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Review

A Review of Reactor Designs and Materials Employed


for Increasing the Rate of Gas Hydrate Formation
Praveen Linga, and Matthew A. Clarke
Energy Fuels, Just Accepted Manuscript DOI: 10.1021/acs.energyfuels.6b02304 Publication Date (Web): 30 Nov 2016
Downloaded from http://pubs.acs.org on December 1, 2016

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A Review of Reactor Designs and Materials Employed for


Increasing the Rate of Gas Hydrate Formation
Linga, P.1, Clarke, M.A.2, *
1. Department of Chemical & Bimolecular Engineering, National University of
Singapore, 4 Engineering Drive, Singapore, 117585
2. Department of Chemical & Petroleum Engineering, University of Calgary,
Calgary, Alberta, T2N 1N4
ABSTRACT
Over the course of the last fifty years, gas hydrates have been proposed for use in a
diverse range of applications including gas storage, gas transportation, gas separation, ice
cream production and seawater desalination. While there have been many studies that
have demonstrated the thermodynamic potential for using gas hydrates in these
applications, the slow kinetics of formation, and to a lesser extent dissociation, have
hindered their adoption. Since the early 1990s, there have been numerous studies that
have highlighted the use of surfactants, such as sodium dodecyl sulfate (SDS), for the
enhancement of gas hydrate kinetics. More recently there has been growing interest in
non-surfactant based methods for enhancing the rate of gas hydrate formation, which
physically increase the surface area available for gas hydrate formation. These methods,
which include hydrate formation in sand packs, silica gels, dry water, foams, nano
particles and hydrogels are relatively recent advances and are discussed in a disparate
array of academic journals. The purpose of this review article is to compile and
summarize this knowledge in a single article and to highlight the prospect and future
challenges.

Keywords: gas hydrates; clathrates; enhanced kinetics; materials; contact mode


Email address: praveen.linga@nus.edu.sg (P. Linga), maclarke@ucalgary.ca (M. A.
Clarke)

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INTRODUCTION
Gas hydrates are an ice like crystalline substance that can form when water and light
gases, including methane and carbon dioxide, are contacted at low temperatures and
elevated pressure1-3. It has long been known3 that gas hydrates possess the remarkable
capacity to compress a large volume of gas into a relatively small volume of hydrate; a
commonly quoted number is that 1 m3 of hydrate, at standard conditions, can contain up
to 170 m3 of natural gas.
Historically, research

related to gas hydrates has either been focused on

suppressing/reversing their formation in pipelines and process equipment3, 4 or, on the


recovery of methane from naturally occurring deposits of gas that are found under the
ocean floor or in the permafrost regions5-8. However, in the last 50 years, there have been
numerous proposals to make use of gas hydrates in water desalination9-15, CO2 capture
and sequestration16-25, food industry26-29, refrigeration30-36, gas separation37-41, gas storage
and transportation42-52. In particular, it is the ability of gas hydrates to selectively trap
gases and to compress gases that has generated interest for employing them in the
aforementioned applications.
All these applications have potential technical challenges that need to be mitigated in
order for them to be commercialized. In all of the applications, mentioned in the previous
paragraph, the thermodynamics has been shown to be favorable. However, making use of
gas hydrates as a technology enabler requires that one is able to form them in a rapid and
predictable manner i.e. kinetics. In order to meet this criterion, one needs to address
several key challenges including the slow kinetics of gas hydrate formation, a large heat
of formation and low conversions of water to hydrate.

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There are two approaches to overcome the slow kinetics of hydrate formation, the first
approach is by the use of kinetic promoters to enhance the kinetics and the second
approach is by the use of innovative gas/liquid contact modes and materials. To date, the
most well researched means for addressing the above challenges particularly that of the
slow kinetics of gas hydrate formation, has been to form the hydrates in the presence of a
surfactant53-58 and more recently amino acids59, 60. As early as 1993, Kalogerakis et al.58
observed various surfactants, when added at the appropriate concentration, could increase
the rate of gas consumption during gas hydrate formation. In a relatively recent review
article, Kumar et al.61 reviewed the compendium of works related to the use of surfactants
in promoting the kinetics of gas hydrate formation, as of 2015. While there is still debate
surrounding the mechanism for hydrate kinetic enhancement in the presence of
surfactants, Kumar et al.61 reports that surfactants enhance the rate of gas hydrate
formation by one or more of the following steps: 1) increasing the solubility of the
hydrate forming gas in the aqueous solution, 2) lowering the interfacial tension at the gasliquid interface and 3) altering the morphology of the growing gas hydrate crystals. Thus,
the use of surfactants in increasing the rate of gas hydrate formation has been relatively
well documented.
Alternatively, over the last ten years, growing attention has been focused on nonsurfactant based methods for increasing the rate of gas hydrate formation. These methods,
which are the focus of the current manuscript, have typically employed novel gas/liquid
contact modes or materials in order to increase the surface area for gas-liquid contact
and/or in order to remove the heat of hydrate formation. The research groups involved in
the relevant studies represent a wide range of disciplines that includes material science,

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chemical engineering and chemistry. As such, the resulting articles have been dispersed
throughout as somewhat disparate collection of journals. The aim of the present
manuscript is to summarize the relevant works in a single article, highlight the prospects
and challenges that lie ahead in a format that is easily accessible to engineers and
scientists.
The techniques that will be reviewed in this manuscript can be broadly categorized into
two groups; those in which the hydrate is formed in a bulk liquid and those in which the
hydrate is formed in a dispersed liquid. The majority of the techniques that will be
addressed in this manuscript involve forming hydrates in a dispersed liquid phase, which
acts to increase the surface area for gas-liquid mass transfer. The order of presentation of
the works will be based upon these two broad categories. It is not to be taken as a
reflection of the authors assessment of the techniques importance.
Gas Hydrate Formation in Packed Beds
The drive to study the kinetics of gas hydrate formation in porous media seems to have
been initially motivated by a desire to better assess the feasibility of recovering methane
from naturally occurring gas hydrates deposits under the ocean floor and in the
permafrost regions. As natural gas hydrates are found in sediments, silica sand seem to be
the natural choice by many researchers to mimic gas hydrate formation in porous media
specific to the context of understanding the formation/dissociation of methane hydrates in
porous sediments. The need for reliable information on the kinetics of gas hydrate
formation in porous medium was recognized as early as 1996 by Melnikov and
Nesterov62 and then later echoed by the likes of Spangenberg63 in 2001 and then again by
Kneasfsey et al.64 in 2007. In many of the studies to be presented, the goal of the studies

