c00307. Kumar, R., Englezos, P., Moudrakovski, I., Ripmeester, J.A., 2009. Structure and
Han, W.S., Lee, S.Y., Lu, C., McPherson, B.J., 2010. Effects of permeability on CO2 composition of CO2/H2 and CO2/H2/C3H8 hydrate in relation to simultaneous CO2
trapping mechanisms and buoyancy-driven CO2 migration in saline formations. capture and H2 production. AIChE J. 55 (6), 1584–1594. https://doi.org/10.1002/
Water Resour. Res. 46 (7). aic.11844.
Handa, N., Ohsumi, T., 1995. Direct Ocean Disposal of Carbon Dioxide. Terra Scientific Kvamme, B., 2022. Mechanisms for CH4/CO2 swapping in natural sediments. Fluids 7
Pub. Co.. https://cir.nii.ac.jp/crid/1130000796010100992 (8), 260. https://www.mdpi.com/2311-5521/7/8/260.
Haneda, H., Yamamoto, Y., Komai, T., Aoki, K., Kawamura, T., Ohga, K., 2002. Artificial Kvamme, B., Aromada, S.A., Saeidi, N., Hustache-Marmou, T., Gjerstad, P., 2020.
Roof Construction By the Formation of CO2 Hydrate in the Development of CH4 Gas Hydrate nucleation, growth, and induction. ACS Omega 5 (6), 2603–2619. https://
Hydrate Proc. 4th Intnl. Conf. on Gas Hydrates, Yokohama, Japan. doi.org/10.1021/acsomega.9b02865.
Hassanpouryouzband, A., Joonaki, E., Edlmann, K., Heinemann, N., Yang, J., 2020. Kvamme, B., Graue, A., Buanes, T., Kuznetsova, T., Ersland, G., 2009. Effects of solid
Thermodynamic and transport properties of hydrogen containing streams. Sci. Data surfaces on hydrate kinetics and stability. Geological Society, London, Special
7 (1), 222. https://doi.org/10.1038/s41597-020-0568-6. Publications 319 (1), 131–144. https://doi.org/10.1144/SP319.11.
Hawtin, R.W., Quigley, D., Rodger, P.M., 2008. Gas hydrate nucleation and cage Le Gallo, Y., Bildstein, O., Brosse, E., 1998. Coupled reaction-flow modeling of diagenetic
formation at a water/methane interface [10.1039/B807455K]. Phys. Chem. Chem. changes in reservoir permeability, porosity and mineral compositions. J. Hydrol. 209
Phys. 10 (32), 4853–4864. https://doi.org/10.1039/B807455K. (1–4), 366–388.
He, Z., Mi, F., Ning, F., 2021. Molecular insights into CO2 hydrate formation in the Lederhos, J.P., Long, J.P., Sum, A., Christiansen, R.L., Sloan, E.D., 1996. Effective kinetic
presence of hydrophilic and hydrophobic solid surfaces. Energy 234, 121260. inhibitors for natural gas hydrates. Chem. Eng. Sci. 51 (8), 1221–1229. https://doi.
https://doi.org/10.1016/j.energy.2021.121260. org/10.1016/0009-2509(95)00370-3.
Holzammer, C., Finckenstein, A., Will, S., Braeuer, A.S., 2016. How sodium chloride salt Lee, J., Mok, J., Choi, W., Seo, Y., 2023. Influence of structural transformation on guest
inhibits the formation of CO2 gas hydrates. J. Phys. Chem. B 120 (9), 2452–2459. exchange behavior in the sII hydrate – (CO2 + N2) replacement for energy recovery
https://doi.org/10.1021/acs.jpcb.5b12487. and CO2 sequestration. Chem. Eng. J. 472, 144680 https://doi.org/10.1016/j.
Hosseini Zadeh, A., Kim, I., Kim, S., 2021. Characteristics of formation and dissociation cej.2023.144680.
of CO2 hydrates at different CO2-Water ratios in a bulk condition. J. Petrol. Sci. Eng. Lehmkühler, F., Paulus, M., Sternemann, C., Lietz, D., Venturini, F., Gutt, C., Tolan, M.,
196, 108027 https://doi.org/10.1016/j.petrol.2020.108027. 2009. The carbon Dioxide− Water interface at conditions of gas hydrate formation.
Hoteit, H., Fahs, M., Soltanian, M.R., 2019. Assessment of CO2 injectivity during J. Am. Chem. Soc. 131 (2), 585–589. https://doi.org/10.1021/ja806211r.
sequestration in depleted gas reservoirs. Geosciences 9 (5), 199. https://doi.org/ Leverett, M., 1941. Capillary behavior in porous solids. Transactions of the AIME 142
10.3390/geosciences9050199. (1), 152–169.