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was not always to achieve an increase in the rate of gas hydrate formation, relative to a
stirred vessel. However, in all of these studies, a noticeable increase in the rate of hydrate
formation was observed.
Linga et al.65 noted in 2009 that, in amongst the aforementioned studies, one aspect that
had not been systematically examined was the relationship between the size of the porous
medium and the rate at which gas hydrates are formed in the porous medium.
Additionally, their apparatus was constructed in such a way as to yield information
surrounding the mechanism for hydrate formation in the porous medium. While the study
of Linga et al.65 was not strictly focused on using the porous medium enhancing the rate
of gas hydrate formation, their experiments showed that gas hydrate formation in porous
media was a relatively rapid process, which resulted in high conversions of water to
hydrate. Of particular importance, were the observations of multiple nucleation sites as
well as the observation of gas hydrate growth occurring in several stages. In the slow
initial growth stage, 43 53% of the water is converted to hydrate. By the end of the third
and final growth stage, the conversion was seen to be as high as 98%. In addition to
observing the rate of gas uptake, the size of the sand pack, from which it was concluded
that it is necessary to account for the size of the porous medium when modeling hydrate
growth in porous media.65 The study by Linga et al.65 subsequently spawned a handful of
other studies of gas hydrate formation in porous media66. Like the study of Linga et al.65
these studies werent explicitly focused on using the porous medium for the purpose of
enhancing the rate of gas hydrate formation but they, nonetheless, observed this
phenomenon.

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Building on the observations made by Linga et al.65 in 2009, Linga et al.67 in 2012
subsequently undertook a comprehensive comparison of the rate of gas hydrate formation
in a packed bed versus that seen in a mechanically stirred. In their study, gas hydrates
were formed from pure methane as well as three different mixtures of methane and/or
propane in both a stirred vessel as well as a bed of silica sand. It was seen that, in the
early phase of gas hydrate growth, the rate of gas uptake was faster than that seen in the
stirred vessel as one would expect compared to a quiescent system. This was attributed to
hydrate nuclei seeding the entire system, as a result of the system being well mixed. As
the experiment proceeded in the stirred vessel, the rate of gas uptake declined rapidly,
due to the difficulty of mixing a liquid phase with a large volume fraction of hydrates.
Eventually, the gas uptake in the packed bed overtook that of the stirred vessel. In all of
the systems that were studied, the conversion of water to hydrate was higher in the
packed bed than in the stirred vessel. The biggest difference in the conversions was seen
in the case of the methane/propane system where the final conversion in the stirred vessel
was 17.3%, whereas that for the packed bed of silica sand was 68.7%. In addition to the
water-to-hydrate conversion, the amount of time required to reach the final conversion of
hydrates was also significantly lower in the packed bed. In the case of the aforementioned
experiments with the methane/propane system the time was reduced from 96.6 hours to
10 hours. Finally, the authors (Linga et al.67) postulated that the increased rate of hydrate
formation and water-to-hydrate conversion was due to several events in the vessel
including gas transport within the bed, the capillary effect of water flow in the porous
hydrate and the tortuous flow paths inside the packed bed. It is noted that sand employed

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in the literature works highlighted so far was non-porous in nature, meaning that the
water was only dispersed in the interstitial spaces of the sand particles.
This observation of rapid clathrate hydrate formation rates in sand for methane/propane
(90.5/9.5mol%) gas mixture was proposed as a method to test the efficacy of kinetic
hydrates inhibitors (KHI) by Daraboina and Linga68 in a follow up study. Daraboina and
Linga68 reported the kinetic inhibition effect of poly-N-vinyl pyrrolidone (PVP) in terms
of rate of hydrate formation vs PVP concentration and benchmarked the results with the
control experiments done without the presence of PVP. A recent study by Babu et al.69
employed a specially design morphology reactor that enabled them to visualize the
hydrate formation in presence of silica sand in order to identify the mechanism and
reason for which the presence of propane-containing gas mixtures in sand exhibited very
fast gas hydrate formation rates. It was reported that for propane containing gas hydrate
systems in porous media, propane showed the remarkable ability to rapidly draw the
dispersed water from sand towards the gas phase to form hydrates. This visual
observation was also corroborated with gas uptake data in this study. The authors
concluded that this mechanism was the possible reason for the rapid hydrate formation
rates observed in propane-containing systems in sand in the earlier works67, 68. The
compilation of gas uptake for hydrate growth to show kinetic enhancement for systems
with the presence propane as a co-guest in hydrocarbon gas/gas mixtures is shown in
Figure 1.

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70

Water Conversion to Hydrates (%)

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30

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90

120

Time (min)
CH4 at 8.0 MPa (Mekala et al. 2014)
CH4 at 8.0 MPa (Linga et al. 2012)
CH4/C2H6 (91.0/9.0%) at 8.0 MPa (Linga et al. 2012)
CH4/C3H8 (90.5/9.5%) at 4.3 MPa (Linga and Daraboina 2013)

Figure 1: Conversion of water to hydrates during 2 hr hydrate growth phase for CH4,
CH4/C2H6 and CH4/C3H8 gas mixtures conducted at driving force of 4.2, 5.9 and 3.4 MPa
respectively (adapted from Babu et al.69).

Silica gel is another porous medium commonly investigated in the literature to enhance
the kinetics of hydrate formation.70-78 A study by Seo et al74 that reported that the kinetics
of hydrate formation can be enhanced by dispersing water inside the pores of silica gels.
Kinetic studies with 1H NMR micro-imaging showed that the dispersed water in the silica
gel pore system reacts readily with the gas, thus obviating the need for a stirred reactor
and excess water. An 85% hydrate yield or water conversion to hydrates was reported in
1h for with silica gel for pure CO2 hydrate formation. Adeyemo et al.75 formed gas
hydrates from flue gas mixtures (CO2/N2) and fuel gas mixtures (CO2/H2) in a column of
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silica gel particles. When the authors examined the effect of the particle size and the pore
size, they found that gas consumption, CO2 recovery factor and water-to-hydrate
conversion were highest in the larger particles and in the larger pore sizes. This was
postulated to be due to the increased diffusion in the larger pores. When Tetra-HydraFuran (THF) was subsequently added to the flue gas mixtures, in order to reduce the
required operating pressure. It was seen that the final gas uptake was approximately one
tenth of that when THF was absent. A similar result was also observed when hydrates
were formed in silica gel from a mixture of fuel gas and THF.
The kinetic enhancement of CO2 mixed hydrates in silica sand and silica gel was
investigated by Babu et al.76, 77 in 2013. Experiments were performed to examine the
effect of both the hydrate formation pressure as well as the water saturation in the given
porous medium. In their experiments, a small amount of propane was added to the CO2 in
order to lower the pressure required for hydrate formation. In both silica sand and silica
gel, the authors noted that the gas uptake as well as the water-to-hydrate conversion
increased as the pressure increased, at a constant temperature. At all of the pressures
studied, it was also seen that the water-to hydrate conversion was higher for silica sand
than it was for silica gel. When the effect of water saturation, in the porous medium, was
studied the authors noted that gas consumption at 50% saturation was 2.3 times that
achieved at 100% saturation. This was attributed to gas molecules being more readily
available for hydrate nucleation at lower water saturation. Finally, the authors noted that
when the hydrates in porous media were decomposed, more gas was recovered when the
system was heated from 274 to 297K as opposed to heating from 274 to 284K.

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In a related subsequent study, Kumar et al.78 examined the effect of particle size of silica
gel as well as the addition of three surfactants on the rate of CO2 gas uptake. It was seen
that increasing the surface area of the silica gel particles enhanced the rate of gas uptake.
The surfactants that were also used in the study were SDS (anionic), DTACI (cationic)
and Tween-80 (non-ionic). SDS was observed to be the most effective of the three
surfactants for promoting hydrate growth in silica gel. Tween-80 was slightly less
effective than SDS; however, both surfactants were significantly more effective than
DTACI. Interestingly, the authors observed that while the presence of a surfactant can
increase the rate of hydrate formation, it had a negligible effect on the final conversion of
water to hydrate. In their work, no mechanism was suggested for how surfactants
enhance the rate of hydrate formation in silica gels.
In 2013, Babu et al.79 investigated the use of polyurethane foam for enhancing the
kinetics of CO2 gas hydrate formation. This particular study was motivated by the
possibility of using gas hydrates as a means of carbon capture. The foam employed in this
work had very good interconnectivity between the pore spaces. Thus, forming hydrates in
a polyurethane foam was qualitatively very similar to forming hydrates in sand (Linga et
al.65, 67). In addition to using polyurethane foam for enhancing the kinetics of hydrate
formation, the authors also made the thermodynamics conditions for hydrate formation
more favourable by adding small amounts of propane to the fuel gas mixture80, 81. Upon
hydrate formation, a notable and sudden increase in temperature was observed. Also, the
rate of gas consumption per unit volume and the final water-to-hydrate conversions were
much larger than those available from a stirred vessel. The authors showed that, at a
given driving force, polyurethane foam provides a higher gas consumption value than

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silica gel and silica sand. The enhanced hydrate formation was attributed to the wellconnected interstitial pore space and, possibly, to the wettability of the water on the
polyurethane foam. A comparison of the hydrate growth kinetics at same experimental
condition for the sand, gel and foam benchmarked against the standard stirred tank
reactor configuration is presented in Figure 2.

Figure 2. Hydrate growth comparison between stirred tank, silica gel, silica sand and
polyurethane foam (Babu et al.18), Reprinted with permission from Energy Journal
(Elsevier Publisher)

A few literature works reported data on fuel gas mixture (CO2/H2) in silica sand, in the
presence of liquid promoters like THF and tetra-n-butyl ammonium bromide (TBAB).82
Strictly speaking, semi-clathrates are a class of clathrate compounds in which a part of
the guest also participates in the cage formation hence termed as semi-clathrates. Some
guest compounds that form semi-clathrates are TBAB, tetra-n-butyl ammonium nitrate
(TBANO3) etc20, 83-87 All of the experiments by Babu et al.82 were performed at a pressure
of 6 MPa and either at 274 or 279K. Two different concentrations of THF (1.0 and 5.53
mol%) and three different concentrations of TBAB (0.3, 1.0 and 3.0 mol%) were used for

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the experiments. At the upper end of the concentration scale, the rate of hydrate growth
was roughly 5 times faster in THF than it was in TBAB and the induction time was
roughly 6.5 times longer in TBAB than it was in THF. Additionally, after 2 hours hydrate
growth had all but ceased in TBAB where as it was still continuing in the THF solution.
Thus, it was concluded that when forming hydrates from fuel gas in silica sand, THF is a
superior additive when compared to TBAB. A recent study by Zheng et al.88 evaluated
the effect of the orientation of the reactor for packed bed configuration for CO2 capture
from pre-combustion stream in the presence of THF as the liquid promoter.
Mekala et al.89 in 2014 examined the effect of water salinity on the kinetics of gas
hydrate formation and decomposition in silica sand. While this paper was not explicitly
focused

on

using

the

silica

sand

for

the

purpose

of

enhancing

the

formation/decomposition kinetics, many important observations were made regarding the


process of gas hydrate formation and decomposition in a porous medium. Mekala et al.89
formed methane hydrates in both pure water and in natural seawater (3.03 wt% NaCl).
The natural seawater was seen to have a significantly detrimental effect on both the rate
of formation as well as on the final water-to-hydrate conversion. At the same temperature
and pressure, the gas uptake in the presence of seawater was one tenth of that in pure
water. Similarly, the final water-to-hydrate conversion in the seawater was one sixth of
that in pure water. It is known that salts act as thermodynamic inhibitors, this study
highlighted the significant extent of kinetic inhibition when salts are present in porous
media for methane hydrate formation. A study later by Chong et al.90 quantified the effect
of NaCl salt concentration (1.5 and 3.0wt% NaCl) on the kinetics of hydrate formation
and dissociation in the presence of sand and reaffirmed the slow kinetics of methane