Ikeda, H., Ito, H., Hikita, M., Yamaguchi, N., Uragami, N., Yokoyama, N., Hirota, Y., Levin, K., Boehm, S., Carter, R., 6 Big findings from the IPCC, 2022. Report on Climate
Kushima, M., Ajioka, Y., Inoue, H., 2018. Raman spectroscopy for the diagnosis of Impacts, Adaptation and Vulnerability.
unlabeled and unstained histopathological tissue specimens. World J. Gastrointest. Li, M., Fan, S., Wang, Y., Lang, X., Li, G., Wang, S., Yu, C., 2022. Effect of surface
Oncol. 10 (11), 439–448. https://doi.org/10.4251/wjgo.v10.i11.439. curvature and wettability on nucleation of methane hydrate. AIChE J. 68 (10),
Ikeda, T., Mae, S., Uchida, T., 1998. Effect of guest–host interaction on Raman spectrum e17823 https://doi.org/10.1002/aic.17823.
of a CO2 clathrate hydrate single crystal. J. Chem. Phys. 108 (4), 1352–1359. Li, X.-Y., Zhong, D.-L., Englezos, P., Lu, Y.-Y., Yan, J., Qing, S.-L., 2021. Insights into the
https://doi.org/10.1063/1.475508. self-preservation effect of methane hydrate at atmospheric pressure using high
Jacobs, P.J., Hemdane, S., Dornez, E., Delcour, J.A., Courtin, C.M., 2015. Study of pressure DSC. J. Nat. Gas Sci. Eng. 86, 103738 https://doi.org/10.1016/j.
hydration properties of wheat bran as a function of particle size. Food Chem. 179, jngse.2020.103738.
296–304.

20
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Li, Y., Maria Gambelli, A., Chen, J., Yin, Z., Rossi, F., Tronconi, E., Mei, S., 2023. Myshakin, E.M., Jiang, H., Warzinski, R.P., Jordan, K.D., 2009. Molecular dynamics
Experimental study on the competition between carbon dioxide hydrate and ice simulations of methane hydrate decomposition. J. Phys. Chem. 113 (10),
below the freezing point. Chem. Eng. Sci. 268, 118426 https://doi.org/10.1016/j. 1913–1921.
ces.2022.118426. Nagashima, H., Miyagi, T., Yasuda, K., Ohmura, R., 2020. Clathrate hydrates at
Li, Y., Qiao, Z., Sun, S., Zhang, T., 2020. Thermodynamic modeling of CO2 solubility in temperatures below the freezing point of water: a review. Fluid Phase Equil. 517,
saline water using NVT flash with the cubic-Plus-association equation of state. Fluid 112610 https://doi.org/10.1016/j.fluid.2020.112610.
Phase Equil. 520, 112657 https://doi.org/10.1016/j.fluid.2020.112657. Nair, V.C., Ramesh, S., Ramadass, G.A., Sangwai, J.S., 2016. Influence of thermal
Li, Z., Liao, K., Qin, H.-B., Chen, J., Ren, L., Li, F., Zhang, X., Liu, B., Chen, G., 2019. The stimulation on the methane hydrate dissociation in porous media under confined
gas-adsorption mechanism of kinetic hydrate inhibitors. AIChE J. 65 (9), e16681 reservoir. J. Petrol. Sci. Eng. 147, 547–559. https://doi.org/10.1016/j.
https://doi.org/10.1002/aic.16681. petrol.2016.09.017.
Liu, F.P., Li, A.R., Qing, S.L., Luo, Z.D., Ma, Y.L., 2022. Formation kinetics, mechanism of Nakano, S., Moritoki, M., Ohgaki, K., 1998. High-pressure phase equilibrium and Raman
CO2 hydrate and its applications. Renew. Sustain. Energy Rev. 159, 112221 https:// microprobe spectroscopic studies on the CO2 hydrate system. J. Chem. Eng. Data 43
doi.org/10.1016/j.rser.2022.112221. (5), 807–810.
Liu, H.-H., Zhang, G., Yi, Z., Wang, Y., 2013. A permeability-change relationship in the Natarajan, V., Bishnoi, P.R., Kalogerakis, N., 1994. Induction phenomena in gas hydrate
dryout zone for CO2 injection into saline aquifers. Int. J. Greenh. Gas Control 15, nucleation. Chem. Eng. Sci. 49 (13), 2075–2087. https://doi.org/10.1016/0009-
42–47. 2509(94)E0026-M.