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hydrate formation in presence of salts in porous media. While methane hydrate formation
kinetics was reported to be sluggish in the presence of salts in porous media, on the
contrary, CO2 hydrate formation in sand in the presence of salts did not show significant
kinetic inhibition. This study highlighted a significant advantage for CO2 formation when
employed for CH4-CO2 exchange in porous natural sediments (particularly in marine
locations where the presence of salts is likely).
The group of Dr. Kumar, at CSIR-NCL Pune evaluated the use of metallic packing to
enhance the kinetics of hydrate formation for CO2 capture. It was reported that the
stainless steel (SS316) packing along with SDS showed better kinetic performance over
silica sand and silica gel packing for pure CO2 hydrate formation and hydrate formation
in a fuel gas (CO2+H2) mixture.91, 92
Hydrates were formed from a gas mixture of CH4/N2/O2 in the presence of 1.0 mol%
THF and pulverized coal particles, by Zhong et al.93, in order to separate methane. The
study found, firstly, that the induction time decreased as the water saturation of the coal
particles was decreased. At 100% water saturation, the induction time was seen to be
almost four times that which was measured at 40% water saturation. The rate of gas
uptake was also seen to be more than double at 40% water saturation than it was at 100 %
water saturation. Overall, the results obtained with pulverized coal were slightly better
than those obtained with a stirred vessel. In 2015, Siangsai et al.94 investigated the effect
of activated carbon particle size on the methane hydrate growth kinetics in a fixed bed
configuration. Activated carbons with different particle sizes, 250-420. m, 420-841. m,
and 841-1680. m, were used in order to investigate their effects on the methane hydrate
formation. The authors reported that 841-1680 m activated carbon showed the highest

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average water conversion to hydrate, due to its large interstitial pore space between the
activated carbon particles and observed a two-step hydrate growth behavior.
Gas Hydrate Formation in the presence of nanoparticles
Since 2013, a handful of researchers have investigated the effect of the presence of
various nanoparticles on the kinetics of gas hydrate formation. Unlike the experiments in
the previous section, many of the studies in this section were performed in a stirred vessel
rather than in a packed bed.
The group of Dr. Prasad, at CSIR-NGRI Hyderabad investigated extensively the use of
nano hollow silica for methane storage in clathrate hydrates.95-100 Chari et al.97 formed
methane hydrates in a packed bed of nano hollow silica particles. Compared to the
formation of hydrates in static or quiescent bulk water, the presence of nano particles had
a dramatic effect on the rate of gas hydrate formation as well as the final water-to-hydrate
conversion. In the presence of static water, the final water-to-hydrate conversion was
only 2.38 % whereas values in the vicinity of 40% and 80% were obtained over a hydrate
formation time period of 300 min or higher when hydrates were formed in the presence
silica nanoparticles at a 1:8 weight ratio (silica to water) and a 1:4 weight ratio,
respectively. As was seen in the studies that were reviewed in the previous section,
decreasing the water saturation seems to have a positive effect on the water-to-hydrate
conversion. The recyclability of the nanoparticle suspension was also examined. When
multiple hydrate formation and decomposition cycles were performed, it was noted that
the water-to-hydrate conversion was roughly constant.
Recently, Veluswamy et al.101 performed morphology experiments to elucidate the
mechanism of hydrate formation in hollow silica and reported that a critical hollow

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silica to water ratio (1:6) existed beyond which the hydrates preferentially crystallized on
the top of the hollow silica bed by drawing water from the interstitial pores. Below the
critical ratio (1:6) the hydrate formation occurred predominantly within the bed between
inter-particular spaces of hollow silica. Due to the very low bulk density of the bed, small
fraction of the hollow silica was observed to be displaced from the bed during the hydrate
formation above the critical hollow silica to water ratio.
The group of Professor Servio, at McGill University, formed carbon dioxide hydrates in
the presence of both as-produced and amine-functionalized multi-wall carbon nanotubes102-104. Pasieka et al.102 investigated the effect of the multi-wall nano-tubes on both
the dissolution of gas as well as the growth of hydrate crystals. The solubility and rate of
dissolution, of CO2 in water, was unaffected by the presence of the multi-wall nanotubes. On the other hand, the multi-wall nano-tubes were seen to have a noticeable effect
on the growth of the hydrate particles. For both as-produced and the amine-functionalized
nano tubes, the growth rate enhancement decreased as the concentration of the nanotubes increased. The authors postulated that the kinetic enhancement was due to the nanotubes breaking up hydrate clusters and thereby increasing the surface area for hydrate
formation. At larger concentrations, the nano-tubes exhibited an inhibiting effect, which
was attributed to the large heat of formation.
In 2015, Govindaraj et al.105 formed methane hydrate in agitated suspensions of activated
carbon, deactivated carbon and nano-silica. It should be noted that, in this study, only the
silica particles were nanoparticles whereas the activated and deactivated carbon particles
were on the micrometer scale. Similar to the study of Pasieka et al.102 Govindaraj et al.105
also performed their experiments in an agitated vessel, all at an initial condition of 275 K

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and 8 MPa. The authors noted that both activated carbon and nano-silica particles
enhanced the growth of gas hydrate particles whereas the deactivated carbon particles
actually inhibited the growth of hydrate particles. Of the two hydrate growth promoters,
activated carbon was observed as being superior to nano-silica. With regard to the
activated carbon particles, it was also noted that there was a clear relationship between
the concentration of particles in solution with the rate of gas uptake; increasing the
concentration of activated carbon particles in solution increased the rate of gas uptake.
On the other hand no such trend was observed with the nano-silica particles, at least at
the examined concentrations; all of the concentrations of nano-silica particles exhibited
approximately the same degree of kinetic enhancement. This result was in contrast to the
results of Chari et al.97, which was explained by Govindaraj et al.105 as being due to the
large difference in particle sizes used in the two studies. It is also noted that the gas
uptake reported in the work of Govindaraj et al.105 in the presence of nano-silica particles
was 0.011 mol of gas/mol of water after an experimental hydrate formation time of 9 hr.
Recently, Said et al.106 formed hydrates from a gas mixture of CO2/CH4 in the presence
of SiO2, Al2O3, Ag and Cu nanoparticles. Experiments were performed in an isochoric
stirred vessel at a temperature of 274 K and an initial pressure of 4.0 MPa and with three
different concentrations of each nanoparticle. The authors observed the effect of
nanoparticles on both the rate of gas dissolution as well as on the rate of hydrate growth.
The solutions containing nanoparticles of SiO2 and Al2O3 both exhibited increased rates
of gas dissolution, in water, whereas the Cu and the Ag nanoparticles caused the rate of
gas dissolution to decrease. Once the hydrates began to form, the SiO2 nanoparticles were
seen to significantly enhance the rate of gas consumption. The Al2O3 and the Cu

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nanoparticles were observed as being moderately effective at enhancing the growth of


hydrate particles at higher concentrations. The Ag nanoparticles, by contrast, enhanced
hydrate growth in the initial stages of the experiments. However, in the later stages of the
experiments, the Ag nanoparticles began to inhibit hydrate growth. The authors did not
speculate as to why the Ag nanoparticles were ineffective at promoting hydrate growth. It
is noted that the normalized gas uptake was low in spite of having a stirred configuration
with the presence of nano-fluids performed over experimental hydrate formation time of
about 80 h.106
In 2016, Mohammadi et al.107 studied the kinetics of CO2 gas hydrate formation in
aqueous solutions of Zn nanoparticles and Zn nanoparticles plus SDS. The experiments
were conducted in an isochoric stirred vessel at several different temperatures and initial
temperatures. For their studies, the concentration of both Zn nanoparticles as well as SDS
was held constant. When compared to pure water, the presence of Zn nanoparticles was
seen to decrease the induction time and to increase the rate of gas consumption. When
SDS was added to the Zn nano-fluid, a further decrease in induction and increase in the
rate of gas consumption was observed. However, the authors offered no speculation
regarding the mechanism for gas hydrate kinetic enhancement in the presence of Zn
nanoparticles.
Gas Hydrate Formation in the presence of dry water and dry gel
Dry water is an example of a water-in-air inverse foam that is formed when water and
hydrophobic nanoparticles are mixed at a high rate. The result, as seen in Figure 3, is a
powder-like substance in which micrometric sized water droplets are surrounded by a
porous network of hydrophobic nanoparticles at the interface between air and water. Dry

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water can contain up to 98% water, by weight, yet it feels completely dry to the touch and
it flows like a powder. Trapped water can be released by the application of shear stress or
by evaporation. Dry water was first reported in the mid-1960s. However, little attention
was paid to dry water until the 1990s at which time cosmetic companies began to realize
the potential for dry water as a carrier system.

Figure 3: Dry water prepared with 5g of hydrophobic silica nanoparticles and 95g of
water. (Wang et al.108) Reprinted with permission from American Chemical Society.

Due to the large surface area that results from the formation of dry water, the group of
Professor Cooper at the University of Liverpool investigated the potential for dry water to
enhance the kinetics of methane hydrate formation108, 109. Dry water particles of varying
size were prepared by mixing water and hydrophobic silica at different mixing speeds;
smaller particles were formed at higher mixing rates. Experiments were performed in a
packed bed of dry water particles and the results were compared to those obtained when

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hydrates were formed in unstirred water. The formation of methane gas hydrates was
significantly faster than in unstirred liquid water. After 1500 minutes, the hydrates
formed in the smallest dry water particles attained a gas storage capacity of 175 m3 CH4
(STP) per m3 of hydrate. The methane storage capacities that were measured were very
favourable. However, after the hydrates were dissociated and then subsequently
reformed, the storage capacity dropped significantly. The authors hypothesized that the
reduction in storage capacity was due to partial agglomeration of water molecules; the
dry water particles were destabilized by the applied freeze-thaw cycle. However, when
the used dry water particles were re-blended, their original gas storage capacity was
restored.
As a follow up to the study mentioned in the previous paragraph, Carter et al.109
examined the effect of temperature and the silica-to-water ratio on the formation of CH4,
CO2 and Kr hydrates in dry water and in dry gels. A dry gel is dry water that has been
formed in the presence of a gelling agent, which was done with the intention of
improving the recyclability of dry water over multiple freeze-thaw cycles. The effect of
temperature was studied by comparing the storage capacity of methane hydrates formed
in dry water. The authors observed that 273 K was the optimal temperature and that there
was a notable reduction in gas storage capacity as the temperature departed from 273K.
When methane hydrates were formed in dry water at different silica-to-water ratios, no
noticeable effect on the gas storage capacity was observed. This was attributed to the
highly dispersed nature of dry water. In order to address the issue of recyclability, gellan
gum was used as a gelling agent. The gelling agent was postulated to provide a second
resistance to the coalescence of dry water droplets. In the presence of the gelling agent,

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there was a notable improvement in the recyclability. After 8 successive


formation/decomposition cycles in the presence of a 20 wt% gellan gum dry water, there
was only a small reduction in the gas storage capacity when compared with the initial
cycle. However, it should be noted that the gas storage capacity of the dry gels were close
to 20% lower than that for the dry water. Finally, when pure CO2 and pure Kr was used to
form hydrates in dry water, it was seen that the rate or formation was significantly
improved. However, the gas storage capacity was seen to be significantly lower than the
maximum value as predicted by thermodynamics.
Hu et al.110 also studied the kinetics of methane hydrate formation in dry water. In their
study five different dry water samples were prepared and two different sets of pressure
and temperature were used for forming methane hydrates. In preparing the dry water
samples, each sample was prepared at one of three different mixing speeds. It was noted
that dry water samples that were prepared at a lower mixing speed exhibited longer
induction times for subsequent hydrate formation. Raman spectroscopic analysis of the
methane hydrates formed in dry water indicated a hydration number of 5.9340.006.
While the spectroscopic measurements of Hu et al.110 complemented previous studies of
hydrate formation in dry water, their results did not uncover any quantifiable trends in the
induction time or in the reaction time.
In the previously noted studies regarding the formation of gas hydrates in dry water, the
focus was on forming hydrates at temperatures above the freezing point of water.
Podenko et al.111 instead opted to investigate the formation of propane hydrates in dry
water, at temperatures below 273K. Propane was selected for their study due to its ability
to form hydrates at relatively mild conditions. Eleven experiments were performed, all at