Liu, J., Wang, H., Guo, J., Chen, G., Zhong, J., Yan, Y., Zhang, J., 2020. Molecular Nghiem, L., Yang, C., Shrivastava, V., Kohse, B., Hassam, M., Chen, D., Card, C., 2009.
insights into the kinetic hydrate inhibition performance of Poly(N-vinyl lactam) Optimization of Residual Gas and Solubility Trapping for CO2 Storage in Saline Aquifers
polymers. J. Nat. Gas Sci. Eng. 83, 103504 https://doi.org/10.1016/j. SPE Reservoir Simulation Symposium. https://doi.org/10.2118/119080-MS.
jngse.2020.103504. Nielsen, R.B., Bucklin, R.W., 1983. Why not use methanol for hydrate control.
Liu, X., Falcone, G., Teodoriu, C., 2016. Liquid loading in gas wells: experimental Hydrocarb. Process. 62 (4), 71–78.
investigation of back pressure effects on the near-wellbore reservoir. J. Nat. Gas Sci. Ochi, J., Vernoux, J.F., 1998. Permeability decrease in sandstone reservoirs by fluid
Eng. 36, 434–441. https://doi.org/10.1016/j.jngse.2016.10.064. injection: hydrodynamic and chemical effects. J. Hydrol. 208 (3), 237–248. https://
Liu, X., Flemings, P.B., 2007. Dynamic multiphase flow model of hydrate formation in doi.org/10.1016/S0022-1694(98)00169-3.
marine sediments. J. Geophys. Res. Solid Earth 112 (B3). https://doi.org/10.1029/ Ott, H., de Kloe, K., Marcelis, F., Makurat, A., 2011. Injection of supercritical CO2 in
2005JB004227. brine saturated sandstone: pattern formation during salt precipitation. Energy Proc.
Liu, Y., Zhang, L., Yang, L., Dong, H., Zhao, J., Song, Y., 2021. Behaviors of CO2 hydrate 4, 4425–4432. https://doi.org/10.1016/j.egypro.2011.02.396.
formation in the presence of acid-dissolvable organic matters. Environ. Sci. Technol. Ott, H., Pentland, C.H., Oedai, S., 2015. CO2–brine displacement in heterogeneous
55 (9), 6206–6213. https://doi.org/10.1021/acs.est.0c06407. carbonates. Int. J. Greenh. Gas Control 33, 135–144. https://doi.org/10.1016/j.
Loeve, D., Hofstee, C., Maas, J.G., 2014. Thermal effects in a depleted gas field by cold ijggc.2014.12.004.
CO2 injection in the presence of methane. Energy Proc. 63, 3632–3647. https://doi. Ott, H., Snippe, J., de Kloe, K., 2021. Salt precipitation due to supercritical gas injection:
org/10.1016/j.egypro.2014.11.393. II. Capillary transport in multi porosity rocks. Int. J. Greenh. Gas Control 105,
Lv, J., Xue, K., Zhang, Z., Cheng, Z., Liu, Y., Mu, H., 2021. Pore-scale investigation of 103233. https://doi.org/10.1016/j.ijggc.2020.103233.
hydrate morphology evolution and seepage characteristics in hydrate bearing Pahlavanzadeh, H., Nouri, S., Aghajanloo, M., Mohammadi, A.H., Mohammadi, S., 2023.
microfluidic chip. J. Nat. Gas Sci. Eng. 88, 103881 https://doi.org/10.1016/j. Experimental measurements and thermodynamic modeling of hydrate dissociation
jngse.2021.103881. conditions for CO2 + THF + MgCl2 + water systems. Fluid Phase Equil. 564, 113626
Ma, S., Zheng, J.-n., Tang, D., Li, Y., Li, Q., Lv, X., 2019. Application of X-ray computed https://doi.org/10.1016/j.fluid.2022.113626.
tomography technology in gas hydrate. Energy Technol. 7 (6), 1800699 https://doi. Pan, L., Lei, L., Seol, Y., 2021. Pore-scale influence of methane hydrate on permeability
org/10.1002/ente.201800699. of porous media. J. Nat. Gas Sci. Eng. 87, 103758 https://doi.org/10.1016/j.
Ma, Z.W., Zhang, P., Bao, H.S., Deng, S., 2016. Review of fundamental properties of CO2 jngse.2020.103758.
hydrates and CO2 capture and separation using hydration method. Renew. Sustain. Pandey, J.S., Strand, O., von Solms, N., Almenningen, S., Ersland, G., 2022. Novel pore-
Energy Rev. 53, 1273–1302. https://doi.org/10.1016/j.rser.2015.09.076. scale visualization during CO2 injection into CH4 hydrate-saturated porous media.
Majid, A.A.A., Koh, C.A., 2021. Self-preservation phenomenon in gas hydrates and its Energy & Fuels 36 (18), 10552–10571. https://doi.org/10.1021/acs.
application for energy storage. In: Bernstein, E.R. (Ed.), Intra- and Intermolecular energyfuels.1c03878.