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a temperature of 272.2 K, and the results were compared to the results obtained when
hydrates were formed in the presence of milled ice. In the presence of both frozen dry
water and milled ice, the authors reported no induction time; they report that hydrate
formation commenced immediately upon filling the reactor with propane gas. The
authors hypothesized that the absence of an induction period, in their experiments, was
due frozen water having significantly more nucleation active sites than unfrozen water.
Finally, the authors noted that the water-hydrate-conversion increases as the silica-towater ratio of the dry water increases. Unfortunately, the authors did not examine how the
gas storage capacity changes with successive hydrate formation and decomposition
cycles.
In 2013, Ding et al.112 examined the effectiveness of porous hydrogel microspheres in
stabilizing dry water during successive hydrate formation and decomposition cycles.
Porous microspheres of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2hydroxyethyl methacrylate-co-methacrylic acid) (PHEMA-co-MAA) were synthesized
and mixed with dry water. Methane hydrates were formed at 273.2 K and an initial
pressure of 4.5 MPa. At the end of the experiments, it was noted that the final gas storage
capacity of methane hydrates was 160 m3 CH4 (STP)/m3 hydrate, when formed in the
presence of dry water without the hydrogel microspheres. When the microspheres were
added, the final gas storage capacities were 154 m3/m3 in the presence of PHEMA
microspheres ( < 100 m), 142 m3/m3 in the presence of PHEMA-co-MAA microspheres
( < 100 m) and 123 m3/m3 in the presence of PHEMA-co-MAA microspheres ( > 100
m). When an initial pressure of 7.5 MPa was used, the final gas storage capacities were
increased for all of the aforementioned cases. The reusability aspect of the mixed dry

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water/hydrogel systems was also investigated. When compared to dry water in the
absence of the hydrogel, the presence of the hydrogel was seen to greatly increase the
reusability. In the case of PHEMA-co-MAA microspheres ( < 100 m) with an initial
pressure of 4.5 MPa, the storage capacity dropped by roughly 10% after the first hydrate
formation/decomposition cycle but then remained constant for the following seven
cycles. In all of the other cases, the storage capacity decreased continually during the first
three cycles, after which no further hydrate formation/decomposition cycles were carried
out.
In a follow up study Shi et al.113 used the shrinking core model to correlate the previously
measured kinetics of methane hydrate formation in the presence of dry water with and
without porous hydrogels. In their model, the formation of methane hydrates occurs
following the diffusion of methane molecules through the layer of porous silica
nanoparticles. This leads to the formation of a hydrate shell whose thickness increases
with time. Their model also considers the formation of hydrates in free water as well as in
the pore water of the hydrogel. The formation of hydrates in both the free water and the
hydrogel was also described using the shrinking core model. In their model it was
assumed that hydrate formation always proceeded inwards, all of the dry water particles,
hydrogel particles and free water droplets were assumed to be spherical, there is
sufficient heat transfer to maintain isothermal conditions, only gaseous methane was
involved in hydrate formation and the volume of water changed by a factor of 1.25 from
liquid water to hydrated water. The model was able to correlate the data reasonably well.
However, it should be noted that for each hydrate formation/decomposition cycle there
were a total of seven adjustable parameters that were fitted. Additionally, no statistical

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analysis of the parameters was presented. Thus, it is not clear as to how useful the model
would be outside of the conditions at which the parameters were obtained.
Wang et al.114 performed experiments to compare the kinetics of CO2 gas hydrate
formation in dry water and in foam and in hydrophobic sand. Teflon particles were used
as a stabilizer for the dry water and the effect of the Teflon particle diameter, on the
hydrate induction time, was observed. It was seen that smaller diameter particles were
more efficient. The authors hypothesized that this was due to the higher surface area of
the hydrophobic particles. When CO2 hydrates were formed in the presence of foam,
which was stabilized with hydrophobic silica nanoparticles, the formation of hydrates
occurred almost instantaneously. When the two techniques were compared, the authors
concluded that foam had a greater enhancing effect on the kinetics of CO2 hydrate
formation, which the authors attributed to the greater curvature of the interfaces.
In 2015, Park et al.115 examined the stability of dry water under successive methane
hydrate formation/decomposition cycles. A total of twelve formation/decomposition
cycles were performed with a dry water sample that was made from 5 wt% silica and 9
wt% water. In the initial cycle, the water-to-hydrate conversion was 77%. In successive
cycles, the conversion decreased exponentially to 49% after the second cycle all the way
to 22% by the end of the twelfth cycle. The authors observed that the formation of
hydrates destabilizes dry water resulting in a separate free water phase, which was
visually observable by the end of the twelfth cycle. It was hypothesized that the
formation of a hydrate film was affecting the interaction between the water and the silica,
which resulted in small amounts of water being excluded from the dry water particle. The

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authors suggested that further studies are required to quantify how the formation of a
hydrate layer affects the interaction between silica particles and water droplets.
Most recently, in 2016, Yang et al.116 formed methane hydrates in the presence of a gelsupported surfactant dry solution. The gel-supported surfactant dry solution was formed
by mixing an SDS solution with nano-sized silica particles and gellan gum, which was
used as a stabilizing agent. The silica-to-solution ratio was fixed at 7.5 wt% and four
different concentrations of SDS were used. The experiments were all conducted at a
temperature of 273.15 K and with an initial pressure of 5.0 MPa. Compared to gelstabilized dry water, gel-supported surfactant dry solutions had a gas uptake that was as
much as three times faster. However, it was seen that the reusability of the gel-supported
surfactant dry solutions was disappointing; the gel-supported surfactant dry solution
droplets quickly agglomerated, which resulted in an exponential decrease in the gas
storage capacity, over success formation/decomposition cycles.
Finally, in 2016, Zarenezhad and Montazeri117 formed CO2 gas hydrates in a
nanographene oxide nanofluid. The intent of their study was to investigate the possibility
of developing low-cost hydrate-based CO2 recovery plants in the petroleum industry. The
experiments of Zarenezhad and Montazeri117 observed that the rate of CO2 gas hydrate
formation exhibited a maximum for a nanofluid with 30 ppm of graphene oxide particles.
At higher concentrations of graphene oxide particles, the rate of CO2 gas hydrate
formation decreased, eventually to a rate that was only marginally faster than that seen in
a pure water solution. The authors reported a normalized gas uptake of 0.0414 mol of
CO2/mol of water in 2.5 h when 30 ppm nanofluid was used along with an impeller speed
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Gas Hydrate Formation in the presence of foams, hydrogels or polymers


In addition to packed beds of small particles, nanoparticles and dry water gas hydrate
formation kinetics have been studied in the presence of various foams, hydrogels and
porous polymers. In all of these cases the formation kinetics seem to be enhanced
primarily by increasing the surface area. Additionally, some of the systems also enhance
hydrate formation kinetics by removing the heat of formation.
In 2011, Yang et al.118 studied the effects of aluminum foam on the formation of methane
hydrates. Metal foams, including aluminum foam, are porous metal media that have a
large rough surface area. As seen in Figure 4, the porous foam provides many, what the
authors call, natural micro-vessels. In addition to providing a large surface area for gasliquid contact, the porous aluminum foam also dissipates a significant amount of the heat
of formation associated with gas hydrate formation. The thermal conductivity of the
aluminum foam was stated118 as being approximately 400 times greater than that of
methane hydrate. In their experiments, methane hydrates were formed at 273 K in the
presence of aluminum foam along with both pure water and with a 0.03 wt % solution of
SDS. When formed in the presence of pure water, the authors noted that the formation
rate of methane hydrate was minimal. However, in the presence of 0.03 wt % SDS, the
authors observed rapid formation of gas hydrates. The authors concluded that, in their
experiments, the aluminum foams main effect was the removal of heat. It should be
noted, however, that the Authors used an aluminum foam with a relatively large average
pore diameter, which was 1 mm. When the authors compared the formation rate of
methane hydrate in the presence of aluminum foam and SDS to the case where hydrates
are formed only in the presence of SDS they observed that in both cases the formation

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rate rapidly rose to a maximum and then, almost as rapidly, declined to zero. In the case
of the aluminum foam and SDS, the maximum formation rate was approximately five
minutes earlier than in the presence of an SDS solution alone. The maximum formation
rate was also seen to be approximately 20% larger when aluminum foam was present.
When experiments were subsequently performed to examine the effect of the initial
pressure on the formation rate, it was seen that there was an almost linear correlation
between the rate of methane hydrate formation and the initial pressure in the isochoric
reactor.

Figure 4 Sample of Aluminum foam. (Fan et al.119) Reprinted with permission from
Elsevier.

In a follow up study, Fan et al.119 proposed a mathematical model to correlate the results
obtained by Yang et al.118 Their model was based upon heat transfer in multi-layer

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cylindrical walls. Specifically, it was assumed that gas hydrates in the pores were
spherical, there is negligible free and contact resistance between the hydrate particles and
the aluminum foam, the hydrates and the aluminum foam are homogenous and the heat
flow is unidirectional. The results from the model consistently under-predicted the
measured experimental results. The authors speculated that this may be due to mass
transfer resistances, which were not accounted for in their model.
Rather than using a metal foam, Nambiar et al.120 instead used a cellulose foam as a
medium for forming gas hydrates from a mixture of CO2/H2/C3H8. Figure 5 shows an
SEM image of the Cellulose foam. The cellulose foam that was used had a pore volume
of 4.49 cm3/g and an average pore diameter of 80 m. Experiments were performed with
100% and 50% water saturated, using both fresh water and memory water. In all cases,
the measured induction time was seen to be very short; it was always between 0.39 and
1.83 minutes. Additionally, in the case of the 50% saturated foam the water-to-hydrate
conversion was higher than in the case of 100% saturated foam. The authors postulated
that this was due to a higher availability of gas in the pores, torturous pathways for water
migration and gas transport in the interstitial pore spaces during hydrate formation and a
larger gas-liquid contact area. The experimental data was subsequently correlated using
the Avrami model. It was seen that, in the cellulose foam, the Avrami model was able to
correlate the data for the first 40 minutes of hydrate formation.

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Figure 5: SEM of cellulose foam pores (Nambiar et al.120) Reprinted with permission
from Canadian Jounrnal of Chemistry.

Rather than employing a type of foam, Su et al.121 instead employed an ultralow density,
emulsion template polymerized high internal phase emulsion (polyHIPE) as a medium
for the formation of gas hydrates in the presence of hydrogen. The polyHIPE material
consisted of interconnected open-cells with an average pore volume of 9.1 m and a
measured surface area of 230 cm2/g. A 5.56 mol% THF solution was used for forming
the hydrogen hydrates in the polyHIPE. The experiments showed that the formation of
hydrates occurred with almost no induction time, in the presence of polyHIPE. When the
authors performed successive hydrate formation/decomposition cycles they made the
interesting observation that the gas uptake rate increased on the second cycle and then
remained constant for cycles 3 through 5. The authors speculated that this was due to the
limited wettability of the plyHIPE material as well as the enhanced dispersion of the
aqueous solution. While the reusability aspect of polyHIPE was promising, the authors
noted that the cumulative uptake of hydrogen was too small to be of any practical use.

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In a subsequent study to that mentioned in the previous paragraph, Su et al.122 formed


hydrogen hydrates in a solution of THF, in the presence of a hydrogel formed from
lightly crosslinked poly(acrylic acid) sodium salt (PSA). The polymer particles were
initially immersed in the THF solution where they swelled to form a hydrogel. These
superabsorbent gels can hold a large amount of water; Su et al.122 were able to disperse
20 g of THF solution in only 1 g of PSA particles. Another practical advantage of the
hydrogel system is that the swollen particles do not agglomerate. As was seen in the
previous study (Su et al.121) the rate of gas hydrate formation is greatly increased by the
presence of the hydrogel. When compared to the results obtained in the presence of
polyHIPE particles, the initial gas uptake in the hydrogel system was seen to be slower.
However, the final hydrogen storage capacity was significantly higher in the systems
containing the hydrogel. The authors (Su et al.122) also observed that the hydrogel system
exhibited a high degree of reusability. After four hydrate formation/decomposition
cycles, the rate of gas uptake and the gas storage capacity were almost unchanged.
Challenges for Future Studies
In the previous sections, many technical challenges were outlined. For example in the
presence of dry water, reusability of the material is a significant limitation to its use in
developing hydrate based gas storage systems. In other systems, such as packed beds or
in the presence of nanoparticles, the inability to disperse the heat of hydrate formation is
the most significant limiting factor.
The use of materials to enhance the rate of hydrate formation by increasing the surface
are of contact between gas and liquid also has process challenges that needs to be
understood. In the context of gas separations like carbon capture, the use of porous

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materials can be viewed as favorable as this involves the selective partition of a gas
component between the residual gas and the solid hydrate phase and the kinetics is
enhanced the presence of porous media. These operations are static and are likely to be
operated like a fixed bed reactor analogous to the conventional pressure/temperature
swing adsorption process or tray column operation. The schematic of a hydrate based gas
separation cycle is presented in Figure 6.