Interactions between Non-covalently Bonded Species. Elsevier, pp. 267–285. https:// Pandey, J.S., Strand, Ø., von Solms, N., Ersland, G., Almenningen, S., 2021. Direct
doi.org/10.1016/B978-0-12-817586-6.00008-6. visualization of CH4/CO2 hydrate phase transitions in sandstone pores. Cryst.
Maloney, D., Briceno, M., 2009. Experimental investigation of cooling effects resulting Growth Des. 21 (5), 2793–2806. https://doi.org/10.1021/acs.cgd.0c01714.
from injecting high pressure liquid or supercritical CO2 into a low pressure gas Parmesan, C., Morecroft, M.D., Trisurat, Y., 2022. Climate Change 2022: Impacts,
reservoir. Petrophysics 50, 335–344. Adaptation and Vulnerability GIEC.
Martinez, C., Sandoval, J.F., Ortiz, N., Ovalle, S., Beltran, J.G., 2022. Mechanisms, Peter, A., Yang, D., Eshiet, K.I.-I.I., Sheng, Y., 2022. A review of the studies on CO2 - brine
growth rates, and morphologies of gas hydrates of carbon dioxide, methane, and - rock interaction in geological storage process. Geosciences 12 (4), 168.
their mixtures. Methane 1 (1), 2–23. https://www.mdpi.com/2674-0389/1/1/2. https://www.mdpi.com/2076-3263/12/4/168.
Mathias, S.A., Gluyas, J.G., Oldenburg, C.M., Tsang, C.F., 2010. Analytical solution for Peters, D., Lacy, R., Dykhno, L., 2012. Flow Assurance in the Design and Operability of a
Joule–Thomson cooling during CO2 geo-sequestration in depleted oil and gas CO2 Transportation System. Offshore Technology Conference.
reservoirs. Int. J. Greenh. Gas Control 4 (5), 806–810. https://doi.org/10.1016/j. Pini, R., Krevor, S.C., Benson, S.M., 2012. Capillary pressure and heterogeneity for the
ijggc.2010.05.008. CO2/water system in sandstone rocks at reservoir conditions. Adv. Water Resour. 38,
Mekala, P., Busch, M., Mech, D., Patel, R.S., Sangwai, J.S., 2014. Effect of silica sand size 48–59.
on the formation kinetics of CO2 hydrate in porous media in the presence of pure Priegnitz, M., Thaler, J., Spangenberg, E., Schicks, J.M., Schrötter, J., Abendroth, S.,
water and seawater relevant for CO2 sequestration. J. Petrol. Sci. Eng. 122, 1–9. 2015. Characterizing electrical properties and permeability changes of hydrate
https://doi.org/10.1016/j.petrol.2014.08.017. bearing sediments using ERT data. Geophys. J. Int. 202 (3), 1599–1612.
Mestdagh, T., De Batist, M., 2015. Evaluation and Modelling of the Response of Gas Pruess, K., Müller, N., 2009. Formation dry-out from CO2 injection into saline aquifers: 1.
Hydrate Reservoirs to Changing Environmental Conditions across a High-Latitude Effects of solids precipitation and their mitigation. Water Resour. Res. 45 (3).
Continental Margin. Radhakrishnan, R., Trout, B.L., 2002. A new approach for studying nucleation
Meyer, D.W., Flemings, P.B., DiCarlo, D., 2018. Effect of gas flow rate on hydrate phenomena using molecular simulations: application to CO2 hydrate clathrates.
formation within the hydrate stability zone. J. Geophys. Res. Solid Earth 123 (8). J. Chem. Phys. 117 (4), 1786–1796. https://doi.org/10.1063/1.1485962.
https://doi.org/10.1029/2018JB015878. Rehman, A.N., Bavoh, C.B., Pendyala, R., Lal, B., 2021. Research advances, maturation,
Mirzaeifard, S., Servio, P., Rey, A.D., 2019. Characterization of nucleation of methane and challenges of hydrate-based CO2 sequestration in porous media. ACS Sustain.
hydrate crystals: interfacial theory and molecular simulation. J. Colloid Interface Sci. Chem. Eng. 9 (45), 15075–15108. https://doi.org/10.1021/
557, 556–567. https://doi.org/10.1016/j.jcis.2019.09.056. acssuschemeng.1c05423.
Mohammadi, A.H., Richon, D., 2015. Hydrate phase equilibria of gaseous mixtures of Rempel, A., Buffett, B., 1997. Formation and accumulation of gas hydrate in porous
methane + carbon dioxide + hydrogen sulfide. Chem. Eng. Commun. 202 (5), media. J. Geophys. Res. Solid Earth 102 (B5), 10151–10164.