Figure 6: Hydrate based gas separation (HBGS) process cycle (Babu et al.79), reprinted
with permission from American Chemical Society

It is expected that after the end of the formation cycle, the hydrated or fractionated gas
will be recovered and the fixed bed will be put to operation again for another hydrate
formation cycle. On the other hand, when considering the use of porous materials for the
energy storage option employing the clathrate hydrate technology, there are additional
challenges. It is also noted that while the presence of nano-silica or nano-fluids in a
stirred system enhance the kinetics of CO2 hydrate systems efforts are still needed to
demonstrate such operation in a non-stirred manner, due to the high energy costs

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involved in the employment of stirred tank reactor for CO2 capture using the hydrate
technology.
These efforts include the decrease in the storage capacity in the volumetric or gravimetric
basis that includes the presence of these porous materials. For example a light-weight
material like nano hollow silica will decrease the volumetric capacity significantly.
Similarly, the use of aluminum foam will result in a decrease in gravimetric capacity of
energy storage. In addition, it is likely that the production plants and the storage or end
users are going to be distant. This adds a few operational challenges that come in the
form of pelletizing hydrates, that are present with the porous materials and the discharge
of the materials at the end user terminals after the stored gas is recovered. It is also noted
that many advancements in the kinetics of hydrate formation with the use of novel
materials have been also linked with the use of SDS in small quantities in water.
Thus, addressing the technical challenges associated with the accelerated formation of
gas hydrates will require an interdisciplinary approach. It seems highly unlikely that any
significant breakthroughs will come from the solo efforts of research groups that
specialize in the properties of gas hydrates. Material scientists, surface scientists and
process scientists will likely play an important role in the eventual commercialization of
hydrate based technologies.
The importance of interdisciplinary collaboration is reflected in the works that have been
outlined in the previous section. Of the works that were reviewed in the previous section,
the majority involved collaborations between different departments and/or different
institutions. The most common collaborations were between members of a chemical
engineering department with members of a government laboratory. The second most

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common collaboration was between chemists and chemical engineers. Outside of


chemistry and chemical engineering, works were created by power engineers, ocean
engineers, geologists and geophysicists.
While the backgrounds of the researchers are fairly diverse, the aim of the studies has
been much more focused. With the exception of the works related to hydrate formation in
packed beds, the reviewed articles have all been focused on the discovery of new
materials for enhancing hydrate formation rather than on deducing the mechanism for
hydrate formation in the novel materials. A significant barrier to mechanistic studies can
be found in the equipment that was used. In particular, research groups that are not
dedicated hydrate researchers relied upon relatively simple equipment. Of the
experimental studies that were reviewed, 72% were conducted in an apparatus that could
not maintain a constant pressure during hydrate formation. This makes the quantitative
interpretation of the experimental data, and thus a comprehensive mechanistic study,
significantly less straight forward.
In a similar vein to the previous paragraph, there is also a need for detailed quantitative
analyses if one ever wishes to scale up the technology to the point where hydrate based
gas storage can be considered an industrially important technology. At the time of
writing, only two studies had even attempted to present a comprehensive mathematical
model. As a final note in relationship to quantification of the experimental data, it was
noticed that there is no universally agreed upon metric for assessing the performance of a
kinetic enhancement scheme; metrics that were used include rate of gas uptake,
cumulative gas uptake, gas storage and rate of hydrate formation. Having a single,
universally agreed upon metric for performance could make the comparison of competing

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schemes relatively straightforward. The challenges for future research should be to


maximize the storage (or capture in case of separations) capacity in clathrate hydrates in a
short period of time (within a few minutes) i.e. at a faster rate of hydrate formation. In
addition, another important factor is the process scale-up demonstration of the clathrate
hydrate technologies.
Finally, it should be noted that there have not yet been any detailed studies on handling
these novel materials, in the scope of an industrial-scale plant that employs enhanced
hydrate formation, be it for gas storage or for one of the other possible applications. For
example, what measures would have to be in place to prevent silica sand or nanofluids
from contaminating downstream operations? Also, if metal or cellulose foams are to be
used for enhancing the rate of hydrate formation how would one handle a hydrate-foam
composite material in an industrial process? The authors speculate that these issues would
most likely lead to hydrate-based processes being operated in a batch mode. However,
this is only speculation, at this point in time, and further studies are needed to either
confirm or debunk this hypothesis.
Conclusion
Due to their ability to compress a large volume of gas into a relatively small space, gas
hydrates have the potential to become a medium for gas storage. Gas storage in the form
of hydrates has several potential advantages including relatively mild pressures,
compared to the likes of CNG, reusability and a lack of flammability. However, in order
to transition from the conceptual stage to the commercial stage, the problem of gas
hydrates relatively slow kinetics of formation must be addressed. The initial attempts at
enhancing the rate of gas hydrate formation relied upon using surfactants in stirred

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vessels. While these studies showed promise, their performance is limited by the large
amount of heat that accompanies the formation of a thick hydrate slurry.
Rather than relying solely upon surfactants to enhance the rate of gas hydrate formation,
recent studies have employed novel materials to increase the gas-liquid contact area
and/or to dissipate the heat of formation. The use of nano-particles in solution has a
positive effect on the rate of gas hydrate formation. As was the case with surfactants,
nano-particles effectiveness diminishes as the concentration increases due to excessive
heat generation and an increase in the solutions viscosity. Packed beds of sand, silica or
pulverized coal were seen as an effective means to increase the rate of gas hydrate
formation, as compared to the formation of gas hydrates in stagnant water. A common
observation in all of these studies was that the rate of gas hydrate formation increased as
the water saturation was decreased. Hydrogels, polymers and foams, of either aluminum
or cellulose, exhibited many qualitative similarities to packed beds of sand or silica, with
regards to the rate of hydrate formation. Finally, dry water and dry gels were seen to be
highly effective in storing large amounts of gas with a relatively small weight penalty.
However, the storage capacity of dry water and dry gels decreases significantly over
successive formation/decomposition cycles, due to water being expelled from the dry
water droplet.
Acknowledgements
The authors would like to acknowledge Professor Emeritus P. Raj Bishnoi and Professor
Peter Englezos for their years of mentorship and inspiration. PL would like to
acknowledge the support from Energy Innovation Research Programme (EIRP, Award

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No. NRF2014EWTEIRP003-006), administrated by the Energy Market Authority (EMA)


of Singapore.

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