629–633. https://doi.org/10.1080/00986445.2013.858322. Rodger, P.M., 1990. Stability of gas hydrates. J. Phys. Chem. 94 (15), 6080–6089.
Mooijer, M., 2004. Phase Behaviour and Structural Aspects of Ternary Clathrate Hydrate https://doi.org/10.1021/j100378a082.
Systems. Roels, S.M., El Chatib, N., Nicolaides, C., Zitha, P.L., 2016. Capillary-driven transport of
Moridis, G.J., 2003. Numerical studies of gas production from methane hydrates. SPE J. dissolved salt to the drying zone during CO2 injection in homogeneous and layered
8 (4), 359–370. https://doi.org/10.2118/87330-pa. porous media. Transport Porous Media 111 (2), 411–424.
Mu, L., Cui, Q., 2019. Experimental study on the dissociation equilibrium of (CH4+ CO2+ Rossi, F., Gambelli, A.M., 2021. Thermodynamic phase equilibrium of single-guest
N2) hydrates in the mixed sediments. J. Chem. Eng. Data 64 (12), 5806–5813. hydrate and formation data of hydrate in presence of chemical additives: a review.
Munck, J., Skjold-Jørgensen, S., Rasmussen, P., 1988. Computations of the formation of Fluid Phase Equil. 536, 112958 https://doi.org/10.1016/j.fluid.2021.112958.
gas hydrates. Chem. Eng. Sci. 43 (10), 2661–2672. https://doi.org/10.1016/0009- Rossi, F., Li, Y., Gambelli, A., 2021. Thermodynamic and kinetic description of the main
2509(88)80010-1. effects related to the memory effect during carbon dioxide hydrates formation in a
Muraoka, M., Yamamoto, Y., Tenma, N., 2020. Simultaneous measurement of water confined environment. Sustainability 13, 13797. https://doi.org/10.3390/
permeability and methane hydrate pore habit using a two-dimensional glass su132413797.
micromodel. J. Nat. Gas Sci. Eng. 77, 103279. Saadatpoor, E., Bryant, S.L., Sepehrnoori, K., 2010. New trapping mechanism in carbon
sequestration. Transport Porous Media 82, 3–17.

21
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Sahoo, S.K., Best, A.I., 2021. The influence of gas hydrate morphology on reservoir Wei, Y., Maeda, N., 2023. Mechanisms of the memory effect of clathrate hydrates. Chem.
permeability and geophysical shear wave remote sensing. J. Geophys. Res. Solid Eng. Sci. 270, 118538 https://doi.org/10.1016/j.ces.2023.118538.
Earth 126 (11), e2021JB022206. Wells, J.D., Chen, W., Hartman, R.L., Koh, C.A., 2021. Carbon dioxide hydrate in a
Sayani, J.K.S., Pedapati, S.R., Lal, B., 2020. Phase behavior study on gas hydrates microfluidic device: phase boundary and crystallization kinetics measurements with
formation in gas dominant multiphase pipelines with crude oil and high CO2 mixed micro-Raman spectroscopy. J. Chem. Phys. 154 (11).
gas. Sci. Rep. 10 (1), 14748 https://doi.org/10.1038/s41598-020-71509-6. Wen, Z., Yao, Y., Luo, W., Lei, X., 2021. Memory effect of CO2-hydrate formation in
Semenov, A., Mendgaziev, R., Stoporev, A., Istomin, V., Tulegenov, T., Yarakhmedov, M., porous media. Fuel 299, 120922. https://doi.org/10.1016/j.fuel.2021.120922.
Novikov, A., Vinokurov, V., 2023. Direct measurement of the four-phase equilibrium White, M., 2011. Impact of Kinetics on the Injectivity of Liquid CO2 into Arctic Hydrates.
coexistence vapor–aqueous solution–ice–gas hydrate in water–carbon dioxide OTC Arctic Technology Conference.
system. Int. J. Mol. Sci. 24 (11), 9321. https://www.mdpi.com/1422-0067/24/11 Wroblewski, S., 1882. On the combination of carbonic acid and water. London,
/9321. Edinburgh Dublin Phil. Mag. J. Sci. 13 (80), 228. https://doi.org/10.1080/
Shagapov, V.S., Musakaev, N., Khasanov, M., 2015. Formation of gas hydrates in a 14786448208627173. -228.
porous medium during an injection of cold gas. Int. J. Heat Mass Tran. 84, Wu, G., Tian, L., Ha, L., Feng, F., Yang, Z., Feng, J.C., Coulon, F., Jiang, Y., Zhang, R.,
1030–1039. 2022. Influence of pipeline steel surface on the thermal stability of methane hydrate.
Shen, S., Wang, L., Ge, Y., Chu, J., Liang, H., 2023. The effect of salinity on the strength J. Mol. Liq. 367, 120486 https://doi.org/10.1016/j.molliq.2022.120486.
behavior of hydrate-bearing sands. J. Mar. Sci. Eng. 11 (7), 1350. https://www. Wu, Y., Shang, L., Pan, Z., Xuan, Y., Baena-Moreno, F.M., Zhang, Z., 2021. Gas hydrate
mdpi.com/2077-1312/11/7/1350. formation in the presence of mixed surfactants and alumina nanoparticles. J. Nat.
Shotton, P., Vidal-Gilbert, S., Thibeau, S., Agenet, N., Lesueur, A., Manhes, C., Ninet, C., Gas Sci. Eng. 94, 104049 https://doi.org/10.1016/j.jngse.2021.104049.
2022. Aramis CO2 Storage Case Study – A Geomechanical Assessment of Xie, Q., Saeedi, A., Delle Piane, C., Esteban, L., Brady, P.V., 2017. Fines migration during
Containment 16th Greenhouse Gas Control Technologies Conference. GHGT-16). CO2 injection: experimental results interpreted using surface forces. Int. J. Greenh.
Singh, R.P., Shekhawat, K.S., Das, M.K., Muralidhar, K., 2020. Geological sequestration Gas Control 65, 32–39. https://doi.org/10.1016/j.ijggc.2017.08.011.
of CO2 in a water-bearing reservoir in hydrate-forming conditions. Oil Gas Sci. Xu, J., Bu, Z., Li, H., Wang, X., Liu, S., 2022. Permeability models of hydrate-bearing
Technol. – Rev. IFP Energies nouvelles 75, 51. https://doi.org/10.2516/ogst/ sediments: a comprehensive review with focus on normalized permeability. Energies
2020038. 15 (13), 4524. https://www.mdpi.com/1996-1073/15/13/4524.
Sloan, E.D., 2003. Fundamental principles and applications of natural gas hydrates. Xu, Q., Weir, G., Paterson, L., Black, I., Sharma, S., 2007. A CO2-Rich Gas Well Test and
Nature 426 (6964), 353–359. https://doi.org/10.1038/nature02135. Analyses. Asia Pacific Oil and Gas Conference and Exhibition.
Sloan, E.D., Fleyfel, F., 1991. A molecular mechanism for gas hydrate nucleation from Yagasaki, T., Matsumoto, M., Tanaka, H., 2015. Adsorption mechanism of inhibitor and
ice. AIChE J. 37, 1281–1292. guest molecules on the surface of gas hydrates. J. Am. Chem. Soc. 137 (37),
Sloan, E.D., Koh, C.A., 2008. Clathrate Hydrates of Natural Gases, third ed. CRC Press. 12079–12085. https://doi.org/10.1021/jacs.5b07417.
https://doi.org/10.1201/9781420008494. Yang, M., Dong, S., Zhao, J., Zheng, J.n., Liu, Z., Song, Y., 2021. Ice behaviors and heat
Smith, D.H., Wilder, J.W., Seshadri, K., 2002. Methane hydrate equilibria in silica gels transfer characteristics during the isothermal production process of methane hydrate
with broad pore-size distributions. AIChE J. 48 (2), 393–400. reservoirs by depressurization. Energy 232, 121030. https://doi.org/10.1016/j.
Snippe, J., Berg, S., Ganga, K., Brussee, N., Gdanski, R., 2020. Experimental and energy.2021.121030.
numerical investigation of wormholing during CO2 storage and water alternating gas Yang, M., Song, Y., Liu, W., Zhao, J., Ruan, X., Jiang, L., Li, Q., 2013. Effects of additive
injection. Int. J. Greenh. Gas Control 94, 102901. mixtures (THF/SDS) on carbon dioxide hydrate formation and dissociation in porous
Sokama-Neuyam, Y.A., Yusof, M.A.M., Owusu, S.K., Darkwah-Owusu, V., Turkson, J.N., media. Chem. Eng. Sci. 90, 69–76. https://doi.org/10.1016/j.ces.2012.11.026.
Otchere, A.S., Ursin, J.R., 2023. Experimental and theoretical investigation of the Yang, M., Song, Y., Liu, Y., Chen, Y., Li, Q., 2010. Influence of pore size, salinity and gas
mechanisms of drying during CO2 injection into saline reservoirs. Sci. Rep. 13 (1), composition upon the hydrate formation conditions. Chin. J. Chem. Eng. 18 (2),
9155. https://doi.org/10.1038/s41598-023-36419-3. 292–296. https://doi.org/10.1016/S1004-9541(08)60355-9.
Staykova, D.K., Kuhs, W.F., Salamatin, A.N., Hansen, T., 2003. Formation of porous gas Yang, M., Zhou, H., Wang, P., Song, Y., 2018. Effects of additives on continuous hydrate-
hydrates from ice powders: diffraction experiments and multistage model. J. Phys. based flue gas separation. Appl. Energy 221, 374–385. https://doi.org/10.1016/j.
Chem. B 107 (37), 10299–10311. https://doi.org/10.1021/jp027787v. apenergy.2018.03.187.
Sum, A.K., Burruss, R.C., Sloan, E.D., 1997. Measurement of clathrate hydrates via Yang, S.H.B., Babu, P., Chua, S.F.S., Linga, P., 2016. Carbon dioxide hydrate kinetics in
Raman spectroscopy. J. Phys. Chem. B 101 (38), 7371–7377. porous media with and without salts. Appl. Energy 162, 1131–1140.
Sun, D., Englezos, P., 2016. CO2 storage capacity in laboratory simulated depleted Yin, Z., Moridis, G., Tan, H.K., Linga, P., 2018. Numerical analysis of experimental
hydrocarbon reservoirs – impact of salinity and additives. J. Nat. Gas Sci. Eng. 35, studies of methane hydrate formation in a sandy porous medium. Appl. Energy 220,
1416–1425. https://doi.org/10.1016/j.jngse.2016.03.043. 681–704. https://doi.org/10.1016/j.apenergy.2018.03.075.
Talaghat, M.R., Khodaverdilo, A.R., 2019. Study of different models of prediction of the Yin, Z., Zheng, J., Kim, H., Seo, Y., Linga, P., 2021. Hydrates for cold energy storage and
simple gas hydrates formation induction time and effect of different equations of transport: a review. Advances in Applied Energy 2, 100022. https://doi.org/
state on them. Heat Mass Tran. 55 (5), 1245–1255. https://doi.org/10.1007/ 10.1016/j.adapen.2021.100022.
s00231-018-2508-y. You, K., Flemings, P.B., Malinverno, A., Collett, T.S., Darnell, K., 2019. Mechanisms of
Talman, S., Shokri, A.R., Chalaturnyk, R., Nickel, E., 2020. Salt precipitation at an active methane hydrate formation in geological systems. Rev. Geophys. 57 (4), 1146–1196.
CO2 injection site. Gas injection into geological formations and related topics https://doi.org/10.1029/2018RG000638.
183–199. Yusof, M.A.M., Neuyam, Y.A.S., Ibrahim, M.A., Saaid, I.M., Idris, A.K., Mohamed, M.A.,
Tamáskovics, A., Kummer, N.-A., Amro, M., Alkan, H., 2023. Experimental investigation 2022. Experimental study of CO2 injectivity impairment in sandstone due to salt
on the stability of gas hydrates under near-wellbore conditions during CO2 injection precipitation and fines migration. J. Pet. Explor. Prod. Technol. 12 (8), 2191–2202.
for geologic carbon storage. Gas Science and Engineering 118, 205101. https://doi. https://doi.org/10.1007/s13202-022-01453-w.
org/10.1016/j.jgsce.2023.205101. Zatsepina, O.Y., Buffett, B.A., 2002. Nucleation of CO2-hydrate in a porous medium.
Torré, J.-P., Ricaurte, M., Dicharry, C., Broseta, D., 2012. CO2 enclathration in the Fluid Phase Equil. 200 (2), 263–275. https://doi.org/10.1016/S0378-3812(02)
presence of water-soluble hydrate promoters: hydrate phase equilibria and kinetic 00032-8.
studies in quiescent conditions. Chem. Eng. Sci. 82, 1–13. https://doi.org/10.1016/j. Zha, L., Liang, D.Q., Li, D.L., 2012. Phase equilibria of CO2 hydrate in NaCl–MgCl2
ces.2012.07.025. aqueous solutions. J. Chem. Therm. 55, 110–114. https://doi.org/10.1016/j.
Touil, A., Broseta, D., Desmedt, A., 2019. Gas hydrate crystallization in thin glass jct.2012.06.025.
capillaries: roles of supercooling and wettability. Langmuir 35 (38), 12569–12581. Zhang, G., Liu, B., Xu, L., Zhang, R., He, Y., Wang, F., 2021. How porous surfaces
https://doi.org/10.1021/acs.langmuir.9b01146. influence the nucleation and growth of methane hydrates. Fuel 291, 120142.
Uchida, T., Ebinuma, T., Takeya, S., Nagao, J., Narita, H., 2002. Effects of pore sizes on https://doi.org/10.1016/j.fuel.2021.120142.
dissociation temperatures and pressures of methane, carbon dioxide, and propane Zhang, P., Wu, Q., Mu, C., Chen, X., 2018. Nucleation mechanisms of CO2 hydrate
hydrates in porous media. J. Phys. Chem. B 106 (4), 820–826. reflected by gas solubility. Sci. Rep. 8 (1), 10441 https://doi.org/10.1038/s41598-
Vaessen, R., Van Der Ham, F., Witkamp, G., 2000. Eutectic freeze crystallization using 018-28555-y.
CO2 clathrates. Ann. N. Y. Acad. Sci. 912 (1), 483–495. Zhang, S., Liu, H.H., 2016. Porosity–permeability relationships in modeling salt
Valadbeygian, V., Hajipour, M., Behnood, M., 2023. Static and dynamic evaluation of precipitation during CO2 sequestration: review of conceptual models and
formation damage due to barium sulfate scale during water injection in carbonate implementation in numerical simulations. Int. J. Greenh. Gas Control 52, 24–31.
reservoirs. J. Pet. Explor. Prod. Technol. 13 (8), 1819–1831. https://doi.org/ https://doi.org/10.1016/j.ijggc.2016.06.013.
10.1007/s13202-023-01652-z. Zhang, Z., Guo, G.J., 2017. The effects of ice on methane hydrate nucleation: a
Verma, A., Pruess, K., 1988. Thermohydrological conditions and silica redistribution microcanonical molecular dynamics study [10.1039/C7CP03649C]. Phys. Chem.
near high-level nuclear wastes emplaced in saturated geological formations. Chem. Phys. 19 (29), 19496–19505. https://doi.org/10.1039/C7CP03649C.
J. Geophys. Res. Solid Earth 93 (B2), 1159–1173. Zhao, J., Fan, Z., Dong, H., Yang, Z., Song, Y., 2016. Influence of reservoir permeability
Vlasov, V.A., 2019. Mathematical model of the effect of self-preservation of gas hydrates. on methane hydrate dissociation by depressurization. Int. J. Heat Mass Tran. 103,
J. Eng. Phys. Thermophys. 92 (6), 1406–1414. https://doi.org/10.1007/s10891- 265–276.
019-02057-8. Zhao, J., Tian, Y., Zhao, Y., Cheng, W., 2015a. Experimental investigation of effect on
Wang, L., Dou, M., Wang, Y., Xu, Y., Li, Y., Chen, Y., Li, L., 2022. A review of the effect of hydrate formation in spray reactor. J. Chem. 2015.
porous media on gas hydrate formation. ACS Omega 7 (38), 33666–33679. https:// Zhao, J., Yang, L., Liu, Y., Song, Y., 2015b. Microstructural characteristics of natural gas
doi.org/10.1021/acsomega.2c03048. hydrates hosted in various sand sediments [10.1039/C5CP03698D]. Phys. Chem.
Wang, P., Teng, Y., Zhao, Y., Zhu, J., 2021. Experimental studies on gas hydrate-based Chem. Phys. 17 (35), 22632–22641. https://doi.org/10.1039/C5CP03698D.
CO2 storage: state-of-the-art and future research directions. Energy Technol. 9 (7),
2100004.

22
M. Aghajanloo et al. Gas Science and Engineering 123 (2024) 205250

Zhao, Q., Chen, Z.-Y., Li, X.-S., Xia, Z.-M., 2023. Experimental study of CO2 hydrate Ziabakhsh-Ganji, Z., Kooi, H., 2014. Sensitivity of Joule–Thomson cooling to impure CO2
formation under an electrostatic field. Energy 272, 127119. https://doi.org/ injection in depleted gas reservoirs. Appl. Energy 113, 434–451. https://doi.org/
10.1016/j.energy.2023.127119. 10.1016/j.apenergy.2013.07.059.
Zheng, J.n., Yang, M., Chen, B., Song, Y., Wang, D., 2017. Research on the CO2 gas Zuniga, A.R., 2020. NMR Studies of Natural Gas Hydrates Exposed to Thermally
uptake of different hydrate structures with cyclopentane or methyl-cyclopentane as Controlled CO2 Exchange. The University of Western Australia.
Co-guest molecules. Energy Proc. 105, 4133–4139. https://doi.org/10.1016/j. Zuo, Y.-X., Stenby, E.H., 1997. Prediction of gas hydrate formation conditions in aqueous
egypro.2017.03.877. solutions of single and mixed electrolytes. SPE J. 2 (4), 406–416. https://doi.org/
Zheng, J., Chong, Z.R., Qureshi, M.F., Linga, P., 2020. Carbon dioxide sequestration via 10.2118/31048-pa.
gas hydrates: a potential pathway toward decarbonization. Energy & Fuels 34 (9),
10529–10546. https://doi.org/10.1021/acs.energyfuels.0c02309.

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